Chemistry Books

Book SynopsisA groundbreaking text to the study of textile fibers that bridges the knowledge gap between fiber shape and end uses Textile Fiber Microscopy offers an important and comprehensive guide to the study of textile fibers and contains a unique text that prioritizes a review of fibers' microstructure, macrostructure and chemical composition. The author a noted expert in the field details many fiber types and includes all the possible fiber shapes with a number of illustrative micrographs. The author explores a wealth of topics such as fiber end uses, fiber source and production, a history of each fiber and the sustainability of the various fibers. The text includes a review of environmentally friendly fibers and contains information on the most current fiber science by putting the focus on fibers that have been mechanically or chemically recycled, for use in textile production. The author also offers an exploration of issues of textile waste and the lack of tTable of ContentsPreface ix Acknowledgments xi Introduction xiii 1 Natural Cellulosic Fibers 1 1.1 Seed Fibers 1 1.1.1 Cotton 1 1.1.2 Organic Cotton 4 1.1.3 Kapok Fibers 6 1.1.4 Poplar Fibers 8 1.1.5 Willow Fibers 9 1.1.6 Coir Fibers 11 1.2 Bast Fibers 12 1.2.1 Linen 12 1.2.2 Ramie 16 1.2.3 Hemp 17 1.2.4 Bamboo 21 1.2.5 Jute 22 1.2.6 Fiber Size 22 1.2.7 Nettle 22 1.2.8 Bast Fiber in Its Historical Context 26 1.3 Leaf Fibers 26 1.3.1 Sisal 27 1.3.2 Henequen 27 1.3.3 Abaca 27 1.3.4 Pineapple Leaves 28 References 28 2 Animal Fibers 31 2.1 Wool 31 2.1.1 Cuticle 32 2.1.2 Scale Pattern Type (Animal Hair) 33 2.1.2.1 Mosaic 34 2.1.2.2 Wave 34 2.1.2.3 Chevron 34 2.1.2.4 Petal 36 2.1.3 Types of Scale Margins 36 2.1.4 Cortex 36 2.1.5 Medulla 36 2.1.5.1 Lattice 37 2.1.5.2 Simple Unbroken 37 2.1.5.3 Interrupted 38 2.1.5.4 Fragmental 38 2.1.5.5 Ladder Type of Medulla 38 2.1.6 Fiber Size 39 2.1.7 Fiber Morphology 39 2.1.7.1 Fiber Absorbency 41 2.1.7.2 Fiber Shrinkage 41 2.1.7.3 Wool Varieties 42 2.1.8 Merino Wool and Other Fine Wool Fibers 43 2.1.8.1 Normal Fleece Wool 44 2.1.8.2 Kemp Fibers 44 2.2 Luxury Fibers 45 2.2.1 Cashmere 46 2.2.2 Yangir 49 2.2.3 Mohair 49 2.2.4 Vicuna 54 2.2.5 Camelid Fibers 55 2.2.6 Alpaca 57 2.2.7 Llama 61 2.2.8 Shahtoosh 62 2.2.9 Yak 62 2.2.10 Other Identification Techniques to Note 63 2.3 Silk 66 2.3.1 Peace or Ahimsa Silk 69 2.3.2 Spider Silk 71 References 73 3 Fur Fibers 77 3.1 Animal Fibers 77 3.1.1 Scale Cast 78 3.1.2 Cuticle Scales 79 3.1.3 Rabbit, Hare, and Angora Rabbit Fibers 79 3.1.4 Angora Hair 81 3.2 Other Fur Fibers 84 3.2.1 Mink and Ermine 86 3.2.2 Kolinsky Mink 88 3.2.3 Raccoon Dog 88 3.2.4 Red Fox 89 3.3 Faux Fur 89 3.4 Dog and Cat Fur 94 3.4.1 Karakul 96 3.4.2 Optical Microscopy 97 3.4.3 Measuring Hair Length 98 References 98 4 Regenerated Cellulosic and Protein Fibers 101 4.1 Regenerated Cellulosic Fibers 101 4.1.1 Viscose Rayon 101 4.1.2 Bamboo Rayon 103 4.1.3 High Wet Modulus (HWM) Rayon 104 4.1.4 Cuprammonium Rayon 106 4.1.5 Lyocell Fibers 107 4.1.6 A Review of Cross‐sectional Shapes of Fibers 108 4.1.7 Cross‐sectional Fiber Shape and Luster 109 4.1.8 Acetate Fibers 111 4.2 Regenerated Protein Fibers 113 4.2.1 Soybean Fibers 114 4.2.2 Milk Fibers 117 4.2.3 Composite Cellulose Fibers 117 References 120 5 Synthetic Fibers 123 5.1 Nylon 123 5.2 Polyester 124 5.3 Luster 126 5.4 Delustering 126 5.5 Longitudinal View 128 5.6 Variety of Cross‐sectional Shapes 128 5.7 Comparison Analysis 131 5.8 Fibers in Carpeting 133 5.9 Fabric Tenacity 134 5.10 Performance Textiles 135 5.11 Acrylic Fibers 136 5.12 Fiber Cross‐sections 137 5.13 Fiber Longitudinal View 138 5.14 Spandex 141 5.15 Olefin 143 5.16 Fiber Melting Point 144 5.17 Microfibers 146 5.17.1 Applications of Microfibers 150 5.17.2 Imitation Leather/Suede 157 References 159 6 Nanofibers 161 6.1 Nanotechnology in Textiles 161 6.1.1 Production of Nanofibers 163 6.1.2 Uses of Nanofibers 163 6.1.3 Nanowebs 164 6.1.4 Nanocoatings 166 6.1.5 Nanoparticles 167 6.1.6 Electrically Conductive Fibers 168 6.1.7 Porous Surface Fibers 169 6.1.8 Microscopy 170 References 170 7 Recycled Fibers 173 7.1 Fiber Recycling 173 7.2 Recycled Polyester via Chemical Recycling 173 7.2.1 Microscopic Appearance 174 7.3 Recycled PET via Mechanical Recycling 174 7.3.1 Microscopic Images 176 7.4 Recycling Nylon 177 7.5 Recycled Cotton 177 7.5.1 Microscopic Appearance 179 7.6 Recycled Wool 179 7.6.1 Microscopic Appearance 180 7.7 Other Recycling Methods – Using a Rayon Manufacturing Method to Recycle Fibers – A Dissolution‐Based Recycling Method 181 7.7.1 Microscopic Appearance 182 7.7.2 Recycling Blends 182 References 184 8 Historic Fibers 187 8.1 Textile Fibers and History 187 8.1.1 General Information – Ancient Textiles 188 8.1.2 Greek Textiles 188 8.2 The Use of Hemp in Central Europe 194 8.3 Egyptian Textiles 194 8.3.1 Middle Kingdom Linen Cloth 195 8.3.2 Romano‐Egyptian Textiles 196 References 198 Index 201

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Book SynopsisThis book describes fluorocarbons gases' preparation process, properties, applications and their evolution over time. The impact of fluorocarbons on the ozone layer and global and the development to mitigate those effects have been specially emphasized. The first major industrial fluorinated compound was developed in the 1920's, to replace ammonia and sulfur dioxide refrigerants, at the General Motors Frigidaire Division by Thomas Midgley, Jr. and Albert Leon Henne. They developed a family of fluorocarbons trademarked Freon for auto air conditioning units revolutionizing the auto industry. Other applications were developed over time including fire extinguishers, propellants, blowing agents, cleaners, anesthesia, artificial blood and others impacting every facet of life. In spite of being in broad global use for nearly a century, fluorocarbon gases have gone through great evolution during the last few decades. In the 1980s it was discovered chlorofluorocarbon (CFC) gaseTable of ContentsPreface xi 1 Introduction 1 1.1 Terminology 1 1.2 Production and Consumption Statistics of Fluorocarbons 3 1.2.1 Refrigerants: Market Trends and Supply Chain Assessment 3 1.2.2 Fluorocarbon Consumption Demand 6 1.3 Production and Consumption Statistics of Fluoropolymers 7 1.4 Production and Consumption Statistics of Fluoroelastomers 9 1.5 Production and Consumption Statistics of Fluorinated Coatings 9 1.6 Specialty Fluorochemicals 10 References 10 2 Classification and Description of Commercial Fluorinated Compounds 13 2.1 Fluorine and Fluorochemicals 13 2.2 Fluorocarbons 13 2.3 Designations for Fluorocarbons 15 2.4 Fluoropolymers and Fluoroelastomers 22 2.4.1 Fluoropolymers 23 2.4.2 Fluoroelastomers 24 2.5 Fluorinated Coatings 26 2.6 Summary 27 References 27 3 Fluorine Sources and Basic Fluorocarbon Reactions 29 3.1 Role of Fluorine in Fluorocarbons 29 3.2 Fluorine Sources 30 3.3 Fluorocarbon Compounds 34 3.4 Hydrofluoric Acid 34 3.4.1 Manufacturing Hydrofluoric Acid 34 3.5 Aliphatic Fluorinated Organic Compounds 35 3.6 Synthesis of Fluorocarbons 36 References 38 4 Applications of Fluorocarbon Gases and Liquids 41 4.1 Refrigeration and Air Conditioning 41 4.1.1 Refrigeration Applications 46 4.1.1.1 Chillers 46 4.1.1.2 Cold Storage Warehouses 46 4.1.1.3 Commercial Ice Machines 47 4.1.1.4 Household Refrigerators and Freezers 47 4.1.1.5 Ice Skating Rinks 48 4.1.1.6 Industrial Process Air Conditioning 48 4.1.1.7 Industrial Process Refrigeration 48 4.1.1.8 Motor Vehicle Air Conditioning 48 4.1.1.9 Non-Mechanical Heat Transfer Systems 48 4.1.1.10 Residential and Light Commercial Air Conditioning and Heat Pumps 48 4.1.1.11 Residential Dehumidifiers 48 4.1.1.12 Refrigerated Transport 49 4.1.1.13 Retail Food Refrigeration 49 4.1.1.14 Vending Machines 49 4.1.1.15 Very Low Temperature Refrigeration 49 4.1.1.16 Water Coolers 49 4.2 Oil in Refrigerants 49 4.2.1 Oil Return 51 4.3 Monomers and Intermediates 51 4.4 Foam Blowing 52 4.4.1 Foam Blowing Agents 52 4.4.2 Foaming Process 54 4.4.3 Flexible Polyurethane Foams 59 4.5 Aerosol Propellants 60 4.6 Fire Extinguishing Agents 61 4.6.1 Aerospace Fire Extinguishing 63 4.7 Cleaning and Drying Solvents 66 4.8 Carrier Fluids/Lubricant Deposition 70 4.9 Heat Transfer 71 4.10 Etchants 72 4.10.1 What is Etching? 72 4.10.2 Fluorocarbon Etchants 72 4.11 Medical Applications 74 4.11.1 Enfluorane 76 4.11.2 Isoflurane 77 4.11.3 Desflurane 77 4.11.4 Sevoflurane 78 4.11.5 Methoxyflurane 79 4.12 Usage of HCFCs and HFCs 79 4.12.1 Introduction 80 4.13 Breakdown of Fluorocarbons in Applications 80 4.14 Summary 82 References 84 5 Refrigeration Cycle and Refrigerant Selection: How Refrigerant Gases Work? 87 5.1 Refrigeration Cycle 87 5.1.1 Reversed Carnot Cycle 89 5.1.2 Ideal Vapor-Compression Refrigeration Cycle 91 5.1.3 Actual Vapor-Compression Refrigeration Cycle 91 5.2 Selection of Right Refrigerant 92 5.3 Refrigerant Blends 95 5.4 Comparison of Refrigerator and Air Conditioning Systems 97 References 98 6 Preparation of Fluorocarbons 99 6.1 Introduction 99 6.2 Classification of Fluorocarbons 101 6.3 Preparation of Chlorofluorocarbons (CFCs) 104 6.3.1 Longevity of Process Catalysts 121 6.4 Fluorocarbon Replacements of CFCs 124 6.5 Substitutes for CFCs: HCFC and HFC 125 6.5.1 Preparation of Hydrochlorofluorocarbons (HCFCs) 126 6.5.2 Preparation of Hydrofluorocarbons (HFCs) 131 6.6 Preparation of Hydrofluoroolefins (HFOs) 142 6.7 Preparation Perfluorinated Alkanes 146 6.8 Summary 150 References 150 7 Properties of Fluorocarbons 155 8 Environmental, Safety, Health and Sustainability 217 8.1 Montreal Protocol 217 8.2 Ozone Depletion 224 8.3 Global Warming 230 8.3.1 Paris Agreement 233 8.4 Phase Out of Old Fluorocarbon Gases 234 8.4.1 Status of Phase Out of HCFCs 236 8.5 Summary 237 References 237 9 Fluorocarbon Blends 241 9.1 General Blend Characteristics 245 9.1.1 Azeotropic 245 9.1.2 Zeotropic Blends 245 9.2 Low GWP HFO and HFO/HFC Blends 251 9.3 Flammability of Blends 266 References 266 10 Substitute Fluorocarbons and Other Compounds 267 10.1 SNAP Program (EPA, www.epa.gov/snap/overview-snap) 267 10.2 Guiding Principles of the SNAP Program? 268 10.3 EPA’s Criteria for Evaluating Alternatives? 268 10.3.1 Atmospheric Effects 268 10.3.2 Exposure Assessments 268 10.3.3 Toxicity Data 269 10.3.4 Flammability 269 10.3.5 Other Environmental Impacts 269 10.4 Alternatives for Refrigeration 270 10.4.1 Chillers 270 10.4.2 Cold Storage Warehouses 270 10.4.3 Commercial Ice Machines 270 10.4.4 Household Refrigerators and Freezers 270 10.4.5 Ice Skating Rinks 270 10.4.6 Industrial Process Refrigeration 273 10.4.7 Refrigerated Transport 273 10.4.8 Retail Food Refrigeration 273 10.4.9 Vending Machines 273 10.4.10 Very Low Temperature Refrigeration 273 10.4.11 Water Coolers 273 10.5 Alternatives for Air Conditioning 273 10.5.1 Industrial Process Air Conditioning 273 10.5.2 Motor Vehicle Air Conditioning 279 10.5.3 Non-Mechanical Heat Transfer Systems 279 10.5.4 Residential and Light Commercial Air Conditioning and Heat Pumps 279 10.5.5 Residential Dehumidifiers 279 11 Future Directions of Fluorocarbons 283 11.1 Introduction 283 11.2 Inception and Evolution of Fluorocarbons 284 11.3 Classification of Refrigerants 286 11.3.1 First Generation (Prior to 1930) 286 11.3.2 Second Generation (1931–1990) 288 11.3.3 Third Generation (1990–2010) 288 11.3.4 Fourth Generation (Beyond 2010) 289 11.3.5 Hydrofluoroolefin Fluorocarbons 291 11.4 Natural Refrigerants 296 11.4.1 Carbon Dioxide 299 11.4.2 Hydrocarbons 306 11.4.3 Ammonia 306 11.5 Phase Out of Fluorocarbon Gases 306 11.6 Future Directions of Refrigerants 309 11.6.1 Introduction 309 11.6.2 Towards the Future 309 11.6.2.1 Innovation 310 11.6.2.2 Innovation Accelerating Transition 310 11.6.2.3 Speed Bumps 310 11.6.2.4 New Developments 312 11.7 Conclusions 313 References 313 Appendix I 317 Appendix II 373 Appendix III 381 Index 403

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Book SynopsisThe Advances in Chemical Physics series provides the chemical physics field with a forum for critical, authoritative evaluations of advances in every area of the discipline. This is the only series of volumes available that presents the cutting edge of research in chemical physics.Table of ContentsList of Contributors Volume 162 IX Preface to the Series XI ELECTRONIC STRUCTURE AND DYNAMICS OF SINGLET FISSION IN ORGANIC MOLECULES AND CRYSTALS 1Timothy C. Berkelbach AN APPROACH TO “QUANTUMNESS” IN COHERENT CONTROL 39Torsten Scholak and Paul Brumer ENERGETIC AND NANOSTRUCTURAL DESIGN OF SMALL-MOLECULAR-TYPE ORGANIC SOLAR CELLS 137Masahiro Hiramoto SINGLE MOLECULE DATA ANALYSIS: AN INTRODUCTION 205Meysam Tavakoli, J. Nicholas Taylor, Chun-Biu Li,Tamiki Komatsuzaki, and Steve Pressé CHEMISTRY WITH CONTROLLED IONS 307Stefan Willitsch Index 341

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Book SynopsisA guide to environmental and communication issues related to fracking and the best approach to protect communities Environmental Considerations Associated with Hydraulic Fracturing Operations offers a much-needed resource that explores the complex challenges of fracking by providing an understanding of the environmental and communication issues that are inherent with hydraulic fracturing. The book balances the current scientific knowledge with the uncertainty and risks associated with hydraulic fracking. In addition, the authors offer targeted approaches for helping to keep communities safe. The authors include an overview of the historical development of hydraulic fracturing and the technology currently employed. The book also explores the risk, prevention, and mitigation factors that are associated with fracturing. The authors also include legal cases, regulatory issues, and data on the cost of recovery. The volume presents audit checklists for gatherinTable of ContentsList of Figures xvii List of Tables xxvii Foreword xxxi Acknowledgments xxxiii 1 Introduction 1 1.1 Energy and the Shale Revolution 1 1.2 Cultural Influences 3 1.3 Conventional Versus Unconventional Resources 4 1.4 Well Simulation 5 1.5 Hydraulic Fracturing in the United States 16 1.6 Environmental Considerations 17 1.7 Exercises 22 References 22 Suggested Reading 23 2 Historical Development from Fracturing to Hydraulic Fracturing 25 2.1 Introduction 25 2.2 Explosives and Guns (1820s–1930s) 26 2.3 The Birth of the Petroleum Engineer (1940s–1950s) 38 2.4 Going Nuclear During Peak Oil (1960s to Mid‐1970s) 39 2.5 The Rise of the Unconventionals (Mid‐1970s to Present) 45 2.6 Exercises 49 References 50 Suggested Reading 51 3 Geology of Unconventional Resources 53 3.1 Introduction 53 3.2 Oil Shale Nomenclature 54 3.3 Oil Shale Classification 54 3.4 Types of Shale Formations Based on Production 56 3.5 Geology of United States Shale Deposits 60 3.6 The Role of Natural Fractures 75 3.7 Exercises 76 References 77 Suggested Reading 79 4 Overview of Drilling and Hydraulic Fracture Stimulation Techniques for Tight Oil and Gas Shale Formations 81 4.1 Introduction 81 4.2 Phase 1: Prospect Generation for Unconventional Oil and Gas Targets 85 4.3 Phase 2: Planning Phase 92 4.4 Phase 3: Drilling 94 4.5 Brief Overview of Hydraulic Fracturing 109 4.6 Operators and Contractors 111 4.7 Phase 4: Completion 111 4.8 Overview of Hydraulic Fracturing Process 115 4.9 Single‐Stage Treatment 119 4.10 Fluid Recovery and Waste Management 123 4.11 Oil and Gas Production 123 4.12 Naturally Occurring Radioactive Material (NORM) 126 4.13 Workshop #1: Gas Well Economic Limit 128 4.14 Workshop #2: Oil Well Economics 129 4.15 Well Destruction 129 4.16 Summary 131 4.17 Exercises 131 References 132 Suggested Reading 134 5 Overview of Impacts from Tight Oil and Shale Gas Resource Development 137 5.1 Introduction 137 5.2 Potential Impacts and Risks of Spills 137 5.3 Significance of Impacts 137 5.4 Overview of the Five Main Resource Categories 138 5.5 Primary Wastes Generated 146 5.6 Site‐specific Impact Analysis 146 5.7 Summary of Resources and Issues 163 5.8 Summary 174 5.9 Exercises 176 References 177 Suggested Reading 179 6 Surface and Groundwater Risks, Resource Quality Management, and Impacts 183 6.1 Introduction 183 6.2 The Hydraulic Fracturing Water Cycle 183 6.3 Potential Impacts on Drinking Water Resources 188 6.4 Public Water System (PWS) Sources 189 6.5 Underground Injection Control 190 6.6 Case Histories 196 6.7 Exercises 198 References 198 Suggested Reading 199 7 Induced Seismicity 203 7.1 Introduction 203 7.2 Measuring Earthquake Severity 204 7.3 Anthropogenic‐Induced Earthquakes 208 7.4 Mechanics of Anthropogenic‐Induced Earthquakes 210 7.5 Induced Microseismicity and Microseismic Monitoring 212 7.6 Exercises 212 References 213 Suggested Reading 213 8 Air Quality Resources and Mitigation Measures 215 8.1 Introduction 215 8.2 Unconventional Resource Extraction and Air Quality 215 8.3 Sources of Air Emissions 215 8.4 Worker Safety 220 8.5 Gas Leaks and Vapor Sampling 230 8.6 Biogenic and Thermogenic Hydrocarbon Gases 232 8.7 Gas Leaks 233 8.8 Soil Vapor Intrusion Overview 234 8.9 General Approach to Evaluating Soil Vapor Intrusion 237 8.10 Summary 248 8.11 Exercises 249 References 249 Suggested Reading 253 9 Land Use Resources and Socioeconomics 255 9.1 Introduction 255 9.2 Community Concerns and Land Use Planning 255 9.3 Environmental Justice 259 9.4 Land Disturbance 259 9.5 Light Pollution 261 9.6 Noise 263 9.7 Odor 270 9.8 Socioeconomics 271 9.9 Transportation and Traffic 272 9.10 Visual Aesthetics 277 9.11 Worker Safety 278 9.12 Cumulative Impacts 278 9.13 Exercises 279 References 279 Suggested Reading 281 10 Ecological Resources 283 10.1 Introduction 283 10.2 Ecosystem Resources 283 10.3 Ecosystem Resources 283 10.4 Interim Reclamation 286 10.5 Summary 295 10.6 Exercises 295 References 296 Suggested Reading 297 11 Legislative Trends Associated with Well Stimulation and Hydraulic Fracturing 299 11.1 Introduction 299 11.2 Federal Laws and Regulations 300 11.3 State Legislation and Regulations 304 11.4 Bans and Moratoriums 311 11.5 Exercises 313 References 313 Suggested Reading 314 12 Sampling, Exposure Pathways, and Site Conceptual Models 315 12.1 Introduction 315 12.2 Hypothetical Scenario 317 12.3 Overview of Sampling Procedures 322 12.4 Soil and Water Sampling 327 12.5 Field Screening and Analysis 329 12.6 Other Considerations 332 12.7 Fate and Transport 339 12.8 Summary 342 12.9 Exercises 342 References 345 Suggested Reading 347 13 Financial Issues: Real Estate Values and Selected Contracting Costs of Repairs, Assessment, or Mitigation Activities for Unconventional Oil and Gas Production Areas 351 13.1 Introduction 351 13.2 Valuation of Real Estate 351 13.3 Water Supplies 357 13.4 Other Mitigating Costs 358 13.5 Mitigation of Subsurface Impacts 362 13.6 Remediation Strategies 365 13.7 Budgeting for Costs 369 13.8 Summary 372 13.9 Exercises 373 References 374 Suggested Reading 375 14 Legal Considerations and Case Law 377 14.1 Introduction 377 14.2 Environmental Tort Litigation 382 14.3 Environmental/Citizen Action and Industry Challenges Litigation 383 14.4 Infrastructure‐Related Litigation 384 14.5 Traditional Oil and Gas Issues in Nontraditional Forums 384 14.6 Fracking Bans and Moratoriums 384 14.7 Summary 386 14.8 Exercises 387 Reference 387 Suggested Reading 387 15 Spills, Forensic Evaluation, and Case Studies 389 15.1 Introduction 389 15.2 Spill Studies 389 15.3 Spill Settlement Case Study 392 15.3.1 Rail Case Studies 393 15.3.2 Bakken Crude Oil Characteristics: Two Studies 394 15.3.3 Summary of Bakken Crude Oil Spill Incidents 394 15.3.4 Fate and Transport of Spilled Crude 394 15.3.5 Combustion 398 15.3.6 DOT‐117 Tank Car Design 398 15.4 Violations 399 15.5 Forensic Analysis 399 15.5.1 Gas Chromatograms 400 15.5.2 Tentatively Identified Compounds (TICs) 401 15.5.3 Piper Diagrams 401 15.5.4 Biomarkers 403 15.5.5 Chemical and Biological Transformations 404 15.5.6 Chemical Ratios 406 15.5.7 Geochemical Tracers 406 15.5.8 Isotopes 407 15.5.9 Forensic Isotope Analysis 408 15.5.10 Boron and Strontium Isotope Ratios 409 15.5.11 Radioactive Isotopes 410 15.5.12 Case Studies 411 15.6 Prospective and Retrospective Case Studies 413 15.6.1 US EPA Retrospective Case Study 414 15.6.2 US EPA Retrospective Study Approach and Sampling Activities 415 15.6.3 Main Findings 420 15.6.4 Summary of US EPA Retrospective Studies 438 15.7 Exercises 439 References 440 Suggested Reading 446 16 Conclusions 453 Appendix A Selected University Studies, State, and Federal Reports 455 Appendix B Glossary 461 Appendix C List of Acronyms and Abbreviations 467 Appendix D Conversions 473 Appendix E Summary of Potential Job Hazards During Hydraulic Fracture Stimulation Process 477 Appendix F Chemical Additives Used in the High‐Volume Hydraulic Fracturing Operations 481 Appendix G Exposure Planning, Emergency Response, and Toxicity Tables 485 Appendix H Selected Sampling Methods and Documentation 493 Appendix I Environmental Checklists 503 Appendix J Metric Conversion of Table 3.4 (Metric Units in Bold italics) 523 Appendix K US Crude Oil Prices 1859–2016 525 Index 527

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Book SynopsisBridging the Gap Between Organic Chemistry Fundamentals and Advanced Synthesis Problems Introduction to Strategies of Organic Synthesis bridges the knowledge gap between sophomore-level organic chemistry and senior-level or graduate-level synthesis to help students more easily adjust to a synthetic chemistry mindset. Beginning with a thorough review of reagents, functional groups, and their reactions, this book prepares students to progress into advanced synthetic strategies. Major reactions are presented from a mechanistic perspective and then again from a synthetic chemist's point of view to help students shift their thought patterns and teach them how to imagine the series of reactions needed to reach a desired target molecule. Success in organic synthesis requires not only familiarity with common reagents and functional group interconversions, but also a deep understanding of functional group behavior and reactivity. This book provides clear explanatTable of ContentsPreface xix Acknowlegments xxi CHAPTER 1 Synthetic Toolbox 1: Retrosynthesis and Protective Groups 1 1.1 Retrosynthetic Analysis 3 1.2 Protective Groups 11 CHAPTER 1 Problems Protective Groups 19 CHAPTER 2 Synthetic Toolbox 2: Overview of Organic Transformations 21 2.1 Nucleophiles and Electrophiles 23 2.2 Oxidation and Reduction Reactions 27 CHAPTER 2 Problems Nucleophiles, Electrophiles, and Redox 41 CHAPTER 3 Synthesis of Monofunctional Target Molecules (1-FG TMs) 45 3.1 Synthesis of Alcohols (ROH) and Phenols (ArOH) 47 3.2 Synthesis of Alkyl (RX) and Aryl Halides (ArX) 61 3.3 Synthesis of Ethers (ROR′) 67 3.4 Synthesis of Thiols (RSH) and Thioethers (RSR´) 73 3.5 Synthesis of Amines (RNH2) and Anilines (ArNH2) 77 3.6 Synthesis of Alkenes (R2C¨TCR2) 85 3.7 Synthesis of Alkynes (RC≡CR′) 93 3.8 Synthesis of Alkanes (RH) 97 3.9 Synthesis of Aldehydes and Ketones (RCHO, R2C¨TO) 105 3.10 Synthesis of Carboxylic Acids (RCO2H) 117 3.11 Synthesis of Carboxylic Acid Derivatives 125 CHAPTER 3 Problems 1-FG TMs 139 CHAPTER 4 Synthesis of Target Molecules with Two Functional Groups (2-FG TMs) 143 4.1 Synthesis of β©\Hydroxy Carbonyls and α,β©\Unsaturated Carbonyls 145 4.2 More Enolate Reactions: Synthesis of 1,3©\Dicarbonyls, 1,5©\Dicarbonyls, and Cyclohexenones 157 4.3 “Illogical” 2©\Group Disconnections: Umpolung (Polarity Reversal) 171 CHAPTER 4 Problems 2-FG TMs 183 CHAPTER 5 Synthesis of Aromatic Target Molecules 187 5.1 Electrophilic Aromatic Substitution (ArH + E+ → ArE) 189 5.2 Synthesis of Aromatic TMs via Diazonium Salts (ArN2 + + Nu: → ArNu) 201 5.3 Nucleophilic Aromatic Substitution (ArX + Nu: → ArNu) 205 CHAPTER 5 Problems Aromatic TMs 209 CHAPTER 6 Synthesis of Compounds Containing Rings 211 6.1 Synthesis of Cyclopropanes 213 6.2 Synthesis of Cyclobutanes 215 6.3 Synthesis of Five©\Membered Rings (Radical Cyclization Reactions) 217 6.4 Synthesis of Six©\Membered Rings (Diels–Alder Reaction) 221 CHAPTER 6 Problems Cyclic TMs 231 CHAPTER 7 Predicting and Controlling Stereochemistry 235 7.1 Reactions that Form Racemates 237 7.2 SN2 Mechanism: Backside Attack 243 7.3 Elimination Mechanisms 245 7.4 Additions to Alkenes and Alkynes 247 7.5 Additions to Carbonyls 251 7.6 Additions to Enolates: Aldol Stereochemistry 257 7.7 Enantioselectivity and Asymmetric Syntheses 261 CHAPTER 7 Problems Stereochemistry 269 CHAPTER 8 Transition Metal-Mediated Carbon–Carbon Bond Formation 273 8.1 Transition Metal Coordination Complexes 275 8.2 Organometallic Reaction Mechanisms 283 8.3 Carbonylation and Decarbonylation 291 8.4 (ArX + Alkene → Ar©\Alkene) 295 8.5 Palladium©\Catalyzed Cross©\Coupling Reactions (RX + R′M → R©\R′) 297 8.6 Olefin Metathesis Reactions 303 8.7 Retrosynthesis: Disconnections Based on Metal-Mediated Reactions 307 CHAPTER 8 Problems Transition Metal-Mediated Synthesis 309 SOLUTIONS TO PROBLEMS 313 Index 389

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Book SynopsisThe current volume continues the tradition of the Organic Syntheses series, providing carefully checked and edited experimental procedures that describe important synthetic methods, transformations, reagents, and synthetic building blocks or intermediates with demonstrated utility in organic synthesis.Table of ContentsDIBALH-Mediated Reductive Ring-Expansion Reaction of Cyclic Ketoxime 1Taku Imaizumi, Kentaro Okano, and Hidetoshi Tokuyama Preparation of 2-(2-(Dicyclohexylphosphino)phenyl)-1-methyl-1H-indole (CM-phos) 14Shun Man Wong, On Ying Yuen, Pui Ying Choy, Chau Ming So, and Fuk Yee Kwong Synthesis of 5-(Hydroxymethyl)furfural (HMF) 29Svilen P. Simeonov, Jaime A. S. Coelho, and Carlos A. M. Afonso Erratum for: Titanium-Mediated Addition of Silyl Dienol Ethers to Electrophilic Glycine: 4 Ketopipecolic Acid Hydrochloride 37Clarisse Mühlemann, Peter Hartmann, and Jean-Pierre Obrecht Nickel-Catalyzed Synthesis of Ketones from Alkyl Halides and Acid Chlorides: Preparation of Ethyl 4-Oxododecanoate 50Alexander C. Wotal, Donald C. Batesky, and Daniel J. Weix Trichloroboron-promoted Deprotection of Phenolic Benzyl Ether UsingPentamethylbenzene as a Non Lewis-Basic Cation Scavenger 63Shun Okaya, Keiichiro Okuyama, Kentaro Okano, and Hidetoshi Tokuyama Enantioselective Synthesis of α,α-Disubstituted Lactones via a Chiral Brønsted Acid-Catalyzed Intramolecular Cyclization 75Jennifer E. Wilent, Ghassan Qabaja, and Kimberly S. Petersen Enantioselective Synthesis of α-Bromonitroalkanes for Umpolung Amide Synthesis: Preparation of tert-Butyl ((1R)-1-(4-(benzyloxy)phenyl)-2-bromo-2-nitroethyl)carbamate 88Victoria T. Lim, Sergey V. Tsukanov, Amanda B. Stephens, and Jeffrey N. Johnston Synthesis of 1-Bromopyrene and 1-Pyrenecarbaldehyde 100Matthias Schulze, Alexander Scherer, Colin Diner, and Rik R. Tykwinski Intermolecular [2+2] Cycloaddition of Alkynes with Alkenes Catalyzed by Gold(I) 115M. Elena de Orbe and Antonio M. Echavarren Photochemical Benzannulation of N-Phosphoryl Ynamides and α-Diazo Ketones in Continuous Flow 127John M. Read, Yu-Pu Wang, and Rick L. Danheiser Trifluoromethylation of Aryl Iodides Catalyzed by the Copper(I)-Phen Complex 147Naoto Shimizu, Hideaki Kondo, Masahiro Oishi, Kenichi Fujikawa, Kazuki Komoda, and Hideki Amii Copper-catalyzed Cyanation of Alkenyl Iodides 163Antoine Nitelet, Sara Zahim, Cédric Theunissen, Alexandre Pradal, and Gwilherm Evano Visible Light Photocatalysis of Radical Cation Diels–Alder Cycloadditions: Preparation of Tris(2,2’-bipyrazyl) Ruthenium(II) Bis(tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) 178Shane D. Lies, Shishi Lin, and Tehshik P. Yoon Preparation of Methyl 1,2,3,4-tetra-O-acetyl-β-D-glucopyranuronate 200Aisling Ní Cheallaigh, Garrett T. Potter, John M. Gardiner, and Gavin J. Miller Preparation of 1,5-Dioxaspiro[5.5]undecan-3-one 210Robert A. Craig, II, Russell C. Smith, Beau P. Pritchett, Benzi I. Estipona, and Brian M. Stoltz Oxyboration: Synthesis of Borylated Benzofurans 228Darius J. Faizi, Nicole A. Nava, Mohammad Al-Amin, and Suzanne A. Blum Synthesis of 1-Iodopropyne 245Samuel G. Bartko, James Deng, and Rick L. Danheiser Potassium tert-Butoxide–Catalyzed Dehydrogenative Cross-Coupling of Heteroarenes with Hydrosilanes 263Anton A. Toutov, Wen-Bo Liu, Brian M. Stoltz, and Robert H. Grubbs Synthesis of α-Carboline 272Linli He, Shawn P. Allwein, Benjamin J. Dugan, Kyle W. Knouse, Gregory R. Ott, and Craig A. Zificsak Synthesis of Methyl 1-Formylcyclopropanecarboxylate utilizing Ti-Claisen Condensation 286Yuichiro Ashida, Satomi Kajimoto, Hidefumi Nakatsuji, and Yoo Tanabe Nickel-Catalyzed Suzuki–Miyaura Coupling in t-Amyl Alcohol for the Preparation of 5-(Furan-3-yl)pyrimidine 306Liana Hie and Neil K. Garg Preparation of (S)-Nonafluorobutanesulfinamide 319Apiwat Wangweerawong, Scott Kolmar, and Jonathan A. Ellman Preparation of 1-Methylimidazole-N-oxide (NMI-O) 331James I. Murray and Alan C. Spivey Palladium-Catalyzed Direct Amination of Allylic Alcohols at Room Temperature 341Bao Gao, Lixin Li, Guoying Zhang, and Hanmin Huang Preparation of 1,1-Difluoroallenes by Difluorovinylidenation of Carbonyl Compounds 352Kohei Fuchibe, Masashi Abe, Ken Oh, and Junji Ichikawa Rhodium-Catalyzed Addition of Carboxylic Acids to Terminal Alkynes towards Z-Enol Esters 367Stephanie Ganss, Julia Pedroni, Alexandre Lumbroso, Günther Leonhardt-Lutterbeck, Antje Meißner, Siping Wei, Hans-Joachim Drexler, Detlef Heller, and Bernhard Breit Copper-Catalyzed Semi-Reduction of Alkynes 385Nick Cox, Hester Dang, Aaron M. Whittaker, and Gojko Lalic Synthesis of Cyclobutanes by Lewis Acid-Promoted Ketene-Alkene [2+2] Cycloadditions 401Christopher M. Rasik, Eleni M. Salyers, and M. Kevin Brown Synthesis of 2,2-Dichloroimidazolidine-4,5-diones and their Application in Chlorodehydroxylation 413David Schilter and Christopher W. Bielawski

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Book SynopsisThe Chemistry of Nitrogen-rich Functional Groups, Volume 2 A series of advanced treatises founded by Professor Saul Patai and now under the general editorship of Professors Ilan Marek and Joel F. Liebman PATAI's Chemistry of Functional Groups publishes comprehensive reviews on all aspects of specific functional groups. Each volume contains outstanding surveys on theoretical and computational aspects, NMR, MS, other spectroscopic methods and analytical chemistry, structural aspects, thermochemistry, photochemistry, synthetic approaches and strategies, synthetic uses and applications in chemical and pharmaceutical industries, biological, biochemical, and environmental aspects. To date, over 150 volumes have been published in the series. Recently Published Titles The Chemistry of Peroxides (Volume 2, 2 parts) The Chemistry of Organozinc Compounds (2 parts) The Chemistry of Anilines (2 parts) The Chemistry of Organomagnesium Compounds (2 parts) The Chemistry of Hydroxylamines, Oximes and Hydroxamic Acids (2 volumes, 4 parts) The Chemistry of Metal Enolates (2 parts) The Chemistry of Organocopper Compounds (2 parts) The Chemistry of Organomanganese Compounds The Chemistry of Organic Selenium and Tellurium Compounds (Volume 3, 2 parts) The Chemistry of Organic Selenium and Tellurium Compounds (Volume 4, 2 parts) The Chemistry of Organoiron Compounds The Chemistry of Metal Phenolates The Chemistry of Peroxides (Volume 3, 2 parts) The Chemistry of Organogold Compounds (2 parts) The Chemistry of Organoaluminum Compounds The Chemistry of Metal Enolates (Volume 2) The Chemistry of Metal Phenolates (Volume 2) The Chemistry of Hypervalent Halogen Compounds (2 parts) The Chemistry of Nitrogen-rich Functional Groups The Chemistry of Organoboron Compounds (2 parts) The Chemistry of Organocobalt Compounds The Chemistry of Organofluorine Compounds PATAI Online PATAI's Chemistry of Functional Groups is available in electronic format on Wiley Online Library.

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Book SynopsisThe authors' aim is to offer the reader the fundamentals of numerous mathematical methods with accompanying practical environmental applications. The material in this book addresses mathematical calculations common to both the environmental science and engineering professionals. It provides the reader with nearly 100 solved illustrative examples and the interrelationship between both theory and applications is emphasized in nearly all of the 35 chapters. One key feature of this book is that the solutions to the problems are presented in a stand-alone manner. Throughout the book, the illustrative examples are laid out in such a way as to develop the reader's technical understanding of the subject in question, with more difficult examples located at or near the end of each set. In presenting the text material, the authors have stressed the pragmatic approach in the application of mathematical tools to assist the reader in grasping the role of mathematical skills in environmental prTable of ContentsPreface ix Part I: Introduction 1 1 Fundamentals and Principles of Numbers 3 2 Series Analysis 21 3 Graphical Analysis 29 4 Flow Diagrams 43 5 Dimensional Analysis 53 6 Economics 73 7 Problem Solving 89 Part II: Analytical Analysis 99 8 Analytical Geometry 101 9 Differentiation 115 10 Integration 121 11 Differential Calculus 133 12 Integral Calculus 147 13 Matrix Algebra 161 14 Laplace Transforms 173 Part III: Numerical Analysis 183 15 Trial-and-Error Solutions 185 16 Nonlinear Algebraic Equations 195 17 Simultaneous Linear Algebraic Equations 209 18 Differentiation 219 19 Integration 225 20 Ordinary Differential Equations 235 21 Partial Differential Equations 247 Part IV: Statistical Analysis 259 22 Basic Probability Concepts 261 23 Estimation of Mean and Variance 275 24 Discrete Probability Distribution 287 25 Continuous Probability Distribution 307 26 Fault Tree and Event Tree Analysis 343 27 Monte Carlo Simulation 357 28 Regression Analysis 371 Part V: Optimization 385 29 Introduction to Optimization 387 30 Perturbation Techniques 395 31 Search Methods 405 32 Graphical Analysis 419 33 Analytical Analysis 435 34 Introduction to Linear Programming 449 35 Linear Programming Applications 465

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Book SynopsisThis new volume provides a timely study on the environmental challenges from a specific class of perfluorinated chemical compounds (PFCs) that are now being recognized as a worldwide health threat. Recent studies report that levels of classes of PFCs known as polyfluoroalkyl and perfluoroalkyl (PFASs) exceed federally recommended safety levels in public drinking-water supplies for 6 million people in the United States and that as many as 100 million people could be at risk from exposure to these chemicals. These chemicals occur globally in wildlife and humans. Both PFCAs and PFSAs have been produced for more than 50 years, but have only become of interest to regulators and environmentalists since the late 1990s. Recent advances in analytical methodology has enabled widespread detection in the environment and humans at trace levels. These toxic chemicals have been found in outdoor and indoor air, surface and drinking water, house dust, animal tissue, human blood serum, and humTable of ContentsPreface ix About the Author xv Abbreviations and Acronyms xvii Useful Conversion Factors xxi 1 What Fluoropolymers Are 1 1.1 Introduction 1 1.2 Evolution of Fluoropolymers and the Markets 3 1.3 PFAS Compounds 6 1.3.1 General Description 6 1.3.2 How They Are Made 10 1.3.3 The Proliferation of PFAS 15 1.4 Terminology 17 References 19 2 Definitions, Uses, and Evolution of PFCs 21 2.1 Perfluorinated Chemicals (PFCs) Of Interest 21 2.2 The PFC Family 43 2.3 PFOS 44 2.4 PFOA 49 2.5 Fluorotelomers 50 References 52 3 Fire Fighting Foams 55 3.1 What AFFFs Are 55 3.2 Environmental Impacts 58 References 62 4 Health Risk Studies 63 4.1 General 63 4.2 PFOA 65 4.3 PFOS 77 4.4 EFSA – EU Food and Safety Authority Findings 77 References 90 5 Overview of the Environmental Concerns 91 5.1 Where It All Began 91 5.2 Emerging Contaminants of Concern 93 5.3 PFOS 96 5.4 PFOA 100 References 107 6 The Supply Chain and Pathways to Contamination 109 6.1 Losses Along the Supply Chain and End of Life 109 6.2 Consumer Articles 119 6.3 Consumer Exposure to PFOS and PFOA 124 References 127 7 Standards, Advisories, and Restrictions 129 7.1 Extent of Groundwater Contamination in the United States 129 7.2 The U.S. Water Quality Standards 133 7.3 Remedial Guidelines 142 7.4 Standards in Other Countries 143 7.4.1 United Kingdom 144 7.4.2 Canada 144 7.4.3 Germany 145 7.4.4 Norway 145 7.4.5 European Union (EU) 146 7.4.6 OECD 148 7.4.7 Stockholm Convention on Persistent Organic Pollutants (POPs) 149 7.4.8 United Nation’s Economic Commission for Europe (ECE) 150 References 151 8 Overview of Water Treatment Technology Options 153 8.1 Technology Options 153 8.2 Case Studies, Literature, and Technologies 156 Reference 163 9 Adsorption Technology 165 9.1 Overview 165 9.2 Activated Carbon and Other Carbonaceous Adsorbents 169 9.3 Zeolites 178 9.4 Polymeric Adsorbents 179 9.5 Oxidic Adsorbents 180 9.6 Adsorption Theory Basics and Isotherms 181 9.7 Adsorption of PFOA 186 9.8 Hardware and Operational Considerations 189 9.9 Backwashing 196 9.10 Permitting 197 9.11 Spent Carbon Management 197 9.12 Recommended References 198 References 201 10 Case Studies 203 10.1 PFOA in Southern New Hampshire 203 10.2 Former Wurtsmith Air Force Base 206 10.3 Dupont Washington Works in West Virginia 213 10.4 PFC Contamination in Minnesota 218 References 228 Index 229

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Book SynopsisNONTHERMAL PLASMAS FOR MATERIALS PROCESSING This unique book covers the physical and chemical aspects of plasma chemistry with polymers and gives new insights into the interaction of physics and chemistry of nonthermal plasmas and their applications in materials science for physicists and chemists. The properties and characteristics of plasmas, elementary (collision) processes in the gas phase, plasma surface interactions, gas discharge plasmas and technical plasma sources, atmospheric plasmas, plasma diagnostics, polymers and plasmas, plasma polymerization, post-plasma processes, plasma, and wet-chemical processing, plasma-induced generation of functional groups, and the chemical reactions on these groups along with a few exemplary applications are discussed in this comprehensive but condensed state-of-the-art book on plasma chemistry and its dependence on plasma physics. While plasma physics, plasma chemistry, and polymer science are often handled separately, the aim of the authors iTable of ContentsPreface xiii 1 Introduction 1 References 15 2 Basic Principles of the Plasma State of Matter 17 2.1 Characteristics and Physical Properties of Plasmas 17 2.1.1 Ionization Degree, Energy Content and Classification 17 2.1.2 Quasi-Neutrality, Debye Shielding Length, Plasma Frequency 19 2.1.3 Ambipolar Diffusion 24 2.1.4 High-Frequency Conductivity and Permittivity of Non-Thermal Plasmas 26 2.1.5 Charged Particles in External Magnetic Field 30 2.1.6 Thermal and Non-Thermal Plasmas 34 2.1.7 Plasma Kinetics and Transport Equations 40 References 56 2.2 Elementary Processes and Collision Cross Section 57 2.2.1 Classification of Collision Processes in Non-Thermal Plasmas 57 2.2.2 The Collision Cross Section 64 References 77 2.3 Interaction of Non-Thermal Plasmas with Condensed Matter 79 2.3.1 Stationary Plasma Boundary Sheath and Bohm Criterion 80 2.3.2 Plasma Boundary Sheath in Front of the Floating Surface 83 2.3.3 Generalized Bohm Sheath Criterion 84 2.3.4 High-Voltage Plasma Sheath 84 2.3.5 Non-Stationary Plasma Sheaths 88 References 93 2.4 Non-Thermal Plasmas of Electric Gas Discharges 94 2.4.1 Overview 94 2.4.2 The Electric Breakdown in Gases 95 2.4.3 The Glow Discharge 101 2.4.4 Glow Discharges at Harmonic Electric Fields, RF and MW Plasmas 109 2.4.5 High-Voltage Breakdown at Atmospheric Pressure, Corona and Barrier Discharge 115 References 118 3 Plasma Diagnostics 119 3.1 Introduction 119 3.2 Overview of Diagnostic Methods Used for the Characterization of Non-Thermal Plasmas 119 3.3 Analysis of Charged and Neutral Plasma Particles in Non-Thermal Plasmas 119 3.3.1 Electric Probe Measurements 119 3.3.2 Special Case for Single Electric Probe Measurements in Radio-Frequency (RF) Plasmas 133 3.4 Microwave Interferometry 136 3.4.1 Microwave Propagation in Non-Magnetic Plasmas 136 3.4.2 Heterodyne Microwave Interferometry at 160 GHz 138 3.4.3 Electron Density Analysis in CCP and ICP with Argon and Oxygen as Processing Gas 140 3.5 Mass Spectrometry 143 3.5.1 Principle of Mass Spectrometry 143 3.5.2 Quadrupole Mass Spectrometry 143 3.5.3 Analysis of Low-Pressure Plasmas by Quadrupole Mass Spectrometry 145 References 155 3.6 Plasma and Laser-Induced Optical Emission Spectroscopy 157 3.6.1 Spectral Analysis of Plasma Emission (VUV, UV-vis-NIR) 157 3.6.1.1 Optical Emission Spectroscopy (OES) of Low-Pressure Plasmas – Examples 159 3.6.1.2 Determination of the Rotation Temperature from Atmospheric O2 A Band, PP and PQ Branch 161 3.6.1.3 Determination of Ground State Particle Density from Plasma Emission Spectrum 164 3.6.1.4 Abel Inversion 165 3.6.1.5 Phase Resolved Optical Emission Spectroscopy (PROES) of RF Plasmas 166 3.6.2 Laser-Induced Fluorescence (LIF) Spectroscopy 169 3.7 IR Broadband and IR Laser Absorption Spectroscopy 172 3.7.1 Fourier Transform Infrared (FTIR) Spectroscopy for Gas Phase Analysis 172 3.7.1.1 Principle of FTIR Spectroscopy 172 3.7.1.2 FTIR Gas Phase Spectroscopy of RF Plasma with Precursor Ethylenediamine and Argon 178 3.7.2 Infrared Tunable Diode Laser Absorption Spectroscopy (IR-TDLAS) 180 3.7.2.1 Configuration of the IR-TDLAS Experiment 180 3.7.2.2 Principle Procedure for Measuring Single Absorption Lines 181 3.7.2.3 IR-TDLAS of Fluorocarbon Radicals and Reaction Products in CF4 or CF4+H2 RF Plasmas 183 References 185 4 Methods of Polymer and Polymer Surface Analysis 187 4.1 Introductory Remarks 187 4.2 Photoelectron Spectroscopy (XPS) or Electron Spectroscopy for Chemical Analysis (ESCA) 188 4.3 Secondary Ion Mass Spectrometry 193 4.4 NEXAFS – Use of Synchrotron Radiation 194 4.5 Infrared Reflection Absorption Spectroscopy (IRRAS) 195 4.6 Size-Exclusion Chromatography (SEC)/Gel Permeation Chromatography (GPC) and Field-Flow-Fractionation (FFF) 196 4.7 Matrix-Assisted Laser/Desorption Ionization Time-of-Flight Mass Spectrometry (MALDI-ToF-MS) 197 4.8 Electrospray Ionization Time-of-Flight Mass Spectrometry (ESI-ToF-MS) 199 4.9 Overview of Methods 200 References 202 5 Chemical Interactions Between Polymer and Plasma 203 5.1 Introduction 203 5.2 General Conflict Between High Plasma Energies and Low Dissociation Energies of Bonds in Polymers 203 5.3 Chemical Bonds and Functional Groups in Polymers 206 5.4 Response of Different Types of Polymers to Plasma Exposure 208 References 214 6 Polymer Surface Functionalization 217 6.1 Important Properties of Polymers 217 6.2 Why Pretreatment? 217 6.3 Chemical and Structural Problems of Polymers Provoked by Plasma Pretreatment 220 6.4 Inevitability of Simultaneous Functionalization and Polymer Degradation 221 6.5 Physical and Chemical Attacks of the Plasma to Polyolefin Surfaces 223 6.6 Chemical Grafting onto Plasma-Exposed Polymer Surfaces 224 6.7 Oxidation of Polymers by Exposure to the Oxygen Low-Pressure Plasma 225 6.7.1 Introduction of O-Functional Groups Onto Polymer Surfaces 225 6.7.2 Nature of Oxygen-Plasma Introduced Functional Groups 226 6.7.3 Identification of O-Functional Groups Bonded Onto the Topmost Polymer Surface Layer 226 6.7.4 Fit Strategy of O-Functional Groups as Introduced by D. T. Clark 232 6.7.5 Other Surface-Sensitive Analytical Methods 233 6.7.6 Derivatization of O-Functional Groups 234 6.7.7 Identification of Radicals by Chemical Labeling or ESR Spectroscopy 236 6.7.8 Physical Characterization of Oxygen Plasma 237 6.7.9 Use of Plasma Afterglow for Polymer Modification 238 6.7.10 Surface Oxidation and Etching (see also the special section on etching) 239 6.7.11 Changes in Supermolecular Structure in Subsurface Layers Upon Exposure to Oxygen Plasma 240 6.7.12 Changes in Polymer Structure Generated by Exposure to the Vacuum UV Radiation of the Oxygen Plasma 245 6.7.13 Depth of Modification 248 6.7.14 Accelerated Artificial Aging of Polymers by Exposure to Low-Pressure Oxygen Plasma 251 6.7.15 Kinetics of Crosslinking 253 6.7.16 Time-Dependence of Oxygen Introduction 257 6.7.17 Reaction Details of Poly(ethylene terephthalate) Upon Exposure to Oxygen Plasma 264 6.7.18 Optimum Time of Exposure to Oxygen Plasma for Formation of O-Functional Groups and Preventive Avoidance of Structural Degradation and Decomposition 269 6.7.19 Dependence of Oxygen Introduction on Plasma Parameters 272 6.7.20 Behavior of Molecular Orientation and Chain Structure Upon Exposure to Oxygen Plasma 272 References 279 7 Sensitivity of Polymer Units and Functional Groups Towards Exposure to Oxygen Plasma 291 7.1 Introductory Remarks 291 7.2 Behavior of Polymer Structure Upon Exposure to Oxygen Plasma 291 7.3 Etching Behavior of Polymers Upon Exposure to Oxygen Plasma 294 7.4 Classification of Polymers with Similar Degradation Behavior on Exposure to Oxygen Plasma 299 7.5 Stability of Surface Functionalization and Superposition with Post-Plasma Effects upon Exposure to Air 302 7.6 Surface Oxidation of Polyolefins Using Atmospheric-Pressure Plasmas (DBD, APGD or Corona Discharge, Spark Jet, etc.) 308 7.6.1 Dielectric Barrier Discharge 308 7.6.2 Plasma-Assisted and Plasma-Less Spraying of Intact High-Molecular-Weight Polymers at Atmospheric Pressure 314 7.7 Oxidation of Carbon Nanomaterials 320 7.7.1 Graphene 320 7.7.2 Oxidation of Carbon Fibers 321 7.8 Generation of Monosort O-Functional Groups at Polyolefin Surfaces as Anchor Points for Grafting of Molecules 323 7.8.1 OH Groups 323 7.8.2 COOH Groups 332 7.8.3 CHO Groups 333 7.8.4 Super-Acidic Groups via Oxyfluorination 334 7.8.5 Functionalization of Fluorine-Containing Polymers with O-Functional Groups 337 7.9 Post-Plasma Chemical Grafting of Molecules, Oligomers or Polymers Onto OH-Groups 339 7.10 Course of Oxidation from Virgin Polymer to Oxidized Polymer and Finally to CO2 342 7.10.1 Problems of Depth Profiling of Oxidation at Polymer Surface 342 7.10.2 Binding Energies of Covalent Bonds in Polyolefins 343 7.10.3 Analogy Between Thermal Oxidation and Auto-Oxidation of Paraffins 344 7.10.4 Decarboxylation and Emission of CO2 345 7.10.5 Formation of Gaseous Low-Molecular-Weight Etch Products by Oxygen Plasma Treatment 345 7.10.6 Introduction of Oxygen-Containing Groups at Surface of Polyolefins as a Forerunner of Gasification/Etching 347 7.10.7 Formation and Characterization of Low-Molecular-Weight Oxidized Material (LMWOM) 350 7.10.8 LMWOM Formation by Re-Deposition of Etched Fragments 351 7.10.9 Depth Profiling of O/C from Surface to Bulk 352 7.10.9.1 Angle-Resolved XPS 353 7.10.9.2 Dynamic SIMS 354 7.10.9.3 Sputtering 354 7.10.9.4 Post-Plasma Oxidation 354 7.10.10 Tentative Mechanism 355 References 359 8 Ammonia and Bromine Plasmas 371 8.1 Generation of Monosort NH2 Groups 371 8.1.1 Brief History of Plasma-Induced Introduction of Primary Amino Groups Into the Surface of Polyolefins 371 8.1.2 Ways to Produce Amino Groups at Polymer Surfaces 372 8.1.3 Ammonia, Nitrogen-Hydrogen and Hydrazine Plasmas 373 8.1.4 Carbon Fibers Exposed to Ammonia Plasma 376 8.1.5 Oxygen Post-Plasma Introduction After Ammonia Plasma Exposure 380 8.1.6 Invalidity of Le Chatelier’s Principle in Low-Pressure Plasma 381 8.1.7 Time Dependence of N and NH2 Introduction on Exposure of the Ammonia Plasma into Polyolefin Surfaces 383 8.1.8 Hydrogenation Effect of NH3 Plasma 385 8.1.9 Modification of Polyolefin Within a 2μm-Deep Surface Layer 386 8.1.10 Bulk Analysis by NMR 389 8.1.11 Summary of All Attempts to Increase the Yield in NH2 Groups 391 8.1.12 Ammonia Plasma – Undesired Side and Post-Plasma Reactions 392 8.1.13 Deposition of Plasma Polymers Carrying Amino Groups as an Alternative to Ammonia Plasma Treatment 393 8.1.14 Chemical Labeling and Protection of NH2 Groups 394 8.1.15 Post-Plasma Chemical Grafting Onto NH2-Groups 396 8.1.16 Amino Groups at Polymer Surfaces – A Summary 399 8.2 Bromine Plasma 399 8.2.1 Chemical Aspects 399 8.2.2 Theoretical Considerations of the Plasma Process Using Bromine 404 8.2.3 Comparison of Halogen Chemistry 406 8.2.4 Behavior of Plasma-Brominated Surface Layers in Solvents 408 8.2.5 Plasma Polymerization of Vinyl and Allyl Bromide 410 8.2.6 Attempts to Increase Br Concentration in the Plasma Polymer Layers by Admixture of Br2 to Allyl Bromide or Bromoform 412 8.2.7 Dependence of Bromine Introduction Onto Polyolefin Surfaces on Plasma Parameters 412 8.2.8 Electron Temperature in the Bromoform Plasma 415 8.2.9 Yields in Introduction of Other Halogens 415 8.2.10 Plasma Bromination of Other Polymers 417 8.2.11 Chemical Post-Plasma Synthesis of New Monosort Functional Groups by Conversion of Plasma-Introduced Bromine Groups 418 8.2.12 Grafting of Molecules onto Br Groups by Nucleophilic Substitution 419 8.2.13 Grafting Density at Polyolefin Surfaces 422 8.2.14 Comparison of Surface Bromination of Polyolefins with Other Processes 426 8.2.15 Plasma Bromination of Graphitic and Carbon Surfaces 427 8.2.16 Efficiency in Bromination and Grafting of Carbon in Comparison to Polyolefins 441 8.2.17 Conclusions to Plasma Bromination 445 References 446 9 Noble Gas Plasmas 457 9.1 Characterization of Noble Gas Plasmas 457 9.2 Polymer Crosslinking Caused by Noble Gas Plasmas 458 9.3 Vacuum-Ultra Violet Radiation Emitted by Noble Gas Plasmas 460 References 464 10 Plasma Polymerization 467 10.1 Introduction 467 10.2 Milestones in History 470 10.3 General Features of Plasma Polymers 473 10.4 Mechanisms of Plasma Polymerization 475 10.4.1 Absence of Often Proposed Plasma-Induced Radical Chain-Growth Polymerization to Linear Macromolecules? 477 10.4.2 Radical Polymerization of Allyl Monomers 480 10.4.3 Ion-Molecule Reactions 482 10.4.4 Role of Polymerizing Intermediates 483 10.4.5 Crosslinking 483 10.4.6 Polymerization in Continuous-Wave Plasma 486 10.4.7 Pulsed Plasma Polymerization 491 10.4.8 Pressure- and Plasma-Pulsed Discharge 500 10.5 Special Aspects of Plasma Polymerization 506 10.5.1 Fragmentation-(poly)Recombination 506 10.5.2 Atomic Polymerization 506 10.5.3 Rearrangement and Crosslinking of the Already Deposited Plasma Polymer Layer by Plasma Particle Bombardment and Vacuum-UV Irradiation 507 10.5.4 Formation of Unsaturations 508 10.5.5 Formation of CH3 Groups 510 10.5.6 H/C Ratio in Plasma Polymers and “Quasi-Hydrogen-Plasma” 511 10.5.7 Hydrogen Exchange Between Plasma and Polymer Deposit 516 10.5.8 Existence of Crystalline and Supermolecular Structures in Plasma Polymers 517 10.5.9 Influence of Monomer or Precursor Type 518 10.5.10 Role of Pressure and Flow Rate 518 10.5.11 Role of Energy Dose 520 10.5.12 Plasma Polymerization of n-Hexane and Other Hydrocarbons 520 10.5.13 Dependence of Deposition Rate on Position of Sample in the Plasma Zone 524 10.5.14 Retention of Monomer Structure in Plasma Polymer –Changes in Aromaticity and Substitution 525 10.5.15 Molecular Weight Distribution 527 10.5.16 Energetic Balancing 529 10.6 Locus of Plasma Polymerization 530 10.6.1 Adsorption or Gas Phase? 530 10.6.2 Powder Formation 531 10.6.3 Redeposition of Etched Products as Layer 532 10.6.4 Special Effects of Irradiation of Growing Polymer Layer by Vacuum-UV Radiation from Plasma 533 10.6.5 Formation of a “Polymer Skin” 535 10.6.6 Graft Polymerization 535 10.7 Plasma Polymers with Monosort Functional Groups 537 10.7.1 OH Groups 540 10.7.2 COOH Groups 544 10.7.3 NH2 Groups 548 10.8 Attempts to Increase the Yield of Functional Group 556 10.8.1 Optimization of Plasma Conditions for Generation of NH2 Groups 556 10.8.2 Attempts to Increase the Concentration of NH2 Groups by Addition of Ammonia to Allylamine Plasma Polymerization 556 10.8.3 Alternative Methods 564 10.8.4 Plasma-Produced Amino Groups for Promotion of Adhesion 564 10.9 Plasma Copolymerization 566 10.9.1 General Remarks on the Background of Copolymerization and Its Definition 566 10.9.2 Copolymers with Allyl Alcohol 569 10.9.3 Copolymers with Acrylic Acid 575 10.9.4 Allylamine Copolymers 576 10.10 Grafting Onto Plasma Polymers as Special Case of ‘Graft-Copolymerization’ 580 10.10.1 General Aspects 580 10.10.2 Direct Grafting Onto Radical Sites 582 10.10.3 Grafting Onto Peroxy Radicals/Hydroperoxides 582 10.10.4 Reactions with OH Groups 583 10.10.5 Reactions with COOH Groups 584 10.10.6 Reactions with NH2 Groups 584 10.10.7 Reactions with Br Groups 585 10.10.8 Other Methods 585 10.11 Significant Side Reactions 585 10.11.1 Details of the IR Bands at 2200 cm-1 588 10.11.2 DSC Results 590 10.11.3 Post-Plasma Oxidation 591 10.11.4 Attempts to Eliminate Post-Plasma Oxidations 596 10.12 Plasma Polymers Deposited by Atmospheric-Pressure Plasmas 597 References 598 11 Technical Applications 621 11.1 Introduction 621 11.2 Adhesion Promotion 622 11.2.1 Polymer Surface Modification 624 11.2.2 Combination of Plasma Pretreatment and Wet-Chemical Post-Plasma Treatment 628 11.2.3 Deposition of Adhesion-Promoting Polymer Films 629 11.2.3.1 Direct Grafting 629 11.2.3.2 Grafting via Peroxy Route 630 11.2.3.3 Co-Evaporation or Sputtering of Metals During Plasma Polymerization 630 11.2.3.4 Plasma Polymer Coating 631 11.3 Cleaning 633 11.4 Wettability 635 11.5 Etching of Polymers 637 11.5.1 Preparation and Excavation of Supermolecular Structures of Polymers for Their Characterization by Electron Microscopy 637 11.5.2 Ashing 638 11.6 Barrier Layers or Barrier Formation 638 11.6.1 Organic and Inorganic Barrier Layer for Limiting Diffusion 638 11.6.2 Fluorination of Polymers 639 11.7 Anti-Fouling Layers 641 11.8 Sterilization 642 11.9 Water Purification and Desalination 643 11.10 Flame Protection 643 11.11 Textile Modification 644 11.12 Modification of Carbon Fibers and Nanotubes 644 11.13 Silent Discharge and Excimer Radiation 645 11.14 Conducting Films 646 11.15 Scratch-Resistant Coatings 646 11.16 Underwater Plasma 647 References 650 Index 671

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Book SynopsisThis book focuses on the chemistry of additives for high performance applications and a large number of chemical formulas are displayed in the text. The additives applications include: Analysis and separation techniques, such as high performance liquid chromatography, for example ionic liquids. Additives for electrical applications, such as capacitors, electrokinetic micropumps, lithium-ion batteries, and other battery types. Additives for solar cells for control of the active layer nanomorphology are documented as are additives for electrolyte membranes, fuel cells, such as membrane exchange humidifiers and coolant additives. Medical applications include high performance additives for the manufacture of scaffolds, controlled drug release, and nanofibers. Additives for lubricants including the deposit control, anti-wear additives, fluid loss control additives in drilling applications. Additives for concrete uses such as set rTable of ContentsPreface xi 1 Analysis and Separation Techniques 1 1.1 High Performance Liquid Chromatography 1 1.1.1 Ionic Liquids as Mobile Phase Additives 1 1.1.2 Food Additives 12 1.1.3 Chaotropicity 14 1.1.4 Cigarette Additives 16 1.1.5 Chiral Separation 20 1.1.6 Peptides and Proteins 31 1.1.7 1,4-Dihydroxy-2-Naphthoic Acid 32 1.1.8 Diesel Lubricating Additives 32 1.1.9 Acidic Drugs 34 1.2 Chelation Ion Chromatography 39 1.3 Membranes 40 1.3.1 Carbon Dioxide Separation 40 1.3.2 Hollow Fiber Membranes 41 References 42 2 Electrical Applications 47 2.1 Capacitors 47 2.1.1 Triethanolamine 47 2.1.2 Supercapacitors 47 2.2 Electrokinetic Micropumps 50 2.3 Lead-Acid Batteries 50 2.3.1 Activated Carbon Additives 51 2.3.2 High Performance Positive Electrode 51 2.4 Lithium-Ion Batteries 53 2.4.1 Ionic Diffusion 56 2.4.2 Functional Electrolytes 56 2.4.3 Synergetic Effect of Conductive Additives 58 2.4.4 In-Situ Coating of Cathode by Electrolyte Additive 58 2.4.5 Bipolar Architectures 59 2.4.6 Janus Separator 63 2.4.7 Synthesis of Vanadium Cathodes 64 2.4.8 Graphite 64 2.4.9 Silicon 67 2.4.10 Carbon Nanotubes 69 2.4.11 Carbonate Additives 70 2.4.12 Borate Additives 73 2.4.13 Tris(pentafluorophenyl) Borane 78 2.4.14 Phosphoric Additives 79 2.4.15 Sulfur Additives 83 2.4.16 Isothiocyanates 90 2.4.17 Other Additive Types 92 2.5 Nickel Batteries 101 2.5.1 High-Rate Discharge Performance 106 2.5.2 Multiphase Nano-Nickel Hydroxide 108 2.5.3 Nickel-Metal Hydride Batteries 108 2.6 Sodium-Ion Batteries 112 2.6.1 Antimony-Based Intermetallic Alloy Anodes 112 2.7 Solar Cells 113 2.7.1 Star-Shaped Molecules 113 2.7.2 Dye-Sensitized Solar Cells 115 2.7.3 Perovskite 119 2.7.4 Control of Active Layer Nanomorphology 120 2.7.5 Phosphonium Halides as Processing Additives and Interfacial Modifiers 121 2.7.6 Polymeric Solar Cells 121 2.8 Fuel Cells 123 2.8.1 Porosity Additive 125 2.8.2 Electrolyte Membranes 126 2.8.3 Molybdenum Oxide 130 2.8.4 Nano-Metal Oxides 131 2.8.5 Coolant Additive 131 2.8.6 Membrane Exchange Humidifier 133 2.8.7 Poly(vinyl alcohol)/Titanium Dioxide Nanocomposites 134 3 Medical Uses 145 3.1 High Performance Additive Manufactured Scaffolds 145 3.1.1 Nanotechnology 145 3.1.2 Poly(caprolactone)Tricalcium Phosphate Scaffolds 146 3.1.3 Silk Fibroin Nanofibers 147 3.1.4 Calcium Phosphate, Hydroxyapatite, and Poly(d,l-lactic acid) 152 3.1.5 Propylene Fumarate Lactic Acid Copolymer 152 3.1.6 Thermosensitive Composite Gel 153 3.1.7 Biomimetic Wet-Stable Fibers 153 3.1.8 Poly(ester urea) from l-Leucine 154 3.1.9 Static Cell Seeding Versus Vacuum Cell Seeding 154 3.1.10 Controlled Drug Release 155 References 156 4 Lubricants 159 4.1 Fuels 159 4.1.1 Graphene Oxide 159 4.1.2 Deposit Control 160 4.2 Lubricant Additives 161 4.2.1 GL Ratings 161 4.2.2 Organophosphates 162 4.2.3 Crankcase Oils 162 4.2.4 Low Sulfur and Low Metal Additive Formulations 163 4.2.5 Lithium Soaps 166 4.2.6 Titanium Complex Grease Composition 171 4.2.7 Improving theWetting Properties of Ionic Liquids 176 4.3 Anti-Wear Additives 179 4.3.1 Ionic Liquids 179 4.3.2 Castor Oil Tris(diphenyl phosphate) 179 4.3.3 Bifunctional Hairy Silica Nanoparticles 180 4.3.4 Boron Thiophosphite 180 4.3.5 Hydroxyaromatic Compounds 181 4.4 Fluid Loss Control Additives 183 4.4.1 Graphene Oxide 183 4.4.2 Montmorillonite 183 4.5 Warm Mix Asphalt Additives 184 5 Concrete Additives 189 5.1 Properties of Concrete 189 5.1.1 Pozzolans 191 5.1.2 Calcium Aluminate Cement 191 5.1.3 Rutting of Bituminous Concrete 193 5.2 Set Retarders 193 5.2.1 Superplasticizers 194 5.3 Accelerators 194 5.3.1 Aqueous Dispersions of Silica 195 5.3.2 Non-Chloride Cement Accelerators 195 5.4 Dispersants and Thinners 196 5.4.1 Xylonic Acid 196 5.4.2 Thixotropy 197 5.4.3 Flowability 198 5.5 Defoamers 199 5.5.1 Ethoxylated Fatty Alcohol Acrylates 200 5.5.2 Hydroxyl Alkyl Acrylate 200 5.5.3 Tributyl Phosphate 202 5.5.4 Silicone Oils 202 5.5.5 Other Additives 202 5.6 Shrinkage Compensation 202 5.7 Permeability 203 5.7.1 Expanded Perlite 204 5.7.2 Pozzolanic Materials 204 5.7.3 Cracking Catalyst 205 5.8 Air Entraining Agents 206 5.8.1 Fluorochemical Surfactants 207 5.8.2 Superabsorbent Polymers 207 5.8.3 Rubber Crumb 208 5.8.4 Autoclaved Aerated Concrete 209 5.9 Corrosion Protection 210 5.9.1 Modified Hydrotalcites 210 5.9.2 Chloride Ion Scavenging 210 5.9.3 Dopamelanin 211 5.10 Superabsorbent Polymers 212 5.11 Fibers 212 5.11.1 Poly(oxymethylene) Fibers 212 5.12 Additives fromWastes 214 5.12.1 Waste Rubber 214 5.12.2 anomodified Concrete Additive 216 References 220 6 Other Uses 225 6.1 High Performance Additive for Powder Coatings 225 6.1.1 Antimicrobial Powder Coatings 225 6.2 Radiation Shielding 226 6.3 Superabsorbent Polymers 229 6.4 Laser Additive Manufacturing of High Performance Materials 232 6.4.1 Laser Metal Deposition Additive Manufacturing 232 6.4.2 Hybrid Processes 233 6.5 High Temperature Cooling Application 234 References 236 Index 239 Tradenames 239 Acronyms 242 Chemicals 244 General Index 255

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Book SynopsisHigh Performance Polymers and Their Nanocomposites summarizes many of the recent research accomplishments in the area of high performance polymers, such as: high performance polymers-based nanocomposites, liquid crystal polymers, polyamide 4, 6, polyamideimide, polyacrylamide, polyacrylamide-based composites for different applications, polybenzimidazole, polycyclohexylene dimethyl terephthalate, polyetheretherketone, polyetherimide, polyetherketoneketone, polyethersulfone, polyphenylene sulphide, polyphenylsulfone, polyphthalamide, Polysulfone, self-reinforced polyphenylene, thermoplastic polyimide.Table of ContentsPreface xv 1 High-Performance Polymer Nanocomposites and Their Applications: State of Art and New Challenges 1PM Visakh 1.1 Liquid Crystal Polymers 1 1.2 Polyamide 4, 6, (PA4,6) 3 1.3 Polyacrylamide 4 1.4 Effect of Nanostructured Polyhedral Oligomeric Silsesquioxone on High Performance Poly(urethane-Imide) 5 1.5 Thermoplastic Polyimide 5 1.6 Performance Properties and Applications of Polytetrafluoroethylene (PTFE) 7 1.7 Advances in High-Performance Polymers Bearing Phthalazinone Moieties 9 1.8 Poly(ethylene Terephthalate)—PET and Poly(ethylene Naphthalate)—PEN 11 1.9 High-Performance Oil Resistant Blends of Ethylene Propylene Diene Monomer (EPDM) and Epoxydized Natural Rubber (ENR) 14 1.10 High Performance Unsaturated Polyester/f-MWCNTs Nanocomposites Induced by F- Graphene Nanoplatelets 15 2 Liquid Crystal Polymers 27Andreea Irina Barzic, Raluca Marinica Albu and Luminita Ioana Buruiana 2.1 Introduction and History 27 2.2 Polymerization 29 2.2.1 Synthesis of Lyotropic LC Polymers 30 2.2.2 Synthesis of Thermotropic LC Polymers 31 2.3 Properties 32 2.3.1 Rheology 32 2.3.2 Dielectric Behavior 35 2.3.3 Magnetic Properties 36 2.3.4 Mechanical Properties 36 2.3.5 Phases and Morphology 39 2.4 Processing 41 2.4.1 Injection Molding 41 2.4.2 Extrusion 42 2.4.3 Free Surface Flow 43 2.4.4 LC Polymer Fiber Spinning 44 2.5 Blends Based on Liquid Crystal Ppolymers 44 2.6 Composites of Liquid Crystal Polymers 46 2.7 Applications 49 2.7.1 LC Polymers as Optoelectronic Materials 49 2.7.2 Liquid Crystalline Polymers in Displays 50 2.7.3 Sensors and Actuators 51 2.8 Environmental Impact and Recycling 52 2.9 Concluding Remarks and Future Trends 54 Acknowledgment 54 3 Polyamide 4,6, (PA4,6) 59Emel Kuram and Zeynep Munteha Sahin 3.1 Introduction and History 59 3.2 Polymerization and Fabrication 60 3.3 Properties 69 3.4 Chemical Stability 72 3.5 Compounding and Special Additives 72 3.6 Processing 73 3.7 Applications 83 3.8 Blends of Polyamide 4,6, (PA4,6) 84 3.9 Composites of Polyamide 4,6, (PA4,6) 89 3.10 Nanocomposites of Polyamide 4,6, (PA4,6) 90 3.11 Environmental Impact and Recycling 94 3.12 Conclusions 98 4 Polyacrylamide (PAM) 105Małgorzata Wiśniewska 4.1 Introduction and History 105 4.2 Polymerization and Fabrication 107 4.3 Properties 110 4.4 Chemical Stability 111 4.5 Compounding and Special Additives 112 4.6 Processing 113 4.7 Applications 114 4.8 Blends of Polyacrylamide 116 4.9 Composites of Polyacrylamide 118 4.10 Nanocomposites of Polyacrylamide 119 4.11 Environmental Impact and Recycling 121 4.12 Conclusions 122 5 Effect of Nanostructured Polyhedral Oligomeric Silsesquioxone on High Performance Poly(urethane-imide) 133Dhorali Gnanasekaran 5.1 Introduction 134 5.2 Experimental 136 5.3 Results and Discussion 138 5.4 Conclusions 145 6 Thermoplastic Polyimide (TPI) 149Xiantao Feng and Jialei Liu 6.1 Introduction and History 149 6.2 Polymerization and Fabrication 150 6.2.1 Thermoplastic Polyimides Based on BEPA 150 6.2.2 Thermoplastic Polyimides based on PMDA 153 6.2.3 Thermoplastic Polyimides Based on BTDA 154 6.2.4 Thermoplastic Polyimides Based on ODPA 157 6.2.5 Thermoplastic Polyimides Based on BPDA 157 6.2.6 Thermoplastic Copolyimides 158 6.3 Properties 160 6.3.1 TPI Based on BEPA 160 6.3.2 Thermoplastic Polyimides based on PMDA 163 6.3.3 TPI Based on ODPA 163 6.3.4 Thermoplastic Polyimides Based on BPDA 168 6.3.5 Thermoplastic Copolyimides 170 6.4 Chemical Stability 170 6.4.1 Hydrolytic Stability 170 6.4.2 Oxidative Stability 174 6.5 Compounding 175 6.5.1 Chloromethylation 175 6.5.2 Sulfonation 178 6.5.3 Phosphorylation 178 6.5.4 Bromination 178 6.5.5 Arylation 181 6.6 Processing 181 6.6.1 Injection Molding 181 6.6.2 Compression Molding 182 6.6.3 Extrusion Molding 184 6.6.4 Coating 184 6.6.5 Spinning [40] 186 6.7 Applications 186 6.7.1 Membranes 186 6.7.2 Adhesives 188 6.7.3 Composites 189 6.7.3.1 Skybond 190 6.7.4 Engineering Plastics 190 6.7.4.1 VESPEL Plastics 190 6.7.4.2 ULTEM Plastics [48, 49] 191 6.7.4.3 AURUM Plastics [50] 192 6.7.4.3 Ratem Plastics [51] 192 6.8 Blends of Thermoplastic Polyimide (TPI) 193 6.8.1 TPI Blends with TPI 193 6.8.2 Polyamic Acid Blending 195 6.9 Composites of Thermoplastic Polyimide (TPI) 196 6.9.1 LaRC Composites 197 6.9.2 Skybond 202 6.9.3 PAI Polyamide–Imide Composites 205 6.10 Nanocomposites of Thermoplastic Polyimide (TPI) 208 6.10.1 TPI/silver Nanocomposite 208 6.10.2 TPI/Fe-FeO Nanocomposite 210 6.10.3 TPI/Carbon Nanocomposites 211 6.10.4 TPI/CF/TiO2 Nanocomposite 214 6.11 Environmental Impact and Recycling 214 6.12 Conclusions 215 7 Performance Properties and Applications of Polytetrafluoroethylene (PTFE) – A Review 221E. Dhanumalayan and Girish M Joshi 7.1 Introduction 221 7.2 Properties of PTFE 223 7.2.1 Physical Properties of PTFE 223 Surface Properties 223 7.2.2 Tribological Property of PTFE Surface 224 7.2.3 Mechanical Properties of PTFE 226 7.2.4 Chemical Properties of PTFE 228 Solubility of PTFE 228 7.2.5 Thermal Properties of PTFE 228 Thermal transport property of PTFE composites 229 7.2.6 Electrical Properties of PTFE 229 Dielectric property of PTFE 229 7.2.7 Optical and Spectral Properties of PTFE 230 7.3 Processing and Casting Techniques of PTFE 231 7.3.1 Casting of PTFE by Melt-Processing Method 232 7.3.2 Sintering of PTFE 233 7.3.3 Molding Techniques of PTFE 233 7.3.4 Casting of PTFE by Extrusion 236 7.3.5 Solution Blending of PTFE 237 7.3.6 PTFE Coating Methods 238 7.4 Applications of PTFE in Various Fields 238 7.4.1 PTFE in Automotive Industries 238 7.4.2 PTFE in Petrochemical and Power Industries 239 7.4.3 PTFE in Aerospace Industries 240 7.4.4 PTFE in Food Processing Industries 241 7.4.5 PTFE Applications in Chemical Industries 242 7.4.6 PTFE in Biomedical and Pharmaceutical Applications 242 7.4.7 PTFE in Electrical Applications 243 7.4.8 PTFE for Defense Applications 243 7.4.9 Application of PTFE Ice-Phobic Surfaces 243 7.4.10 Application of PTFE in Water and Air Purification Process 244 7.5 Different Forms of PTFE 244 7.5.1 Fine Powder of PTFE for Foaming Applications 244 7.5.2 Granular Form of PTFE 245 7.5.3 Resin Form of PTFE 245 7.5.4 Paste Form of PTFE 245 7.5.5 Emulsion Form of PTFE 246 7.6 Various Grades of PTFE 246 7.6.1 Carbon-Reinforced PTFE 246 7.6.2 Glass Fiber-Reinforced PTFE 247 7.6.3 Bronze-Filled PTFE Composites 247 7.6.4 Graphite Filled PTFE 248 7.6.5 Molybdenum Disulfide (MoS2)-Filled PTFE 248 7.7 Nanocomposites of PTFE 248 7.8 Future Prospects of PTFE 254 7.9 Conclusion 256 8 Advances in High-Performance Polymers Bearing Phthalazinone Moieties 267Jinyan Wang, Cheng Liu, Shouhai Zhang and Xigao Jian 8.1 Introduction 268 8.2 A New Mmonomer: 1, 2-Dihydro-4-(4-Hydroxyphenyl)-1-(2H)-Phthalazinone 269 8.3 Synthesis and Properties of Phthalazinone-Containing Polyarylethers 271 8.3.1 Poly(phthalazinone Ether Sulfone Ketone)s (PPESKs) 271 8.3.2 Poly(phthalazinone Ether Ketone Ketone) (PPEKK) and Its Copolymers 274 8.3.3 Poly(phthalazinone Ether Nitrile Sulfone Ketone)s (PPENSKs) 275 8.3.4 Poly(aryl Ether) Containing Aryl-S-Triazine and Phthalazinone Moieties 279 8.4 Polyamides and Polyimides Containing Phthalazinone Moieties 285 8.5 Phthalazinone-Containing Polyarylates 291 8.6 Phthalazinone-Containing Ppolybenzimidazole 292 8.7 Conclusions and Prospects 293 Acknowledgments 294 9 Poly(ethylene terephthalate)—PET and Poly(ethylene naphthalate)—PEN 301Luigi Sorrentino, Marco D’ Auria and Eugenio Amendola 9.1 Introduction 302 9.2 Synthesis of PET and PEN 304 9.2.1 PET Production 312 9.3 Processing of Neat Polymers 313 9.3.1 Materials Feeding 315 9.3.2 Melting and Compounding 316 9.3.3 Venting 316 9.3.4 Metering 316 9.3.5 Temperature Managing 317 9.3.6 Die Forming and Post-Die Treatments 317 9.3.7 Tandem Extruders Cconfiguration 317 9.4 Nanocomposites 318 9.4.1 Isodimensional Nanoparticles 319 9.4.2 Clay Nanoparticles 321 9.4.3 Carbon-Based Nanoparticles 324 9.5 Nanocomposites Production Processes 325 9.5.1 In Situ Polymerization 326 9.5.2 Solution Intercalation (Or Solution Blending) 328 9.5.3 Direct Mixing 329 9.5.4 Melt Compounding (High Shear Mixing) 330 9.5.5 Three Roll Milling 332 9.5.6 Dispersion Aids (Ultrasounds) 333 9.5.7 Solid-State Shear Processing 335 9.5.8 Combined Approaches 336 9.6 Structural and Functional Properties 336 9.6.1 Mechanical Behavior 337 9.6.2 Thermal Resistance 340 9.6.3 Transport Properties 341 9.6.4 Electrical Conductivity 343 9.6.5 Rheological Properties 346 10 High-Performance Oil-Resistant Blends of Ethylene Propylene Diene Monomer (EPDM) and Epoxidized Natural Rubber (ENR) 361D.K. Setua and G.B. Nando 10.1 Introduction 362 10.2 Experimental 365 10.3 Result and Discussion 367 10.3.1 Optimization of Curing System for the ENR/EPDM Blends 367 10.3.2 Optimization of Blend Ratio for the ENR/EPDM Blends 369 10.3.3 Optimization of MAH Concentration for Maleation of EPDM 369 10.3.4 Characterization of ENR-MA-G-EPDM Blends 373 10.3.5 Optimization of Processing Temperature for ENR-MA-G-EPDM Blends 375 10.3.6 Compatibility Characteristics of ENR-MA-G-EPDM Blends 375 10.3.6.1 Ultrasonic Velocity Measurements in Solution 375 10.3.6.2 Thermomechanical Analysis (TMA) 377 10.3.6.3 Scanning Electron Microscopy (SEM) Studies 378 10.3.7 Evaluation of the Mechanical Properties of Individual Rubbers and Blends 379 10.3.7.1 Stress–Strain Properties 379 10.3.7.2 Determination of Hardness 382 10.3.7.3 Oil Swelling Studies 383 10.3.7.4 Aging Studies 385 10.3.7.5 Thermogravimetric Analysis (TGA) 386 10.3.8 Effect of Addition of Carbon Black in ENR/MA-G-EPDM Blend 388 10.4 Summary and Conclusions 388 11 High-Performance Unsaturated Polyester/f-MWCNTs Nanocomposites Induced by f-Graphene Nanoplatelets 393Shivkumari Panda, Dibakar Behera, Tapan Kumar Bastia and Prasant Rath 11.1 Introduction and History 394 11.1.1 Polymerization 394 11.1.2 Fabrication 395 11.1.2.1 Hand Lay-Up 395 11.1.2.2 Spray Lay-Up 397 11.1.2.3 Compression Molding 397 11.1.2.4 Filament Winding 398 11.1.3 Chemical Stability of UPE 398 11.1.4 Compounding and Special Additives 398 11.1.5 Applications 401 11.2 Nanocomposites of UPE 11.2.1 Experimental Details 403 11.2.1.1 Materials 403 11.2.1.2 Methods 403 11.2.2 Instruments and Measurements 405 11.2.2.1 Fourier Transform Infrared (FTIR) Spectroscopy 405 11.2.2.2 Scanning Electron Microscopy (SEM) 405 11.2.2.3 Transmission Electron Microscope (TEM) 406 11.2.2.4 Contact Angle Determination 406 11.2.2.5 Dynamic Mechanical Analysis 406 11.2.2.6 Impact Testing 406 11.2.2.7 Water Absorption Capacity Determination 406 11.2.3 Results and Discussion 407 11.2.3.1 FTIR Analysis 407 11.2.3.2 SEM Analysis 408 11.2.3.3 TEM Analysis 410 11.2.3.4 Contact Angle 411 11.2.3.5 Thermomechanical Properties of UPE/Single Filler and UPE/Hybrid Filler Nanocomposites 412 11.2.3.6 Water Absorption Capacity 414

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Book SynopsisThis book offers detailed coverage of color, colorants, the coloring of materials, and reproducing the color of materials through imaging. It combines the clarity and ease of earlier editions with significant updates about the advancement in color theory and technology. Provides guidance for how to use color measurement instrumentation, make a visual assessment, set a visual tolerance, and select a formulation Supplements material with numerical examples, graphs, and illustrations that clarify and explain complex subjects Expands coverage of topics including spatial vision, solid-state lighting, cameras and spectrophotometers, and translucent materials Table of ContentsPreface xi Chapter 1 Physical Properties of Colors 1 A What this Book is about? 1 B The Spectrum and Wave Theory 2 C Light Sources 3 D Conventional Materials 5 Transmission 5 Absorption 6 Surface Scattering 7 Internal Scattering 7 Terminology – Dyes Versus Pigments 10 Spectral Characteristics of Conventional Materials 12 E Fluorescent Materials 12 F Gonioapparent Materials 14 Metallic Materials 14 Pearlescent Materials 14 Interference Materials 15 Diffraction Materials 16 G Photochromic and Thermochromic Colorants 16 H Summary 16 Chapter 2 Color and Spatial Vision 17 A Trichromacy 17 B Light and Chromatic adaptation 21 C Compression 23 D Opponency 23 E Spatial Vision 26 F Observer variability 29 G Summary 34 Chapter 3 Visual Color Specification 37 A One-Dimensional Scales 37 Hue 37 Lightness 38 Chromatic Intensity 39 B Three-Dimensional Systems 39 Geometries 39 Natural Color System 40 Munsell Color System 42 Other Color-Order Systems 46 C Color Appearance: Multidimensional systems 46 D Color-Mixing systems 47 RGB and HSB 47 The Pantone Matching System 48 Limitations of Color-Mixing Systems for Color Specification 49 E Summary 49 Chapter 4 Numerical Color Specification: Colorimetry 51 A Color Matching 51 B Derivation of the Standard observers 53 Theoretical Considerations 53 The Color-Matching Experiment 54 The 1924 CIE Standard Photopic Observer 57 The 1931 CIE Standard Colorimetric Observer 58 The 1964 CIE Standard Colorimetric Observer 61 Cone-Fundamental-Based Colorimetric Observers 62 C Calculating Tristimulus values for Materials 62 D Chromaticity Coordinates and the Chromaticity diagram 63 E Calculating Tristimulus values and Chromaticity Coordinates for sources 67 F Transformation of Primaries 68 Displays 68 Cone Fundamentals 71 G Approximately Uniformly Spaced Systems 71 L* Lightness 72 u′v′ Uniform-Chromaticity Scale Diagram 72 Cieluv 73 Cielab 74 Rotation of CIELAB Coordinates 75 H Color-appearance models 78 I Whiteness and Yellowness 83 Whiteness 83 Yellowness 84 J Summary 84 Chapter 5 Color-Quality Specification 85 A Perceptibility and Acceptability Visual Judgments 85 B Color-Difference Geometry 86 C Ellipses and Ellipsoids 89 D The Color-Difference Problem 92 E Weighted Color-Difference Formulas 96 F CMC(L:C) Color-Difference Formula 99 G Ciede2000 Color-Difference Formula 100 H Uniform Color-Difference Spaces 105 I Determining Color-Tolerance Magnitude 106 J Summary 110 Chapter 6 Color and Material-Appearance Measurement 111 A Basic Principles of Measuring Color and Material Appearance 111 B The Sample 112 C Visual Color Measurement 113 D Measurement geometries 114 Bidirectional Reflectance Distribution Function 115 CIE Recommended Geometries for Measuring Spectral Reflectance Factor 115 CIE Recommended Geometries for Measuring Spectral Transmittance Factor 118 Multiangle Geometries 118 E Spectrophotometry 119 F Spectroradiometry 121 G Fluorescence Measurements 122 H Precision and Accuracy Measurements 124 Repeatability 125 Intramodel Reproducibility 127 Accuracy 128 I spectral Imaging 134 J Material-Appearance Measurements 137 Gloss 137 Microstructure – Bidirectional Reflectance Distribution Function 137 Macrostructure 142 Sparkle and Graininess 143 K Summary 144 Chapter 7 Lighting 145 A Standard Illuminants 145 B Luminance Illuminance and Luminous Efficacy 148 C Correlated Color Temperature 149 D Color Rendition 150 E Summary 155 Chapter 8 Metamerism and Color Inconstancy 157 A Metamerism Terminology 157 B Producing Metamers 158 C Indices of Metamerism 160 Special Index of Metamerism 160 General Index of Metamerism 162 Using Indices of Metamerism 163 D Color Inconstancy and Indices of Color Inconstancy 164 E Summary 168 Chapter 9 Optical Modeling of Colored Materials 169 A Generic Approach to Color Modeling 169 B Modeling Transparent Materials 171 C Modeling Opaque Materials 174 Opaque Paints 176 Opaque Textiles 181 D Modeling Gonioapparent Materials 184 E Color-Formulation Software 184 F Summary 188 Chapter 10 Color Imaging 189 A Analysis and Synthesis 190 B Color Management 191 C Additive versus Subtractive Mixing 195 D Displays and Encoding 198 E Printing 204 F Digital Cameras 212 Colorimetric Accuracy 213 Spectral Accuracy 217 G Spectral Color Reproduction 219 H Summary 219 Bibliography 221 Annotated Bibliography 237 Recommended Books 243 Index 247

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Book SynopsisA fascinating and informative look at state-of-the-art nanotechnology research, worldwide, and its vast commercial potential Nanotechnology Commercialization: Manufacturing Processes and Products presents a detailed look at the state of the art in nanotechnology and explores key issues that must still be addressed in order to successfully commercialize that vital technology. Written by a team of distinguished experts in the field, it covers a range of applications notably: military, space, and commercial transport applications, as well as applications for missiles, aircraft, aerospace, and commercial transport systems. The drive to advance the frontiers of nanotechnology has become a major global initiative with profound economic, military, and environmental implications. Nanotechnology has tremendous commercial and economic implications with a projected $ 1.2 trillion-dollar global market. This book describes current research in the field and details itsTable of ContentsList of Contributors xv Preface xix Editor in Chief xxi 1 Overview: Affirmation of Nanotechnology between 2000 and 2030 1Mihail C. Roco 1.1 Introduction 1 1.2 Nanotechnology – A FoundationalMegatrend in Science and Engineering 2 1.3 Three Stages for Establishing the New General Purpose Technology 9 1.4 Several Challenges for Nanotechnology Development 15 1.5 About the Return on Investment 16 1.6 Closing Remarks 21 Acknowledgments 22 References 22 2 Nanocarbon Materials in Catalysis 25Xing Zhang, Xiao Zhang, and Yongye Liang 2.1 Introduction to Nanocarbon Materials 25 2.2 Synthesis and Functionalization of Nanocarbon Materials 26 2.2.1 Synthesis and Functionalization of Carbon Nanotubes 26 2.2.2 Synthesis and Functionalization of Graphene and Graphene Oxide 27 2.2.3 Synthesis and Functionalization of Carbon Nanodots 29 2.2.4 Synthesis and Functionalization of Mesoporous Carbon 29 2.3 Applications of Nanocarbon Materials in Electrocatalysis 31 2.3.1 Oxygen Reduction Reaction 32 2.3.2 Oxygen Evolution Reaction 36 2.3.3 Hydrogen Evolution Reaction 39 2.3.4 Roles of Nanocarbon Materials in Catalytic CO2 Reduction Reaction 43 2.4 Applications of Nanocarbon Materials in Photocatalysis 47 2.4.1 Application of Nanocarbon Materials as Photogenerated Charge Acceptors 48 2.4.2 Application of Nanocarbon Materials as Electron Shuttle Mediator 48 2.4.3 Application of Nanocarbon Materials as Cocatalyst for Photocatalysts 50 2.4.4 Application of Nanocarbon Materials as Active Photocatalyst 51 2.5 Summary 51 Acknowledgments 52 References 52 3 Controlling and Characterizing Anisotropic Nanomaterial Dispersion 65Virginia A. Davis andMicah J. Green 3.1 Introduction 65 3.2 What Is Dispersion andWhy Is It Important? 66 3.2.1 Factors Affecting Dispersion 73 3.2.2 Thermodynamic Dissolution of Pristine Nanomaterials 73 3.2.3 Intermolecular Potential in Dispersions 74 3.2.4 Functionalization of Nanomaterials 75 3.2.5 Physical Mixing 77 3.2.5.1 Sonication 77 3.2.5.2 Solvent IntercalationMethods 78 3.2.5.3 Shear Mixing Methods 78 3.3 Characterizing Dispersion State in Fluids 81 3.3.1 Visualization 81 3.3.2 Spectroscopy 83 3.3.3 TEM 85 3.3.4 AFM 85 3.3.5 Light Scattering 85 3.3.6 Rheology 86 3.4 Characterization of Dispersion State in Solidified Materials 88 3.4.1 Microscopy 89 3.4.2 Electrical Percolation 89 3.4.3 Mechanical Property Enhancement 89 3.4.4 Thermal Property Changes 90 3.5 Conclusion 90 Acknowledgments 90 References 91 4 High-Throughput Nanomanufacturing via Spray Processes 101Gauri Nabar,Matthew Souva, Kil Ho Lee, Souvik De, Jodie Lutkenhaus, Barbara Wyslouzil, and Jessica O.Winter 4.1 Introduction 101 4.2 Flash Nanoprecipitation 104 4.2.1 Overview 104 4.2.2 Importance of Rapid Mixing 105 4.2.3 Mixers Employed in FNP 106 4.2.3.1 Confined Impinging Jet Mixers (CIJMs) 106 4.2.3.2 Multi-Inlet Vortex Mixers (MIVMs) 107 4.2.3.3 Mixer Selection 107 4.2.4 FNP Product Structure 107 4.2.5 Applications of FNP Nanocomposites 108 4.3 Electrospray 108 4.3.1 Overview 108 4.3.2 Single Nozzle Electrospray 109 4.3.2.1 Forces and Modes of Electrospray 109 4.3.2.2 Applications of Single Nozzle Electrospray 110 4.3.3 Coaxial Electrospray 111 4.3.3.1 Configuration 111 4.3.3.2 Applications 112 4.3.4 Future Directions 113 4.4 Liquid-in-Liquid Electrospray 113 4.4.1 Overview 113 4.4.2 Importance of Relative Conductivities of the Dispersed and Continuous Phases 114 4.4.3 Modified Liquid-in-Liquid Electrospray Designs 115 4.4.4 Applications and Future Directions 117 4.5 Spray-Assisted Layer-by-Layer Assembly 117 4.5.1 Overview 117 4.5.2 Influence of Processing Parameters on Film Quality 119 4.5.2.1 Effect of Concentration 120 4.5.2.2 Effect of Spraying Time 120 4.5.2.3 Effect of Spraying Distance 120 4.5.2.4 Effect of Air Pressure 121 4.5.2.5 Effect of Charge Density 121 4.5.2.6 Effect of Rinsing and Blow-Drying 122 4.5.2.7 Effect of Rinsing Solution 122 4.5.3 Applications 122 4.5.4 Future Directions 123 4.6 Conclusion and Future Directions 123 References 123 5 Overview of Nanotechnology in Military and Aerospace Applications 133Eugene Edwards, Christina Brantley, and Paul B. Ruffin 5.1 Introduction 133 5.2 Implications of Nanotechnology in Military and Aerospace Systems Applications 134 5.3 Nano-Based Microsensor Technology for the Detection of Chemical Agents 135 5.3.1 Surface-Enhanced Raman Spectroscopy 135 5.3.1.1 Design Approach 136 5.3.1.2 Experiment 137 5.3.1.3 Results 138 5.3.2 Voltammetric Techniques 139 5.3.2.1 Design Approach 140 5.3.2.2 Experimental/Test Setup 142 5.3.2.3 Results 143 5.3.3 Functionalized Nanowires – Zinc Oxide 145 5.3.3.1 Design Approach 145 5.3.3.2 Experimental/Test Setup 146 5.3.3.3 Results 146 5.3.4 Functionalized Nanowires – Tin Oxide 147 5.3.4.1 Design Approach 148 5.3.4.2 Prototype Configuration/Testing 148 5.3.4.3 Results 148 5.4 Nanotechnology for Missile Health Monitoring 149 5.4.1 Nanoporous Membrane Sensors 150 5.4.1.1 Design Approach 150 5.4.1.2 Experimental Setup and Prototype Configuration 150 5.4.1.3 Results 152 5.4.2 Multichannel Chip with Single-Walled Carbon Nanotubes Sensor Arrays 154 5.4.2.1 Design Concept 154 5.4.2.2 Experimental Configuration 154 5.4.2.3 Results 155 5.4.3 Optical Spectroscopic Configured Sensing Techniques – Fiber Optics 155 5.4.3.1 Design Concept Spectroscopic Sensing 156 5.4.3.2 Experimental Approach/Aged Propellant Samples 156 5.4.3.3 Results from Absorption Measurements 157 5.5 Nanoenergetics – Missile Propellants 158 5.5.1 Multiwall Carbon Nanotubes 158 5.5.1.1 Design Approach 158 5.5.1.2 Experiment 159 5.5.1.3 Results 160 5.5.2 Single-Wall Carbon Nanotubes 160 5.5.2.1 Design Approach 160 5.5.2.2 Experiment 161 5.5.2.3 Results 162 5.6 Nanocomposites for Missile Motor Casings and Structural Components 162 5.6.1 Thermal Methods 162 5.6.2 VibrationalMethods 164 5.6.2.1 Design Approach 164 5.6.2.2 Experiment 164 5.6.2.3 Results 165 5.7 Nanoplasmonics 167 5.7.1 Metallic Nanostructures 168 5.7.2 Gallium-Based UV Plasmonics 169 5.8 Nanothermal Batteries and Supercapacitors 169 5.9 Conclusion 172 References 173 6 Novel Polymer Nanocomposite Ablative Technologies for Thermal Protection of Propulsion and Reentry Systems for Space Applications 177Joseph H. Koo and Thomas O. Mensah 6.1 Introduction 177 6.2 Motor Nozzle and Insulation Materials 179 6.2.1 Behavior of Ablative Materials 182 6.3 Advanced Polymer Nanocomposite Ablatives 184 6.3.1 Polymer Nanocomposites for Motor Nozzle 185 6.3.1.1 Phenolic Nanocomposites Studies byThe University of Texas at Austin 185 6.3.1.2 Phenolic-MWNT Nanocomposites Studies by Texas State University-San Marcos 188 6.3.2 Polymer Nanocomposites for Internal Insulation 189 6.3.2.1 Thermoplastic Polyurethane Nanocomposite (TPUN) Studies by The University of Texas at Austin 190 6.4 New Sensing Technology 195 6.4.1 In situ Ablation Recession and Thermal Sensors 196 6.4.1.1 Production of the C/C Sensor Plugs 198 6.4.1.2 Ablation Test Results of Carbon/Carbon Sensors 200 6.4.1.3 Ablation Test Results of Carbon/Phenolic Carbon Sensors 209 6.4.1.4 Other Ablation Sensors Results 211 6.4.1.5 Summary and Conclusions 212 6.4.2 Char Strength Sensor 213 6.4.2.1 Setup and Calibration of Compression Sensor 214 6.4.2.2 Analysis Method 215 6.4.2.3 Char Compressive Strength Results 216 6.4.2.4 Additional Considerations on the Interpretation of the Data 223 6.4.2.5 Concluding Remarks 226 6.5 Technologies Needed to Advance Polymer Nanocomposite Ablative Research 227 6.5.1 Thermophysical Properties Characterization 227 6.5.1.1 Thermal Conductivity 227 6.5.1.2 Thermal Expansion 228 6.5.1.3 Density and Composition 228 6.5.1.4 Microstructure 229 6.5.1.5 Elemental Composition 229 6.5.1.6 Char Yield 229 6.5.1.7 Specific Heat 229 6.5.1.8 Heat of Combustion 230 6.5.1.9 Optical Properties 230 6.5.1.10 Porosity 230 6.5.1.11 Permeability 230 6.5.2 Ablation Modeling 231 6.6 Summary and Conclusion 236 Nomenclature 236 Acronyms 237 Acknowledgments 237 References 238 7 Manufacture of Multiscale Composites 245David O. Olawale,Micah C. McCrary-Dennis, and Okenwa O. Okoli 7.1 Introduction 245 7.1.1 Multifunctionality of Multiscale Composites 245 7.1.2 Nanomaterials 247 7.2 Nanoconstituents Preparation Processes 249 7.2.1 Functionalization of CNTs 249 7.2.1.1 Chemical Functionalization 249 7.2.1.2 Physical (Noncovalent) Functionalization 250 7.2.2 Dispersion of Carbon Nanotubes 252 7.2.2.1 Ultrasonication 254 7.2.2.2 Calendering Process 255 7.2.2.3 Ball Milling 256 7.2.2.4 Stir and Extrusion 256 7.2.3 Alignment of CNTS 258 7.2.3.1 Ex situ Alignment 258 7.2.3.2 Force Field-Induced Alignment of CNTs 259 7.2.3.3 Magnetic Field-Induced Alignment of CNTs 259 7.2.3.4 Electrospinning-Induced Alignment of CNTs 260 7.2.3.5 Liquid Crystalline Phase-induced Alignment of CNTs 261 7.3 Liquid Composites Molding (LCM) Processes for Multiscale Composites Manufacturing 261 7.3.1 Resin Transfer Molding (RTM) 262 7.3.2 Vacuum-Assisted Resin Transfer Molding (VARTM) 263 7.3.3 Resin Film Infusion (RFI) 265 7.3.4 The Resin Infusion under Flexible Tooling (RIFT) and Resin Infusion between Double Flexible Tooling (RIDFT) 266 7.3.5 Autoclave Manufacturing 267 7.3.6 Out-of-Autoclave Manufacturing: Quickset 268 7.3.6.1 Quickstep 268 7.4 Continuous Manufacturing Processes for Multiscale Composites 269 7.4.1 Pultrusion 269 7.4.2 FilamentWinding 270 7.5 Challenges and Advances in Multiscale Composites Manufacturing – Environmental, Health, and Safety (E, H, & S) 271 7.5.1 Nanoconstituents Processing Hazards 271 7.5.2 Composite Production and Processing 272 7.5.3 Life Cycle Assessment – Use and Disposal 273 7.6 Modeling and Simulation Tools for Multiscale Composites Manufacture 273 7.6.1 Nanoparticle Modeling 274 7.6.2 Molecular Modeling 274 7.6.3 Simulation 274 7.7 Conclusion 275 References 276 8 Bioinspired Systems 285Oluwamayowa Adigun, Alexander S. Freer, LaurieMueller, Christopher Gilpin, BryanW. Boudouris, and Michael T. Harris 8.1 Introduction and Literature Overview 285 8.2 Electrical Properties of a Single Palladium-Coated Biotemplate 289 8.3 Materials and Methods 290 8.4 Results and Discussion 293 8.5 Conclusion and Outlook 297 Acknowledgments 300 References 300 9 Prediction of Carbon Nanotube Buckypaper Mechanical Properties with Integrated Physics-Based and Statistical Models 307KanWang, Arda Vanli, Chuck Zhang, and BenWang 9.1 Introduction 307 9.2 Manufacturing Process of Buckypaper 310 9.3 Finite Element-Based ComputationalModels for Buckypaper Mechanical Property Prediction 313 9.4 Calibration and Adjustment of FE Models with Statistical Methods 322 9.5 Summary 331 References 332 10 Fabrication and Fatigue of Fiber-Reinforced Polymer Nanocomposites – A Tool for Quality Control 335Daniel C. Davis and Thomas O. Mensah 10.1 Introduction 335 10.2 Materials 336 10.2.1 Carbon Fabric and Fiber 337 10.2.2 Glass Fabric and Fibers 337 10.2.3 Polymer Resin 337 10.2.4 Carbon Nanotubes 338 10.2.5 Carbon Nanofibers 339 10.2.6 Nanoclays 340 10.3 Composite Fabrication 341 10.3.1 Hand Layup 341 10.3.2 Resin Transfer Molding 342 10.4 Discussion – Fatigue and Fracture 344 10.4.1 Fatigue and Durability 344 10.4.2 Carbon Nanotube – Polymer Matrix Composites 347 10.4.3 Carbon Nanofiber – Polymer Matrix Composites 349 10.4.4 Nanoclay – PolymerMatrix Composites 354 10.5 Summary and Conclusion 359 Acknowledgments 360 References 360 11 Nanoclays: A Review of Their Toxicological Profiles and Risk Assessment Implementation Strategies 369Alixandra Wagner, Rakesh Gupta, and Cerasela Z. Dinu 11.1 Introduction 369 11.2 Nanoclay Structure and Resulting Applications 369 11.3 Nanoclays in Food Packaging Applications 370 11.4 Possible Toxicity upon Implementation of Nanoclay in Consumer Applications 375 11.4.1 In Vitro Studies Reveal the Potential of Nanoclay to Induce Changes in Cellular Viability 376 11.4.2 Proposed Mechanisms of Toxicity for the In Vitro Cellular Studies 380 11.4.3 In Vivo Evaluation of Nanoclay Toxicity 383 11.5 Conclusion and Outlook 385 Acknowledgments 387 References 388 12 Nanotechnology EHS: Manufacturing and Colloidal Aspects 395Geoffrey D. Bothun and Vinka Oyanedel-Craver 12.1 Introduction 395 12.1.1 Challenges 397 12.1.2 Recent Initiatives and Reviews 399 12.2 Colloidal Properties and Environmental Transformations 400 12.3 Assessing Nano EHS 402 12.3.1 Example: Silver Nanoparticles (AgNPs) 407 12.3.2 Role of Manufacturing 407 Summary 409 Acknowledgments 409 References 409 Index 417

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Book SynopsisProvides a comprehensive description of mass spectrometry basics, applications, and perspectives Mass spectrometry is a modern analytical technique, allowing for fast and ultrasensitive detection and identification of chemical species. It can serve for analysis of narcotics, counterfeit medicines, components of explosives, but also in clinical chemistry, forensic research and anti-doping analysis, for identification of clinically relevant molecules as biomarkers of various diseases. This book describes everything readers need to know about mass spectrometryfrom the instrumentation to the theory and applications. It looks at all aspects of mass spectrometry, including inorganic, organic, forensic, and biological MS (paying special attention to various methodologies and data interpretation). It also contains a list of key terms for easier and faster understanding of the material by newcomers to the subject and test questions to assist lecturers. Knowing how cruciaTable of ContentsList of Contributors xvii Preface xxi 1 Introduction 1Jerzy Silberring and Marek Smoluch 2 A Brief History of Mass Spectrometry 5Marek Smoluch and Jerzy Silberring 3 Basic Definitions 9Marek Smoluch and Kinga Piechura 4 Instrumentation 13 4.1 Ionization Methods 13 4.1.1 Electron Ionization (EI) 13Claudio Iacobucci 4.1.2 Chemical Ionization (CI) 15Claudio Iacobucci 4.1.2.1 Principle of Operation: Positive and Negative Ion Modes 15 4.1.3 Atmospheric Pressure Ionization (API) 21 4.1.3.1 Atmospheric Pressure Chemical Ionization (APCI) 21Claudio Iacobucci 4.1.3.2 Electrospray Ionization (ESI) 22Piotr Suder 4.1.3.3 Nanoelectrospray 38Piotr Suder 4.1.3.4 Desorption Electrospray Ionization (DESI) 42Anna Bodzon‐Kulakowska and Anna Antolak 4.1.3.5 Laser Ablation Electrospray Ionization (LAESI) 49Anna Bodzon‐Kulakowska and Anna Antolak 4.1.3.6 Photoionization 51Jerzy Silberring 4.1.4 Ambient Plasma‐Based Ionization Techniques 54Marek Smoluch 4.1.4.1 Introduction 54 4.1.4.2 Direct Analysis in Real Time (DART) 54 4.1.4.3 Flowing Atmospheric Pressure Afterglow (FAPA) 59 4.1.4.4 Dielectric Barrier Discharge Ionization (DBDI) 61 4.1.5 Matrix‐Assisted Laser Desorption/Ionization (MALDI) 64 4.1.5.1 Introduction 64Przemyslaw Mielczarek and Jerzy Silberring 4.1.5.2 The Role of Matrix 66Przemyslaw Mielczarek and Jerzy Silberring 4.1.5.3 Atmospheric Pressure MALDI 67Giuseppe Grasso 4.1.5.4 MALDI Mass Spectra Interpretation 71Przemyslaw Mielczarek and Jerzy Silberring 4.1.5.5 Desorption/Ionization on Porous Silicon (DIOS) 72Przemyslaw Mielczarek and Jerzy Silberring 4.1.5.6 Surface‐Enhanced Laser Desorption/Ionization (SELDI) 73Przemyslaw Mielczarek and Jerzy Silberring 4.1.5.7 Nanostructure‐Enhanced Laser Desorption/Ionization (NALDI) 74Przemyslaw Mielczarek and Jerzy Silberring 4.1.5.8 Summary 75Przemyslaw Mielczarek and Jerzy Silberring 4.1.6 Inductively Coupled Plasma Ionization (ICP) 78Aleksandra Pawlaczyk and Małgorzata Iwona Szynkowska 4.1.6.1 Introduction 78 4.1.6.2 ICP as a Technique of Elemental Analysis and ICP Principle 78 4.1.6.3 Ionization of Elements and Ionization Efficiency 81 4.1.6.4 Mechanism of ICP Formation 82 4.1.6.5 Ways of Plasma View and Plasma Generation 84 4.1.6.6 Sample Introduction 84 4.1.6.7 Measurement in the ICP‐MS Technique 87 4.1.6.8 Analyzers in ICP‐MS Spectrometers 87 4.1.7 Secondary Ion Mass Spectrometry with Time‐of‐Flight Analyzer (TOF‐SIMS) 93Nunzio Tuccitto 4.1.7.1 Introduction 93 4.1.7.2 TOF‐SIMS Principle of Operation 93 4.1.7.3 The Sputtering of the Sample Surface 94 4.1.7.4 Ionization (Generating Secondary Ions) 95 4.1.7.5 Construction of TOF‐SIMS 96 4.1.7.6 Analytical Capabilities of TOF‐SIMS 98 4.1.7.7 Examples and Spectra Interpretation 102 4.2 Analyzers 107 4.2.1 Time of Flight (TOF) 107Anna Bodzon-Kulakowska and Anna Antolak 4.2.1.1 Introduction 107 4.2.1.2 The Working Rule of TOF Analyzer 108 4.2.1.3 Linear Mode of Operation of TOF 109 4.2.1.4 The Spread of the Kinetic Energy Regarding the Ions of the Same Mass 110 4.2.1.5 Delayed Ion Extraction 111 4.2.1.6 The Reflection Mode 113 4.2.1.7 Orthogonal Acceleration TOF Analyzer 114 4.2.1.8 Summary 116 4.2.2 Ion Mobility Analyzer (IM) 118Anna Antolak and Anna Bodzon-Kulakowska 4.2.2.1 Principle of IM Operation 118 4.2.2.2 Drift Time IMS 118 4.2.2.3 High Field Asymmetric Waveform Ion Mobility Spectrometer (FAIMS) 119 4.2.2.4 Traveling Wave Ion Guides (TWIG) 121 4.2.2.5 IM Spectrum 122 4.2.2.6 Applications 122 4.2.3 Quadrupole Mass Analyzer 124Anna Antolak and Anna Bodzon-Kulakowska 124 4.2.3.1 Construction and Principles of Operation of a Quadrupole 124 4.2.3.2 Behavior of an Ion Inside the Quadrupole 126 4.2.3.3 How Mass Spectrum Is Generated? Changes of U and V 128 4.2.3.4 Spectrum Quality 128 4.2.3.5 Applications of the Quadrupole Analyzer 129 4.2.3.6 Quadrupoles, Hexapoles, and Octapoles as Focusing Elements: Ion Guides 129 4.2.4 Ion Trap (IT) 131Anna Bodzon-Kulakowska and Anna Antolak 4.2.4.1 Introduction 131 4.2.4.2 Behavior of an Ion Inside the Ion Trap 132 4.2.4.3 Analysis of the Ions 133 4.2.4.4 Mass Selective Instability Mode 134 4.2.4.5 Resonant Ejection Mode 135 4.2.4.6 Axial Modulation 137 4.2.4.7 Nonlinear Resonance 137 4.2.4.8 Linear Ion Trap (LIT) 137 4.2.4.9 Applications 139 4.2.5 High‐Resolution Mass Spectrometry 141Piotr Stefanowicz and Zbigniew Szewczuk 4.2.5.1 Introduction 141 4.2.6 Ion Cyclotron Resonance (ICR) 142Piotr Stefanowicz and Zbigniew Szewczuk 4.2.6.1 Introduction 142 4.2.6.2 Cyclotron Frequency 142 4.2.6.3 ICR: Principles of Operation 143 4.2.6.4 Injection of Ions into the ICR Cell 144 4.2.6.5 Trapping Electrodes 145 4.2.6.6 Excitation Electrodes 145 4.2.6.7 Detection Electrodes and Fourier Transform 145 4.2.6.8 FT‐ICR Properties as m/z Analyzer 147 4.2.7 Orbitrap 150Piotr Stefanowicz and Zbigniew Szewczuk 4.2.7.1 History of Development and Principles of Operation 150 4.2.7.2 Analyzing Ions in the Orbitrap 151 4.2.7.3 Orbitrap Properties as m/z Analyzer 152 4.2.7.4 Analytical and Proteomic Applications of Orbitrap 153 4.2.8 Hybrid Mass Spectrometers 158Giuseppe Di Natale 4.2.8.1 A Brief Comparison of Mass Analyzers 158 4.2.8.2 Triple Quadrupoles 159 4.2.8.3 Q‐IT 162 4.2.8.4 Q‐Orbitrap 162 4.2.8.5 Q‐TOF 163 4.2.8.6 IT‐TOF 165 4.2.8.7 IT‐Orbitrap 165 4.2.9 Sector Instruments 169Anna Antolak and Anna Bodzon-Kulakowska 4.2.9.1 Introduction 169 4.2.9.2 Rule of Operation of Magnetic Analyzer (B) 169 4.2.9.3 Electrostatic Sector (E) 172 4.2.9.4 Mass Spectrometers with Magnetic and Electrostatic Sector 174 4.3 Ion Detectors 176 4.3.1 Introduction 176 4.3.2 Electron Multiplier 176 4.3.3 Microchannel Detector 177 4.3.4 Medipix/Timepix Detector 178 4.3.5 Ion Detection in ICR and Orbitrap‐Based Mass Spectrometers 179 5 Hyphenated Techniques 181 5.1 Gas Chromatography Combined with Mass Spectrometry (GC‐MS) 181Anna Drabik 5.1.1 Introduction 181 5.1.2 Detectors 183 5.1.3 Chemical Modifications: Derivatization 186 5.1.4 GC‐MS Analysis 186 5.1.5 Two‐Dimensional Gas Chromatography Linked to Mass Spectrometry 2D GC‐MS 187 5.2 Liquid Chromatography Linked to Mass Spectrometry (LC‐MS) 193 5.2.1 Introduction 193Francesco Bellia 5.2.2 Introduction to Liquid Chromatography 193Anna Drabik 5.2.3 Types of Detectors 195Anna Drabik 5.2.4 Chromatographic Columns 197Anna Drabik 5.2.5 Chromatographic Separation and Quantitation Using MS as a Detector 200Anna Drabik 5.2.6 Construction of an Interface Linking Liquid Chromatograph to the Mass Spectrometer 202Anna Drabik 202 5.2.6.1 Introduction 202 5.2.6.2 ESI Interface 203 5.2.6.3 APCI Connection to MS 204 5.2.6.4 APPI Interface 205 5.2.6.5 LC Connection to MALDI‐MS 205 5.2.6.6 Multidimensional Separations 206 5.3 Capillary Electrophoresis Linked to Mass Spectrometry 209Przemysław Mielczarek and Jerzy Silberring 5.3.1 Introduction 209 5.3.2 Types of Electrophoretic Techniques 210 5.3.3 Capillary Electrophoresis Linked to ESI 211 5.3.3.1 Introduction 211 5.3.3.2 Liquid Sheath Connection 212 5.3.3.3 Sheath‐Free Connection 212 5.3.3.4 Liquid Junction 213 5.3.4 Capillary Electrophoresis Linked to Matrix‐Assisted Laser Desorption/Ionization 214 5.3.4.1 Offline CE‐MALDI‐TOF 214 5.3.4.2 Direct CE‐MALDI‐TOF 214 5.3.4.3 Online CE‐MALDI‐TOF 215 5.3.5 Summary 215 6 Mass Spectrometry Imaging 217Anna Bodzon‐Kulakowska and Anna Antolak 6.1 Introduction 217 6.2 SIMS 218 6.3 MALDI‐IMS 220 6.4 DESI 221 6.5 Analysis of Tissue Sections Using MSI Techniques 221 6.6 Analysis of Individual Cells and Cell Cultures Using MSI Techniques 223 6.7 Analysis with MSI Techniques: Examples 224 6.8 Combinations of Different Imaging Techniques 225 6.9 Summary 227 7 Tandem Mass Spectrometry 231Piotr Suder 7.1 Introduction 231 7.2 Principles 231 7.3 Strategies for MS/MS Experiments 233 7.3.1 Tandem in Space 233 7.3.2 Tandem in Time 234 7.3.3 Multiple Fragmentation 236 7.4 Fragmentation Techniques 236 7.4.1 Introduction 236 7.4.2 (Low‐Energy) Collision‐Induced Dissociation (CID) 237 7.4.3 High‐Energy Collisional Dissociation (HCD) 237 7.4.4 Pulsed Q Collision‐Induced Dissociation (PQD) 238 7.4.5 Electron Capture Dissociation (ECD) 239 7.4.6 Electron Transfer Dissociation (ETD) 239 7.4.7 Electron Detachment Dissociation (EDD) 241 7.4.8 Negative Electron Transfer Dissociation (NETD) 241 7.4.9 Infrared Multiphoton Dissociation (IRMPD) 241 7.4.10 Blackbody Infrared Radiative Dissociation (BIRD) 242 7.4.11 Post‐source Decay (PSD): Metastable Ion Dissociation 242 7.4.12 Surface‐Induced Dissociation (SID) 243 7.4.13 Charge Remote Fragmentation 243 7.4.14 Chemically Activated Fragmentation (CAF) 243 7.4.15 Proton Transfer Reaction (PTR) 244 7.5 Practical Aspects of Fragmentation in Mass Spectrometers 245 7.5.1 In‐Source Fragmentation 245 7.5.2 Triple Quadrupole Fragmentation 246 7.5.3 Ion Traps 249 7.5.4 Time‐of‐Flight Analyzers 250 7.5.5 Combined Time‐of‐Flight Analyzers (TOF/TOF) 251 7.5.6 Hybrid Instruments 252 7.5.7 Mass Spectrometers Equipped with Orbitrap Analyzer 253 7.6 Applications of Tandem Mass Spectrometry in Life Sciences 254 7.7 SWATH Fragmentation 256 8 Mass Spectrometry Applications 261 8.1 Mass Spectrometry in Proteomics 261 8.1.1 Introduction 261Vincenzo Cunsolo and Salvatore Foti 8.1.2 Bottom‐Up Versus Top‐Down Proteomics 262Vincenzo Cunsolo and Salvatore Foti 8.1.2.1 Bottom‐Up Proteomics 262 8.1.2.2 Top‐Down Proteomics 265 8.1.3 Database Search and Protein Identification 267 8.1.4 In‐Depth Structural Characterization of a Single Protein: An Example 269 8.1.5 Quantitative Analysis in Proteomics 273Joanna Ner‐Kluza, Anna Drabik, and Jerzy Silberring 8.1.5.1 Introduction 273 8.1.5.2 Isobaric Tags for Relative and Absolute Quantitation (iTRAQ) 274 8.1.5.3 Isotope‐Coded Affinity Tagging (ICAT) 276 8.1.5.4 Stable Isotope Labeling in Culture (SILAC) 279 8.1.5.5 Stable Isotope Labeling of Mammals (SILAM) 280 8.1.5.6 Mass‐Coded Abundance Tagging (MCAT) 281 8.1.5.7 Label‐Free Techniques 281 8.2 Food Proteomics 285Vera Muccilli and Rosaria Saletti 8.3 Challenges in Analysis of Omics Data Generated by Mass Spectrometry 293Katarzyna Pawlak, Emma Harwood, Fang Yu, and Pawel Ciborowski 8.3.1 Introduction 293 8.3.1.1 How Big Must Big Data Be? 294 8.3.1.2 Do Omics Experiments Generate Unstructured Data? 294 8.3.2 Targeted and Full Unbiased Omics Analysis Based on MS Technology 295 8.3.2.1 Factors Affecting Data Quality 296 8.3.2.2 Speed of MS Data Acquisition: Why Does It Matter? 297 8.3.2.3 Analytical Strategies in Omics Studies 298 8.3.3 Data Analysis and Visualization of Mass Spectrometry Omics Data 300 8.3.3.1 A Brief Introduction to Data Visualization 301 8.3.3.2 Exploration and Preparation of Data for Downstream Statistics and Visualization 304 8.3.3.3 Differential Expression Analysis 305 8.3.3.4 Strategies for Visualization Beyond Three Dimensions 310 8.3.3.5 Bioinformatics Tools 312 8.3.4 Databases and Search Algorithms 315 8.3.4.1 Databases for Proteomics 315 8.3.5 Validation of High‐Throughput Data: Current Challenges 318 8.3.5.1 Analytical Validation 319 8.3.5.2 Statistical Validation 320 8.3.5.3 Bioinformatics Validation 321 8.3.6 Summary and Conclusions 322 8.4 Application of the Mass Spectrometric Techniques in the Earth Sciences 326Robert Anczkiewicz 8.4.1 Introduction 326 8.4.2 Conventional Geochronology 326 8.4.3 In Situ Geochronology 327 8.4.4 Geochemical and Isotopic Tracing 331 8.5 Mass Spectrometry in Space 335Kathrin Altweg 8.5.1 Solar Wind and Plasma 339 8.5.2 Atmospheres of Planets and Moons 339 8.5.3 Comets 340 8.5.4 Interstellar and Cometary Dust 341 8.6 Mass Spectrometry in the Study of Art and Archaeological Objects 345Giuseppe Spoto 8.6.1 Introduction 345 8.6.2 MS Methods for the Study of Inorganic Components of Art and Archaeological Objects 345 8.6.3 MS Methods for the Study of Organic Components of Art and Archaeological Objects 346 8.7 Application of ICP‐MS for Trace Elemental and Speciation Analysis 351Aleksandra Pawlaczyk and Małgorzata Iwona Szynkowska 8.7.1 Introduction 351 8.7.2 Speciation Analysis by ICP‐MS: Examples of Applications 352 8.7.3 Single‐Particle and Single‐Cell Analysis by ICP‐MS: Examples of Applications 353 8.7.4 Imaging by LA‐ICP‐MS Technique 355 8.7.5 Improvements of LA‐ICP‐MS Technique 358 8.7.6 LA‐ICP Mass Spectrometer with LIBS 359 8.8 Mass Spectrometry in Forensic Research 362Marek Smoluch and Jerzy Silberring 8.8.1 Introduction 362 8.8.2 Forgery in Art 362 8.8.3 Psychoactive Substances and Narcotics 363 8.8.4 Counterfeit Drugs and Generation of Metabolites 366 8.8.5 Terrorism/Explosives/Chemical Warfare 367 8.8.6 Future Prospects 368 8.9 Doping in Sport 372Dorota Kwiatkowska 8.10 Miniaturization in Mass Spectrometry 384Marek Smoluch and Jerzy Silberring 9 Appendix 389Kinga Piechura and Marek Smoluch 389 9.1 Pressure Units 389 9.2 Most Commonly Detected Fragments Generated by Electron Impact (EI) Ionization 389 9.3 Trypsin Autolysis Products 393 9.4 Proteolytic Enzymes for Protein Identification 394 9.5 Molecular Masses of Amino Acid Residues 395 9.6 Molecular Masses of Less Common Amino Acid Residues 397 9.7 Internet Databases 400 9.7.1 Literature Databases 400 9.7.2 Scientific Journals 401 9.7.2.1 Journals Related to Mass Spectrometry 402 9.7.3 Bioinformatics Databases 402 9.7.3.1 Protein Databases 402 9.7.3.2 Database of Structures and Functions of Protein 403 9.7.3.3 Other Databases 404 9.7.4 Bioinformatics Tools 404 9.7.5 Useful Websites 405 10 Abbreviations 407Kinga Piechura and Marek Smoluch Index 413

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Book SynopsisBio-Based Packaging Bio-Based PackagingAn authoritative and up-to-date review of sustainable packaging development and applicationsBio-Based Packaging explores using renewable and biodegradable materials as sustainable alternatives to non-renewable, petroleum-based packaging. This comprehensive volume surveys the properties of biopolymers, the environmental and economic impact of bio-based packaging, and new and emerging technologies that are increasing the number of potential applications of green materials in the packaging industry. Contributions address the advantages and challenges of bio-based packaging, discuss new materials to be used for food packaging, and highlight cutting-edge research on polymers such as starch, protein, polylactic acid (PLA), pectin, nanocellulose, and their nanocomposites.In-depth yet accessible chapters provide balanced coverage of a broad range of practical topics, including life cycle assessment (LCA) of bio-baseTable of ContentsList of Contributors xix Series Preface xxvii Preface xxix 1 Starch-Based Packaging Materials 1Ying Chen, Kai Lu, Hongsheng Liu, and Long Yu 1.1 Introduction 1 1.2 Macrostructures and Phase Transitions of Starch 2 1.2.1 Microstructures of Starch Granules 2 1.2.2 Phase Transition During Thermal Processing 3 1.3 Extrusion Processing for Starch 5 1.3.1 Phase Transition During Extrusion 5 1.3.2 Rheological Behaviors of Starch-Based Materials 6 1.4 Improving Mechanical Properties by Reinforcement 7 1.4.1 Reinforcement by Natural Fillers 7 1.4.2 Starch-Based Nanocomposites 9 1.4.3 Self-Reinforced Composites 11 1.4.4 Blending with Other Natural Polymers 12 1.4.5 Functionalized Composites 14 1.5 Reducing Moisture Sensitivity by Coating 15 1.6 Applications in Packaging 16 1.7 Summary and Future Work 17 Acknowledgments 19 References 19 2 Protein-Based Materials for Packaging Applications 27V. G. Martins, V. P. Romani, P. C. Martins, and D. Nogueira 2.1 Introduction 27 2.2 Proteins 28 2.3 Protein Films for Food Packaging 29 2.4 Film Production Processes 32 2.5 Characterization of Films 34 2.5.1 Mechanical Properties 34 2.5.2 Barrier Properties 35 2.5.3 Structural Properties 36 2.5.4 Thermal and Optical Properties 37 2.5.5 Biodegradability of Polymers 37 2.6 Protein Films Application 38 2.7 Challenges and Future Perspectives 41 2.8 Conclusions 43 References 43 3 Protein-Based Biodegradable Polymer: From Sources to Innovative Sustainable Materials for Packaging Applications 51Huafeng Tian, Yunxuan Weng, Rakesh Kumar, Priya Rani, and Gaiping Guo 3.1 Introduction 51 3.2 Forms of Packaging Materials 52 3.3 Commercially Available Proteinous Material for Packaging 52 3.4 Preparation Methods for Protein-Based Materials for Different Packaging Applications 53 3.5 Properties of Protein-Based Packaging Materials 54 3.5.1 Mechanical Properties 54 3.5.2 Moisture Resistance 56 3.5.3 Barrier Properties 56 3.5.4 Biodegradability 57 3.5.5 Antimicrobial Properties 58 3.6 Nanomaterials Incorporated Protein-Based Packaging Materials 58 3.6.1 Protein/Inorganic Filler Nanocomposites 58 3.6.2 Protein/Organic Filler Nanocomposites 60 3.7 Protein-Based Blends as Packaging Materials 61 3.7.1 Protein/Natural Polymer Blends 61 3.7.2 Protein/Synthetic Biopolymeric Blends 62 3.8 Conclusions 63 References 63 4 Chitin/Chitosan Based Films for Packaging Applications 69J.M. Moura, B.S. Farias, T.R.S. Cadaval, and L.A.A. Pinto 4.1 Introduction 69 4.2 Chitin and Chitosan 70 4.3 Physicochemical and Biological Properties of Chitosan-Based Films 72 4.3.1 Mechanical and Barrier Properties 72 4.3.2 Antimicrobial Properties 78 4.3.3 Antioxidant Characteristics 79 4.4 Conclusion and Future Perspectives 80 References 81 5 Perspectives for Chitin/Chitosan Based Films as Active Packaging Systems on a Food Product 85Ewelina Jamróz, Piotr Kulawik, and Fatih Özogul 5.1 Introduction 85 5.2 The Effect of the Incorporation of Chitosan on the Properties of Films 86 5.3 Blends of Chitosan and Other Biopolymers 88 5.4 Characterization of Chitosan Films with Nanofillers 89 5.5 Preparation of Chitosan Films with Active Compounds 92 5.6 Chitosan-Based Films as Packaging Material Systems 93 5.7 Conclusions 98 References 99 6 Pectin-Based Bionanocomposite Coating for Food Packaging Applications 105Dr. M. Vishnuvarthanan 6.1 Introduction 105 6.2 Polymers in Food Packaging 106 6.3 Surface Modification of Polymers 106 6.4 Antimicrobial Packaging 106 6.5 Biopolymers 106 6.6 Pectin 107 6.7 Bionanocomposites 107 6.8 Nanoclay 107 6.9 Silver Nanoparticles 107 6.10 Pectin-Based Bionanocomposite Coating 108 6.10.1 Preparation and Coating of Pectin-Based Bionanocomposite 108 6.10.2 Tensile Strength 109 6.10.3 Oxygen Transmission Rate 110 6.10.4 Water Vapor Transmission Rate 111 6.10.5 Surface Color and Opacity 112 6.10.6 Contact Angle Analysis 113 6.10.7 Coating Adhesion Strength 114 6.10.8 Antimicrobial Properties 115 6.11 Conclusions 116 References 116 7 Nanocomposite: Potential Nanofiller for Food Packaging Applications 119Rafeeya Shams, Qurat ul eain Hyder Rizvi, Aamir Hussain Dar, Ishrat Majid, and Shafat Khan 7.1 Introduction 119 7.2 Nanofillers 120 7.2.1 Nanoclays 121 7.2.2 Silica (SiO2) 122 7.2.3 Silver 122 7.2.4 Gold 123 7.2.5 Metal Oxide 123 7.2.6 Zinc Oxide 123 7.2.7 Titanium Dioxide 124 7.2.8 Copper Oxide 124 7.2.9 Chitosan Nanostructures 124 7.2.10 Carbon Nanotubes 125 7.3 Nanocomposites in Active Packaging 125 7.4 Nanocomposites in Intelligent Packaging 126 7.5 Nanomaterial Migration into the Food Matrix 126 7.6 Commercial Aspects of Food Packaging 127 7.7 Conclusion and Future Trends 127 References 128 8 Nanocellulose Reinforced Polypropylene and Polyethylene Composite for Packaging Application 133Mohd Nor Faiz Norrrahim, Tengku Arisyah Tengku Yasim-Anuar, S.M. Sapuan, R.A. Ilyas, Mohd Idham Hakimi, Syed Umar Faruq Syed Najmuddin, and Mohd Azwan Jenol 8.1 Introduction 133 8.2 Plastic Packaging 135 8.3 Nanocellulose 136 8.4 Polypropylene and Polyethylene Nanocellulose Composites 137 8.5 Compatibility Between Nanocellulose with Polyethylene and Polypropylene Matrices 137 8.6 Processing Method of PP- and PE-Nanocellulose Composites 139 8.6.1 Solvent Casting 140 8.6.2 Melt Compounding 140 8.6.3 Injection and Compression Molding 141 8.6.4 One-Pot 141 8.7 Factors Influencing the Performance of the PP- and PE-Nanocellulose Composites 142 8.7.1 Drying Effect of Nanocellulose 143 8.7.2 Chemical Composition of Nanocellulose 143 8.8 Characteristics of the PP- and PE- Nanocellulose Composites 143 8.9 Conclusion and Future Recommendations 146 References 146 9 Green Food Packaging from Nanocellulose-Based Composite Materials 151Abdel Rehim M.H. 9.1 Introduction 151 9.2 Synthesis of Cellulose Nanostructures 152 9.3 Modification of Nanocellulose 153 9.4 Properties of Nanocellulose-Based Nanocomposites 154 9.5 Active Packaging Material 156 9.6 Nanocellulose in Smart Packaging 157 9.7 Future Trends and Conclusions 158 References 159 10 Nanocellulose Polylactide-Based Composite Films for Packaging Applications 165Dogan Arslan, Emre Vatansever, and Mohammadreza Nofar 10.1 Introduction 165 10.2 Polylactide 167 10.3 Nanocellulose Classification 168 10.4 PLA/Nanocellulose Nanocomposites 171 10.4.1 Processing 171 10.4.2 Mechanical Properties 173 10.4.3 Crystallization Behavior 179 10.4.4 Barrier Properties 181 10.4.5 Applications 184 10.5 Conclusion and Future Perspectives 184 References 185 11 Nanocellulose Composite Films for Packaging Applications 193Latifah Jasmani, Sharmiza Adnan, Z.M.A. Ainun, S.M. Sapuan, and R.A. Ilyas 11.1 Introduction 193 11.2 Preparation of Nanocellulose 194 11.2.1 Nanocrystalline Cellulose 195 11.2.2 Nanofibrillated Cellulose 196 11.2.3 Bacterial Cellulose 196 11.3 Nanocellulose Barrier Property 196 11.4 Nanocellulose in Films 197 11.4.1 Extrusion of Nanocellulose Composite 197 11.4.2 Casting of Nanocellulose Films 198 11.4.3 Filtration of Nanocellulose Composite 199 11.4.4 Coating 200 11.5 Nanocellulose Film in Packaging 200 11.5.1 Food and Beverage Industry 201 11.5.2 Medicine and Pharmaceuticals 201 11.6 Conclusion 202 References 202 12 Utilization of Rice Straw as a Raw Material for Food Packaging 205Rushdan Ibrahim, S.M Sapuan, R.A Ilyas, and M.S.N. Atikah 12.1 Introduction 205 12.2 Selling Rice Straw 206 12.3 Selling Pulp 207 12.4 Selling Pulp Molded Products 211 12.5 Selling Paper 214 12.6 Cost of Commercialization of Products from Rice Straw 218 12.7 Conclusions 220 References 222 13 Sustainable Paper-Based Packaging 225Latifah Jasmani, Z.M.A. Ainun, Sharmiza Adnan, Rushdan Ibrahim, S.M. Sapuan, and R.A. Ilyas 13.1 Introduction 225 13.2 Types of Raw Material for Paper-Based Packaging 227 13.2.1 Source of Fiber 227 13.2.2 Types of Pulp 230 13.2.2.1 Chemical Pulp 230 13.2.2.2 Mechanical Pulp 231 13.2.2.3 Recovered Paper 231 13.2.2.4 Non-fiber Material 232 13.3 Papermaking 232 13.4 Types of Paper-Based Packaging 232 13.4.1 Boxes 234 13.4.1.1 Folding Cartons 234 13.4.1.2 Rigid Boxes 234 13.4.1.3 Corrugated Boxes 235 13.4.1.4 Molded Pulp Containers 235 13.4.2 Paper Sheet 235 13.4.2.1 Greaseproof Paper 235 13.4.2.2 Glassine Paper 236 13.4.2.3 Vegetable Parchment 237 13.4.2.4 Waxed Paper 238 13.4.2.5 Decorative Paper 239 13.4.3 Using Types of Paper-Based Packaging 239 13.4.3.1 Food and Beverages Industries 239 13.4.3.2 Transportation Industries 240 13.5 Packaging Requirement for Paper-Based Packaging 242 13.5.1 Physical and Mechanical Characteristics of Paper 242 13.5.2 Other Requirements 242 References 243 14 Properties and Food Packaging Application of Poly-(Lactic) Acid 245N.H Sari, S. Suteja, S.M Sapuan, and R.A Ilyas 14.1 Introduction: Background and Driving Forces 245 14.2 Properties of PLA 246 14.2.1 Melt and Transition Temperature 246 14.2.2 Crystallinity 247 14.3 Mechanical 250 14.3.1 Physical 251 14.3.2 Thermal Properties 253 14.3.3 Optical 254 14.3.4 Flame Retardancy 254 14.3.5 Water Resistance 255 14.3.6 Grease Permeability 256 14.3.7 Water Vapor Permeability (WVP) 256 14.3.8 Biodegradation Properties as a Packaging 256 14.4 Food Packaging Application of PLA 257 14.5 Conclusions 260 References 260 15 Poly(Lactic) Acid Modified Films for Packaging Applications 265Jissy Jacob, Sabu Thomas, and Sravanthi Loganathan 15.1 Introduction 265 15.2 Biopolymers 266 15.2.1 Classification of Biopolymers 267 15.2.2 Poly(Lactic) Acid (PLA) 267 15.3 Modified PLA Films 267 15.3.1 PLA/Clay Composites 267 15.3.2 PLA/Carbonaceous Composites 270 15.3.3 PLA/Bio Filler Composites 271 15.3.4 PLA-Mesoporous Silica Composites 274 15.4 Conclusions 275 References 276 16 Polyhydroxyalkanoates for Packaging Application 279Tengku Arisyah Tengku Yasim-Anuar, Mohd Nor Faiz Norrrahim, S.M. Sapuan, R.A. Ilyas, Mohd Azwan Jenol, Nur Amira Mamat Razali, Mohd Idham Hakimi, Nur Farisha Abd Rahim, and Syed Umar Faruq Syed Najmuddin 16.1 Introduction 279 16.2 Biopolymers 281 16.3 Polyhydroxyalkanoates 282 16.3.1 Characteristic of PHAs 282 16.3.2 Biodegradability and Enzymatic Degradability of PHAs 284 16.3.3 Application of PHAs 284 16.4 Polyhydroxyalkanoate-Based Composites for Packaging Applications 286 16.5 Chemical Recycling of PHAs 287 16.5.1 Pyrolysis of PHAs 287 16.5.2 Application of Crotonic Acid, 2-Pentenoic Acid, and its Derivatives 288 16.6 Future Direction and Recommendations 289 References 290 17 Manufacturing of Biobased Packaging Materials 295Min Min Aung, Hiroshi Uyama, Marwah Rayung, Lu Lu Taung Mai, Moe Tin Khaing, S.M. Sapuan, and R.A. Ilyas 17.1 Introduction 295 17.2 Bio-Based Packaging Materials 296 17.3 Food Packaging Materials 297 17.3.1 Biomass Plastic in Food Packaging 298 17.3.1.1 Eucommia Elastomer 300 17.3.1.2 Biopolyurethane Using Vegetable Oils 302 17.4 Properties of Bio-Based Packaging Materials 305 17.4.1 Biodegradable Plastic 305 17.4.2 Biodegradable Polyester Composite 309 17.5 Manufacturing Food Applications 312 17.6 Food Industry and Bio-Based Materials Demand 314 17.7 Conclusions and Remarks 315 Acknowledgments 316 References 316 18 Bioplastics: An Introduction to the Role of Eco-Friendly Alternative Plastics in Sustainable Packaging 319Usman Lawal and Ravi Babu Valapa 18.1 Introduction 319 18.2 Important Biopolymers for Food Packaging 321 18.2.1 Starch 322 18.2.2 Polylactic Acid (PLA) 322 18.2.3 Cellulose 323 18.2.4 Chitosan 323 18.2.5 Polyhydroxyalkanoates (PHAs) 324 18.3 Important Properties of Biopolymers for Food Packaging Applications 325 18.3.1 Mechanical Properties of Biopolymers 325 18.3.2 Barrier Property 325 18.3.3 Antimicrobial Properties 327 18.3.4 Optical Properties 328 18.3.5 Combination with Plasticizers 328 18.4 Biopolymers and the Future of Food Packaging 329 18.5 Conclusions 330 Acknowledgment 330 References 330 19 Bioplastics: The Future of Sustainable Biodegradable Food Packaging 335S. Ayu Rafiqah, A Khalina, Khairul Zaman, ISMA Tawakkal, A.S Harmaen, and N Mohd Nurrazi 19.1 Introduction 335 19.2 Types of Plastic for Food Packaging 336 19.2.1 Biopolymer 337 19.2.2 Biodegradable Polymer – Polybutylene Succinate 338 19.2.3 Biodegradable Polymer – Polylactic Acid 340 19.3 Food Packaging 341 19.3.1 Starch-Based Bioplastic Packaging 343 19.3.2 Oxygen Transmission Rate 344 19.3.3 Water Vapor Transmission Rate (WVTR) 345 19.4 Active Food Packaging 346 19.4.1 Antimicrobial Food Packaging 347 References 348 20 Renewable Sources for Packaging Materials 353R.A Ilyas, S.M Sapuan, H.A Aisyah, Rushdan Ibrahim, M.S.N. Atikah, H.N. Salwa, Min Min Aung, S.O.A. SaifulAzry, L.N. Megashah, and Z.M.A. Ainun 20.1 Introduction 354 20.2 Packaging Materials from Bio-based Materials 355 20.3 Development of Bio-based Packages 356 20.3.1 Polycarbonates from Sugars and Carbon Dioxide 356 20.3.2 Chitosan 359 20.3.3 Plant Cell Wall Biopolymers 359 20.3.4 Polyhydroxyalkanoate 359 20.3.5 Polylactic Acid 359 20.3.6 Starch 360 20.3.7 Protein 360 20.3.8 Chitin and Chitosan 360 20.4 Decomposition of Biodegradable Plastics 361 20.5 Renewable Energy Production Using Biobased Packaging Waste 363 20.6 Cost of Bio-based Materials 363 20.7 Life Cycle Assessment 364 20.8 Social Consumption Behavior 364 20.9 Conclusions 365 Acknowledgment 365 References 365 21 Environmental Advantages and Challenges of Bio-Based Packaging Materials 371R.A Ilyas, S.M. Sapuan, Rushdan Ibrahim, M.S.N. Atikah, M.R.M. Asyraf, Mohd Nor Faiz Norrrahim, S.O.A. SaifulAzry, and Z.M.A. Ainun 21.1 Introduction 372 21.2 Advantages of Bio-Based Packaging Materials 373 21.2.1 Reduction of Waste 373 21.2.2 Reduction in Greenhouse Gas Emission 373 21.2.3 Rapid Decomposition 373 21.2.4 Sustainability 374 21.2.5 New Marketing Opportunities and Export Industries 374 21.3 Challenges of Bio-Based Packaging Materials 375 21.3.1 Inappropriate Regulations 375 21.3.2 Lack of Composting Facilities 375 21.3.3 Manufacturing Costs 376 21.4 Conclusions 377 References 377 22 Life Cycle Assessment of Bio-Based Packaging Products 381H.N. Salwa, S.M. Sapuan, M.T. Mastura, M.Y.M Zuhri, and R.A. Ilyas 22.1 Packaging: Function and Materials 381 22.1.1 Bio-Based Materials for Packaging Applications 383 22.1.2 Packaging Product Life Cycle 385 22.2 Life Cycle Assessment (LCA) 390 22.2.1 Background of LCA 390 22.2.2 LCA Approaches 391 22.3 LCA Goal and Scope (Definition of a Functional Unit and System Boundary) 392 22.3.1 Functional Unit (FU) 392 22.3.2 System Boundary 393 22.4 Life Cycle Inventory (LCI) 396 22.5 Life Cycle Impact Assessment (LCIA) 398 22.6 Life Cycle Results Interpretation 402 22.7 Conclusions 407 Acknowledgments 408 References 408 23 Reuse and Recycle of Biobased Packaging Products 413R.A. Ilyas, S.M. Sapuan, F.A. Sabaruddin, M.S.N. Atikah, Rushdan Ibrahim, M.R.M. Asyraf, M.R.M. Huzaifah, S.O.A. SaifulAzry, and Z.M.A. Ainun 23.1 Introduction 413 23.2 Waste Management Efficiency for Bioplastics 417 23.3 Prevention and Reduction 418 23.4 Reuse Bio-Based Products 418 23.5 Packaging Material Recycling 418 23.6 Mechanical Recycling Process 421 23.7 Organic Recycling or Composting 421 23.8 Impact of Aging and Recycling on the Quality of Plastic Materials 421 23.9 Conclusions 422 References 423 24 Socioeconomic Impact of Bio-Based Packaging Bags 427M. Chandrasekar, T. Senthil Muthu Kumar, K. Senthilkumar, S.M. Sapuan, R.A. Ilyas, M.R. Ishak, R.M. Shahroze, and Suchart Siengchin 24.1 Introduction 427 24.2 Socioeconomic Factors Influencing the Bioplastic-Based Packaging Materials 428 24.2.1 Interest from the Investors 428 24.2.1.1 Market Projection on the Production of Bioplastic Materials 429 24.2.2 Commercial Producers of Bio-Based Packaging Materials and Scope of Application 430 24.2.3 Policy Making and Support from the Government 431 24.2.4 Consumer Perception and Acceptance by Consumers (According to Countries) 432 24.2.5 Challenges for Bioplastics in Packaging Applications 432 24.2.5.1 Material Performance 432 24.2.5.2 Recycling 432 24.3 Future Scope 433 24.4 Conclusion 434 References 434 25 The Assessment of Supply Chains, Business Strategies, and Markets in Biodegradable Food Packaging 437K. Norfaryanti, Z.M.A. Ainun, and S. Zaiton 25.1 The Context of Bio-Packaging 437 25.2 Types of Biodegradable Food Packaging and Its Characteristics 438 25.2.1 Active Packaging 439 25.2.2 Intelligent Packaging 439 25.2.3 Biodegradable Packaging 440 25.3 Biodegradable Food Packaging Supply/Value Chain 440 25.4 Business Strategies and Market Assessment 442 25.4.1 Strategy and Market Projection 443 25.4.2 Biodegradable Food Packaging Trends 447 25.5 Conclusion 448 Acknowledgments 448 References 448 26 The Market for Bio-Based Packaging: Consumers’ Perceptions and Preferences Regarding Bio-Based Packaging 453Carsten Herbes 26.1 Introduction: The Need for Bio-Based Packaging 453 26.2 Bio-Based Packaging: An Overview 455 26.3 Consumer Perception of Bio-Based Plastics 456 26.4 Consumer Perception of Bio-Based Packaging 458 26.5 Consumer Identification of Bio-Based Packaging 460 26.6 Industry Perspectives 460 26.7 Conclusion: Problems and Potential Solutions 460 References 462 27 Regulations for Food Packaging Materials 467R.A Ilyas, S.M Sapuan, L.N. Megashah, Rushdan. Ibrahim, M.S.N. Atikah, Z.M.A. Ainun, Min Min Aung, S.O.A. SaifulAzry, and C.H. Lee 27.1 Introduction 468 27.2 Asia 470 27.2.1 Malaysia 470 27.2.2 Japan 472 27.2.3 China 473 27.2.4 India 474 27.3 Europe 475 27.4 North America and South America 479 27.4.1 History of Formal Food Packaging Regulation in the US 481 27.4.2 US Food Packaging Regulations 482 27.4.3 Environmental Impact of Materials Used in Food Packaging 483 27.4.4 Rigid Plastic Containers 483 27.4.5 Regulations 483 27.4.6 The US Exposure Approach to FCM Legislation 485 27.4.7 The Regulatory Enforcement Process in the United States 485 27.4.8 A Practical Approach to the US Food Contact Materials Regulatory Regime 486 27.5 Australia and Africa 487 27.5.1 Regulations for Food Packaging Materials in Australia 487 27.5.2 Reducing Environmental Harm in the Natural Environment 488 27.6 Regulation for Food Packaging Materials in Africa 488 27.6.1 Foods Based on Cereals and Wheat Production 488 27.6.2 Beers 488 27.6.3 Food Packaging; Reuse, Reduce, and Recycle 490 27.7 Conclusion 491 References 491 Index 495

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Book SynopsisThe first statistics guide focussing on practical application to process control design and maintenance Statistics for Process Control Engineers is the only guide to statistics written by and for process control professionals. It takes a wholly practical approach to the subject.Table of ContentsPreface xiii About the Author xix Supplementary Material xxi Part 1: The Basics 1 1. Introduction 3 2. Application to Process Control 5 2.1 Benefit Estimation 5 2.2 Inferential Properties 7 2.3 Controller Performance Monitoring 7 2.4 Event Analysis 8 2.5 Time Series Analysis 9 3. Process Examples 11 3.1 Debutaniser 11 3.2 De-ethaniser 11 3.3 LPG Splitter 12 3.4 Propane Cargoes 17 3.5 Diesel Quality 17 3.6 Fuel Gas Heating Value 18 3.7 Stock Level 19 3.8 Batch Blending 22 4. Characteristics of Data 23 4.1 Data Types 23 4.2 Memory 24 4.3 Use of Historical Data 24 4.4 Central Value 25 4.5 Dispersion 32 4.6 Mode 33 4.7 Standard Deviation 35 4.8 Skewness and Kurtosis 37 4.9 Correlation 46 4.10 Data Conditioning 47 5. Probability Density Function 51 5.1 Uniform Distribution 55 5.2 Triangular Distribution 57 5.3 Normal Distribution 59 5.4 Bivariate Normal Distribution 62 5.5 Central Limit Theorem 65 5.6 Generating a Normal Distribution 69 5.7 Quantile Function 70 5.8 Location and Scale 71 5.9 Mixture Distribution 73 5.10 Combined Distribution 73 5.11 Compound Distribution 75 5.12 Generalised Distribution 75 5.13 Inverse Distribution 76 5.14 Transformed Distribution 76 5.15 Truncated Distribution 77 5.16 Rectified Distribution 78 5.17 Noncentral Distribution 78 5.18 Odds 79 5.19 Entropy 80 6. Presenting the Data 83 6.1 Box and Whisker Diagram 83 6.2 Histogram 84 6.3 Kernel Density Estimation 90 6.4 Circular Plots 95 6.5 Parallel Coordinates 97 6.6 Pie Chart 98 6.7 Quantile Plot 98 7. Sample Size 105 7.1 Mean 105 7.2 Standard Deviation 106 7.3 Skewness and Kurtosis 107 7.4 Dichotomous Data 108 7.5 Bootstrapping 110 8. Significance Testing 113 8.1 Null Hypothesis 113 8.2 Confidence Interval 116 8.3 Six-Sigma 118 8.4 Outliers 119 8.5 Repeatability 120 8.6 Reproducibility 121 8.7 Accuracy 122 8.8 Instrumentation Error 123 9. Fitting a Distribution 127 9.1 Accuracy of Mean and Standard Deviation 130 9.2 Fitting a CDF 131 9.3 Fitting a QF 134 9.4 Fitting a PDF 135 9.5 Fitting to a Histogram 138 9.6 Choice of Penalty Function 141 10. Distribution of Dependent Variables 147 10.1 Addition and Subtraction 147 10.2 Division and Multiplication 148 10.3 Reciprocal 153 10.4 Logarithmic and Exponential Functions 153 10.5 Root Mean Square 162 10.6 Trigonometric Functions 164 11. Commonly Used Functions 165 11.1 Euler’s Number 165 11.2 Euler–Mascheroni Constant 166 11.3 Logit Function 166 11.4 Logistic Function 167 11.5 Gamma Function 168 11.6 Beta Function 174 11.7 Pochhammer Symbol 174 11.8 Bessel Function 176 11.9 Marcum Q-Function 178 11.10 Riemann Zeta Function 180 11.11 Harmonic Number 180 11.12 Stirling Approximation 182 11.13 Derivatives 183 12. Selected Distributions 185 12.1 Lognormal 186 12.2 Burr 189 12.3 Beta 191 12.4 Hosking 195 12.5 Student t 204 12.6 Fisher 208 12.7 Exponential 210 12.8 Weibull 213 12.9 Chi-Squared 216 12.10 Gamma 221 12.11 Binomial 225 12.12 Poisson 231 13. Extreme Value Analysis 235 14. Hazard Function 245 15. Cusum 253 16. Regression Analysis 259 16.1 F Test 275 16.2 Adjusted R 2 278 16.3 Akaike Information Criterion 279 16.4 Artificial Neural Networks 281 16.5 Performance Index 286 17. Autocorrelation 291 18. Data Reconciliation 299 19. Fourier Transform 305 Part 2: Catalogue of Distributions 315 20. Normal Distribution 317 20.1 Skew-Normal 317 20.2 Gibrat 320 20.3 Power Lognormal 320 20.4 Logit-Normal 321 20.5 Folded Normal 321 20.6 Lévy 323 20.7 Inverse Gaussian 325 20.8 Generalised Inverse Gaussian 329 20.9 Normal Inverse Gaussian 330 20.10 Reciprocal Inverse Gaussian 332 20.11 Q-Gaussian 334 20.12 Generalised Normal 338 20.13 Exponentially Modified Gaussian 345 20.14 Moyal 347 21. Burr Distribution 349 21.1 Type I 349 21.2 Type II 349 21.3 Type III 349 21.4 Type IV 350 21.5 Type V 351 21.6 Type VI 351 21.7 Type VII 353 21.8 Type VIII 354 21.9 Type IX 354 21.10 Type X 355 21.11 Type XI 356 21.12 Type XII 356 21.13 Inverse 357 22. Logistic Distribution 361 22.1 Logistic 361 22.2 Half-Logistic 364 22.3 Skew-Logistic 365 22.4 Log-Logistic 367 22.5 Paralogistic 369 22.6 Inverse Paralogistic 370 22.7 Generalised Logistic 371 22.8 Generalised Log-Logistic 375 22.9 Exponentiated Kumaraswamy–Dagum 376 23. Pareto Distribution 377 23.1 Pareto Type I 377 23.2 Bounded Pareto Type I 378 23.3 Pareto Type II 379 23.4 Lomax 381 23.5 Inverse Pareto 381 23.6 Pareto Type III 382 23.7 Pareto Type IV 383 23.8 Generalised Pareto 383 23.9 Pareto Principle 385 24. Stoppa Distribution 389 24.1 Type I 389 24.2 Type II 389 24.3 Type III 391 24.4 Type IV 391 24.5 Type V 392 25. Beta Distribution 393 25.1 Arcsine 393 25.2 Wigner Semicircle 394 25.3 Balding–Nichols 395 25.4 Generalised Beta 396 25.5 Beta Type II 396 25.6 Generalised Beta Prime 399 25.7 Beta Type IV 400 25.8 Pert 401 25.9 Beta Rectangular 403 25.10 Kumaraswamy 404 25.11 Noncentral Beta 407 26. Johnson Distribution 409 26.1 S N 409 26.2 S U 410 26.3 S l 412 26.4 S B 412 26.5 Summary 413 27. Pearson Distribution 415 27.1 Type I 416 27.2 Type II 416 27.3 Type III 417 27.4 Type IV 418 27.5 Type V 424 27.6 Type VI 425 27.7 Type VII 429 27.8 Type VIII 433 27.9 Type IX 433 27.10 Type X 433 27.11 Type XI 434 27.12 Type XII 434 28. Exponential Distribution 435 28.1 Generalised Exponential 435 28.2 Gompertz–Verhulst 435 28.3 Hyperexponential 436 28.4 Hypoexponential 437 28.5 Double Exponential 438 28.6 Inverse Exponential 439 28.7 Maxwell–Jüttner 439 28.8 Stretched Exponential 440 28.9 Exponential Logarithmic 441 28.10 Logistic Exponential 442 28.11 Q-Exponential 442 28.12 Benktander 445 29. Weibull Distribution 447 29.1 Nukiyama–Tanasawa 447 29.2 Q-Weibull 447 30. Chi Distribution 451 30.1 Half-Normal 451 30.2 Rayleigh 452 30.3 Inverse Rayleigh 454 30.4 Maxwell 454 30.5 Inverse Chi 458 30.6 Inverse Chi-Squared 459 30.7 Noncentral Chi-Squared 460 31. Gamma Distribution 463 31.1 Inverse Gamma 463 31.2 Log-Gamma 463 31.3 Generalised Gamma 467 31.4 Q-Gamma 468 32. Symmetrical Distributions 471 32.1 Anglit 471 32.2 Bates 472 32.3 Irwin–Hall 473 32.4 Hyperbolic Secant 475 32.5 Arctangent 476 32.6 Kappa 477 32.7 Laplace 478 32.8 Raised Cosine 479 32.9 Cardioid 481 32.10 Slash 481 32.11 Tukey Lambda 483 32.12 Von Mises 486 33. Asymmetrical Distributions 487 33.1 Benini 487 33.2 Birnbaum–Saunders 488 33.3 Bradford 490 33.4 Champernowne 491 33.5 Davis 492 33.6 Fréchet 494 33.7 Gompertz 496 33.8 Shifted Gompertz 497 33.9 Gompertz–Makeham 498 33.10 Gamma-Gompertz 499 33.11 Hyperbolic 499 33.12 Asymmetric Laplace 502 33.13 Log-Laplace 504 33.14 Lindley 506 33.15 Lindley-Geometric 507 33.16 Generalised Lindley 509 33.17 Mielke 509 33.18 Muth 510 33.19 Nakagami 512 33.20 Power 513 33.21 Two-Sided Power 514 33.22 Exponential Power 516 33.23 Rician 517 33.24 Topp–Leone 517 33.25 Generalised Tukey Lambda 519 33.26 Wakeby 521 34. Amoroso Distribution 525 35. Binomial Distribution 529 35.1 Negative-Binomial 529 35.2 Pόlya 531 35.3 Geometric 531 35.4 Beta-Geometric 535 35.5 Yule–Simon 536 35.6 Beta-Binomial 538 35.7 Beta-Negative Binomial 540 35.8 Beta-Pascal 541 35.9 Gamma-Poisson 542 35.10 Conway–Maxwell–Poisson 543 35.11 Skellam 546 36. Other Discrete Distributions 549 36.1 Benford 549 36.2 Borel–Tanner 552 36.3 Consul 555 36.4 Delaporte 556 36.5 Flory–Schulz 558 36.6 Hypergeometric 559 36.7 Negative Hypergeometric 561 36.8 Logarithmic 561 36.9 Discrete Weibull 563 36.10 Zeta 564 36.11 Zipf 565 36.12 Parabolic Fractal 567 Appendix 1 Data Used in Examples 569 Appendix 2 Summary of Distributions 577 References 591 Index 593

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Book SynopsisThis book provides an unparalleled contemporary assessment of hydrocarbon chemistry presenting basic concepts, current research, and future applications. Comprehensive and updated review and discussion of the field of hydrocarbon chemistry Includes literature coverage since the publication of the previous edition Expands or adds coverage of: carboxylation, sustainable hydrocarbons, extraterrestrial hydrocarbons Addresses a topic of special relevance in contemporary science, since hydrocarbons play a role as a possible replacement for coal, petroleum oil, and natural gas as well as their environmentally safe use Reviews of prior edition: ...literature coverage is comprehensive and ideal for quickly reviewing specific topics...of most value to industrial chemists... (Angewandte Chemie) and ...useful for chemical engineers as well as engineers in the chemical and petrochemical industries. (Petroleum Science and Technology)Table of ContentsVolume 1 Preface to the Third Edition xiii Preface to the Second Edition xv Preface to the First Edition xvii Introduction xix Introduction and General Aspects 1 1.1 Hydrocarbons and Their Classes 1 1.2 Energy–Hydrocarbon Relationships 2 1.3 Hydrocarbon Sources 4 Extraterrestrial Hydrocarbons 15 1.4 Hydrocarbon Production from Natural Sources 16 1.5 Hydrocarbon Synthesis 20 1.6 Nonrenewable and Renewable Hydrocarbons 27 1.7 Regenerative Hydrocarbons from CO2 Emission Capture and Recycling 29 1.8 Hydrocarbon Functionalization Reactions 30 1.9 Use of Hydrocarbons, Petroleum Oil 35 1.9.1 Energy Generation, Storage, and Delivery: Heating 36 1.9.2 Transportation Fuels 36 1.9.3 Chemical Products, Plastics, and Pharmaceuticals 38 References 38 Hydrocarbons from Petroleum and Natural Gas 49 2.1 Cracking 49 2.2 Reforming 62 Hydroforming 64 Metal-Catalyzed Reforming 65 2.3 Dehydrogenation with Olefin Production 71 Heterogeneous Catalysts 73 Homogeneous Catalysts 78 C2–C3 Alkenes 85 C4 Alkenes 86 Buta-1,3-diene and Isoprene 87 Higher Olefins 88 Styrene 88 2.4 Upgrading of Natural-Gas Liquids 89 2.5 Aromatics Production 89 References 102 Synthesis from C Sources 125 3.1 Aspects of C1 Chemistry 126 3.2 Chemical Reduction to Methanol and Oxygenates; Recycling of CO2 127 Heterogeneous Hydrogenation 129 Homogeneous Hydrogenation 137 Ionic Reduction 143 Electrochemical and Electrocatalytic Reduction 143 Photoreduction 146 Enzymatic Reduction 148 3.3 Fischer–Tropsch Chemistry 149 3.4 Oxygenation of Methane 166 Methanol Synthesis 166 3.5 Oligocondensation of Methane 173 3.6 Hydrocarbons from Methane Derivatives 186 Methanol Conversion to Hydrocarbons 186 Methanol to Hydrocarbon Technologies 196 Methanol to Gasoline 196 Methanol to Olefin 197 Methanol to Propylene 198 References 200 Isomerization 237 4.1 Acid-Catalyzed and Bifunctional Isomerization 238 Mechanism 243 Side-Chain Isomerization 250 Positional Isomerization 250 4.2 Base-Catalyzed Isomerization 262 4.2.1 Alkenes 262 4.3 Metal-Catalyzed Isomerization 266 4.4 Pericyclic Rearrangements 277 4.5 Practical Applications 284 Alkanes 284 Alkenes 285 4.5.2 Isomerization of Xylenes 286 References 287 Alkylations 305 5.1 Acid-Catalyzed Alkylation 305 Alkylolysis (Alkylative Cleavage) 317 Alkylation of Alkenes with Organic Halides 318 Alkylation of Alkynes 320 Alkylation with Carbonyl Compounds: The Prins Reaction 320 Catalysts 324 Alkylation with Alkyl Halides 326 Alkylation with Alkenes 331 Alkylation with Alkanes 335 Alkylation with Other Reagents 338 5.2 Base-Catalyzed Alkylation 350 5.3 Alkylation through Organometallics 352 5.4 Miscellaneous Alkylations 356 5.5 Practical Applications 360 References 369 Addition Reactions 389 6.1 Hydration 389 Production of Alcohols by Hydration of Alkenes 395 Production of Octane-Enhancing Oxygenates 396 Acetaldehyde 397 6.2 HX Addition 398 Alkenes 398 Dienes 403 Alkynes 404 Ethyl Chloride 411 Hydrochlorination of Buta-1,3-diene 411 Vinyl Chloride 411 Ethylene Chlorohydrin 412 Propylene Chlorohydrin 412 Adiponitrile 412 Acrylonitrile 413 6.3 Halogen Addition 413 Vinyl Chloride 422 Chlorination of Buta-1,3-diene 424 6.4 Addition to Form C–N Bonds 424 6.5 Addition to Form C–O, C–S, and C–P Bonds 433 6.6 Hydrometalation 439 Alkenes 440 Dienes 446 Alkynes 448 Alkenes 452 Dienes 456 Alkynes 457 6.7 Halometalation 462 6.8 Solvometalation 465 6.9 Carbometalation 466 6.10 Cycloaddition 471 References 477 Carbonylation and Carboxylation 509 7.1 Carbonylation 509 Hydroformylation in Biphasic Solvent Systems 515 The Use of Heterogeneous Catalysts 516 Hydroformylation of Higher Alkenes 518 Hydroformylation of Internal Alkenes 519 Asymmetric Hydroformylation 520 7.2 Carboxylation 533 Saturated Hydrocarbons 534 Aromatic Hydrocarbons 536 Hydrocarboxylation and hydroesterification 539 Aminocarboxylation 545 Neocarboxylic Acids 547 Hydrocarboxymethylation of Long-Chain Alkenes 547 Propionic Acid 547 Acrylic Acid and Acrylates 548 References 548 Acylation 569 8.1 Acylation of Aromatics 569 New Soluble Catalysts 573 Solid Catalysts 575 The Gattermann–Koch Reaction 577 The Gattermann Reaction 579 Other Formylations 580 8.2 Acylation of Aliphatic Compounds 581 References 586 Index 000 Volume 2 Preface to the Third Edition xi Preface to the Second Edition xiii Preface to the First Edition xv Introduction xvii Oxidation–Oxygenation 593 9.1 Oxidation of Alkanes 594 Autoxidation of Alkanes 594 Oxidation of Methane 596 Oxidation with Stoichiometric Oxidants 606 Oxidation Catalyzed by Enzymes and Metalloporphyrins 613 Metal-Catalyzed Oxidation in the Homogeneous Phase 616 Oxidation Induced by Heterogeneous Catalysts 619 Metal Oxidants 623 Electrophilic Reagents 624 Oxygenolysis 628 9.2 Oxidation of Alkenes 630 Direct Oxidation with Stoichiometric Oxidants 630 Metal-Catalyzed Epoxidation 635 Epoxidation Catalyzed by Metalloporphyrins 644 Asymmetric Epoxidation 647 Autoxidation 650 Reactions with Singlet Oxygen 650 Bis-Hydroxylation 656 Bis-Acetoxylation 663 Oxidation with Palladium in the Homogeneous Phase 664 Oxidation with Other Reagents 669 Vinylic Acetoxylation 671 Ozonation 673 Mechanism 673 Synthetic Applications 676 Other Oxidants 678 Allylic Hydroxylation and Acyloxylation 681 Oxidation to α,β-Unsaturated Carbonyl Compounds 686 9.3 Oxidation of Alkynes 690 9.4 Oxidation of Aromatics 693 Oxidation to Phenols 693 Ring Acyloxylation 701 Oxidation to Quinones 702 Oxidation to Arene Oxides and Arene Diols 703 Oxidation with Singlet Oxygen 704 Oxidation of Methyl-Substituted Aromatics 706 Oxidation of Other Arenes 708 Benzylic Acetoxylation 711 9.5 Practical Applications 712 Acetic Acid 712 Maleic Anhydride 713 Oxidation of Cyclohexane 715 Oxidation of Cyclododecane 715 sec-Alcohols 715 Ethylene Oxide 716 Propylene Oxide 718 Acetaldehyde and Acetone 719 Vinyl Acetate 719 1,4-Diacetoxybut-2-ene 720 Acrolein and Acrylic Acid 720 Methacrolein and Methacrylic Acid 721 Acrylonitrile 721 Other Processes 722 Phenol and Acetone 722 Benzoic Acid 723 Terephthalic Acid 723 Maleic Anhydride 724 Phthalic Anhydride 725 Anthraquinone 727 References 727 Heterosubstitution 795 10.1 Electrophilic (Acid-Catalyzed) Substitution 795 Halogenation 796 Nitration 798 Sulfuration 799 Halogenation 800 Nitration 804 Sulfonation 808 Synthesis of Sulfoxides and Sulfones 810 Chlorobenzene 811 Nitration of Benzene and Toluene 811 Sulfonation of Benzene and Alkylbenzenes 811 10.2 Free-Radical Substitution 812 Chlorination 812 Fluorination 817 Bromination 818 Iodination 819 Side-Chain Halogenation of Arylalkanes 819 Chlorination of Alkanes 824 Side-Chain Chlorination of Toluene 826 Unsaturated Chlorides 826 Sulfochlorination of Alkanes 827 Nitroalkanes 827 10.3 Formation of C–N Bonds 827 10.4 Formation of Carbon–Metal Bonds 831 Borylation 837 Silylation 840 Al, Ge, and Sn Derivatives 841 10.5 Miscellaneous Derivatives 842 References 843 Reduction–Hydrogenation 863 11.1 Heterogeneous Catalytic Hydrogenation 864 Mechanism 866 Stereochemistry 870 11.2 Homogeneous Catalytic Hydrogenation 886 Mechanism 891 Selectivity and Stereochemistry 893 Asymmetric Hydrogenation 896 11.3 Transfer Hydrogenation 904 11.4 Chemical and Electrochemical Reduction 906 Mechanism 911 Selectivity 911 11.5 Ionic Hydrogenation 913 11.6 Hydrogenolysis of Saturated Hydrocarbons 918 11.7 Practical Applications 931 C2 Hydrorefining 931 C3 Hydrorefining 931 C4 Hydrorefining 931 Gasoline Hydrorefining 932 References 934 Metathesis 959 12.1 Metathesis of Acyclic Alkenes 960 12.2 Alkane Metathesis 973 12.3 Metathesis of Alkynes 976 12.4 Ring-Closing Metathesis 978 12.5 Ring-Opening Metathesis and Ring-Opening Metathesis Polymerization 979 12.6 Practical Applications 983 References 986 Oligomerization and Polymerization 1001 13.1 Oligomerization 1001 Practical Applications 1006 Alkenes 1008 Alkynes 1013 Cyclooligomerization 1014 Practical Applications 1018 13.2 Polymerization 1021 Ziegler–Natta Catalysts 1038 The Phillips Catalyst 1041 Group IV Metallocene Catalysts 1042 Postmetallocene Catalysts 1047 Stereoregular Polymerization of Propylene 1058 Isospecific Polymerization 1059 Syndiospecific Polymerization 1064 Stereoregular Polymerization of Dienes 1065 Ethylene Polymers 1072 Polypropylene 1074 Polybutylenes 1075 Styrene Polymers 1076 Polydienes 1077 References 1078 Outlook 1111 14.1 Sustainable Hydrocarbon Chemistry for the Future 1111 14.2 Extraterrestrial Hydrocarbon Chemistry 1114 References 1115 Index 000

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Book SynopsisAn introduction to the principles and practices of soil and groundwater remediation Soil and Groundwater Remediation offers a comprehensive and up-to-date review of the principles, practices, and concepts of sustainability of soil and groundwater remediation. The book starts with an overview of the importance of groundwater resource/quality, contaminant sources/types, and the scope of soil and groundwater remediation. It then provides the essential components of soil and groundwater remediation with easy-to-understand design equations/calculations and the practical applications. The book contains information on remediation basics such as subsurface chemical behaviors, soil and groundwater hydrology and characterization, regulations, cost analysis, and risk assessment. The author explores various conventional and innovative remediation technologies, including pump-and-treat, soil vapor extraction, bioremediation, incineration, thermally enhanced techniquesTable of ContentsAbout the Author xv Preface xvii Acknowledgments xxi Whom This Book is Written For xxiii To the Instructor xxv List of Symbols xxvii About the Companion Website xxxiii 1 Sources and Types of Soil and Groundwater Contamination 1 1.1 Uses of Surface Water vs. Groundwater 1 1.2 Groundwater Quantity vs. Groundwater Quality 4 1.3 Major Factors Affecting Groundwater Quality 6 1.4 Soil and Groundwater Contaminant Sources in the United States 8 1.4.1 Superfund Sites and Brownfields 9 1.4.2 RCRA Facilities and Underground Storage Tanks 12 1.4.3 DoD/DoE Sites 14 1.5 Contaminated Soil and Groundwater: A Global Perspective 14 1.6 Soil and Groundwater Remediation 16 1.6.1 Unique Challenges Relative to Air and Surface Water Pollution 16 1.6.2 Scope of Environmental Remediation 17 Bibliography 17 2 Subsurface Contaminant Fate and Transport 21 2.1 Frequent Soil and Groundwater Contaminants 22 2.1.1 Aliphatic and Aromatic Hydrocarbons 23 2.1.2 Halogenated Aliphatic Hydrocarbons 24 2.1.3 Halogenated Aromatic Hydrocarbons 25 2.1.4 Nitrogen‐containing Organic Compounds 26 2.1.5 Oxygenated Organic Compounds 27 2.1.6 Sulfur‐ and Phosphorus‐containing Organic Compounds 28 2.1.7 Inorganic Nonmetals, Metals, and Radionuclides 29 2.2 Abiotic and Biotic Chemical Fate Processes 30 2.2.1 Hydrolysis 31 2.2.2 Oxidation and Reduction 32 2.2.3 Biodegradation 35 2.3 Interphase Chemical Transport 35 2.3.1 Volatilization 36 2.3.2 Solubilization, Precipitation, and Dissolution 38 2.3.2.1 Solubility and Solubility Product for Inorganic Compounds 38 2.3.2.2 Solubility and Kow for Organic Compounds 41 2.3.3 Sorption and Desorption 42 2.4 Intraphase Chemical Movement 48 2.4.1 Advection 49 2.4.2 Dispersion and Diffusion 49 Bibliography 53 3 Soil and Groundwater Hydrology 59 3.1 Soil Composition and Properties 60 3.1.1 Constituents of Soils 60 3.1.2 Soil Physical and Chemical Properties 62 3.2 Basic Concepts of Aquifer and Wells 66 3.2.1 Vertical Distribution of Aquifer 66 3.2.2 Groundwater Well and Well Nomenclature 68 3.2.3 Hydrogeological Parameters 68 3.2.3.1 Specific Yield and Specific Retention 68 3.2.3.2 Hydraulic Conductivity and Permeability 70 3.2.3.3 Transmissivity and Storativity 71 3.3 Groundwater Movement 73 3.3.1 Flow in Saturated Zone 74 3.3.2 Flow in Unsaturated Zone 77 3.3.3 Flow to Wells in a Steady‐State Confined Aquifer 80 3.3.4 Flow to Wells in a Steady-State Unconfined Aquifer 82 3.3.5 Flow of Nonaqueous Phase Liquid 84 Bibliography 86 4 Legal, Economical, and Risk Assessment Considerations 91 4.1 Soil and Groundwater Protection Laws 92 4.1.1 Relevant Soil and Groundwater Laws in the United States 92 4.1.1.1 Safe Drinking Water Act 93 4.1.1.2 Resource Conservation and Recovery Act 94 4.1.1.3 Comprehensive Environmental Response, Compensation and Liability Act 95 4.1.1.4 Hazardous and Solid Waste Amendment 95 4.1.1.5 Superfund Amendment and Reauthorization Act 96 4.1.1.6 Small Business Liability Relief and Brownfields Revitalization Act 96 4.1.2 Framework of Environmental Laws in Other Countries 96 4.2 Cost Constraints in Remediation 97 4.2.1 Remediation Cost Elements 99 4.2.2 Basis for Remediation Cost Estimates 99 4.2.3 Cost Comparisons among Remediation Alternatives 101 4.3 Risk‐based Remediation 104 4.3.1 How Clean is Clean 104 4.3.2 Estimate Environmental Risk from Carcinogenic Compounds 108 4.3.3 Estimate Environmental Risk from Noncarcinogenic Compounds 112 4.3.4 Determine Risk-Based Cleanup Levels for Soil and Groundwater 113 4.3.4.1 Determining Maximum Concentration in Drinking Water and Air 114 4.3.4.2 Determining Allowable Soil Cleanup Level 115 4.3.4.3 Risk Involving Multimedia 116 Bibliography 118 5 Site Characterization for Soil and Groundwater Remediation 123 5.1 General Consideration of Site Characterization 124 5.1.1 Objectives and Scopes of Site Characterization 124 5.1.2 Basic Steps: Phase I, II, and III Assessment 125 5.1.2.1 Phase I Environmental Site Assessment 125 5.1.2.2 Phase II Environmental Site Assessment 126 5.2 Soil and Geologic Characterization 130 5.2.1 Stratigraphy, Lithology, and Structural Geology 130 5.2.2 Direct Drilling Methods 130 5.2.3 Drive Method Using Cone Penetrometer 132 5.2.4 Indirect Geophysical Methods 132 5.3 Hydrogeologic Site Investigation 138 5.3.1 Well Installation, Development, and Purging 138 5.3.2 Hydraulic Head and Flow Direction 139 5.3.2.1 Methods to Measure Hydraulic Head 140 5.3.2.2 Groundwater Flow Direction 140 5.3.3 Aquifer Tests to Estimate Hydraulic Conductivity 141 5.3.3.1 Slug Test: Hvorslev Method 142 5.3.3.2 Slug Test: Bouwer and Rice Method 143 5.3.3.3 Pumping Test: Theis Type‐Curve Method 143 5.4 Environmental Sampling and Analysis 146 5.4.1 Common Soil Samplers 146 5.4.2 Groundwater Sampling 148 5.4.2.1 Groundwater Sampling Tools 148 5.4.2.2 Cross‐Contamination in Groundwater Sampling 149 5.4.3 Vadose Zone Soil Gas and Water Sampling 150 5.4.4 Instruments for Chemical Analysis 150 Bibliography 152 6 Overview of Remediation Options 157 6.1 Types of Remediation Technologies 158 6.1.1 Classifications of Remediation Technologies 158 6.1.2 Common and Frequently Used Remediation Technologies 162 6.1.3 Technologies from Contaminant Perspectives 163 6.2 Development and Selection of Remediation Technologies 168 6.2.1 Remedial Investigation/Remedial Feasibility Study 172 6.2.2 Remediation Technologies Screening and Selection Criteria 174 6.2.3 Green and Sustainable Remediation 178 6.3 A Snapshot of Remediation Technologies 179 6.3.1 Description of Various Treatments 180 6.3.2 Treatment Train 180 Bibliography 183 7 Pump‐and‐Treat Systems 187 7.1 General Applications of Conventional Pump‐and‐Treat 188 7.1.1 Contaminant Removal versus Hydraulic Containment 188 7.1.2 Schemes of Injection/Extraction Well Placement 191 7.2 Design of Pump‐and‐Treat Systems 192 7.2.1 Capture Zone Analysis of Pump‐and‐Treat Optimization 194 7.2.2 Aboveground Treatment of Contaminated Groundwater 198 7.2.2.1 General Treatment Technologies Available 198 7.2.2.2 Design Considerations for Air Stripping 200 7.2.2.3 Design Considerations for Activated Carbon 202 7.3 Pump‐and‐Treat Limitations and Alterations 204 7.3.1 Residual Saturations of Nonaqueous Phase Liquid 204 7.3.1.1 Dissolved Contaminant from NAPLs 204 7.3.1.2 Residual Saturation 205 7.3.2 Tailing and Rebound Problems 209 7.3.2.1 Slow NAPL Dissolution 209 7.3.2.2 Slow Contaminant Desorption/Precipitate Dissolution 210 7.3.2.3 Slow Matrix Diffusion 211 7.3.2.4 Groundwater Velocity Variation 211 7.3.3 Alterations of Conventional Pump‐and‐Treat 212 7.3.3.1 Chemical Enhancement to Increase Contaminant Mobility and Solubility 213 7.3.3.2 Horizontal Wells, Inclined Wells, Interceptor Trenches, and Drains 213 7.3.3.3 Phased Extraction Wells, Adaptive Pumping, and Pulsed Pumping 215 7.3.3.4 Induced Fractures 216 7.3.3.5 Pumping in Conjunction with Permeable and Impermeable Barriers 217 Bibliography 219 8 Soil Vapor Extraction and Air Sparging 225 8.1 General Applications and Limitations of Vapor Extraction 226 8.1.1 Process Description and System Components 226 8.1.2 Chemical and Geologic Parameters Affecting Vapor Extraction 227 8.1.3 Pros and Cons of Vapor Extraction and Air Sparging 229 8.2 Soil Vapor Behavior and Gas Flow in Subsurface 231 8.2.1 Airflow Patterns in Subsurface 231 8.2.2 Vapor Equilibrium and Thermodynamics 233 8.2.3 Kinetics of Volatilization, Vapor Diffusion, and NAPL Dissolution 239 8.2.4 Darcy’s Law for Advective Vapor Flow 241 8.3 Design for Vapor Extraction and Air Sparging Systems 245 8.3.1 Quantitative Analysis for the Appropriateness of Soil Venting 245 8.3.2 Well Number, Flow Rate, and Well Location 249 8.3.3 Other Design Considerations 251 Bibliography 257 9 Bioremediation and Environmental Biotechnology 263 9.1 Principles of Bioremediation and Biotechnology 264 9.1.1 Microorganisms and Microbial Growth 265 9.1.1.1 Types of Microorganisms 265 9.1.1.2 Cell Growth on Contaminant 267 9.1.2 Reaction Stoichiometry and Kinetics 271 9.1.3 Biodegradation Potentials and Pathways 275 9.1.3.1 Biodegradation of Petroleum Aliphatic Hydrocarbons 276 9.1.3.2 Biodegradation of Single‐Ring Petroleum Aromatic Hydrocarbon (BTEX) 276 9.1.3.3 Biodegradation of Fuel Additives (MTBE) 278 9.1.3.4 Biodegradation of Polycyclic Aromatic Hydrocarbons (PAHs) 278 9.1.3.5 Biodegradation of Chlorinated Aliphatic Hydrocarbons (CAHs) 279 9.1.3.6 Biodegradation of Chlorinated Aromatic Compounds 280 9.1.3.7 Biodegradation of Explosive Compounds 280 9.1.4 Optimal Conditions for Bioremediation 281 9.1.4.1 Hydrogeologic Parameters 282 9.1.4.2 Soil/Groundwater Physicochemical Parameters 283 9.1.4.3 Microbial Presence 285 9.1.4.4 Contaminant Characteristics 285 9.2 Process Description of Bioremediation and Biotechnologies 286 9.2.1 In Situ Bioremediation 287 9.2.2 Ex Situ Biological Treatment 290 9.2.2.1 Biopiles and Composting 290 9.2.2.2 Landfarming 292 9.2.2.3 Bioslurry Reactors 293 9.2.3 Sanitary Landfills 293 9.2.4 Phytoremediation and Constructed Wetland 294 9.3 Design Considerations and Cost‐Effectiveness 300 9.3.1 General Design Rationales 300 9.3.1.1 Design for In Situ Groundwater Bioremediation 300 9.3.1.2 Design for Bioventing 301 9.3.1.3 Design for Biosparging 301 9.3.1.4 Design for Biopiles and Composting 301 9.3.1.5 Design of Landfill 302 9.3.2 Cost Effectiveness Case Studies 302 Bibliography 305 10 Thermal Remediation Technologies 315 10.1 Thermal Destruction by Incineration 316 10.1.1 Principles of Combustion and Incineration 316 10.1.1.1 Combustion Chemistry and Combustion Efficiency 316 10.1.1.2 Heating Values of Fuels/Wastes 319 10.1.1.3 Oxygen (Air) Requirement 320 10.1.1.4 Three T’s of the Combustion/Incineration 323 10.1.2 Components of Hazardous Waste Incinerator Systems 324 10.1.2.1 General Applications: Pros and Cons 324 10.1.2.2 Incinerator System Components 325 10.1.2.3 Four Types of Combustion Chambers 326 10.1.3 Design Considerations for Incineration 328 10.1.3.1 Incinerator Size and Dimensions 329 10.1.3.2 Factors Affecting Incinerator Performance 331 10.1.4 Regulatory and Siting Considerations 332 10.2 Thermally Enhanced Technologies 332 10.2.1 Temperature Effects on Physicochemical and Biological Properties 333 10.2.2 Heat Transfer Mechanisms in Soil and Groundwater 338 10.2.3 Required Heat‐Up Time and Radius of Influence 338 10.2.4 Use of Hot Air, Steam, Hot Water, and Electro‐Heating 339 10.2.4.1 Hot Air, Steam, Hot Water, and Electro-Heating 339 10.2.4.2 Flow Chart to Select Thermal Processes 343 10.3 Vitrification 344 Bibliography 347 11 Soil Washing and Flushing 353 11.1 Basic Principles of Soil Washing and Flushing 354 11.1.1 Overview of Soil Washing and Flushing 354 11.1.2 Surfactant‐Enhanced Contaminant Solubilization 356 11.1.3 Surfactant‐Enhanced Contaminant Mobilization 358 11.1.4 Cosolvent Effects on Solubility and Mobilization 361 11.2 Process Description, Technology Applicability, and Limitations 363 11.2.1 Ex Situ Soil Washing 364 11.2.2 In Situ Soil Flushing and Cosolvent Flooding 368 11.3 Design and Cost‐Effectiveness Considerations 370 11.3.1 Chemical Additives in Soil Washing and Flushing 370 11.3.2 Recycle of Chemical Additives and Disposal of Flushing Wastes 373 Bibliography 375 12 Permeable Reactive Barriers 379 12.1 Reaction Mechanisms and Hydraulics in Reactive Barriers 380 12.1.1 Barrier Technologies as a Viable Option for Pump‐and‐Treat 380 12.1.2 Dechlorination Mediated through Redox Reactions by Zero‐Valent Iron 381 12.1.3 Other Abiotic and Biotic Processes in Reactive Barriers 384 12.1.4 Hydraulics and Fouling Problems in Reactive Barriers 386 12.2 Process Description of Reactive Barriers 388 12.2.1 Configurations of Reactive Barriers 388 12.2.2 Available Reactive Media and Selection 389 12.2.2.1 Types of Reactive Media 389 12.2.2.2 Reactive Media Selection 391 12.3 Design and Construction Considerations 392 12.3.1 Barrier Design Concept 392 12.3.2 Construction Methods 394 Bibliography 400 13 Modeling of Groundwater Flow and Contaminant Transport 403 13.1 Governing Equations for Groundwater Flow 404 13.1.1 Saturated Groundwater Flow under Steady‐State Condition (Laplace Equation) 404 13.1.2 Saturated Groundwater Flow under Transient Condition 406 13.1.3 Unsaturated Groundwater Flow under Transient Condition (Richards Equation) 407 13.2 Governing Equations for Contaminant Transport 408 13.2.1 General Mass Balance Equations Considering Advection and Dispersion 408 13.2.2 Governing Equations for Contaminant Transport in Unsaturated Zone 411 13.2.3 Governing Equations Incorporating Adsorption and Reaction 412 13.2.4 General Concepts and Equations Describing Multiphase Flow and Transport 415 13.2.4.1 Processes Relevant to Multiphase and Multiple Components 415 13.2.4.2 Framework of Governing Equations for Multiphase Flow and Transport 417 13.3 Analytical Solutions to Flow and Transport Processes 420 13.3.1 Darcy’s Law: 1‐D Flow in Unconfined Aquifer (Dupuit Equation) 420 13.3.2 Fick’s Second Law: 1‐D Diffusion Only Solutions 422 13.3.3 Advection and Dispersion: 1‐D, 2‐D, and 3‐D Solutions to Slug Injection 424 13.3.4 Advection and Dispersion: 1‐D Solutions to Continuous Injection 425 13.3.5 Advection and Dispersion: 2‐D and 3‐D Solutions to Continuous Injection 427 13.4 Numerical Solutions to Flow and Transport Processes 430 13.4.1 Partial Differential Equations and Numerical Methods 430 13.4.2 2‐D Laplace Equation Using Finite Difference Method 433 Bibliography 436 Appendix A Common Abbreviations and Acronyms 439 Appendix B Definition of Soil and Groundwater Remediation Technologies 445 Appendix C Structures and Properties of Important Organic Pollutants in Soil and Groundwater 451 Appendix D Unit Conversion Factors 459 Appendix E Answers to Selected Problems 461 Index 465 IUPAC Periodic Table of the Elements 477

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Book SynopsisIntroduces the key areas of chemistry required for all pharmacy degree courses and focuses on the properties and actions of drug molecules This new edition provides a clear and comprehensive overview of the various areas of general, organic, and natural products chemistry (in relation to drug molecules). Structured to enhance student understanding, it places great emphasis on the applications of key theoretical aspects of chemistry required by all pharmacy and pharmaceutical science students. This second edition particularly caters for the chemistry requirements in any Integrated Pharmacy Curricula', where science in general is meant to be taught not in isolation', but together with, and as a part of, other practice and clinical elements of the course. Chemistry for Pharmacy Students: General, Organic and Natural Product Chemistry, 2nd Edition is divided into eight chapters. It opens with an overview of the general aspects of chemistry and their importancTable of ContentsPreface to the second edition xv Preface to the first edition xvii Chapter 1: Introduction 1 1.1 Role of Chemistry in Modern Life 1 1.2 Solutions and Concentrations 4 1.3 Suspension, Colloid and Emulsion 6 1.4 Electrolytes, Nonelectrolytes and Zwitterions 7 1.5 Osmosis and Tonicity 8 1.6 Physical Properties of Drug Molecules 10 1.6.1 Physical State 10 1.6.2 Melting Point and Boiling Point 10 1.6.3 Polarity and Solubility 11 1.7 Acid–Base Properties and pH 13 1.7.1 Acid–Base Definitions 14 1.7.2 Electronegativity and Acidity 18 1.7.3 Acid–Base Properties of Organic Functional Groups 19 1.7.4 pH, pOH and pKa Values 22 1.7.5 Acid–Base Titration: Neutralization 30 1.8 Buffer and its Use 32 1.8.1 Common Ion Effects and Buffer Capacity 34 Chapter 2: Atomic Structure and Bonding 37 2.1 Atoms, Elements and Compounds 37 2.2 Atomic Structure: Orbitals and Electronic Configurations 39 2.3 Chemical Bonding Theories: Formation of Chemical Bonds 43 2.3.1 Lewis Structures 43 2.3.2 Resonance and Resonance Structures 47 2.3.3 Electronegativity and Chemical Bonding 48 2.3.4 Various Types of Chemical Bonding 49 2.4 Bond Polarity and Intermolecular Forces 54 2.4.1 Dipole–Dipole Interactions 54 2.4.2 van der Waals Forces 55 2.4.3 Hydrogen Bonding 56 2.5 Hydrophilicity and Lipophilicity 57 2.6 Significance of Chemical Bonding in Drug–Receptor Interactions 60 2.7 Significance of Chemical Bonding in Protein–Protein Interactions 63 2.8 Significance of Chemical Bonding in Protein–DNA Interactions 63 Chapter 3: Stereochemistry 65 3.1 Stereochemistry: Definition 66 3.2 Isomerism 66 3.2.1 Constitutional Isomers 66 3.2.2 Stereoisomers 67 3.3 Stereoisomerism of Molecules with More than One Stereocentre 82 3.3.1 Diastereomers and Meso Structures 82 3.3.2 Cyclic Compounds 84 3.3.3 Geometrical Isomers of Alkenes and Cyclic Compounds 85 3.4 Significance of Stereoisomerism in Determining Drug Action and Toxicity 88 3.5 Synthesis of Chiral Molecules 91 3.5.1 Racemic Forms 91 3.5.2 Enantioselective Synthesis 92 3.6 Separation of Stereoisomers: Resolution of Racemic Mixtures 93 3.7 Compounds with Stereocentres Other than Carbon 94 3.8 Chiral Compounds that Do Not Have Four Different Groups 94 Chapter 4: Organic Functional Groups 97 4.1 Organic Functional Groups: Definition and Structural Features 97 4.2 Hydrocarbons 100 4.3 Alkanes, Cycloalkanes and Their Derivatives 100 4.3.1 Alkanes 100 4.3.2 Cycloalkanes 108 4.3.3 Alkyl Halides 111 4.3.4 Alcohols 119 4.3.5 Ethers 125 4.3.6 Thiols 129 4.3.7 Thioethers 131 4.3.8 Amines 134 4.4 Carbonyl Compounds 140 4.4.1 Aldehydes and Ketones 140 4.4.2 Carboxylic acids 148 4.4.3 Acid Chlorides 154 4.4.4 Acid Anhydrides 155 4.4.5 Esters 157 4.4.6 Amides 160 4.4.7 Nitriles 163 4.5 Alkenes and their Derivatives 164 4.5.1 Nomenclature of Alkenes 165 4.5.2 Physical Properties of Alkenes 166 4.5.3 Structure of Alkenes 167 4.5.4 Industrial uses of Alkenes 167 4.5.5 Preparations of Alkenes 168 4.5.6 Reactivity and Stability of Alkenes 168 4.5.7 Reactions of Alkenes 169 4.6 Alkynes and their Derivatives 169 4.6.1 Nomenclature of Alkynes 170 4.6.2 Structure of Alkynes 170 4.6.3 Acidity of Terminal Alkynes 171 4.6.4 Heavy Metal Acetylides: Test for Terminal Alkynes 171 4.6.5 Industrial Uses of Alkynes 172 4.6.6 Preparations of Alkynes 172 4.6.7 Reactions of Alkynes 172 4.6.8 Reactions of Metal Alkynides 174 4.7 Aromatic Compounds and their Derivatives 174 4.7.1 History 175 4.7.2 Definition: Hückel’s Rule 175 4.7.3 General Properties of Aromatic Compounds 175 4.7.4 Classification of Aromatic Compounds 176 4.7.5 Pharmaceutical importance of Aromatic Compounds: Some Examples 177 4.7.6 Structure of Benzene: Kekulé Structure of Benzene 179 4.7.7 Nomenclature of Benzene Derivatives 183 4.7.8 Electrophilic Substitution of Benzene 184 4.7.9 Alkylbenzene: Toluene 190 4.7.10 Phenols 192 4.7.11 Aromatic Amines: Aniline 199 4.7.12 Polycyclic Benzenoids 207 4.8 Importance of Functional Groups in Determining Drug Actions and Toxicity 209 4.8.1 Structure-Activity Relationships of Sulpha Drugs 210 4.8.2 Structure-Activity Relationships of Penicillins 211 4.8.3 Paracetamol Toxicity 213 4.9 Importance of Functional Groups in Determining Stability of Drugs 213 Chapter 5: Organic Reactions 215 5.1 Types of Organic Reactions Occur with Functional Groups 215 5.2 Reaction Mechanisms and Types of Arrow in Chemical Reactions 216 5.3 Free Radical Reactions: Chain Reactions 217 5.3.1 Free Radical Chain Reaction of Alkanes 217 5.3.2 Relative Stabilities of Carbocations, Carbanions, Radicals and Carbenes 219 5.3.3 Allylic Bromination 221 5.3.4 Radical Inhibitors 222 5.4 Addition Reactions 223 5.4.1 Electrophilic Additions to Alkenes and Alkynes 223 5.4.2 Symmetrical and Unsymmetrical Addition to Alkenes and Alkynes 226 5.4.3 Nucleophilic Addition to Aldehydes and Ketones 240 5.5 Elimination Reactions: 1,2-Elimination or β-Elimination 254 5.5.1 E1 Reaction or First Order Elimination 255 5.5.2 E2 Reaction or Second Order Elimination 256 5.5.3 Dehydration of Alcohols 257 5.5.4 Dehydration of Diols: Pinacol Rearrangement 259 5.5.5 Base-Catalysed Dehydrohalogenation of Alkyl Halides 260 5.6 Substitution Reactions 265 5.6.1 Nucleophilic Substitutions 266 5.6.2 Nucleophilic Substitutions of Alkyl Halides 273 5.6.3 Nucleophilic Substitutions of Alcohols 276 5.6.4 Nucleophilic Substitutions of Ethers and Epoxides 282 5.6.5 Nucleophilic Acyl Substitutions of Carboxylic Acid Derivatives 286 5.6.6 Substitution Versus Elimination 293 5.7 Electrophilic Substitutions 294 5.7.1 Electrophilic Substitution of Benzene 294 5.8 Hydrolysis 300 5.8.1 Hydrolysis of Carboxylic Acid Derivatives 300 5.9 Oxidation–Reduction Reactions 305 5.9.1 Oxidizing and Reducing Agents 305 5.9.2 Oxidation of Alkenes 305 5.9.3 Oxidation of Alkynes 307 5.9.4 Hydroxylation of Alkenes 307 5.9.5 Oxidative Cleavage of syn-Diols 308 5.9.6 Ozonolysis of Alkenes 308 5.9.7 Ozonolysis of Alkynes 309 5.9.8 Oxidation of Alcohols 309 5.9.9 Oxidation of Aldehydes and Ketones 311 5.9.10 Baeyer–Villiger Oxidation of Aldehydes or Ketones 312 5.9.11 Reduction of Alkyl Halides 312 5.9.12 Reduction of Organometallics 312 5.9.13 Reduction of Alcohols via Tosylates 313 5.9.14 Reduction of Aldehydes and Ketones 313 5.9.15 Clemmensen Reduction 315 5.9.16 Wolff–Kishner Reduction 316 5.9.17 Reduction of Acid Chlorides 316 5.9.18 Reduction of Esters 317 5.9.19 Hydride Reduction of Carboxylic Acids 318 5.9.20 Reduction of Oximes or Imine Derivatives 318 5.9.21 Reduction of Amides, Azides and Nitriles 319 5.9.22 Reductive Amination of Aldehydes and Ketones 320 5.10 Pericyclic Reactions 320 5.10.1 Diels–Alder Reaction 320 5.10.2 Essential Structural Features for Dienes and Dienophiles 321 5.10.3 Stereochemistry of the Diels–Alder Reaction 322 5.10.4 Sigmatropic Rearrangements 323 5.10.5 Hydrogen Shift 323 5.10.6 Alkyl Shift: Cope Rearrangement 324 5.10.7 Claisen Rearrangement 324 Chapter 6: Heterocyclic Compounds 327 6.1 Heterocyclic Compounds and their Derivatives 327 6.1.1 Medicinal Importance of Heterocyclic Compounds 328 6.1.2 Nomenclature of Heterocyclic Compounds 329 6.1.3 Physical Properties of Heterocyclic Compounds 331 6.2 Pyrrole, Furan and Thiophene: Unsaturated Heterocycles 332 6.2.1 Physical Properties of Pyrrole, Furan and Thiophene 333 6.2.2 Preparations of Pyrrole, Furan and Thiophene 333 6.2.3 Reactions of Pyrrole, Furan and Thiophene 335 6.3 Pyridine 339 6.3.1 Physical Properties of Pyridine 339 6.3.2 Preparations of Pyridine 340 6.3.3 Reactions of Pyridine 340 6.4 Oxazole, Imidazole and Thiazole 342 6.4.1 Physical Properties of Oxazole, Imidazole and Thiazole 343 6.4.2 Preparations of Oxazole, Imidazole and Thiazole 344 6.4.3 Reactions of Oxazole, Imidazole and Thiazole 345 6.5 Isoxazole, Pyrazole and Isothiazole 346 6.5.1 Physical Properties of Isoxazole, Pyrazole and Isothiazole 348 6.5.2 Preparations of Isoxazole, Pyrazole and Isothiazole 348 6.5.3 Reactions of Isoxazole, Pyrazole and Isothiazole 348 6.6 Pyrimidine 349 6.6.1 Physical Properties of Pyrimidine 350 6.6.2 Preparations of Pyrimidine 350 6.6.3 Reactions of Pyrimidine 351 6.7 Purine 352 6.7.1 Physical Properties of Purine 353 6.7.2 Preparations of Purine 353 6.7.3 Reactions of Purine 353 6.8 Quinoline and Isoquinoline 354 6.8.1 Physical Properties of Quinoline and Isoquinoline 354 6.8.2 Preparations of Quinoline and Isoquinoline 355 6.8.3 Reactions of Quinoline and Isoquinoline 357 6.9 Indole 358 6.9.1 Physical Properties of Indole 359 6.9.2 Preparations of Indole 359 6.9.3 Reactions of Indole 360 6.9.4 Test for Indole 361 Chapter 7: Nucleic Acids 363 7.1 Nucleic Acids 363 7.1.1 Synthesis of Nucleosides and Nucleotides 365 7.1.2 Structure of Nucleic Acids 366 7.1.3 Nucleic Acids and Heredity 370 7.1.4 DNA Fingerprinting 373 7.2 Amino Acids and Peptides 373 7.2.1 Fundamental Structural Features of an Amino acid 376 7.2.2 Essential Amino Acids 376 7.2.3 Glucogenic and Ketogenic Amino Acids 377 7.2.4 Amino Acids in Human Body 377 7.2.5 Acid–Base Properties of Amino Acids 378 7.2.6 Isoelectric Points of Amino Acids and Peptides 378 Chapter 8: Natural Product Chemistry 381 8.1 Introduction to Natural Products 381 8.1.1 Natural Products 381 8.1.2 Natural Products in Medicine 382 8.1.3 Drug Discovery and Natural Products 385 8.2 Alkaloids 390 8.2.1 Properties of Alkaloids 391 8.2.2 Classification of Alkaloids 391 8.2.3 Tests for Alkaloids 410 8.3 Carbohydrates 410 8.3.1 Classification of Carbohydrates 411 8.3.2 Stereochemistry of Sugars 414 8.3.3 Cyclic Structures of Monosaccharides 415 8.3.4 Acetal and Ketal Formation in Sugars 416 8.3.5 Oxidation, Reduction, Esterification and Etherification of Monosaccharides 417 8.3.6 Pharmaceutical Uses of Monosaccharides 420 8.3.7 Disaccharides 420 8.3.8 Polysaccharides 423 8.3.9 Miscellaneous Carbohydrates 426 8.3.10 Cell Surface Carbohydrates and Blood Groupings 428 8.4 Glycosides 429 8.4.1 Biosynthesis of Glycosides 430 8.4.2 Classification 430 8.4.3 Test for Hydrocyanic Acid (HCN) 432 8.4.4 Pharmaceutical Uses and Toxicity 432 8.4.5 Anthracene/Anthraquinone Glycosides 433 8.4.6 Isoprenoid Glycosides 436 8.4.7 Iridoid and Secoiridoid Glycosides 440 8.5 Terpenoids 442 8.5.1 Classification 442 8.5.2 Biosynthesis of Terpenoids 443 8.5.3 Monoterpenes 445 8.5.4 Sesquiterpenes 446 8.5.5 Diterpenes 455 8.5.6 Triterpenes 461 8.5.7 Tetraterpenes 465 8.6 Steroids 466 8.6.1 Structures of Steroids 467 8.6.2 Stereochemistry of Steroids 468 8.6.3 Physical Properties of Steroids 468 8.6.4 Types of Steroid 469 8.6.5 Biosynthesis of Steroids 471 8.6.6 Synthetic Steroids 472 8.6.7 Functions of Steroids 473 8.7 Phenolics 476 8.7.1 Phenylpropanoids 477 8.7.2 Coumarins 478 8.7.3 Flavonoids and Isoflavonoids 481 8.7.4 Lignans 486 8.7.5 Tannins 489 Index 493

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Book SynopsisPractical reference on the latest sensory and consumer evaluation techniques available to professionals and academics working in food and consumer goods product development and marketing This unique manual describes how to implement specific sensory and consumer methods based on context and objective. Presented in a direct and straightforward language that will speak to the industry professionals and academics who are on the ground attempting to solve technical questions, it reviews, step by step, the various stages of a product evaluation. Included are practical examples from many industries that practitioners can relate to. The book also shows how to build a sustainable short-, medium-, and long-term product evaluation strategy, and guides readers on how to create customized methods, or even completely new approaches. Consumer and Sensory Evaluation Techniques speaks to management and decision-makers within organizations and addresses the main questionsTable of ContentsPreface xi Acknowledgements xiii 1 The Pillars of Good Consumer and Sensory Studies 1 1.1 Leveraging Existing Consumer Insight Prior to Building a Test Plan: What Do We Already Know? 1 1.2 Pillars of a Test Design 5 1.2.1 What Are We Testing? 5 1.2.1.1 Circumscribe the Test Product 5 1.2.1.2 Do We Test Blind or Identified Products? 8 1.2.1.3 How Is the Product ‘Dressed Up’: Packaging, Fragrance? 11 1.2.1.4 Experimental Design: Order of Product Presentation 13 1.2.2 With Whom Are We Testing? 16 1.2.2.1 Who Are the Competitors and Benchmarks? 16 1.2.2.2 Who Is the Target (Age, Gender, Socio]Economic Background, Users of and so Forth)? 18 1.2.3 Where Are We Testing? 21 1.2.3.1 Circumscribe the Geographical Region or Country 21 1.2.3.2 What Is the Impact of Local Culture? 23 1.2.3.3 Do We Test In]Home or in a Central Location? 24 1.2.4 When Are We Testing? 26 1.2.4.1 How Important Are Consumer Habits? 26 1.2.4.2 Is There Any Seasonal Impact? 27 1.2.5 Target Segmentation Principles: Do We Need to Define Different Consumer Cells? 27 References 28 2 Sensory Profile of a Product: Mapping Internal Sensory Properties 33 2.1 Origins of Sensory Evaluation 33 2.2 Definition of Descriptive Sensory Analysis 33 2.3 Existing Descriptive Methods, Advantages and Disadvantages 34 2.3.1 Quantitative Descriptive Analysis (QDA) 34 2.3.1.1 Main Characteristics of QDA 34 2.3.1.2 Discussion on Inter]Individual Variability 39 2.3.1.3 Discussion on Inter]Panel Variability 40 2.3.1.4 Variants to QDA 42 2.3.1.5 Typical Representations 42 2.3.2 Free]Choice Profile 49 2.3.3 Flash Profile 50 2.3.4 Spectrum 50 2.3.5 Time Intensity 51 2.3.6 Comparative Advantages and Limits in Each Method 52 2.3.7 Cost Considerations 54 References 55 3 The Foundations of Consumer Evaluation 63 3.1 Qualitative Consumer Studies: When We Are at the Stage of Proof of Concept 63 3.1.1 When to Take a Qualitative Approach? 63 3.1.2 Define the Test Design: With or Without Product Testing 65 3.1.3 Define the Market and Consumer Sample: Sample Size, Focus Groups or One]on]One Interviews 67 3.1.4 Define a Timeline 76 3.1.5 Analysis and Deliverables 77 3.1.6 Budget Considerations 80 3.2 Quantitative Consumer Studies: As We Get Close to Product Launch 82 3.2.1 When to Move Forward with a Quantitative Approach 82 3.2.2 Define the Test Design: One or Multiple Products 83 3.2.3 Define the Market 94 3.2.4 Define the Sample: Sample Size and Confidence Level 94 3.2.5 Define a Timeline 95 3.2.6 Analysis and Deliverables 96 3.2.7 Budget Considerations 108 3.3 Ethnographic Studies: In]Depth Exploration of Consumer Needs and Expectations 109 3.3.1 When to Conduct an Ethnographic In]Depth Study 109 3.3.2 Define the Market and Sample 110 3.3.3 Define the Test Design 110 3.3.4 Define a Timeline 111 3.3.5 Analysis and Deliverables 112 3.3.6 Budget Considerations 112 3.4 Additional Approaches to Detect Breakthrough Innovations: How to Assess the ‘Wow’ Factors? 113 3.4.1 Less Conventional Methods 113 3.4.1.1 Kano 113 3.4.1.2 Thurstone Scaling 116 3.4.2 Thinking Out of the Box 117 References 118 4 Study Plans and Strategy: Sustainable Short], Mid] and Long]Term Vision 123 4.1 Definition of Key Performance Indicators 123 4.2 Exploratory Phase 127 4.2.1 Use of Consumer Insight 128 4.2.2 Use of Sensory Evaluation 128 4.2.3 Use of a Qualitative Approach 130 4.2.4 Use of a Mini]Quantitative Approach 133 4.3 Confirmatory Phase 136 4.3.1 Use of a Quantitative Approach 136 4.3.2 Product Validation 137 4.3.3 R&D and Marketing Intertwined Roles 139 4.4 Necessary Reconsiderations and Back and Forth 139 4.5 Spin]Offs to Capitalize on Successful Products 140 References 141 5 Real]Life Anticipation with Market Factors: Brand, Concept, Market Channel, Price 143 5.1 Highly Challenging Markets 143 5.2 Blind Versus Identified Quantitative Tests 144 5.3 Specificity of Concept Tests 145 5.4 Notions of Modellization 147 5.5 Preference Mapping and Its Variants 149 5.6 Incorporation of Market Factors in Modellizations 151 References 152 6 Internal Studies Versus Sub]Contracting 155 6.1 Outsourcing: When and When Not? 155 6.2 Precautions When Outsourcing 157 6.3 Criteria to Select a Market]Research Company for a Specific Study 159 References 160 Appendix 161 Index 187

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Book SynopsisThis book details the latest R&D in electrochemical energy storage technologies for portable electronics and electric vehicle applications. During the past three decades, great progress has been made in R & D of various batteries in terms of energy density increase and cost reduction. One of the biggest challenges is increasing the energy density to achieve longer endurance time. In this book, recent research and development in advanced electrode materials for electrochemical energy storage devices is covered. Topics covered in this important book include: Carbon anode materials for sodium-ion batteriesLithium titanate-based lithium-ion batteriesRational material design and performance optimization of transition metal oxide-based lithium ion battery anodesEffects of graphene on the electrochemical properties of the electrode of lithium ion batteriesSilicon-based lithium-ion battery anodesMo-based anode materials for alkali metal ion batteriesLithium-sulfur batteriesGraphene in Li

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Book SynopsisWritten by one of the world''s foremost authorities on the subject, this is the most comprehensive and in-depth treatment available to environmental engineers and scientists for the remediation of groundwater, one of the earth''s most precious resources. Groundwater is one of the Earth''s most precious resources. We use it for drinking, bathing, and many other purposes. Without clean water, humans would cease to exist. Unfortunately, because of ignorance or lack of caring, groundwater is often contaminated through industrialization, construction or any number of other ways. It is the job of the environmental engineer to remediate the contaminated groundwater and make what has been tainted safe again.Selecting the proper remediation strategy and process is the key to moving forward, and, once this process has been selected, it must be executed properly, taking into consideration the costs, the type of contaminants that are involved, time frames, and many other factors.<Table of ContentsPreface xi About the Author xv 1 Conducting Groundwater Quality Investigations 1 1.1 Introduction 1 1.2 Evolution of Site Assessments 2 1.3 Technology Limitations and Cleanup Goals 14 1.4 Conceptual Models 14 1.4.1 Source and Release Information 15 1.4.2 Geologic and Hydrogeologic Characterization 16 1.4.3 Contaminant Distribution, Transport and Fate 17 1.4.4 Geochemistry Impacting Natural Biodegradation 17 1.5 Risk Assessment Concepts 18 1.6 Institutional Controls 20 1.7 Risk-Based Cleanup Goals and Screening Level Evaluations 20 1.8 Assessing Plume Migration Potential 25 2 The Family of DNAPLs 37 2.1 Defining DNAPL 37 2.2 Chemicals and Origins 38 2.2.1 Creosote and Coal Tars 38 2.2.2 Polychlorinated Biphenyls 41 2.2.3 Chlorinated Solvents 44 2.2.4 Mixtures 48 2.3 DNAPL Behavior 49 2.3.1 General Behavior and Concepts 49 2.3.2 Important Parameters for Site Characterization 56 2.4 Overview of Remediation Strategies 59 2.4.1 Remediation Goals 59 2.4.2 Technologies 63 2.4.2.1 Pump-and-Treat 63 2.4.2.2 Permeable Reactive Barriers 63 2.4.2.3 Physical Barriers 64 2.4.2.4 Enhanced Biodegradation 64 2.4.2.5 Thermal Technologies 64 2.4.2.6 Chemical Flushing 65 2.4.2.7 Excavation and Removal 65 2.4.2.8 Soil Vacuum Extraction 66 2.4.2.9 Water Flooding 66 2.4.2.10 Air Sparging 66 3 Hydrocarbons 69 3.1 Fate and Transport 69 3.1.1 General 69 3.1.2 Advective Transport 70 3.1.3 Dispersion 70 3.1.4 Sorption 71 3.1.5 Dilution and Recharge 73 3.1.6 Volatilization 73 3.2 Gasoline Compounds 74 3.2.1 General Description 74 3.2.2 The BTEX Compounds and MTBE 74 3.2.3 Properties of VOCs 75 3.2.4 Degradation 75 3.2.5 Half-Lifes 77 3.3 Pump and Treat 79 3.3.1 Concept 79 3.3.2 Non-Aqueous Phase Liquids 85 3.3.3 Contaminant Desorption and Precipitate Dissolution 86 3.3.4 Remedial Technologies 87 3.3.5 EPA Cost Data for Pump-and-Treat 89 4 1,4-Dioxane 95 4.1 Overview 95 4.2 Properties, Fate and Transport 98 4.3 Health Effects and Regulations 103 4.4 Remediation Technologies 104 4.4.1 Advanced Oxidation (Ex Situ) 109 4.4.2 Adsorption (GAC) (Ex Situ) 113 4.4.3 Bioremediation 113 4.4.4 Treatment in Soil 114 5 Perfluorinated Compounds (PFCS) 117 5.1 Overview 117 5.2 Origins of the Contaminants 118 5.3 PFAs Properties and Structures 121 5.3.1 General Description 121 5.3.2 Variations of PFAS 123 5.3.3 PFOS 126 5.3.4 PFOA 129 5.4 Environmental Fate and Transport 130 5.5 Groundwater Contamination 144 5.6 Water Treatment 149 5.7 Estimating Carbon Treatement Costs 157 6 Chlorinated Solvents 163 6.1 Physico-Chemical Properties of Chlorinated Solvents 163 6.2 Origins of Groundwater Contamination 167 6.3 Fate and Transport 168 6.3.1 Properties 168 6.3.2 Degradation and Daughter Products 170 6.3.3 Biodegradation Half-Life 173 6.3.4 DNAPL Migration 185 6.4 Groundwater Remediation Strategies 188 6.4.1 Preliminary Considerations 188 6.4.2 Soil Excavation, Treatment and Disposal 195 6.4.3 Soil Vapor Extraction 197 6.4.4 Enhanced Methods of Soil Vapor Extraction 201 6.4.5 In Situ Air Sparging 202 6.4.6 Enhanced Biodegradation 210 6.4.7 In-well Aeration and Recirculation 215 6.4.8 Reactive and Permeable Walls 216 6.5 Costs 217 6.5.1 Soil Excavation, Treatment and Disposal 217 6.5.2 Soil Vapor Extraction 220 6.5.3 Air Sparging Comparisons to other Technologies 227 7 Mineral Ions and Natural Groundwater Contaminants 233 7.1 Overview 233 7.2 Secondary Drinking Water Standards 236 7.3 Irrigation Water Quality Standards 238 7.3.1 Salts 238 7.3.2 Water Analysis Terminology 238 7.3.3 Types of Salt Problems 239 7.3.4 Salinity Hazard 241 7.3.5 Sodium Hazard 242 7.3.6 Trace Elements and Limits 242 7.4 Water Treatment Membrane Technologies 247 7.4.1 Overview 247 7.4.2 Reverse Osmosis (RO) 248 7.4.3 Nanofiltration 255 7.4.4 Microfiltration 258 7.4.5 Ultrafiltration 260 7.4.6 Treatment Costs 262 7.4.7 Secondary Wastes 265 7.4.8 Selection Criteria 265 7.5 Ion Exchange 266 7.5.1 Technology Description 266 7.5.2 Chelating Agents 271 7.5.3 Batch and Column Exchange Systems 272 7.5.4 Process Equipment 272 7.5.5 Cost Data 275 7.6 Crystallization 279 7.6.1 Technology Description 279 7.6.2 Forced-Circulation Crysallizers 286 7.6.3 Draft-tube Crystallizers and Draft-tube-baffle Crystallizers 288 7.6.4 Surface-Cooled Crystallizers 289 7.6.5 Oslo Crystallizers 291 7.6.6 Fluid-Bed Type Crystallizers 292 8 Heavy Metals and Mixed Media Remediation Technologies for Contaminated Soils and Groundwater 299 8.1 Nature of the Problem 299 8.2 Toxic Metal Chemical Forms, Speciation and Properties 300 8.3 Remedial Technology Strategies 306 8.3.1 Isolation 306 8.3.2 Capping 306 8.3.3 Subsurface Barriers 313 8.3.4 Immobilization 315 8.3.5 Solidification/Stabilization 317 8.3.6 Vitrification 321 8.3.7 Toxicity and Mobility Reduction 323 8.3.8 Wet Oxidation Process 331 8.3.9 Advanced Oxidation Technologies 333 8.3.10 Permeable Treatment Walls 343 8.3.11 Biological Treatment 344 8.3.12 Physical Separation 346 8.3.13 Extraction 349 8.3.14 Soil Washing 349 8.3.15 Soil Screening 350 8.3.16 Chemical Treatment 350 8.3.17 Physical Treatment 351 8.3.18 Pyrometallurgical Extraction 352 8.3.19 In Situ Soil Flushing 352 8.3.20 Electrokinetic Treatment 352 8.4 Cost Data 353 8.4.1 General Cost Information 353 8.4.2 Site Capping 356 8.4.3 In situ Solidification/Stabilization 358 8.4.4 Ex Situ Solidification/Stabilization 361 8.4.5 Soil Washing 365 8.4.6 Slurry Walls 367 Index 379

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Book SynopsisThis all-new revised edition of a modern classic is the most comprehensive and up-to-date coverage of the green process of desalination in industrial and municipal applications, covering all of the processes and equipment necessary to design, operate, and troubleshoot desalination systems. This is becoming increasingly more important for not only our world''s industries, but our world''s populations, as pure water becomes more and more scarce. Blue is the new green. This is an all-new revised edition of a modern classic on one of the most important subjects in engineering: Water. Featuring a total revision of the initial volume, this is the most comprehensive and up-to-date coverage of the process of desalination in industrial and municipal applications, a technology that is becoming increasingly more important as more and more companies choose to go green. This book covers all of the processes and equipment necessary to design, operate, and troubleshoot desalination s

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Book SynopsisFiesers'' Reagents for Organic Synthesis provides an up-to-date, A-to-Z listing of reagents cited in synthetic literature. Covers, in volume 29, chemical literature and methodologies from 2013-mid 2014 Features entries with concise descriptions, illustrations of chemical reactions, selected examples of applications Includes author indexes and subject indexes Offers practical information on reagents' usefulness, where to find complete detailsTable of ContentsPreface vii General Abbreviations ix Reference Abbreviations xiii Chapter A 1 Chapter B 19 Chapter C 129 Chapter D 301 Chapter F 325 Chapter G 329 Chapter H 379 Chapter I 395 Chapter L 435 Chapter M 441 Chapter N 453 Chapter O 463 Chapter P 481 Chapter R 603 Chapter S 637 Chapter T 663 Chapter U 731 Chapter V 733 Chapter X 735 Chapter Y 737 Chapter Z 741 Author Index 753 Subject Index 865

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Book SynopsisLearn about the analytical tools used to characterize particulate drug delivery systems with this comprehensive overview Edited by a leading expert in the field, Characterization of Pharmaceutical Nano- and Microsystems provides a complete description of the analytical techniques used to characterize particulate drug systems on the micro- and nanoscale. The book offers readers a full understanding of the basic physicochemical characteristics, material properties and differences between micro- and nanosystems. It explains how and why greater experience and more reliable measurement techniques are required as particle size shrinks, and the measured phenomena grow weaker. Characterization of Pharmaceutical Nano- and Microsystems deals with a wide variety of topics relevant to chemical and solid-state analysis of drug delivery systems, including drug release, permeation, cell interaction, and safety. It is a complete resource for those interesteTable of ContentsList of Contributors xiii Series Preface xvii List of Abbreviations xix 1 Selecting a Particle Sizer for the Pharmaceutical Industry 1Margarida Figueiredo, M. José Moura and Paulo J. Ferreira 1.1 Introduction 1 1.1.1 Relevance of Particle Size in the Pharmaceutical Industry 1 1.1.2 Main Goals 2 1.1.3 Why it is So Difficult to Select a Particle Sizer 2 1.2 Particle Size Distribution 3 1.2.1 Equivalent Diameter 3 1.2.2 Reporting Particle Size 5 1.2.3 Distribution Statistics 7 1.3 Selecting a Particle Sizer 8 1.3.1 Classification 8 1.3.2 Selection Criteria 9 1.4 Aspects of Some Selected Methods 13 1.4.1 Optical Microscopy-based Methods 13 1.4.2 Laser Light-scattering Techniques 15 1.4.2.1 Laser Diffraction and Static Light Scattering 16 1.4.2.2 Dynamic Light Scattering 19 1.4.3 The Time-of-Flight Counter 20 1.4.4 Cascade Impactor 21 1.5 Conclusions 22 Acknowledgements 22 References 23 2 Spectroscopic Methods in Solid-state Characterization 27Clare Strachan, Jukka Saarinen, Tiina Lipiäinen, Elina Vuorimaa-Laukkanen, Kaisa Rautaniemi, Timo Laaksonen, Marcin Skotnicki and Martin Dračínský 2.1 Solid-state Structure of Particulates 27 2.2 Spectroscopy Overview 28 2.3 Spectroscopic Data Analysis 30 2.3.1 Band Assignment 30 2.3.2 Statistical Analysis 30 2.4 Infrared Spectroscopy 35 2.4.1 Principle 35 2.4.2 MIR Applications 37 2.4.3 MIR Imaging 40 2.5 Near-infrared Spectroscopy 40 2.5.1 Principle 40 2.5.2 NIR Applications 41 2.5.3 NIR Imaging 45 2.6 Terahertz Spectroscopy 46 2.6.1 Principle 46 2.6.2 Terahertz Applications 48 2.6.3 Terahertz Imaging 50 2.7 Raman Spectroscopy 50 2.7.1 Principle 50 2.7.2 Raman Applications 53 2.7.3 Raman Imaging 57 2.8 Nonlinear Optics 59 2.8.1 Principle 59 2.8.2 Nonlinear Optics Applications 61 2.8.3 Nonlinear Optical Imaging 61 2.9 Fluorescence Spectroscopy 65 2.9.1 Principle 65 2.9.2 Fluorescence from Solid-state Samples 67 2.9.3 Intrinsic Fluorophores in Solid Samples 68 2.9.4 Fluorescence Imaging 69 2.9.5 Fluorescence Lifetime Imaging Microscopy 70 2.10 Solid-state Nuclear Magnetic Resonance 71 2.10.1 The Basic Theory of NMR Spectroscopy 71 2.10.2 Solid-state NMR Technique 72 2.10.2.1 Dipole–Dipole Interactions 72 2.10.2.2 Chemical Shift Anisotropy 72 2.10.2.3 Quadrupolar Coupling 73 2.10.2.4 Indirect Coupling 73 2.10.2.5 Magic-angle Spinning and High-power Proton Decoupling 73 2.10.3 Solid-state NMR Experiments 75 2.10.3.1 Sample Preparation 75 2.10.3.2 Cross-polarization 76 2.10.3.3 Heteronuclear Correlation Experiments 77 2.10.4 Pharmaceutical Applications of Solid-state NMR 77 2.11 Conclusions 82 References 84 3 Microfluidic Analysis Techniques for Safety Assessment of Pharmaceutical Nano- and Microsystems 97Tiina M. Sikanen, Iiro Kiiski and Elisa Ollikainen 3.1 Microfluidic Bioanalytical Platforms 97 3.2 Microfabrication Methods and Materials 98 3.3 Microfluidic Cell Cultures 101 3.3.1 Selection of the Microfabrication Material by Design 102 3.3.2 Additional Design Considerations 104 3.3.3 Characterization of Pharmaceutical Nano- and Microsystems Using Organ-on-a-chip 108 3.4 Immobilized Enzyme Microreactors for Hepatic Safety Assessment 109 3.4.1 Nanoparticle Impacts on the Hepatic Clearance of Xenobiotics 109 3.4.2 Cytochrome P450 Interaction Studies in Through-flow Conditions 112 3.4.2.1 Immobilization Strategies for Cytochrome P450 Enzymes 113 3.4.2.2 Microfabrication Materials and Design Considerations 116 3.5 Microfluidic Total Analysis Systems 120 3.5.1 Microfluidic Separation Systems 121 3.5.2 Toward n-in-one Analytical Platforms 124 3.6 Epilogue 126 References 126 4 In Vitro–In Vivo Correlation for Pharmaceutical Nano- and Microsystems 137Preshita P. Desai and Vandana B. Patravale 4.1 Introduction 137 4.2 In Vitro Dissolution and In Vivo Pharmacokinetics 138 4.3 Levels of Correlation 143 4.3.1 Level A Correlation 143 4.3.2 Level B Correlation 144 4.3.3 Level C Correlation 145 4.3.4 Multiple Level C Correlation 145 4.3.5 Level D Correlation 145 4.4 Models of IVIVC 145 4.4.1 Deconvolution Model 146 4.4.2 Convolution Model 149 4.4.3 Miscellaneous Models 149 4.5 IVIVC Model Validation: Predictability Evaluation 150 4.6 IVIVC Development Step-by-Step Approach 151 4.7 Brief Introduction to Micro/Nanosystems and IVIVC Relevance 152 4.7.1 Selection of Appropriate Dissolution Method 153 4.7.2 Selection of Appropriate Dissolution Medium 155 4.7.3 Selection of Appropriate IVIVC Mathematical Model 157 4.8 Applications of IVIVC for Micro/nanoformulations 158 4.8.1 Formulation Optimization 162 4.8.2 Surrogate for Bioequivalence Studies and Biowaivers 165 4.9 Softwares Used for IVIVC 165 4.10 Conclusion and Future Prospects 166 References 166 5 Characterization of Bioadhesion, Mucin-interactions and Mucosal Permeability of Pharmaceutical Nano- and Microsystems 171Ellen Hagesaether, Malgorzata Iwona Adamczak, Marianne Hiorth and Ingunn Tho 5.1 Introduction 171 5.2 Background and Theory 172 5.3 Mucosal Membranes 174 5.3.1 Oral Mucosa 174 5.3.2 Gastrointestinal Mucosa 176 5.3.3 Pulmonary Mucosa 176 5.3.4 Nasal Mucosa 181 5.3.5 Ocular Mucosa 182 5.3.6 Vaginal Mucosa 182 5.4 Use of Mucosal Membranes in Studies of Micro- and Nanoparticles 183 5.4.1 Diffusion Chambers 183 5.4.2 Permeability Support for Cell-based Systems 184 5.5 Selection of Biological Models 185 5.5.1 Tissue-based Models 185 5.5.2 Cell-based Models 185 5.5.3 Mucus as Models 187 5.5.4 Artificial Models 188 5.6 Methods for Testing Biocompatibility 189 5.6.1 Viability 189 5.6.2 Cytotoxicity 189 5.6.3 Paracellular Permeability 189 5.7 Methods for Testing Mucoadhesion 190 5.7.1 Atomic Force Microscopy (AFM) 190 5.7.2 Quartz Crystal Microbalance (QCM) 191 5.7.3 Rheology 192 5.7.4 Rheology in Combination with Light Scattering (Rheo-SALS) 192 5.7.5 Dynamic Light Scattering (DLS) and Zeta Potential Measurements 193 5.7.6 Mechanical Methods 194 5.7.7 Mucin Adsorption Study 194 5.7.8 Wash-off Tests 194 5.8 Methods for Testing Mucopenetration 195 5.8.1 Fluorescent Recovery after Photobleaching (FRAP) and Multiple Image Photography (MIP) 195 5.8.2 Permeability Studies 195 5.8.3 Water-assisted Transport Through Mucus 196 5.8.4 Particles with Dynamic Properties 196 5.9 Methods for Assessing Cell Interactions 197 5.9.1 Cell Adhesion 197 5.9.2 Cellular Uptake 197 5.9.3 Transcellular Transport 199 5.10 Concluding Remarks 203 References 203 6 Cell–Nanoparticle Interactions: Toxicity and Safety Issues 207Flavia Fontana, Nazanin Zanjanizadeh Ezazi, Nayab Tahir and Helder A. Santos 6.1 Introduction 207 6.1.1 Role of Nanoparticles in Modern Medicine and Applications 207 6.1.2 Cell–NP Interactions 208 6.1.2.1 Size 208 6.1.2.2 Shape 208 6.1.2.3 Surface Charge 209 6.1.2.4 Surface Functionalization and Hydrophobicity 210 6.1.2.5 Protein Corona 211 6.1.3 NP Toxicity 211 6.2 Mechanisms of NP-Induced Cellular Toxicity 211 6.2.1 Damage to the Plasma Membrane 211 6.2.2 Alterations or Disruptions in the Cytoskeleton 211 6.2.3 Mitochondrial Toxicity 216 6.2.4 Nuclear Damage 216 6.2.5 Reactive Oxygen Species (ROS) 216 6.2.6 Interference in the Signaling Pathways 216 6.3 In Vitro Assays to Evaluate Cell–NP Interactions 216 6.3.1 Traditional Assays 217 6.3.2 Innovative Assays 217 6.4 Metal Oxide Nanoparticles 217 6.4.1 Zinc Oxide 217 6.4.2 Cerium Oxide 220 6.4.3 Iron Oxide 221 6.5 Non-metallic Nanoparticles 223 6.5.1 Liposomes 223 6.5.2 Polymeric Delivery Systems 224 6.5.3 Dendrimers 230 6.5.4 Silicon/Silica-based Drug Delivery Systems 232 6.6 Conclusions and Future Perspectives 235 Acknowledgements 235 References 236 7 Intestinal Mucosal Models to Validate Functionalized Nanosystems 243Cláudia Azevedo, Inês Pereira and Bruno Sarmento 7.1 Introduction 243 7.2 Intestinal Mucosal Characteristics 244 7.2.1 Intestinal Morphology 244 7.2.2 Transport Mechanisms 246 7.3 In Vitro Models 248 7.3.1 Monoculture Models 249 7.3.2 Co-culture Models 252 7.3.2.1 The Caco-2/HT29-MTX Model 252 7.3.2.2 The Caco-2/Raji B Model 253 7.3.2.3 The Caco-2/HT29-MTX/Raji B Model 253 7.3.3 3D Co-culture Models 253 7.3.4 Gut-on-a-Chip 254 7.4 Ex Vivo Intestinal Models for In Vitro/In Vivo Correlation of Functionalized Nanosystems 258 7.4.1 Diffusion Chambers 258 7.4.1.1 Ussing Chamber 258 7.4.1.2 Franz Cell 258 7.4.2 Everted Intestinal Sac Model 259 7.4.3 Non-everted Intestinal Sac Model 260 7.4.4 Everted Intestinal Ring 260 7.5 In Situ Models 260 7.5.1 Intestinal Perfusion 262 7.5.2 Intestinal Loop 264 7.5.3 Intestinal Vascular Cannulation 264 7.6 In Vivo Models 264 7.7 Conclusion 265 Acknowledgements 266 References 267 8 Biodistribution of Polymeric, Polysaccharide and Metallic Nanoparticles 275Nazl𝚤 Erdoğar, Gamze Varan, Cem Varan and Erem Bilensoy 8.1 Introduction 275 8.2 Biodistribution and Pharmacokinetics 276 8.3 Mechanisms Affecting Biodistribution 277 8.3.1 Nanoparticle Properties 277 8.3.1.1 Effect of Particle Size 277 8.3.1.2 Effect of Surface Charge 279 8.3.1.3 Effect of Particle Shape 280 8.3.2 Dosing and Toxicity 281 8.3.3 Effect of Coating 282 8.4 Conclusion 285 References 286 9 Opportunities and Challenges of Silicon-based Nanoparticles for Drug Delivery and Imaging 291Didem Şen Karaman, Martti Kaasalainen, Helene Kettiger and Jessica M. Rosenholm 9.1 Synthesis and Characteristics of Silica-based Nanoparticles 292 9.1.1 Nonporous Silica NPs 292 9.1.2 Mesoporous Silica NPs 295 9.1.3 Core@Shell Materials 297 9.1.4 Hollow Silica Nanoparticles 298 9.1.5 Porous Silicon (PSi) 300 9.2 Solid-state Characterization 303 9.2.1 Porosity and Morphology on the Nanoscale 303 9.2.2 Structural Analysis 305 9.2.3 Methods for Determination of Surface Functionalization 306 9.3 Medium-dependent Characterization 307 9.3.1 Hydrodynamic Size 307 9.3.1.1 Dynamic Light Scattering 309 9.3.2 Surface Charge and Zeta Potential 309 9.3.3 Colloidal Stability 311 9.3.4 Challenges in Particularly Porous Nanoparticle Characterization 312 9.4 Incorporation of Active Molecules 314 9.4.1 Drug Loading 314 9.4.2 Labeling with Imaging Agents 317 9.5 Biorelevant Physicochemical Characterization 319 9.5.1 Biodegradation/Dissolution of Silica 321 9.5.2 Biocompatibility and Nano–Bio Interactions 323 9.5.3 Drug Release 324 9.5.4 Label-free (Imaging) Technologies 326 9.6 Conclusions 328 References 329 10 Statistical Analysis and Multidimensional Modeling in Research 339Osmo Antikainen 10.1 Measurement in Research 339 10.2 Mean and Sample Mean 339 10.3 Correlation 341 10.4 Modeling Relationships Between Series of Observations 343 10.5 Quality of a Model 344 10.5.1 The Meaning of R2 in Linear Regression 344 10.5.2 Cross-validation 345 10.6 Multivariate Data 350 10.6.1 Screening Designs 351 10.6.2 Full Factorial Designs 352 10.6.2.1 Full Factorial Designs in Two Levels 352 10.6.2.2 Full Factorial Designs in Three Levels (3n Design) 355 10.7 Principal Component Analysis (PCA) 362 10.8 Conclusions 366 References 366 Index 369

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Book SynopsisBridges the gaps between regulatory, engineering, and science disciplines in order to comprehensively cover pollutant fate and transport in environmental multimedia This book presents and integrates all aspects of fate and transport: chemistry, modeling, various forms of assessment, and the environmental legal framework. It approaches each of these topics initially from a conceptual perspective before explaining the concepts in terms of the math necessary to model the problem so that students of all levels can learn and eventually contribute to the advancement of water quality science. The first third ofPollutant Fate and Transport in Environmental Multimediais dedicated to the relevant aspects of chemistry behind the fate and transport processes. It provides relatively simple examples and problems to teach these principles. The second third of the book is based on the conceptual derivation and the use of common models to evaluate the importance of model parameters and sensitivity aTable of ContentsPreface xi Acknowledgments xiii Acronyms xv Glossary xix About the Companion Website xxiii To the Instructor xxv To the Student xxvii To the Environmental Professional xxix How to Use the Book with Fate® and Associated Software xxxi Instructor/Student Resources xxxiii Part I Introduction 1 1 Sources and Types of Pollutants, Why We Need Modeling, and the Need to Study Historical Pollution Events 3 1.1 Introduction 3 1.2 Need for Modeling of Pollutants in Environmental Media 4 1.3 Pollution versus Contamination; Pollutant versus Contaminant 4 1.4 Pollution Classifications 5 1.5 Sources of Pollution 5 1.6 Historic Examples of Where Fate and Transport Modeling Are Useful 10 1.7 Environmental Laws 21 Concepts 22 Exercises 22 Bibliography 22 Part II Chemistry of Fate and Transport Modeling 25 2 Basic Chemical Processes in Pollutant Fate and Transport Modeling 27 2.1 The Liquid Medium: Water and the Water Cycle 27 2.2 Unique Properties of Water 28 2.3 Concentration Units 32 2.4 Chemical Aspects of Environmental Systems 32 2.5 Reactions and Equilibrium 44 2.6 Complexation 53 2.7 Equilibrium Sorption Phenomena 54 2.8 Transformation/Degradation Reactions 63 2.9 Fugacity Concepts and Modeling 67 2.10 Summary 68 Concepts 68 Exercises 68 References 69 3 Quantitative Aspects of Chemistry Toward Modeling 71 3.1 Introduction 71 3.2 Calculation of the Free Metal Ion Concentration in Natural Waters 71 3.3 Methods for Determining Kd and Kp 83 3.4 Kinetics of the Sorption Process 85 3.5 Sorption Isotherms 87 3.6 Kinetics of Transformation Reactions 89 3.7 Numerical Chemical Speciation Models 90 3.8 Putting It All Together: Where Chemistry Enters Into the Modeling Effort 91 3.9 Basic Approach to Fate and Transport Modeling 93 Exercises 95 Bibliography 99 Part III Modeling 101 4 An Overview of Pollutant Fate and Transport Modeling 103 4.1 Modeling Approaches 103 4.2 Quality of Modeling Results 109 4.3 What Do You Do with Your Modeling Results? 109 Bibliography 110 5 Fate and Transport Concepts for Lake Systems 111 Case Study 1: Lake Onondaga 111 Case Study 2: Lake Erie, A More Positive Example 112 Chapter Overview 112 5.1 Introduction 112 5.2 Types of Lakes and Lake-forming Events 113 5.3 Input Sources 117 5.4 Stratification of Lake Systems 118 5.5 Environmental Sampling of Lake Systems 120 5.6 Important Factors in the Modeling of Lakes: Conceptual Model Development 122 5.7 Two Basic Mathematical Models for Lakes (Derivation by John Brooksbank in the Chapter Appendix) 126 5.8 Sensitivity Analysis 130 5.9 Limitations of Our Models 131 5.10 Remediation 131 5.11 Numerical Modeling Approaches for Large Lakes 133 5.12 Useful Algebraic Model Formulation 133 5.A Derivation of the two basic forms of fate and transport models for lake system: step (continuous) model and pulse (instantaneous) (derivations by John Brooksbank) 134 Concepts 136 Exercises 136 Bibliography 139 6 Fate and Transport of Pollutants in Rivers and Streams 141 Case Study: The Rhine River 141 6.1 Introduction 141 6.2 Examples of Rivers and Volumetric Flows of Water 142 6.3 Input Sources 143 6.4 Sampling of Surface Waters 143 6.5 Important Factors in the Modeling of Streams: Conceptualization of Terms 144 6.6 Mathematical Development of Transport Models (Derivations by John Brooksbank, Here and in Chapter Appendix) 147 6.7 Sensitivity Analysis 151 6.8 Limitations of Our Models 151 6.9 Remediation of Polluted Stream Systems 152 Suggested Papers for Class Discussion 153 Concepts 153 Exercises 153 Spreadsheet Exercise 156 6.A Model Derivatives for River and Stream Systems (Derivations by John Brooksbank) 156 Bibliography 161 7 Dissolved Oxygen Sag Curves in Streams: The Streeter–Phelps Equation 163 Case Study: Any Stream, Anywhere in the World 163 7.1 Introduction 163 7.2 Basic Input Sources (Wastewater Flow Rates and BOD Levels) 166 7.3 Sampling of Wastewater 168 7.4 Mass Balance-Based Development of the Basic Streeter–Phelps Model 168 7.5 Sensitivity Analysis 175 7.6 Limitations of Our Basic Model and More Elaborate Models 175 7.7 Remediation 175 7.8 One Last Note on Estuaries 177 Suggested Reading for Discussion 178 Concepts 178 Exercises 178 Spreadsheet Exercise 182 7.A Derivation of the Streeter-Phelps (DO Sag Curve) Equation (By John Brooksbank 182 Bibliography 184 8 Fate and Transport Concepts for Groundwater Systems 187 Case Study: The Test Area North Deep Well Injection Site at the Idaho National Environmental and Engineering Laboratory (INEEL) 187 8.1 Introduction 187 8.2 Input Sources 188 8.3 Monitoring Wells 189 8.4 Groundwater Sampling Equipment 195 8.5 Chemistry Experiments Used to Support Modeling Efforts 195 8.6 Direction of Water Flow (The Three-Point Problem) 200 8.7 Physical Parameters Important in Pollutant Fate and Transport 202 8.8 Derivation of Mathematical Models for Groundwater 208 8.9 Sensitivity Analysis 213 8.10 Limitations of Our Models 213 8.11 Remediation 214 8.12 Numerical Models Used by Professionals 216 Suggested Papers for Class Discussion 216 Concepts 216 Exercises 216 Spreadsheet Exercise 219 Bibliography 219 9 Fate and Transport Concepts Atmospheric Systems 221 Case Study: The Union Carbide-Bhopal Accident 221 9.1 Introduction 222 9.2 Input Sources 222 9.3 Atmospheric Sampling Equipment and Efforts 222 9.4 Important Factors in the Modeling of Atmospheric Pollution: Conceptual Model Development 224 9.5 Mathematical Development of Model 227 9.6 Sensitivity Analysis 233 9.7 Limitations of Our Model 234 9.8 Remediation 235 9.9 Models Used by Professionals 235 Concepts 235 Suggested Reading for Class Discussions 235 Exercises 235 Plume (step or continuous) Input Problems 236 Puff (Pulse or Instantaneous) Pollutant Inputs 236 Spreadsheet Exercise 237 Bibliography 237 10 Regulatory Environmental Modeling Practices and Software 239Raymond C. Whittemore 10.1 Introduction 239 10.2 Generic Model Types 239 10.3 Model Availability 240 10.4 Atmospheric Quality Models 240 10.5 Surface Water Models 242 10.6 Large-Scale Watershed Models 246 10.7 Subsurface or Groundwater Models 248 10.8 Modeling of Toxic Substances 250 10.9 Human Health Risk Assessment 251 10.10 Other Useful Regulatory Models 251 Exercises 251 Bibliography 252 Part IV Toxicology and Risk Assessment 255 11 Toxicology, Risk Assessment, Cost–Benefit Analysis, and Life Cycle Assessment 257 11.1 Introduction 257 11.2 Toxicology 257 11.3 Risk Assessment 258 11.4 Life Cycle Assessment (LCA) 274 11.5 Benefit–Cost Analysis 276 11.6 Summary 276 Concepts 276 Exercises 277 Bibliography 280 Part V Environmental Legislation in the United States 281 12 US Environmental Laws 283Frank Dunnivant, Lance DeMuth, Savanna Ferguson, Rose Kormanyos, Loren Sackett, and Jill Schulte 12.1 Environmental Movements in the United States 283 12.2 The History of the Environmental Protection Agency (US EPA) 284 12.3 Major US Environmental Laws 285 12.4 EPA’s Record 300 12.5 Environmental Permitting and Compliance 302 12.6 International Agreements/Treaties Involving the United States 302 12.7 Summary 305 Exercises 305 Disclaimer 305 Bibliography 305 13 Environmental Policy in the European Union 307Steven Woolston and Aisha Kimbrough 13.1 Introduction to the European Union 307 13.2 The Environment and the European Union 307 13.3 The Early Stages of the EU’s Environmental Efforts 307 13.4 Existing Environmental Legislation 308 13.5 Waste Management Legislation 308 13.6 Water Legislation 309 13.7 Air Quality Legislation 309 13.8 Environmental Disasters 310 Bibliography 310 14 Environmental Laws in China 311Zeyu Liu (刘泽宇) and Yi Xu (徐逸) 14.1 Environmental Law and Policy in the People’s Republic of China 311 14.2 Brief Introduction to China 311 14.3 Economy and the Environment 311 14.4 History of Environmental Law and Policy 312 14.5 Existing Environmental Law and Policy 314 14.6 Challenges and the Future of Environmental Governance 314 14.7 Can China Take on the Leading Role in the Global Environmental Governance? 315 Bibliography 316 Part VI World Class Pollutants 319 15 World Class Pollutants 321Frank Dunnivant and Emily Welborn 15.1 Mercury 321 15.2 Lead 323 15.3 PCBs 325 15.4 DDT 326 15.5 Endocrine Disruptors 328 15.6 Plastics 330 15.7 Carbon Dioxide and Climate Change 331 Bibliography 332 Part VII Supporting Laboratory Experiments 335 16 Laboratory Experiments 337 16.1 Introduction 337 16.2 Keeping a Legally Defensible Laboratory Notebook 337 16.3 Quarter- and Semester-Long Experiments 338 16.4 Pollutant Fate and Transport Experiments for the Last Two Dispersion Experiments 338 16.5 The Measurement of Dispersion in a Simulated River System 355 16.6 The Measurement of Dispersion and Sorption in a Simulated Groundwater System 358 Bibliography 365 Index 367

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Book SynopsisAn in-depth overview of what computation can do in bioinorganic chemistry, written for experimentalists and theoreticians working at the interface between chemistry and biology Until recently, the field of computational bioinorganics has been governed by the application of quantum mechanical approaches. The emergence of metal-related biomolecular fields and increased computational capabilities have enabled the development of novel artificial metalloenzymes, new metallodrugs strategies, and advanced biosensor technologies. Advances in Computational Bioinorganics: From Description to Prediction provides a state-of-the-art overview of the field, covering a wide range of computational approaches, strategies, and applications. Contributions from a team of experts in bioinorganic chemistry discuss recent advances in sequence and structural bioinformatics, multi-scale strategies, large-scale molecular dynamics, and more. Divided into three parts, the book opens with a thorough introduction to

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Book SynopsisProvides a concise yet comprehensive introduction to XPS and AES techniques in surface analysis This accessible second edition of the bestselling book, An Introduction to Surface Analysis by XPS and AES, 2nd Edition explores the basic principles and applications of X-ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES) techniques. It starts with an examination of the basic concepts of electron spectroscopy and electron spectrometer design, followed by a qualitative and quantitative interpretation of the electron spectrum. Chapters examine recent innovations in instrument design and key applications in metallurgy, biomaterials, and electronics. Practical and concise, it includes compositional depth profiling; multi-technique analysis; and everything about samplesincluding their handling, preparation, stability, and more. Topics discussed in more depth include peak fitting, energy loss background analysis, multi-technique analysis, andTable of ContentsPreface to First Edition xi Preface to Second Edition xiii Acknowledgements xvii 1 Electron Spectroscopy: Some Basic Concepts 1 1.1 Analysis of Surfaces 1 1.2 Notation 3 1.2.1 Spectroscopists’ Notation 3 1.2.2 X‐ray Notation 4 1.3 X‐ray Photoelectron Spectroscopy 4 1.4 Auger Electron Spectroscopy (AES) 8 1.5 Scanning Auger Microscopy 12 1.6 The Depth of Analysis in Electron Spectroscopy 13 1.7 Comparison of XPS and AES/SAM 16 1.8 The Availability of Surface Analytical Equipment 17 2 Electron Spectrometer Design 19 2.1 Introduction 19 2.2 The Vacuum System 19 2.3 X‐ray Sources for XPS 22 2.3.1 Choice of X‐ray Anode 23 2.3.2 X‐ray Monochromators 27 2.3.3 Synchrotron Sources 30 2.4 The Electron Gun for AES 31 2.4.1 Electron Sources 31 2.4.1.1 Thermionic Emitter 32 2.4.1.2 Lanthanum Hexaboride Emitter 32 2.4.1.3 Cold Field Emitter 32 2.4.1.4 Hot Field Emitter 33 2.4.1.5 Comparison of Electron Emitters for AES 34 2.4.2 The Electron Column 35 2.4.3 Spot Size 35 2.5 Analysers for Electron Spectroscopy 37 2.5.1 The Cylindrical Mirror Analyser 38 2.5.2 The Hemispherical Sector Analyser 41 2.5.2.1 CAE Mode of Operation 42 2.5.2.2 CRR Mode of Operation 44 2.5.2.3 Comparison of CAE and CRR Modes 46 2.5.2.4 The Transfer Lens 47 2.5.3 Calibration of the Electron Spectrometer Energy Scale 48 2.6 Near Ambient Pressure XPS 49 2.7 Detectors 52 2.7.1 Channel Electron Multipliers 52 2.7.2 Microchannel Plates 54 2.7.3 Two‐Dimensional Detectors 54 2.7.3.1 The Resistive‐Anode Detector 55 2.7.3.2 The Delay‐Line Detector 55 2.8 Small Area XPS 56 2.8.1 Lens‐Defined Small Area XPS 56 2.8.2 Source-defined Small Area Analysis 57 2.9 XPS Imaging and Mapping 57 2.9.1 Serial Acquisition 58 2.9.2 Parallel Acquisition 59 2.9.2.1 Parallel Imaging Using a Hemispherical Spectrometer 59 2.9.2.2 Parallel Imaging Using a Spherical Mirror Analyser 60 2.9.2.3 Spatial Resolution and Chemical Imaging 61 2.10 Angle Resolved XPS 64 2.11 Automation 66 3 The Electron Spectrum: Qualitative and Quantitative Interpretation 69 3.1 Introduction 69 3.2 Qualitative Analysis 69 3.2.1 Unwanted Features in Electron Spectra 72 3.2.2 Data Acquisition 72 3.2.2.1 Core Level Spectra 72 3.2.2.2 Valence Band Spectra 73 3.3 Chemical State Information 74 3.3.1 X‐ray Photoelectron Spectroscopy 74 3.3.2 Peak Fitting of XPS Spectra 78 3.3.3 Auger Electron Spectroscopy 81 3.3.4 X‐AES 82 3.3.5 Chemical State Plots 84 3.3.6 Shakeup Satellites 86 3.3.7 Multiplet Splitting 87 3.3.8 Plasmons 87 3.4 Quantitative Analysis 88 3.4.1 Quantification in XPS 89 3.4.1.1 Calculating Atomic Concentration 89 3.4.1.2 Measuring Peak Intensity 92 3.4.2 Quantification in AES 94 4 Compositional Depth Profiling 97 4.1 Introduction 97 4.2 Non‐destructive Depth Methods 98 4.2.1 Measurements at a Single Emission Angle 98 4.2.2 Angle Resolved XPS Measurements 99 4.2.3 Measurement of Overlayer Thickness Using ARXPS 101 4.2.4 Elastic Scattering 103 4.2.5 Multilayer Thickness Calculations Using ARXPS 104 4.2.6 Compositional Depth Profiles from ARXPS Measurements 107 4.2.7 Variation of Analysis Depth with Electron Kinetic Energy 110 4.2.8 Background Analysis 112 4.3 Depth Profiling by Sputtering with Energetic Ions 115 4.3.1 The Sputtering Process 115 4.3.2 Experimental Method 116 4.3.3 The Nature of the Ion Beam 118 4.3.3.1 Noble Gas Ions 118 4.3.3.2 Cluster Ions 119 4.3.3.3 Metal Ions 121 4.3.4 Sputter Yield and Etch Rate 122 4.3.5 Factors Affecting the Etch Rate 123 4.3.5.1 Material 123 4.3.5.2 Ion Current 123 4.3.5.3 Ion Energy 123 4.3.5.4 Nature of the Ion Beam 124 4.3.5.5 Angle of Incidence 124 4.3.6 Factors Affecting the Depth Resolution 124 4.3.6.1 Ion Beam Characteristics 124 4.3.6.2 Crater Quality 125 4.3.6.3 Beam Impurities 125 4.3.6.4 Information Depth 126 4.3.6.5 Original Surface Roughness 127 4.3.6.6 Induced Roughness 127 4.3.6.7 Preferential Sputtering 127 4.3.6.8 Redeposition of Sputtered Material 128 4.3.7 Calibration 128 4.3.8 Ion Gun Design 128 4.3.8.1 Electron Impact Ion Guns 128 4.3.8.2 Argon‐Cluster Ion Guns 129 4.3.8.3 Liquid Metal Ion Guns 131 4.4 Sectioning 131 4.4.1 FIB Sectioning 131 4.4.2 Angle Lapping 132 4.4.3 Ball Cratering 133 5 Multi‐technique Analysis 135 5.1 Introduction 135 5.2 Ultraviolet Photoelectron Spectroscopy (UPS) 135 5.3 Low Energy Ion Scattering Spectroscopy (LEISS) 137 5.4 Reflection Electron Energy Loss Spectroscopy (REELS) 139 5.4.1 Elastic Scattering 140 5.4.2 Inelastic Scattering 141 5.5 Work Function Measurements 142 5.6 Energy Dispersive X‐ray Analysis (EDX) 143 6 The Sample 145 6.1 Sample Handling 145 6.2 Sample Preparation 147 6.3 Sample Mounting 149 6.4 Sample Stability 149 6.5 Contamination and Damage During Analysis 151 6.6 Controlling Sample Charging 152 6.6.1 Sample Charging in XPS 152 6.6.2 Sample Charging in AES 154 7 Applications of Electron Spectroscopy in Materials Science 157 7.1 Introduction 157 7.2 Metallurgy 157 7.2.1 Grain Boundary Segregation 158 7.2.2 Electronic Structure of Metallic Alloys 160 7.2.3 Surface Engineering 163 7.3 Corrosion Science 168 7.4 Ceramics 176 7.5 Microelectronics and Semiconductor Materials 181 7.5.1 Mapping Semiconductor Devices Using AES 182 7.5.2 XPS Failure Analysis of Microelectronic Devices 186 7.5.3 Depth Profiling of Semiconductor Materials 188 7.5.3.1 Transistor Gate Dielectrics 188 7.5.3.2 Inorganic Chemical State Profiling 189 7.5.3.3 Organic Semiconductor Profiling 190 7.6 Polymeric Materials 193 7.7 Adhesion Science 202 7.8 Nanotechnology 210 7.9 Biology 215 7.10 Energy 219 8 Comparison of XPS and AES with Other Analytical Techniques 223 Glossary 229 Bibliography 239 Appendix 1 247 Auger Electron Energies 247 Appendix 2 249 Table of Binding Energies Accessible with Al Kα Radiation 250 Appendix 3 255 Documentary Standards in Surface Analysis 255 The Scope of TC201 255 The Purpose of TC201 255 International Standards Relevant to Electron Spectroscopies 256 Index 259

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Book SynopsisA unique approach to a core topic in organic chemistry presented by an experienced teacher to students and professionals Heterocyclic rings are present in the majority of known natural products, contributing to enormous structural diversity. In addition, they often possess significant biological activity. Medicinal chemists have embraced this last property in designing most of the small molecule drugs in use today. This book offers readers a fundamental understanding of the basics of heterocyclic chemistry and their occurrence in natural products such as amino acids, DNA, vitamins, and antibiotics. Based on class lectures that the author has developed over more than 40 years of teaching, it focuses on the chemistry of such heterocyclic substances and how they differ from carbocyclic systems. Introductory Heterocyclic Chemistry offers in-depth chapters covering naturally occurring heterocycles; properties of aromatic heterocycles; p-deficient heteroTable of ContentsPreface ix Acknowledgments xi 1 Some Biologically Important Heterocycles of Nature 1 1.1 Vitamins 3 1.2 Antibiotics and Tetrapyrroles 8 References 10 2 Orbitals and Aromaticity; Chemical Reactivity 11 References 15 3 A Prelude to Synthesis 17 References 21 4 π‐Deficient Heterocycles: Some Physical Properties 23 References 25 5 π‐Deficient Heterocycles: De Novo Syntheses 27 5.1 De Novo Syntheses, Pyrimidines 32 5.2 Fused‐Ring Systems, Quinolines 33 5.2.1 Isoquinolines 34 References 37 6 π‐Deficient Heterocycles: Introduction of New Substituents: Nucleophilic Substitution 39 References 48 7 π‐Deficient Heterocycles: Introduction of New Substituents: Heterocyclic N‐Oxides 49 7.1 Further Reactions of N‐Oxides 61 References 73 8 π‐Deficient Heterocycles: Introduction of New Substituents: Quinolines and Isoquinolines 75 References 86 9 π‐Deficient Heterocycles: Manipulation of Existing Substituents 89 9.1 Summary 103 References 105 10 π‐Excessive Heterocycles: General Properties 107 References 114 11 π‐Excessive Heterocycles: De Novo Syntheses 115 11.1 Synthesis of 1,3‐Azoles 127 11.2 Synthesis of 1,2‐Azoles 131 11.3 Fischer Indole Synthesis 133 References 136 12 π‐Excessive Heterocycles: Introduction of New Substituents 139 References 153 13 Ring Transformations of π‐Excessive Heterocycles: Diels‐Alder Reactions 157 References 175 14 Heterocycles as Synthons 177 References 205 15 1,3‐Dipolar Cycloadditions—An Overview 207 References 234 16 Back to Basics 239 References 245 17 A Brief Synopsis 247 Index 251

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Book SynopsisAn introduction to the rapidly evolving methodology of electronic excited states For academic researchers, postdocs, graduate and undergraduate students, Quantum Chemistry and Dynamics of Excited States: Methods and Applications reports the most updated and accurate theoretical techniques to treat electronic excited states. From methods to deal with stationary calculations through time-dependent simulations of molecular systems, this book serves as a guide for beginners in the field and knowledge seekers alike. Taking into account the most recent theory developments and representative applications, it also covers the often-overlooked gap between theoretical and computational chemistry. An excellent reference for both researchers and students, Excited States provides essential knowledge on quantum chemistry, an in-depth overview of the latest developments, and theoretical techniques around the properties and nonadiabatic dynamics of chemical systemsTable of ContentsList of Contributors xix Preface xxiii 1 Motivation and Basic Concepts 1Sandra Gómez, Ignacio Fdez. Galván, Roland Lindh, and Leticia Gonzalez 1.1 Mission and Motivation 1 1.2 Atomic Units 4 1.3 The Molecular Hamiltonian 5 1.4 Dirac or Bra-Ket Notation 6 1.5 Index Definitions 7 1.6 Second Quantization Formalism 7 1.7 Born–Oppenheimer Approximation and Potential Energy Surfaces 9 1.8 Adiabatic Versus Diabatic Representations 10 1.9 Conical Intersections 11 1.10 Further Reading 12 1.11 Acknowledgments 12 Part I Quantum Chemistry 13 2 Time-Dependent Density Functional Theory 15Miquel Huix-Rotllant, Nicolas Ferre, and Mario Barbatti 2.1 Introduction 15 2.2 TDDFT Fundamentals 16 2.2.1 The Runge–Gross Theorems 16 2.2.2 The Time-Dependent Kohn–Sham Approach 18 2.2.3 Solutions of Time-Dependent Kohn–Sham Equations 19 2.2.3.1 Real-Time TDDFT 19 2.2.3.2 Linear-Response TDDFT 20 2.3 Linear-Response TDDFT in Action 22 2.3.1 Vertical Excitations and Energy Surfaces 22 2.3.1.1 Vertical Excitations: How Good are They? 23 2.3.1.2 Reconstructed Energy Surfaces: How Good are They? 25 2.3.2 Conical Intersections 28 2.3.3 Coupling Terms and Auxiliary Wave Functions 30 2.3.3.1 The Casida Ansatz 30 2.3.3.2 Time-Derivative Non-Adiabatic Couplings 31 2.3.4 Non-Adiabatic Dynamics 32 2.4 Excited States and Dynamics with TDDFT Variants and Beyond 34 2.5 Conclusions 35 Acknowledgments 36 References 36 3 Multi-Configurational Density Functional Theory: Progress and Challenges 47Erik Donovan Hedegård 3.1 Introduction 47 3.2 Wave Function Theory 50 3.3 Kohn–Sham Density Functional Theory 50 3.3.1 Density Functional Approximations 53 3.3.2 Density Functional Theory for Excited States 54 3.3.2.1 Issues Within the Time-Dependent Density Functional Theory Ansatz 55 3.3.2.2 Self-Interaction Error 55 3.3.2.3 Degeneracies, Near-Degeneracies and the Symmetry Dilemma 56 3.4 Multi-Configurational Density Functional Theory 57 3.4.1 Semi-Empirical Multi-Configurational Density Functional Theory 57 3.4.2 Multi-Configurational Density Functional Theory Based the On-Top Pair Density 58 3.4.2.1 Density Matrices and the On-Top Pair Density 59 3.4.2.2 Energy Functional and Excited States with the On-Top Pair Density 60 3.4.3 Multi-Configurational Density Functional Theory Based on Range-Separation 61 3.4.3.1 Energy Functional and Excited States in Range-Separated Methods 62 3.4.3.2 The Range-Separation Parameter in Excited State Calculations 62 3.5 Illustrative Examples 64 3.5.1 Excited States of Organic Molecules 64 3.5.2 Excited States for a Transition Metal Complex 65 3.6 Outlook 66 Acknowledgments 67 References 67 4 Equation-of-Motion Coupled-Cluster Models 77Monika Musiał 4.1 Introduction 77 4.2 Theoretical Background 79 4.2.1 Coupled-ClusterWave Function 79 4.2.2 The Equation-of-Motion Approach 80 4.2.3 Similarity-Transformed Hamiltonian 81 4.2.4 Davidson Diagonalization Algorithm 82 4.3 Excited States: EE-EOM-CC 84 4.3.1 EE-EOM-CCSD Model 84 4.3.2 EE-EOM-CCSDT Model 86 4.3.3 EE-EOM-CC Results 87 4.4 Ionized States: IP-EOM-CC 89 4.4.1 IP-EOM-CCSD Model 89 4.4.2 IP-EOM-CCSDT Model 89 4.4.3 IP-EOM-CC Results 90 4.5 Electron-Attached States: EA-EOM-CC 91 4.5.1 EA-EOM-CCSD Model 92 4.5.2 EA-EOM-CCSDT Model 92 4.5.3 EA-EOM-CC Results 92 4.6 Doubly-Ionized States: DIP-EOM-CC 94 4.6.1 DIP-EOM-CCSD Model 95 4.6.2 DIP-EOM-CCSDT Model 95 4.6.3 DIP-EOM-CC Results 96 4.7 Doubly Electron-Attached States: DEA-EOM-CC 97 4.7.1 DEA-EOM-CCSD Model 98 4.7.2 DEA-EOM-CCSDT Model 98 4.7.3 DEA-EOM-CC Results 98 4.8 Size-Extensivity Issue in the EOM-CC Theory 100 4.9 Final Remarks 102 References 103 5 The Algebraic-Diagrammatic Construction Scheme for the Polarization Propagator 109Andreas Dreuw 5.1 Original Derivation via Green’s Functions 110 5.2 The Intermediate State Representation 112 5.3 Calculation of Excited State Properties and Analysis 114 5.3.1 Excited State Properties 114 5.3.2 Excited-State Wave Function and Density Analyses 116 5.4 Properties and Limitations of ADC 117 5.5 Variants of EE-ADC 119 5.5.1 Extended ADC(2) 119 5.5.2 Unrestricted EE-ADC Schemes 120 5.5.3 Spin-Flip EE-ADC Schemes 121 5.5.4 Spin-Opposite-Scaled ADC Schemes 122 5.5.5 Core-Valence Separated (CVS) EE-ADC 123 5.6 Describing Molecular Photochemistry with ADC Methods 125 5.6.1 Potential Energy Surfaces 125 5.6.2 Environment Models within ADC 126 5.7 Brief Summary and Perspective 126 Bibliography 127 6 Foundation of Multi-Configurational Quantum Chemistry 133Giovanni Li Manni, Kai Guther, Dongxia Ma, and Werner Dobrautz 6.1 Scaling Problem in FCI, CAS and RASWave Functions 136 6.2 Factorization and Coupling of Slater Determinants 138 6.2.1 Slater Condon Rules 140 6.3 Configuration State Functions 141 6.3.1 The Unitary Group Approach (UGA) 142 6.3.1.1 Analogy between CSFs and Spherical Harmonics 143 6.3.1.2 Gel’fand-Tsetlin Basis 143 6.3.1.3 Paldus andWeyl Tables 145 6.3.1.4 The Step-Vector 148 6.3.2 The Graphical Unitary Group Approach (GUGA) 148 6.3.3 Evaluation of Non-Vanishing Hamiltonian Matrix Elements 153 6.3.3.1 One-Body Coupling Coefficients 154 6.3.3.2 Two-Body Matrix Elements 157 6.4 Configuration Interaction Eigenvalue Problem 158 6.4.1 Iterative Methods 159 6.4.1.1 Lanczos Algorithm 159 6.4.1.2 Davidson Algorithm 160 6.4.2 Direct-CI Algorithm 162 6.5 The CASSCF Method 165 6.5.1 The MCSCF Parameterization 167 6.5.2 The MCSCF Gradient and Hessian 169 6.5.3 One-Step and Two-Step Procedures 170 6.5.4 Augmented Hessian Method 171 6.5.5 Matrix form of the First and Second Derivatives in MCSCF 171 6.5.6 Quadratically Converging Method with Optimal Convergence 175 6.5.7 Orbital-CI Coupling Terms 178 6.5.8 Super-CI for the Orbital Optimization 179 6.5.9 Redundancy of Active Orbital Rotations 181 6.6 Restricted and Generalized Active Space Wave Functions 182 6.6.1 GUGA Applied to CAS, RAS and GAS Wave Functions 184 6.6.2 Redundancies in GASSCF Orbital Rotations 186 6.6.3 MCSCF Molecular Orbitals 187 6.6.4 GASSCF Applied to the Gd2 Molecule 188 6.7 Excited States 189 6.7.1 Multi-State CI Solver 190 6.7.2 State-Specific and State-Averaged MCSCF 191 6.8 Stochastic Multiconfigurational Approaches 191 6.8.1 FCIQMC Working Equation 192 6.8.2 Multi-Wave Function Approach for Excited States 196 6.8.3 Sampling Reduced Density Matrices 196 Bibliography 198 7 The Density Matrix Renormalization Group for Strong Correlation in Ground and Excited States 205Leon Freitag and Markus Reiher 7.1 Introduction 205 7.2 DMRG Theory 207 7.2.1 Renormalization Group Formulation 207 7.2.2 Matrix Product States and Matrix Product Operators 210 7.2.3 MPS-MPO Formulation of DMRG 214 7.2.4 Connection between the Renormalization Group and the MPS-MPO Formulation of DMRG 217 7.2.5 Developments to Enhance DMRG Convergence and Performance 218 7.3 DMRG and Orbital Entanglement 218 7.4 DMRG in Practice 220 7.4.1 Calculating Excited States with DMRG 220 7.4.2 Factors Affecting the DMRG Convergence and Accuracy 220 7.4.3 Post-DMRG Methods for Dynamic Correlation and Environment Effects 221 7.4.4 Analytical Energy Gradients and Non-Adiabatic Coupling Matrix Elements 222 7.4.5 Tensor Network States 224 7.5 Applications in Quantum Chemistry 225 7.6 Conclusions 230 Acknowledgment 231 References 231 8 Excited-State Calculations with Quantum Monte Carlo 247Jonas Feldt and Claudia Filippi 8.1 Introduction 247 8.2 Variational Monte Carlo 249 8.3 Diffusion Monte Carlo 252 8.4 Wave Functions and their Optimization 256 8.4.1 Stochastic Reconfiguration Method 258 8.4.2 Linear Method 259 8.5 Excited States 261 8.5.1 Energy-Based Methods 261 8.5.2 Time-Dependent Linear-Response VMC 263 8.5.3 Variance-Based Methods 264 8.6 Applications to Excited States of Molecular Systems 265 8.7 Alternatives to Diffusion Monte Carlo 269 Bibliography 270 9 Multi-Reference Configuration Interaction 277Felix Plasser and Hans Lischka 9.1 Introduction 277 9.2 Basics 278 9.2.1 Configuration Interaction and the Variational Principle 278 9.2.2 The Size-Extensivity Problem of Truncated CI 280 9.2.3 Multi-Reference Configuration Spaces 282 9.2.4 Many-Electron Basis Functions: Determinants and CSFs 286 9.2.5 Workflow 287 9.3 Types of MRCI 289 9.3.1 Uncontracted and Contracted MRCI 289 9.3.2 MRCI with Extensivity Corrections 291 9.3.3 Types of Selection Schemes 293 9.3.4 Construction of Orbitals 293 9.4 Popular Implementations 294 9.5 Conclusions 295 References 295 10 Multi-Configurational Reference Perturbation Theory with a CASSCF Reference Function 299Roland Lindh and Ignacio Fdez. Galván 10.1 Rayleigh–Schrödinger Perturbation Theory 300 10.1.1 The Single-State Theory 300 10.1.1.1 The Conventional Projectional Derivation 300 10.1.1.2 The Bi-Variational Approach 304 10.1.2 Convergence Properties and Intruder States 308 10.1.2.1 Real and Imaginary Shift Techniques 310 10.2 Møller–Plesset Perturbation Theory 313 10.2.1 The Reference Function 314 10.2.2 The Partitioning of the Hamiltonian 315 10.2.3 The First-Order Interacting Space and Second-Order Energy Correction 316 10.3 State-Specific Multi-Configurational Reference Perturbation Methods 320 10.3.1 The Generation of the Reference Hamiltonian 321 10.3.2 CAS-MP2 Theory 322 10.3.3 CASPT2 Theory 323 10.3.3.1 The Partitioning of the Hamiltonian 324 10.3.3.2 The First-Order Interacting Space 325 10.3.3.3 Other Active Space References 328 10.3.3.4 Benchmark Results 329 10.3.3.5 IPEA Shift 330 10.3.4 MRMP2 Theory 331 10.3.4.1 The Partitioning of the Hamiltonian 331 10.3.4.2 The First-Order Interacting Space 332 10.3.5 NEVPT2 Theory 333 10.3.5.1 The Partitioning of the Hamiltonian 333 10.3.5.2 The First-Order Interacting Space 335 10.3.6 Performance Improvements 336 10.4 Quasi-Degenerate Perturbation Theory 338 10.5 Multi-State Multi-Configurational Reference Perturbation Methods 341 10.5.1 Multi-State CASPT2 Theory 341 10.5.2 Extended MS-CASPT2 Theory 342 10.6 Summary and Outlook 343 Acknowledgments 345 References 345 Appendix 350 Part II Nuclear Dynamics 355 11 Exact Quantum Dynamics (Wave Packets) in Reduced Dimensionality 357Sebastian Reiter, Daniel Keefer, and Regina de Vivie-Riedle 11.1 Introduction 357 11.2 Fundamentals of Molecular Quantum Dynamics 358 11.2.1 Wave Packet Dynamics 358 11.2.2 Time-Propagator Schemes 360 11.2.3 Excited State Wave Packet Dynamics 362 11.2.4 Surfaces and Coupling Elements in Reactive Coordinates 362 11.3 Choice of Dynamical Coordinates and Hamiltonian in Reduced Dimensionality 364 11.3.1 Manual Selection by Chemical Intuition 364 11.3.2 The G-Matrix Formalism 365 11.3.2.1 General Setup 366 11.3.2.2 Practical Computation of the G-Matrix Elements 367 11.3.2.3 Photorelaxation of Uracil in Linear Reactive Coordinates 367 11.3.3 Automatic Generation of Linear Coordinates 369 11.3.3.1 IRC Based Approach 369 11.3.3.2 Trajectory-Based Approach 371 11.3.3.3 Comparison of Both Techniques for Linear Subspaces 372 11.3.4 Automatic Generation of Non-Linear Coordinates 374 11.4 Summary and Further Remarks 378 References 379 12 Multi-Configuration Time-Dependent Hartree Methods: From Quantum to Semiclassical and Quantum-Classical 383M. Bonfanti, G. A. Worth, and I. Burghardt 12.1 Introduction 383 12.2 Time-Dependent Variational Principle and MCTDH 385 12.2.1 Variational Principle and Tangent Space Projections 385 12.2.2 MCTDH: Variational Multi-Configurational Wave Functions 386 12.2.2.1 MCTDH Wave Function Ansatz 386 12.2.2.2 MCTDH Equations of Motion 388 12.2.3 ML-MCTDH: Hierarchical Representations 389 12.3 Gaussian-Based MCTDH 390 12.3.1 G-MCTDH and vMCG 390 12.3.1.1 G-MCTDH Wave Function Ansatz 391 12.3.1.2 G-MCTDH Equations of Motion 392 12.3.1.3 vMCG Equations of Motion 393 12.3.2 2L-GMCTDH 394 12.3.2.1 Wave Function Ansatz 394 12.3.2.2 Equations of Motion 395 12.4 Quantum-Classical Multi-Configurational Approaches 396 12.4.1 Quantum-Classical Limit of G-MCTDH 396 12.4.2 Quantum-Classical Scheme with Finite-Width Wave Packets 398 12.4.3 Related Approaches 399 12.5 How to use MCTDH & Co 399 12.6 Synopsis and Application to Donor–Acceptor Complex 400 12.6.1 Hamiltonian, Spectral Densities, and Potential Surfaces 400 12.6.2 Ultrafast Coherent Charge Transfer Dynamics 402 12.6.3 Comparison of Methods 403 12.7 Conclusions and Outlook 405 Acknowledgments 406 References 406 13 Gaussian Wave Packets and the DD-vMCG Approach 413Graham A. Worth and Benjamin Lasorne 13.1 Historical Background 413 13.2 Basic Theory 415 13.2.1 Gaussian Wave Packets 415 13.2.2 General Equations of Motion 418 13.2.2.1 Coefficients and Parameters 418 13.2.2.2 CX-Formalism 419 13.2.2.3 Nuclear and Electronic Degrees of Freedom 420 13.2.3 Variational Multi-Configurational Gaussian Approach 422 13.3 Example Calculations 424 13.4 Tunneling Dynamics: Salicylaldimine 425 13.5 Non-Adiabatic Dynamics: The Butatriene Cation 426 13.6 Direct Non-Adiabatic Dynamics: Formamide 428 13.7 Summary 431 13.8 Practical Implementation 431 Acknowledgments 431 References 431 14 Full and Ab Initio Multiple Spawning 435Basile F. E. Curchod 14.1 Introduction 435 14.2 Time-Dependent Molecular Schrödinger Equation in a Gaussian Basis 436 14.2.1 Central Equations of Motion 436 14.2.2 Dynamics of the Trajectory Basis Functions 439 14.3 Full Multiple Spawning 440 14.3.1 Full Multiple Spawning Equations 440 14.3.2 Spawning Algorithm 442 14.4 Extending Full Multiple Spawning 443 14.4.1 External Field in Full Multiple Spawning 444 14.4.2 Spin-Orbit Coupling in Full Multiple Spawning 445 14.5 Ab Initio Multiple Spawning 447 14.5.1 From Full- to Ab Initio Multiple Spawning 447 14.5.2 Testing the Approximations of Ab Initio Multiple Spawning 449 14.5.3 On-the-Fly Ab Initio Multiple Spawning 450 14.5.4 Ab Initio Multiple Spawning versus Trajectory Surface Hopping 451 14.6 Dissecting an Ab Initio Multiple Spawning Dynamics 454 14.6.1 The Different Steps of an Ab Initio Multiple Spawning Dynamics 454 14.6.2 Example of Ab Initio Multiple Spawning Dynamics – the Photo-Chemistry of Cyclohexadiene 455 14.7 In Silico Photo-Chemistry with Ab Initio Multiple Spawning 459 14.8 Summary 462 References 463 15 Ehrenfest Methods for Electron and Nuclear Dynamics 469Adam Kirrander and Morgane Vacher 15.1 Introduction 469 15.2 Theory of the (Simple) Ehrenfest Method 470 15.2.1 Wave Function Ansatz 471 15.2.2 Equations of Motion 472 15.3 Theory of the Multi-Configurational Ehrenfest Method 474 15.3.1 Wave Function Ansatz 474 15.3.2 Equations of Motion 476 15.3.3 Computational Aspects 479 15.4 Applications 480 15.4.1 Coupled Electron and Nuclear Dynamics Upon Sudden Ionization 481 15.4.2 Ultrafast Scattering as a Probe of Nuclear Dynamics 485 15.5 Conclusion 490 References 491 16 Surface Hopping Molecular Dynamics 499Sebastian Mai, Philipp Marquetand, and Leticia Gonzalez 16.1 Introduction 499 16.2 Basics of Surface Hopping 500 16.2.1 Advantages and Disadvantages 500 16.2.2 General Algorithm 501 16.3 Surface Hopping Ingredients 503 16.3.1 Nuclear Motion 503 16.3.2 Wave Function Propagation 504 16.3.3 Decoherence 505 16.3.4 Surface Hopping Algorithm 507 16.3.5 Kinetic Energy Adjustment and Frustrated Hops 509 16.3.6 Coupling Terms and Representations 511 16.4 Practical Remarks 513 16.4.1 Choice of the Electronic Structure Method 513 16.4.2 Initial Conditions 516 16.4.3 Example Application and Trajectory Analysis 518 16.5 Popular Implementations 521 16.6 Conclusion and Outlook 522 Acknowledgments 522 References 522 17 Exact Factorization of the Electron–Nuclear Wave Function: Theory and Applications 531Federica Agostini and E. K. U. Gross 17.1 Introduction 531 17.2 The Time-Dependent Molecular Problem in the Exact-Factorization Formulation 533 17.2.1 Wave Function Ansatz 533 17.2.2 Equations of Motion 535 17.3 The Born–Oppenheimer Framework and the Exact Factorization 536 17.3.1 One-Dimensional Case: Time-Dependent Potential Energy Surface 538 17.3.2 Two-Dimensional Case: Time-Dependent Potential Energy Surface and Time-Dependent Vector Potential 542 17.4 Trajectory-Based Solution of the Exact-Factorization Equations 545 17.4.1 CT-MQC: The Approximations 546 17.4.2 CT-MQC: Photo-Induced Ring Opening in Oxirane 549 17.4.3 CT-MQC: The Algorithm 551 17.5 The Molecular Berry Phase 553 17.6 Conclusions 556 Acknowledgments 556 References 556 18 Bohmian Approaches to Non-Adiabatic Molecular Dynamics 563Guillermo Albareda and Ivano Tavernelli 18.1 Introduction 563 18.2 A Practical Overview of Bohmian Mechanics 565 18.2.1 The Postulates 565 18.2.2 Computation of Bohmian Trajectories 566 18.2.2.1 Trajectories from the Schrödinger Equation 566 18.2.2.2 Trajectories from the Hamilton–Jacobi Equation 567 18.2.2.3 Trajectories from a Complex Action 568 18.2.3 Computation of Expectation Values 569 18.3 The Born–Huang Picture of Molecular Dynamics 569 18.3.1 The Molecular Schrödinger Equation in Position Space 569 18.3.2 Schrödinger Equation in the Born–Huang Basis 570 18.3.2.1 The Born–Oppenheimer Approximation: The Adiabatic Case 571 18.3.2.2 Non-Adiabatic Dynamics 572 18.4 BH-Based Approaches 573 18.4.1 The Non-Adiabatic Bohmian Dynamics Equations (NABDY) 573 18.4.2 Implementation in Molecular Dynamics: The Adiabatic Case 575 18.4.3 The Approximate Quantum Potential Approach 577 18.5 Non-BH Approaches 579 18.5.1 The ConditionalWave Function Approach 579 18.5.1.1 Hermitian ConditionalWave Function Approach 581 18.5.2 The Interacting ConditionalWave Function Approach 582 18.5.3 Time-Dependent Quantum Monte Carlo 585 18.6 Conclusions 588 References 589 19 Semiclassical Molecular Dynamics for Spectroscopic Calculations 595Riccardo Conte and Michele Ceotto 19.1 Introduction 595 19.2 From Feynman’s Path Integral to van Vleck’s Semiclassical Propagator 598 19.3 The Semiclassical Initial Value Representation and the Heller–Herman–Kluk–Kay Formulation 601 19.4 A Derivation of the Heller–Herman–Kluk–Kay Propagator 603 19.5 The Time-Averaging Filter 604 19.6 The Multiple Coherent States SCIVR 606 19.7 The “Divide-and-Conquer” SCIVR 610 19.8 Mixed SCIVR Dynamics: Towards Semiclassical Spectroscopy in Condensed Phase 615 19.9 Semiclassical Spectroscopy Workflow 618 19.10 A Taste of Semiclassical Spectroscopy 619 19.11 Summary and Conclusions 622 Acknowledgments 624 Bibliography 624 20 Path-Integral Approaches to Non-Adiabatic Dynamics 629Maximilian A. C. Saller, Johan E. Runeson, and Jeremy O. Richardson 20.1 Introduction 629 20.2 Semiclassical Theory 631 20.2.1 Mapping Approach 631 20.2.2 Linearized Semiclassical Dynamics 632 20.3 Non-Equilibrium Dynamics 633 20.3.1 Spin-Boson Systems 634 20.3.2 Non-Equilibrium Correlation Functions 636 20.4 Non-Adiabatic Path-Integral Theory 640 20.4.1 Mean-Field Path-Integral Sampling 640 20.4.2 Non-Adiabatic Ring-Polymer Molecular Dynamics 641 20.4.3 Alleviation of the Negative Sign 644 20.4.4 Practical Implementation of Monte Carlo Sampling 644 20.5 Equilibrium Correlation Functions 646 20.6 Conclusions 648 Acknowledgments 649 References 649 Index 655

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Book SynopsisBefore the 1970s, most information concerning the conservation and restoration of paintings, wood, and archaeological artefacts were focused on the history of the artefacts, previous attempts of conservation, and the future use of these artefacts. The technical methods of how the restoration and conservation were made were dealt with only very briefly. Today, sophisticated methods of scientific analysis such as DNA are common place, and this encourages conservators and scientists to work together to work out the development of new methods for analysis and conservation of artefacts. This book focuses on the chemicals used for conservation and restoration of various artefacts in artwork and archaeology, as well as special applications of these materials. Also the methods used, both methods for cleaning, conservation and restoration, as well as methods for the analysis of the state of the respective artefacts. Topics include oil paintings, paper conservation, textiles and dyes fTable of ContentsPreface xiii 1 Paintings 1 1.1 Cleaning 1 1.2 Varnishes 41 1.3 Methods and Materials for Conservation 47 1.4 Analysis and Analytical Methods 70 1.5 Forgeries 81 2 Textiles 95 2.1 Textile Colors 95 2.2 Textiles from Various Locations 101 2.3 Processing Methods 108 3 Archaeological Wood 113 3.1 Analysis Methods 113 3.2 Materials for Conservation 122 3.3 Degradation 131 3.4 Special Properties 137 4 Fossils 149 4.1 Monograph 149 4.2 Paleontological Skill and the Role of the Fossil Preparator 149 4.3 Analysis Methods 150 4.4 Conservation Methods 163 5 Stones 177 5.1 Deterioration Processes 178 5.2 Analytical Methods 187 5.3 Conservation Methods 193 6 Glass 213 6.1 Analytical Methods 213 6.2 Cleaning Methods 217 6.3 Production Practices 229 6.4 Special Uses of Glass Materials 231 7 Archaeological Metals 237 7.1 Cleaning Methods 247 7.2 Special References 262 Index 267 Acronyms 267 Chemicals 269 General Index 273

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Book SynopsisGet to know the sociopolitical context behind microaggressions Microaggressions are brief, everyday exchanges that send denigrating messages to certain individuals because of their group membership (e.g., race, gender, culture, religion, social class, sexual orientation, etc.). These daily, common manifestations of aggression leave many people feeling vulnerable, targeted, angry, and afraid. How has this become such a pervasive part of our social and political rhetoric, and what is the psychology behind it? In Microaggression Theory, the original research team that created the microaggressions taxonomy, Gina Torino, David Rivera, Christina Capodilupo, Kevin Nadal, and Derald Wing Sue, address these issues head-on in a fascinating work that explores the newest findings of microaggressions in their sociopolitical context. It delves into how the often invisible nature of this phenomenon prevents perpetrators from realizing and confronting their own complicitTable of ContentsAcknowledgments xi About the Editors xiii About the Authors xv Part I Microaggression Theory 1 1 Everything YouWanted to Know About Microaggressions but Didn’t Get a Chance to Ask 3Gina C. Torino, David P. Rivera, Christina M. Capodilupo, Kevin L. Nadal, and DeraldWing Sue 2 Aversive Racism, Implicit Bias, and Microaggressions 16John F. Dovidio, Adam R. Pearson, and Louis A. Penner 3 MultidimensionalModels of Microaggressions and Microaffirmations 32James M. Jones and Rosalie Rol´on-Dow 4 Intersectionality Theory and Microaggressions: Implications for Research, Teaching, and Practice 48Jioni A. Lewis, Marlene G.Williams, Anahvia T. Moody, Erica J. Peppers, and Cecile A. Gadson Part II Detrimental Impact of Microaggressions 65 5 Microaggressions: Clinical Impact and Psychological Harm 67Jesse Owen, KarenW. Tao, and Joanna M. Drinane 6 Microaggressions: Considering the Framework of Psychological Trauma 86Thema Bryant-Davis 7 Factors Contributing to Microaggressions, Racial Battle Fatigue, Stereotype Threat, and Imposter Phenomenon for Nonhegemonic Students: Implications for Urban Education 102Jennifer L.Martin 8 Microaggressions and Internalized Oppression: Intrapersonal, Interpersonal, and Institutional Impacts of “Internalized Microaggressions” 121E.J.R. David, Jessica Petalio, and Maria C. Crouch 9 “I Didn’t Know ThatWas Racist”: Costs of Racial Microaggressions To White People 138D Anthony Clark and Lisa Spanierman Part III Manifestation of Microaggressions 157 10 The 360-Degree Experience of Workplace Microaggressions: Who Commits Them? How Do Individuals Respond? What Are the Consequences? 159Jennifer Young-Jin Kim, Duoc Nguyen, and Caryn Block 11 Microaggressions: Toxic Rain in Health Care 178Silvia L. Mazzula and Rebecca R. Camp´on 12 From Racial Microaggressions to Hate Crimes: A Model of Online Racism Based on the Lived Experiences of Adolescents of Color 194Brendesha M. Tynes, Fantasy T. Lozada, Naila A. Smith, and AshleyM. Stewart 13 EnvironmentalMicroaggressions: Context, Symbols, and Mascots 213Jesse A. Steinfeldt, Jacqueline Hyman, and M. Clint Steinfeldt Part IV Microaggressions and Social Policies and Practices 227 14 Microaggressions and Student Activism: Harmless Impact and Victimhood Controversies 229DeraldWing Sue 15 “Radical by Necessity, Not by Choice”: From Microaggressions to Social Activism 244Michelle Fine,Maria E. Torre, David Frost, and Allison Cabana Part V Microaggressions: Interventions and Strategies 259 16 Microaggressions:Workplace Interventions 261Aisha M. B. Holder 17 “Compliments”and “Jokes”: Unpacking Racial Microaggressions in the K-12 Classroom 276Rita Kohli, Nallely Arteaga, and Elexia R. McGovern 18 Microaggressions in Higher Education: Embracing Educative Spaces 291Kathryn S. Young andMyron R. Anderson Part VI The Future of Microaggression Theory 307 19 Microaggression Theory:What the Future Holds 309Gina C. Torino, David P. Rivera, Christina M. Capodilupo, Kevin L. Nadal, and DeraldWing Sue Author Index 329 Subject Index 343

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Book SynopsisThe updated third edition of the definitive text on health social work Thoroughly revised and updated, the third edition of Handbook of Health Social Work is an authoritative text that offers a comprehensive review of the diverse field of health social work. With contributions from a panel of international experts in the field, the book is theory driven and solidly grounded in evidence-based practice. The contributors explore both the foundation of social work practice and offer guidance on effective strategies, policies, and program development. The text provides information that is essential to the operations of social workers in health care including the conceptual underpinnings and the development of the profession. The authors explore the practice issues such as theories of health behavior, assessment, communication and the intersections between health and mental health. The authors also examine a wide range of examples of social work practices incluTable of ContentsForeword ix Robyn Golden Acknowledgments xi About the Editors xiii List of Contributors xv About the Companion Website xix Introduction xxi Part I The Foundations of Social Work in Health Care 1 1 The Conceptual Underpinnings of Social Work in Health Care 3 Sarah Gehlert 2 Social Work Roles and Healthcare Settings 21 Teri Browne 3 Ethics in Health Care 39 Kimberly Strom‐Gottfried 4 Global Health Social Work 71 In Han Song, Varda Soskolne, Zhang Zuojian, Teri Browne, and Johnston Wong 5 Public Health Social Work 93 Betty Ruth, Madi Knight Wachman, and Jamie Marshall 6 Health Policy and Social Work 119 Julie S. Darnell and Heidi L. Allen 7 Theories of Health Behavior 143 Sarah Gehlert and Trina Salm Ward Part II Health Social Work Practice: A Spectrum of Critical Considerations 165 8 Community and Health 167 Sarah Kye Price and Christopher Masi 9 The Implementation of Integrated Behavioral Health Models 189 Lisa de Saxe Zerden, Gracelyn Cruden, Brianna M. Lombardi, Lexie R. Grove, Sheila V. Patel, and Byron J. Powell 10 Social Work Practice and Disability Issues 209 Teresa Moro and Rebecca Brashler 11 Translation of Evidence‐Based Practices in Health 229 Lawrence A. Palinkas and Sapna J. Mendon 12 Communication in Health Care 249 Sarah Gehlert, Seul Ki Choi, and Daniela B. Friedman 13 Religion, Belief, and Spirituality in Health Care 279 Panagiotis Pentaris 14 Developing a Shared Understanding: When Medical Patients Use Complementary and Alternative Approaches and Seek Integrative Systems 303 Penny B. Block 15 Families, Health, and Illness 331 John S. Rolland Part III Health Social Work: Selected Areas of Practice 359 16 Social Work With Children and Adolescents with Medical Conditions 361 Barbara L. Jones, Casey Walsh, and Fayra Phillips 17 Social Work with Older Adults in Healthcare Settings 381 Shantha Balaswamy, Sang E. Lee, and Sadhna Diwan 18 Nephrology Social Work 411 Teri Browne, Joseph R. Merighi, Tiffany Washington, Tamara Savage, Cassidy Shaver, and Katie Holland 19 Oncology Social Work 441 Hee Yun Lee, Mi Hwa Lee, and Karen Kayser 20 Chronic Disease and Social Work: Diabetes, Heart Disease, and HIV/AIDS 463 Wendy Auslander, Donald Gerke, and Stacey Freedenthal 21 Social Work and Genetics 499 Allison Werner‐Lin, Maya H. Doyle, Shana Merrill, and Sarah Gehlert 22 Pain Management and Palliative Care 535 Terry Altilio, Shirley Otis‐Green, Susan Hedlund, and Iris Cohen Fineberg 23 End‐of‐Life Care 569Yvette Colón and Stephanie P. Wladkowski Index 587

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Book SynopsisAn important guide that highlights the multiphase chemical processes for students and professionals who want to learn more about aerosol chemistry Atmospheric Multiphase Reaction Chemistry provides the information and knowledge of multiphase chemical processes and offers a review of the fundamentals on gas-liquid equilibrium, gas phase reactions, bulk aqueous phase reactions, and gas-particle interface reactions related to formation of secondary aerosols. The authorsnoted experts on the topicalso describe new particle formation, and cloud condensation nuclei activity. In addition, the text includes descriptions of field observations on secondary aerosols and PM2.5. Atmospheric aerosols play a critical role in air quality and climate change. There is growing evidence that the multiphase reactions involving heterogeneous reactions on the air-particle interface and the reactions in the bulk liquid phase of wet aerosol and cloud/fog droplets are important proTable of ContentsPreface xiii 1 Historical Background of Atmospheric Secondary Aerosol Research 1 1.1 Introduction 1 1.2 Secondary Inorganic Aerosols 1 1.2.1 Sulfate 2 1.2.2 Nitrate 3 1.3 Secondary Organic Aerosols 4 1.3.1 Photochemical Smog 5 1.3.2 Blue Haze 6 References 7 2 Fundamentals of Multiphase Chemical Reactions 13 2.1 Introduction 13 2.2 Gas–Liquid Phase Equilibrium and Equilibrium in Liquid Phase 13 2.2.1 Fundamentals of Thermodynamics 14 2.2.1.1 Internal Energy and Enthalpy 14 2.2.1.2 Entropy 16 2.2.1.3 Gibbs Energy 18 2.2.1.4 Chemical Potential 19 2.2.2 Chemical Equilibrium and Equilibrium Constant 21 2.2.2.1 Chemical Equilibrium 21 2.2.2.2 Equilibrium Constant of Gas-Phase Reaction 22 2.2.2.3 Equilibrium Constant of Liquid-Phase Reaction 24 2.2.2.4 Temperature Dependence of Equilibrium Constant 26 2.2.3 Gas–Liquid Equilibrium and Henry’s Law Constant 29 2.2.4 Hydration of Carbonyl Compounds and Effective Henry’s Law Constant 31 2.2.5 pH and Equilibrium in the Aqueous Solution 32 2.2.5.1 Dissociation Equilibrium of Pure Water and pH 32 2.2.5.2 Ion Dissociation and Equilibrium in Aqueous Solution 33 2.3 Reactions in the Liquid Phase 35 2.3.1 Thermodynamics and Activity Coefficients of Nonideal Solutions 35 2.3.1.1 Salting-in, Salting-out 38 2.3.2 Chemical Kinetics of Aqueous-Phase Reaction 39 2.3.2.1 Diffusion Process and Chemical Reaction Kinetics 39 2.3.2.2 Transition State Theory of Solution Reaction and Thermodynamic Expression 42 2.3.3 Cage Effect and Aqueous-Phase Solvent Effect 46 2.3.3.1 Cage Effect 46 2.3.3.2 Solvent Effect in the Aqueous Phase 48 2.4 Uptake Coefficient and Resistance Model 51 2.4.1 Accommodation Coefficient and Uptake Coefficient 52 2.4.2 Resistance Model 54 2.5 Physical Chemistry of Interface Reaction 56 2.5.1 Langmuir-Hinshelwood Mechanism and Eley-Rideal Mechanism 56 2.5.2 Resistance Model Including Interface Reaction 59 2.5.3 Surface Tension of Air–Water Interface and Thermodynamics of Accommodation Coefficient 65 2.5.3.1 Surface Tension 65 2.5.3.2 Thermodynamics of Accommodation Coefficient at Air–Water Interface 68 2.6 Chemical Compositions and Physical Characters of Particles 71 2.6.1 Elemental and Molecular Composition of Particles 72 2.6.1.1 Inorganic Elements and Compounds 72 2.6.1.2 Organic Compounds 74 2.6.1.3 van Krevelen Diagram 77 2.6.2 Molecular Composition and Vapor Pressure 78 2.6.3 Gas-Particle Partitioning and Volatility Basis Set Model 84 2.6.3.1 Gas-Particle Partitioning and SOA Formation Yield 84 2.6.3.2 Volatility Basis Set Model 88 2.6.3.3 Gas-Aqueous Phase Partitioning of Hydrophilic Compounds 90 2.6.4 Phase State of Particles and Mass Transfer 93 References 95 3 Gas-Phase Reactions Related to Secondary Organic Aerosols 107 3.1 Introduction 107 3.2 Ozone Reactions 107 3.2.1 Properties and Reactions of Criegee Intermediates 108 3.2.1.1 Direct Detection of Criegee Intermediate and Molecular Structure 110 3.2.1.2 Formation of CH2OO in Ozone-Ethene Reaction 115 3.2.1.3 Formation of syn- and anti-CH3CHOO in Ozone-Alkene Reactions 118 3.2.2 Alkenes and Dialkenes 130 3.2.2.1 Ethene 130 3.2.2.2 >C3 Alkenes 132 3.2.2.3 1,3-Butadiene 134 3.2.3 Isoprene 135 3.2.4 Cycloalkenes 139 3.2.4.1 Cyclohexene 139 3.2.4.2 1-Methylcyclohexene 141 3.2.4.3 Methylenecyclohexane 144 3.2.5 Monoterpenes 144 3.2.5.1 α-Pinene 145 3.2.5.2 β-Pinene 148 3.2.5.3 Limonene 150 3.2.6 Sesquiterpenes 155 3.3 OH Radical-Induced Oxidation Reactions 160 3.3.1 Alkanes 160 3.3.1.1 Reactions of Alkyl Peroxy Radicals 165 3.3.1.2 Reactions of Alkoxy Radicals 165 3.3.2 Alkynes 170 3.3.3 Alkenes, Dialkenes, and Cycloalkenes 171 3.3.3.1 Alkenes 171 3.3.3.2 1,3-Butadiene 173 3.3.3.3 Cycloalkenes and Methylene cyclohexane 174 3.3.4 Isoprene 175 3.3.4.1 Fundamental Processes of OH-Induced Oxidation Reaction 175 3.3.4.2 HOx Radicals Regeneration Reaction 178 3.3.4.3 Formation of Isoprene Hydroxy Hydroperoxide (ISOPOOH) and Isoprene Epoxydiol (IEPOX) 179 3.3.4.4 Formation of Hydroxy Isoprene Nitrates 180 3.3.4.5 Reactions of Methyl Vinyl Ketone and Methacrolein 182 3.3.5 Monoterpenes 183 3.3.5.1 α-Pinene 183 3.3.5.2 β-Pinene 185 3.3.5.3 Limonene 187 3.3.6 Monocyclic Aromatic Hydrocarbons 189 3.3.6.1 Benzene 189 3.3.6.2 Toluene 192 3.3.7 Polycyclic Aromatic Hydrocarbons 195 3.3.7.1 Naphthalene 196 3.3.7.2 Other Polycyclic Aromatic Hydrocarbons 198 3.3.8 Carbonyl Compounds: OH Radical Reactions and Photolysis 199 3.3.8.1 Glyoxal 199 3.3.8.2 Methylglyoxal 202 3.3.8.3 Glycolaldehyde 204 3.3.8.4 Hydroxyacetone 207 3.4 NO3 Oxidation Reactions 209 3.4.1 Isoprene 209 3.4.2 Monoterpenes 213 3.4.2.1 α-Pinene 213 3.4.2.2 β-Pinene 214 3.4.2.3 Limonene 215 3.4.3 Monocyclic and Polycyclic Aromatic Hydrocarbons 217 3.4.3.1 Phenol, and Cresol 217 3.4.3.2 Naphthalene 218 3.4.3.3 Other Polycyclic Aromatic Hydrocarbons 219 References 219 4 Aqueous-Phase Reactions Related to Secondary Organic Aerosols 245 4.1 Introduction 245 4.2 OH Radical Reactions 246 4.2.1 UV Absorption Spectrum of OH Radicals in Aqueous Solution 246 4.2.2 Formation of OH Radicals in Cloud/Fog Droplets and Deliquescent Aerosols 248 4.2.3 Reaction Rate Constants of OH Radicals in the Aqueous Phase 254 4.2.4 Reactions of Formaldehyde and OH Radical Chain Reaction 257 4.2.5 OH Radical Reactions and Photolysis of ≥C2 Carbonyl Compounds 262 4.2.5.1 Glyoxal and Glyoxylic Acid 262 4.2.5.2 Methylglyoxal, Pyruvic Acid, and Acetic Acid 264 4.2.5.3 Glycolaldehyde and Glycolic Acid 267 4.2.5.4 Methacrolein and Methyl Vinyl Ketone 268 4.2.6 Oligomer Formation Reactions from ≥C2 Carbonyl Compounds 270 4.2.6.1 Glyoxal and Methylglyoxal 272 4.2.6.2 Methyl Vinyl Ketone and Methacrolein 273 4.3 Nonradical Reactions 275 4.3.1 Diels-Alder Reaction 276 4.3.2 Hemiacetal and Acetal Formation Reactions 277 4.3.2.1 Glyoxal 279 4.3.2.2 Methylglyoxal 280 4.3.2.3 1,4-Hydroxycarbonyl Compounds 281 4.3.3 Aldol Reaction 281 4.3.3.1 Acetaldehyde 282 4.3.3.2 Methylglyoxal 283 4.3.3.3 Methyl Vinyl Ketone and Methacrolein 284 4.3.4 Esterification Reactions 285 4.4 Formation Reactions of Organic Sulfates 287 4.4.1 C2 and C3 Carbonyl Compounds 287 4.4.2 Monoterpenes 288 4.4.3 Isoprene 291 4.4.4 Monocyclic and Polycyclic Aromatic Hydrocarbons 291 4.5 Formation Reactions of Organic Nitrogen Compounds 292 4.5.1 Organic Nitrates 292 4.5.2 Imidazoles 293 References 295 5 Heterogeneous Oxidation Reactions at Organic Aerosol Surfaces 309 5.1 Introduction 309 5.2 Aging of Organic Aerosols in the Atmosphere 309 5.3 Reactions of Ozone 313 5.3.1 Oleic Acid and Unsaturated Long-Chain Carboxylic Acids 314 5.3.2 Squalene 316 5.3.3 Polycyclic Aromatic Hydrocarbons 318 5.4 Reactions of OH Radicals 320 5.4.1 Squalane and Long-Chain Alkanes 320 5.4.2 Levoglucosan, Erythritol, and Hopane 325 5.4.3 Saturated Dicarboxylic Acids 326 5.4.4 Squalene and Long-Chain Unsaturated Carboxylic Acids 328 5.4.5 Polycyclic Aromatic Hydrocarbons 330 5.5 Reactions of NO3 Radicals 332 5.5.1 Levoglucosan, Squalane, Long-Chain Alkane, and Alkanoic Acid 332 5.5.2 Squalene and Oleic Acid 334 5.5.3 Polycyclic Aromatic Hydrocarbons 334 References 336 6 Reactions at the Air–Water and Air–Solid Particle Interface 343 6.1 Introduction 343 6.2 Molecular Pictures and Reactions at the Air–Water Interface 344 6.2.1 Thermodynamics of Adsorption 345 6.2.1.1 OH, HO2, and O3 346 6.2.1.2 Organic and Inorganic Compounds 348 6.2.2 Microscopic Picture of Molecules 349 6.2.2.1 Air–Pure Water Interface 350 6.2.2.2 Hydrophilic Organic Compounds 352 6.2.2.3 Amphiphilic Organic Compounds (Surfactants) 356 6.2.2.4 Hydrophobic Organic Compounds 357 6.2.2.5 NH3 and SO2 358 6.2.3 Reactions of O3 and Organic Compounds 359 6.2.3.1 Oleic Acid 360 6.2.3.2 Sesquiterpene Criegee Intermediates 360 6.2.3.3 Polycyclic Aromatic Hydrocarbons 361 6.2.4 Reactions of OH Radicals and Organic Compounds 362 6.2.4.1 Carboxylic and Dicarboxylic Acids 362 6.2.4.2 Organic Sulfur Compounds 364 6.3 Air–Sea Salt Particle, Seawater, and Sulfate/Nitrate Aerosol Interface 365 6.3.1 Microscopic View of Interface of Air and Alkaline Halide Aqueous Solution 366 6.3.2 Reactions at the Interface of Sea Salt and Alkali Halide Aqueous Solution 368 6.3.2.1 Reaction with O3 369 6.3.2.2 Reaction with OH Radicals 371 6.3.2.3 Uptake of HO2 Radicals 372 6.3.2.4 Reaction with N2O5 372 6.3.2.5 Reaction with HNO3 373 6.3.3 Reactions of Organic Compounds at the Air–Seawater and Air–Sea Salt Interface 375 6.3.4 Microscopic View of the Interface of Air and Sulfate/Nitrate Aqueous Solution 377 6.3.4.1 Sulfate Ion (SO4 2−) 377 6.3.4.2 Nitrate Ion (NO3 −) 378 6.4 Reactions on Snow/Ice Surface 379 6.4.1 Formation of NOy in the Photochemical Reaction of NO3 − 379 6.4.2 Formation of Inorganic Halogens on the Snow Ice and Sea Ice Surface 382 6.4.2.1 Reaction with O3 382 6.4.2.2 Reaction with OH Radicals 383 6.4.2.3 Reactions with N2O5 384 6.5 Interface of Water and Mineral Dust, Quartz, and Metal Oxide Surface 385 6.5.1 Microscopic View of Adsorbed Water on Mineral Surface 386 6.5.2 HONO Formation Reaction from NO2 on the Mineral Surface 390 6.5.2.1 Dark Reaction 390 6.5.2.2 Photochemical Reaction 392 6.5.3 Reaction of Organic Monolayer on Mineral Surface 394 References 396 7 Atmospheric New Particle Formation and Cloud Condensation Nuclei 415 7.1 Introduction 415 7.2 Classical Homogeneous Nucleation Theory 415 7.2.1 Homogeneous Nucleation in One-Component Systems 415 7.2.2 Homogeneous Nucleation in Two-Component Systems 419 7.3 Atmospheric New Particle Formation 422 7.3.1 New Particle Formation Rate and Growth Rate 422 7.3.2 Sulfuric Acid in New Particle Formation 425 7.3.3 Basic Substances in New Particle Formation 427 7.3.4 Organic Species in New Particle Formation 430 7.3.5 Other Species in New Particle Formation 433 7.3.5.1 Iodine Oxides 433 7.3.5.2 Atmospheric Ions 434 7.3.6 Field Observation of Nanoclusters 435 7.4 Aerosol Hygroscopicity and Cloud Condensation Nuclei 436 7.4.1 Köhler Theory 436 7.4.2 Nonideality of Solution in a Droplet 441 7.4.3 Hygroscopicity Parameter, 𝜅 442 References 446 8 Field Observations of Secondary Organic Aerosols 453 8.1 Introduction 453 8.2 Global Budget of Aerosols 453 8.3 Analysis Methods of Ambient Aerosol Compositions 458 8.3.1 Positive Matrix Factorization 458 8.3.2 Mass Spectrum Peak Intensity and Elemental Ratio 459 8.3.3 Elemental Composition 460 8.4 Marine Air 461 8.5 Forest Air 465 8.5.1 Amazon Tropical Forest 465 8.5.2 Finland Boreal Forest 469 8.6 Urban/Rural Air 472 8.6.1 Characterization of Ambient Aerosols 472 8.6.1.1 PMF Analysis 472 8.6.1.2 Mass Signal Intensity Ratio and Elemental Ratio 474 8.6.1.3 Particle Size Distribution 477 8.6.1.4 Elemental Composition 478 8.6.2 Molecular Composition 479 8.6.2.1 Dicarboxylic Acid 480 8.6.2.2 Plant Origin VOC Tracers 481 8.6.2.3 Anthropogenic VOC Tracer 484 8.6.2.4 Organic Sulfate 485 8.6.2.5 Organic Nitrates and Imidazoles 486 8.6.2.6 High-Molecular-Weight Compounds and Oligomers 489 References 493 Index 509

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Book SynopsisThe book deals with novel applications of plant derived natural agents and their derivatives in the food, textile dyeing, medicinal, and environmental areas. Plant based natural products and their derivatives have strong influence on our everyday lives. They are needed for many everyday applications ranging from food, medicine, agriculture, textiles, and healthcare. This new book presents significant research advances about the use of plant-based natural products, mainly dyes and pigments, bioactive compounds and other plant extracts in the textile coloration, food, medicine, bioremediation and environmental applications. The topics of the ten informative chapters in Plant-Based Natural Products include the following: potential resurgence of natural dyes in applied fields; natural colorants from indigoid rich plants; phytochemical and pharmacological aspects of Butea monosperma plant; irradiation as novel pretreatment methods to improve wash fastness propTable of Contents Preface xiii 1 Potential Resurgence of Natural Dyes in Applied Fields 1Shahid Adeel, Sana Rafi, Mahwish Salman, Fazal-Ur-Rehman and Shazia Abrar 1.1 Introduction 1 1.2 History 3 1.3 Advantages of Natural Dyes 4 1.4 Classification 5 1.5 Methods of Extraction and Dyeing 10 1.6 Potential Application of Natural Dyes 12 1.7 Conclusion 20 Acknowledgment 20 References 20 2 Natural Dyes from Indigoid-Rich Plants: An Overview 27Mohd Yusuf and Shahid-ul-Islam 2.1 Introduction to Natural Dyes 27 2.2 Indigoid Dyes: An Overview 29 2.4 Safety Aspects and Sustainability 43 2.5 Conclusion and Future Outlook 43 References 44 3 Phytochemical and Pharmacological Aspects of Butea monosperma L. 47Shahid-ul-Islam, Mohd Yusuf and Faqeer Mohammad 3.1 Introduction 48 3.2 Phytochemical Aspects 49 3.3 Sterols 52 3.4 Imides 52 3.5 Terpenoids 54 3.6 Miscellaneous Compounds 55 3.7 Biological Activities 55 3.8 Conclusion 61 References 61 4 Radiation Pretreatment: A Potential Novel Technology to Improve Fastness Properties of Plant-Derived Natural Dyes 65Shahid Adeel, Shumaila Kiran, Sana Rafi, Tayyaba Ayesha, Fazal-Ur-Rehman, Tahsin Gulzar and M.Zuber 4.1 Introduction 66 4.2 Chemistry of Fabrics 69 4.3 Mordants and their Classification 73 4.4 Radiation and its Role in Dyeing 76 4.5 Applications of Mordants 78 4.6 Conclusion 81 Acknowledgments 81 References 82 5 Natural Colorant from Lawsonia inermis Leaves: Reflectance Spectroscopy-Induced Optimal Conditions of Extraction and Dyeing 89Mohd Yusuf and Faqeer Mohammad 5.1 Introduction 89 5.2 Materials and Methods 91 5.3 Results and Discussion 93 5.4 Conclusion 98 Acknowledgement 100 References 100 6 Plant Food By-products and their Application in Food Industry 103Kaiser Younis, Ovais Shafiq Qadri, Khalid Bashir and Shahid-ul-Islam 6.1 Introduction 103 6.2 Plant Origin Food By-products 105 6.3 Effects on the Quality Parameters of Food Products Incorporated with Plant By-products 112 6.4 Conclusion 121 References 122 7 Effect of Drumstick Leaves (Moringa oleifera) Incorporation on Quality of Khakhra 129TaranjitKaur Maghu, Alka Sharma and Kaiser Younis 7.1 Introduction 130 7.2 Materials and Methods 131 7.3 Results and Discussions 134 Conclusion 142 Acknowledgments 142 References 142 8 Curcumin and Its Derivatives – Isolation, Synthesis, and Applications 145Ovas Ahmad Dar, Manzoor Ahmad Malik, Shahid-ul-Islam, Parveez Gull and Athar Adil Hashmi 8.1 Introduction 145 8.2 Isolation 147 8.3 Metal Complexes as Derivatives of Curcumin 147 8.4 Applications of Curcumin and its Derivatives 156 8.5 Conclusions and Future Perspective 166 Abbreviations 167 References 168 9 Investigating the Functional Properties of Pineapple Pomace Powder and Its Incorporation in Buffalo Meat Products 175Kaiser Younis and Saghir Ahmad 9.1 Introduction 175 9.2 Materials and Methods 176 9.3 Results and Discussion 180 Conclusion 189 Acknowledgment 190 References 190 10 Green Adsorbents from Plant Sources for the Removal of Arsenic: An Emerging Wastewater Treatment Technology 193Sharf Ilahi Siddiqui, Saif Ali Chaudhry and Shahid-ul-Islam 10.1 Introduction 194 10.2 Arsenic Toxicity 195 10.3 Detoxification and Remediation of Arsenic 196 10.4 Adsorption as an Emerging Technology 197 10.5 Mechanism Followed by Green Adsorbent 205 10.6 Water Constraints Effect on Green Adsorbent 207 10.7 Regeneration of Green Adsorbent 208 10.8 Advantages, Shortcomings, and Recent Advances 210 10.9 Conclusion and Future Prospects 211 Acknowledgment 211 References 211

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Book SynopsisOrganic Reaction Mechanisms 2017, the 53rd annual volume in this highly successful and unique series, surveys research on organic reaction mechanisms described in the available literature dated 2017. The following classes of organic reaction mechanisms are comprehensively reviewed: Reaction of Aldehydes and Ketones and their Derivatives Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and their Derivatives Oxidation and Reduction Carbenes and Nitrenes Nucleophilic Aromatic Substitution Electrophilic Aromatic Substitution Carbocations Nucleophilic Aliphatic Substitution Carbanions and Electrophilic Aliphatic Substitution Elimination Reactions Polar Addition Reactions Cycloaddition Reactions Molecular RearrangementsAn experienced team of authors compile these reviews every year, so that the reader can rely on a continuing quality of selection and presentation.Table of Contents1 Reactions of Aldehydes and Ketones and their Derivatives 1S. R. Hussaini 2 Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and their Derivatives 63C. T. Bedford 3 Oxidation and Reduction 93R. N. Mehrotra 4 Carbenes and Nitrenes 179E. Gras and S. Chassaing 5 Aromatic Substitution 213M. R. Crampton 6 Carbocations 297P. Angelov 7 Nucleophilic Aliphatic Substitution 317J. G. Moloney and M. G. Moloney 8 Carbanions and Electrophilic Aliphatic Substitution 343M. L. Birsa 9 Elimination Reactions 365M. L. Birsa 10 Addition Reactions: Polar Addition 377P. Kočovský 11 Addition Reactions: Cycloaddition 501N. Dennis 12 Molecular Rearrangements 527J. M. Coxon Author Index 585 Subject Index 631

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Book SynopsisThe first comprehensive textbook on the timely and rapidly developing topic of inorganic porous materials This is the first textbook to completely cover a broad range of inorganic porous materials. It introduces the reader to the development of functional porous inorganic materials, from the synthetic zeolites in the 50's, to today's hybrid materials such as metal-organic frameworks (MOFs), covalent organic frameworks (COFs) and related networks. It also provides the necessary background to understand how porous materials are organized, characterized, and applied in adsorption, catalysis, and many other domains. Additionally, the book explains characterization and application from the materials scientist viewpoint, giving the reader a practical approach on the characterization and application of the respective materials. Introduction to Inorganic Porous Materials begins by describing the basic concepts of porosity and the different types of pores, surfaces, and amorphous versus crysTrade Review"... an excellent book, one that is long overdue, one that should be in all inorganic materials' laboratories and one that should be a must read for any new PhD student starting research on materials.... These chapters are just packed with data and ideas. Read them and you will be keen to put on your lab coat and start to make these materials and apply them to your own work."—Peter Myers, Chromatographia, December 2019Table of ContentsPreface xi About the Authors xiii 1 Nature’s Porous Materials: From Beautiful to Practical 1 1.1 Living Porosity 1 1.1.1 Butterflies 1 1.1.2 Algae 4 1.1.3 Bamboo 8 1.2 Clay Minerals 8 1.2.1 Natural Clays 8 1.2.2 Pillared Interlayered Clays – PILCs 12 References 13 2 Theory of Adsorption and Catalysis: Surface Area and Porosity 15 2.1 Determination of Surface Area and Porosity by Gas Sorption 15 2.1.1 Introduction 15 2.1.2 Chemisorption and Physisorption 15 2.1.3 Reversible Monolayer Adsorption – The Langmuir Isotherm 16 2.2 The BET (Brunauer, Emmet, Teller) Model 21 2.2.1 The BET Equation 21 2.2.2 Multipoint BET Analysis 23 2.3 Capillary Condensation and Pore Size, the Type IV Isotherm 25 2.3.1 The Kelvin and the Halsey Equation 25 2.3.2 Barrett, Joyner, Halenda (BJH) Pore Size Distributions 27 2.3.3 Types of Adsorption Isotherms 32 2.3.4 Adsorption Hysteresis 34 2.3.5 Evaluation of Micropores 36 2.4 Liquid Phase Adsorption – Langmuir and Freundlich Isotherms 37 2.4.1 Adsorption Kinetics 38 2.4.2 Adsorption Isotherms 40 2.5 Heterogeneous Catalysis 42 2.5.1 Introduction 42 2.5.2 Types of Catalysis 44 2.5.3 Toward Green and Sustainable Industrial Chemistry 46 2.5.4 Kinetics in a Heterogeneous Catalytic Reaction 50 2.5.5 Diffusion Phenomena 57 2.A Appendix 66 Exercises 68 Answers to the Problems 71 References 73 3 Zeolites and Zeotypes 75 3.1 Crystallographic Directions and Planes 75 3.1.1 Crystallographic Directions 75 3.1.2 Crystallographic Planes 77 3.2 X-Ray Diffraction 80 3.3 Zeolite Structures 82 3.4 Applications of Zeolites 85 3.4.1 Ion-Exchange, Water Softening 85 3.4.2 Catalysis 88 3.4.3 Gas Sorption and Purification 109 3.5 Solid-State NMR 111 3.5.1 Introduction to the Technique NMR 111 3.5.2 Nuclear Magnetic Resonance: The Basics 112 3.5.3 Solid-State NMR: The Challenges 115 3.5.4 The Application of Solid-State NMR 118 References 118 4 Silica, A Simple Oxide – A Case Study for FT–IR Spectroscopy 121 4.1 Different Methods to Synthesize Silica 121 4.1.1 Silica Gels and Sols 121 4.1.2 Pyrogenic Silicas 126 4.1.3 Precipitated Silicas 127 4.2 The Surface of Silica 127 4.3 Fourier Transform Infrared Spectroscopy 129 4.3.1 Principles of Infrared Spectroscopy 130 4.3.2 Principles of FT–IR 133 4.3.3 DRIFTS – Diffuse Reflectance Infrared Fourier Transform Spectroscopy 138 4.3.4 Attenuated Total Reflection 140 References 142 5 Ordered Mesoporous Silica 145 5.1 MCM-41 and MCM-48 – Revolution by the Mobil Oil Company 145 5.1.1 The Original Papers and Patents 145 5.1.2 Calculating the Wall Thickness 150 5.1.3 Interaction Between Surfactant and Inorganic Precursor 151 5.1.4 The Surfactant Packing Parameter 154 5.1.5 Hexagonal Mesoporous Silica 156 5.1.6 Stable Ordered Mesoporous Silica – SBA 157 5.1.7 Plugged Hexagonal Templated Silica 161 5.1.8 The New MCM-48: KIT-6 163 5.1.9 Further Developments of Mesoporous Silica 165 5.1.10 Pore Size Engineering 167 5.1.11 Making Thin Films – The EISA Principle 167 5.2 Applications of Mesoporous Silica 168 5.2.1 In Heterogeneous Catalysis – Functionalization of Mesoporous Silica 168 5.2.2 In Adsorption 183 5.2.3 As a Drug Carrier 188 5.2.4 Low-k Dielectrics 189 References 191 6 Carbons 195 6.1 Activated Carbon 195 6.2 General Introduction to Mesoporous Carbons 197 6.2.1 Synthesis of Hard-Templated Mesoporous Carbons 198 6.2.2 Synthesis of Soft-Templated Mesoporous Carbons 204 6.2.3 Influence of Synthesis Conditions on the Soft-Templated Method 207 6.2.4 Transformation of Polymer into Carbon, the Carbonization Temperature 215 6.2.5 (Hydro)Thermal and Mechanical Stability 216 6.3 Surface Modification of Mesoporous Polymers and Carbons 217 6.3.1 Pre-Modification of Polymers/Carbons 218 6.3.2 Post-Modification of Polymers/Carbons 218 6.4 Nanocarbons 218 6.4.1 Fullerenes 219 6.4.2 Carbon Nanotubes 224 6.5 Application of Porous Carbon-Based Materials 227 6.5.1 The Adsorption of Pollutants 227 6.5.2 As Catalytic Support or Direct Heterogeneous Catalyst 231 6.5.3 Electrochemical Applications: Energy Storage 237 Exercises 243 Answers to the Problems 243 References 245 7 The Era of the Hybrids – Part 1: Periodic Mesoporous Organosilicas or PMOS 249 7.1 Introduction 249 7.2 Synthesis of PMOs 253 7.2.1 General Aspects of PMO Synthesis 253 7.2.2 PMOs with Aliphatic Bridges 257 7.2.3 PMOs with Olefinic and Aromatic Bridges 258 7.2.4 PMOs with Multi-Organic Bridges 264 7.3 General Properties of PMOs 265 7.3.1 Pore Size Engineering 265 7.3.2 (Hydro)thermal and Chemical Stability 267 7.3.3 Metamorphosis in PMOs 269 7.4 Post-Modification of PMOs 270 7.4.1 Post-Functionalization of the Unsaturated Bridges 271 7.4.2 Post-Modification of the Aromatic Ring 275 7.5 Applications of PMOs 276 7.5.1 As Heterogeneous Catalysts 276 7.5.2 As Adsorbents of Metals, Organic Compounds, and Gases 290 7.5.3 As Solid Chromatographic Packing Materials 294 7.5.4 As Low-k Films 297 7.5.5 As Biomedical Supports 298 Exercises 300 Answers to the Problems 302 References 303 8 Era of the Hybrids – Part 2: Metal–Organic Frameworks 309 8.1 Introduction 309 8.2 Isoreticular Synthesis 312 8.3 Well-Known MOFs 313 8.3.1 Cu-BTC 314 8.3.2 MIL-53 314 8.3.3 MIL-101 315 8.3.4 UiO-66 315 8.3.5 NU-1000 317 8.3.6 ZIF-8 318 8.4 Stability of MOFs 318 8.5 Preparation of MOFs 320 8.5.1 Hydro- and Solvothermal Synthesis 320 8.5.2 Microwave-Assisted Synthesis 320 8.5.3 Electrochemical Synthesis Route 321 8.5.4 High-Throughput Analysis 321 8.6 Functionalities in MOFs 321 8.6.1 Active Sites in MOFs 321 8.6.2 Multifunctional MOFs 322 8.7 Applications of MOFs 332 8.7.1 MOFs in Gas Storage and Gas Separation 332 8.7.2 MOFs in Catalysis 351 8.7.3 Luminescent MOFs 355 8.8 Industrial Applications of MOFs 364 8.9 Transmission Electron Microscopy 366 8.9.1 Electron Diffraction and Bright Field Imaging 367 8.9.2 High-Resolution Transmission Electron Microscopy 368 8.9.3 Scanning Transmission Electron Microscopy 369 8.9.4 Energy Dispersive X-Ray Spectroscopy 371 8.9.5 Electron Energy Loss Spectroscopy 371 8.9.6 Electron Tomography 371 Exercises 372 Answers to the Problems 374 References 377 9 Beyond the Hybrids – Covalent Organic Frameworks 381 9.1 Classification and Nature of COFs 381 9.2 Design of COFs 383 9.3 Boron-Based COFs 386 9.3.1 Introduction 386 9.3.2 Other Synthetic Routes to Obtain Boron-Based COFs 389 9.3.3 Methods to Increase the Stability of Boron-Based COFs 391 9.3.4 Applications of Boron-Containing COFs 392 9.4 Covalent Triazine Frameworks 395 9.4.1 Ionothermal Synthesis of Covalent Triazine Frameworks 395 9.4.2 Acid Assisted Synthesis Route 398 9.4.3 Mechanochemical Synthesis 398 9.4.4 Applications of CTFs 399 9.5 Imine COFs 404 9.5.1 Solvothermal Synthesis: COF-300 404 9.5.2 Room Temperature Synthesis of Imine COFs 406 9.5.3 Liquid Assisted Grinding 407 9.5.4 Applications of Imine COFs 408 Exercises 414 Answers to the Problems 415 References 417 Index 419

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Book SynopsisA guide to the fundamental chemistry and recent advances of battery materials In one comprehensive volume, Inorganic Battery Materials explores the basic chemistry principles, recent advances, and the challenges and opportunities of the current and emerging technologies of battery materials. With contributions from an international panel of experts, this authoritative resource contains information on the fundamental features of battery materials, discussions on material synthesis, structural characterizations and electrochemical reactions. The book explores a wide range of topics including the state-of-the-art lithium ion battery chemistry to more energy-aggressive chemistries involving lithium metal. The authors also include a review of sulfur and oxygen, aqueous battery chemistry, redox flow battery chemistry, solid state battery chemistry and environmentally beneficial carbon dioxide battery chemistry. In the context of renewable energy utilization and transportation electrificatTable of ContentsContributors ix Series Preface xiii Volume Preface xv Part 1: Chemistry of Li-Ion Battery Materials 1 Silicon-Based Anodes for Advanced Lithium-Ion Batteries 3Junhua Song, Xiaolin Li and Ji-Guang Zhang Surface Chemistry of Alkali-Ion Battery Cathode Materials 15Muhammad M. Rahman and Feng Lin Part 2: Lithium Metal Battery Materials 39 Li–CO2 Batteries 41Zhaojun Xie and Zhen Zhou S Electrode Materials 59Feng Li Lithium Metal Anode 75Siyuan Li, Jixiang Yang and Yingying Lu Lithium Oxygen Battery 97Raymond A. Wong, Hye Ryung Byon, Morgan L. Thomas, Kaoru Dokko and Masayoshi Watanabe Structural Engineering of Cathode Materials for Lithium–Sulfur Batteries 121Ligui Li, Jingping Yu, Nan Wang, Jun Zhao, Bin Fan, Shuaibo Zeng and Shaowei Chen Part 3: Materials and Chemistry of Non-Lithium Batteries 151 How to Maximize the Potential of Zn–Air Battery: Toward Acceptable Rechargeable Technology with or without Electricity 153Joohyuk Park, Jang-Soo Lee and Jaephil Cho Solid State and Materials Chemistry for Sodium-Ion Batteries 161Divya Sehrawat, Neeraj Sharma and Jennifer H. Stansby Multivalent Metallic Anodes for Rechargeable Batteries 197Jennifer L. Schaefer and Laura C. Merrill Redox-Active Inorganic Materials for Redox Flow Batteries 211Bo Hu, Jian Luo, Camden DeBruler, Maowei Hu, Wenda Wu and T. Leo Liu Electrode and Electrolyte Interaction in Aqueous Electrochemical Energy Storage 237Xiaowei Teng Na-Ion Batteries: Positive Electrode Materials 253Elizabeth H. Driscoll, Laura L. Driscoll and Peter R. Slater Part 4: Electrolyte Chemistry for Rechargeable Batteries 267 Solid-State Electrolyte 269Wei Luo, Chuang Yu and Liangbing Hu Chemistry of Soft Matter Battery Electrolytes 279Jelena Popovic Modeling Solid State Batteries 291Ting Hei Wan, Ziheng Lu and Francesco Ciucci Part 5: Advanced Characterizations of Inorganic Battery Materials 309 TEM Studies on Electrode Materials for Secondary Ion Batteries 311Sooyeon Hwang and Dong Su Synchrotron-Based Soft X-Ray Spectroscopy for Battery Material Studies 339Wanli Yang Solid Electrolyte Interphase in Lithium-Based Batteries 359Feifei Shi and Philip N. Ross Application of In Situ Electrochemical-Cell Transmission Electron Microscopy for the Study of Rechargeable Batteries 377Wentao Yao and Reza Shahbazian-Yassar Index 387

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Book SynopsisX-ray absorption spectroscopy and X-ray emission spectroscopy are complementary to crystallographic methods, particularly for materials science and the study of nanostructure and systems with partial disorder and partial local order, including solutions, gases, liquids, glasses and powders. This new volume of International Tables for Crystallography has nine parts and over 150 chapters contributed by a wide range of international experts. Part 1 provides a brief overview and introduction to the background of X-ray absorption spectroscopy (XAS) and experimental facilities. Part 2 discusses the quantum theory of XAS and related approaches. Part 3 describes both standard and advanced experimental methods used in XAS, X-ray emission spectroscopy (XES) and related techniques. Part 4 covers both standard and more advanced pre-processing of data. Part 5 gives an extensive overview of the analysis of experimental data.

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Book SynopsisA practical approach to environmental chemistry, Elements of Environmental Chemistry, 3rd Edition provides readers with the fundamentals of environmental chemistry and a toolbox for putting them into practice. This is a concise, accessible, and hands-on volume designed for students and professionals working in the chemical and environmental sciences. The 3rd Edition has been completely revised and rearranged. The first chapter on tool skills has been expanded to include thermodynamic considerations and measurement issues. The former chapter on the partitioning of organic compounds has been expanded to cover the fates of organic compounds, with an emphasis on developing the reader?s ?chemical intuition? for predicting a chemical?s fate based on structure. The material on lead, mercury, pesticides, PCBs, dioxins, and flame retardants has been expanded and combined into the last chapter and supplemented with more references to the literature. TTable of ContentsPreface xi 1 Simple Tool Skills 1 1.1 Unit Conversions 1 1.2 Estimating 4 1.3 Ideal Gas Law 6 1.4 Stoichiometry 9 1.5 Thermodynamic Considerations 10 1.5.1 Enthalpy 11 1.5.2 Entropy 13 1.5.3 Gibbs Free Energy 14 1.6 Measurement Issues 15 1.7 Problem Set 24 2 Mass Balance and Kinetics 29 2.1 Steady-State Mass Balance 29 2.1.1 Flows, Stocks, and Residence Times 29 2.1.2 Adding Multiple Flows 35 2.1.3 Fluxes Are Not Flows! 37 2.2 Nonsteady-State Mass Balance 39 2.2.1 Up-Going Curve 40 2.2.2 Down-Going Curve 43 2.2.3 Working with Real Data 45 2.3 Chemical Kinetics 49 2.3.1 First-Order Reactions 50 2.3.2 Second-Order Reactions 50 2.3.3 Michaelis–Menten Kinetics 52 2.4 Problem Set 56 3 Atmospheric Chemistry 63 3.1 Atmospheric Structure 63 3.2 Light and Photochemistry 65 3.3 Atmospheric Oxidants 69 3.4 Kinetics of Atmospheric Reactions 70 3.4.1 Pseudo-Steady-State Example 70 3.4.2 Arrhenius Equation 71 3.5 Stratospheric Ozone 72 3.5.1 Formation and Loss Mechanisms 72 3.5.2 Chapman Reaction Kinetics 77 3.6 Smog 80 3.7 Problem Set 84 4 Climate Change 93 4.1 Historical Perspective 93 4.2 Blackbody Radiation and Earth’s Temperature 94 4.3 Absorption of Infrared Radiation 97 4.4 Greenhouse Effect 98 4.5 Earth’s Radiative Balance 99 4.5.1 Greenhouse Gases 99 4.5.2 Albedo 101 4.5.3 Solar Constant 101 4.5.4 Combined Effects 101 4.6 Aerosols and Clouds 101 4.7 Radiative Forcing 103 4.8 Global Warming Potentials 104 4.9 Concluding Remarks 106 4.10 Problem Set 108 5 Carbon Dioxide Equilibria 113 5.1 pH and Equilibrium Constants 113 5.2 Pure Rain 116 5.3 Polluted Rain 119 5.4 Additional Acid Rain Chemistry and Implications 123 5.5 Surface Water 125 5.6 Ocean Acidification 128 5.7 Problem Set 132 6 Fates of Organic Compounds 139 6.1 Molecular Interactions 140 6.1.1 Electronegativity 140 6.1.2 Molecular Dipoles and Quadrupoles 141 6.1.3 Types of Weak Interactions 142 6.2 Vapor Pressure 145 6.3 Aqueous Solubility 149 6.3.1 Solubility of Pure Liquids and Solids 149 6.3.2 Solubility of Gases 154 6.4 Partitioning into Organic Phases 158 6.5 Partitioning into Biota 160 6.5.1 Bioconcentration 161 6.5.2 Bioaccumulation 161 6.5.3 Biomagnification 162 6.6 Adsorption 162 6.7 Water–Air Transfer 165 6.8 Reactive Fates of Organic Pollutants 168 6.9 Putting It All Together: Partitioning and Persistence 169 6.10 Problem Set 172 7 Toxic Stuff: Mercury, Lead, Pesticides, Polychlorinated Biphenyls, Dioxins, and Flame Retardants 181 7.1 Mercury 181 7.2 Lead 183 7.3 Pesticides 188 7.3.1 Pesticide History 189 7.3.2 Legacy Pesticides 190 7.3.3 Current Use Herbicides 194 7.3.4 Current Use Insecticides 198 7.3.5 Current Use Fumigants 201 7.3.6 Current Use Fungicides 203 7.4 Polychlorinated Biphenyls (PCBs) 203 7.4.1 PCB Nomenclature 204 7.4.2 PCB Production and Use 205 7.4.3 PCBs in the Hudson River 206 7.4.4 PCBs in Bloomington, Indiana 209 7.4.5 Yusho and Yu-Cheng Diseases 211 7.4.6 PCB Conclusions 213 7.5 Polychlorinated Dibenzo-p-dioxins and Dibenzofurans 214 7.5.1 Dioxin Nomenclature 214 7.5.2 Chick Edema Disease 215 7.5.3 Agent Orange 216 7.5.4 Times Beach, Missouri 218 7.5.5 Seveso, Italy 219 7.5.6 Combustion Sources of Dioxins 222 7.5.7 US Dioxin Reassessment and Conclusions 224 7.6 Brominated and Other Flame Retardants 225 7.6.1 Polybrominated Biphenyls 226 7.6.2 Polybrominated Diphenyl Ethers 228 7.6.3 Other Flame Retardants 229 7.7 Lessons Learned 231 A Primer on Organic Structures and Names 233 B Periodic Table of the Elements 243 C Useful Physical and Chemical Constants 245 D Answers to Problem Sets 247 Chapter 1 247 Chapter 2 248 Chapter 3 251 Chapter 4 252 Chapter 5 254 Chapter 6 257 Index 259

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Book SynopsisAn Updated Reference on Human Exposure to Environmental Toxicants and A Study of Their Impact on Public Health With the 4th edition of Environmental Toxicants: Human Exposures and Their Health Effects, readers have access to up-to-date information on the study and science of environmental toxicology and public health worldwide. Practitioners and professionals can use this resource to understand newly discovered information on the adverse health effects of toxins and pollutants in air, water, and occupational and environmental environments on large human populations. The 4th edition of this book is updated to reflect new knowledge and research on: ? Performing risk assessments on exposed individuals ? Assessing the effects of toxicants and substances on large populations for health and medical professionals ? Patterns of human exposure to select chemical toxicants ? World Trade Center dust, agents for chemical terrorism, and nanTable of ContentsContributors xiii Preface xvii 1 Introduction and Background 1 1.1 Characterization of Chemical Contaminants 2 1.2 Human Exposures and Dosimetry 7 1.3 Chemical Exposures and Dose to Target Tissues 8 1.4 Concentration of Toxic Chemicals in Human Microenvironments 9 1.5 Inhalation Exposures and Respiratory Tract Effects 13 1.6 Ingestion Exposures and Gastrointestinal Tract Effects 19 1.7 Skin Exposure and Dermal Effects 20 1.8 Absorption Through Membranes and Systemic Circulation 21 1.9 Accumulation in Target Tissues and Dosimetric Models 22 1.10 Indirect Measures of Past Exposures 23 1.11 Characterization of Health 24 1.12 Exposure–Response Relationships 26 1.13 Study Options for Health Effects Studies 32 References 37 2 Perspectives on Individual and Community Risk 41 2.1 Nature of Risk 42 2.2 Identification and Quantification of Risks 46 2.3 Risk Communication 51 2.4 Risk Reduction 54 References 58 3 Reducing Risks: An Environmental Engineering Perspective 65 3.1 Introduction 65 3.2 Environmental Risk‐Based Decision Making 66 3.3 Applications and Use 70 3.4 Historic Background 78 3.5 Integrated Assessments 82 3.6 Summary 83 References 83 4 Clinical Perspective on Respiratory Toxicology 87 4.1 Concepts of Exposure 88 4.2 Tools for Studying Individuals 90 4.3 Tools for Studying Populations 101 4.4 Cardiovascular Responses 108 4.5 Limitations of Clinical and Epidemiological Assessments of the Effects of Inhaled Agents 110 4.6 Climate Change and Health 111 4.7 Novel Exposures 111 4.8 Advice and Counseling of Patients 112 4.9 Summary 115 References 116 5 Industrial Perspectives: Translating the Knowledge Base into Corporate Policies, Programs, and Practices for Health Protection 127 5.1 Introduction 127 5.2 The Life Cycle of a Chemical: Many Points for Possible Intervention 128 5.3 The Knowledge Base for the Identification of Hazard and Health Protection Control Strategies 129 5.4 Industrial Hygiene and Occupational Health Programs : Implementing the Knowledge Base 131 5.5 Product Stewardship 138 5.6 Responsible Care 142 5.7 Concluding Perspective 145 Acknowledgment 145 References 145 6 Food Constituents and Contaminants 149 6.1 Introduction 149 6.2 Legal and Regulatory Framework in the United States 152 6.3 Safety Criteria and Their Scientific Bases 155 6.4 Nutrients 163 6.5 Substances Intentionally Introduced into Food 164 6.6 Food Contaminants of Industrial Origin 171 6.7 Constituents and Contaminants of Natural Origin 179 6.8 Compounds Produced During Food Storage and Preparation 189 6.9 Dietary Supplements 191 6.10 Food Safety Institutions Around the World 192 6.11 Summary and Conclusion 193 Acronyms 194 References 195 7 Acrolein and Unsaturated Aldehydes 205 7.1 Background 205 7.2 Cellular Exposure and Metabolism 212 7.3 Single Exposure Health Effects 230 7.4 Repeated Exposure Health Effects 235 7.5 Conclusion 239 References 240 8 Chemical Weapons 261 8.1 Overview 261 8.2 Nerve Agents 262 8.3 Respiratory Toxicants 265 8.4 Vesicants 266 8.5 Rodenticides 271 8.6 Arsenicals 273 8.7 Metabolic Poisons 274 8.8 Summary 275 Acknowledgments 275 References 275 9 Ambient Air Particulate Matter 285 9.1 Introduction 285 9.2 Background 286 9.3 Sources and Pathways for Human Exposure 290 9.4 Ambient Air PM Concentrations 291 9.5 Population Exposures to Ambient Air PM 292 9.6 Evidence for Adverse Human Health Effects Due to the Inhalation of Ambient Air PM 293 9.7 Health Effects of Specific PM Components 301 9.8 Chronic Exposures to PM2.5 and Components on Annual Mortality 312 9.9 Pediatric Responses to Long‐Term PM Exposures 321 9.10 Other Morbidity Responses Affected by PM2.5 Components 323 9.11 Controlled Short‐Term Human Inhalation Exposure Studies 325 9.12 Animal Inhalation Studies with Concentrated PM (Caps) 326 9.13 Effects of PM Source Mixture Inhalation Exposures in Laboratory Animals 332 9.14 NPACT Subchronic Caps Mouse Inhalation Studies 335 9.15 Consistency, Coherence, and Implications to Public Health 337 9.16 Most Influential PM2.5 Components as Causal Factors 338 9.17 Daily Morbidity Effects and Coherence with Excess Daily Mortality 339 9.18 Effects of PM2.5 Components in Toxicological Studies 342 9.19 The Roles of PM2.5 Components on Health‐Related Responses 343 9.20 Coherence of NPACT Toxicological and Epidemiological Responses 344 9.21 Coherence of NPACT Study of CVD Effects in People and in Mice 344 9.22 Coherence: Annual Human Annual Mortality with Aortic Plaque Progression in Apoe−/− Mice 345 9.23 Traffic and So4 = in the NPACT Studies 345 9.24 Holistic Perspectives on the Role of PM2.5 in CVD Effects 346 9.25 Setting of NAAQS and/or Control Strategies for Ambient Air PM 348 9.26 Research Needs 351 9.27 Need for a More Comprehensive Air Quality Monitoring Program 351 9.28 Conclusions 352 References 353 10 Arsenic 367 10.1 Introduction 367 10.2 Kinetics of as Uptake, Distribution, and Elimination 373 10.3 Toxicity and Mechanisms of Toxicity 375 10.4 Evidence of Human Diseases Caused by Arsenic 377 10.5 Conclusions 380 References 380 11 Asbestos and Other Mineral and Vitreous Fibers 389 11.1 Introduction 389 11.2 Inhalation Exposures to Fibers 393 11.3 Fiber Deposition in the Respiratory Tract 395 11.4 Fiber Retention, Translocation, Disintegration, and Dissolution 397 11.5 Fiber‐Related Diseases/Processes 403 11.6 Biological Effects of Size‐Classified Fibers in Laboratory Animals and Humans 405 11.7 Critical Fiber Parameters Affecting Disease Pathogenesis 407 11.8 Exposure–Response Relationships for Asbestos‐Related Lung Disease: Human Experience 416 11.9 Exposure–Response Relationships for SVF‐Related Disease: Human Experience 421 11.10 Summary of Human Responses to Long‐Term Fiber Inhalation Exposures 424 11.11 Summary of Pulmonary and Pleural Responses in Animals 426 11.12 Overall Summary of In Vivo Biological Responses to Various Durable Fibers 430 11.13 Risk Assessment Issues 430 11.14 Risk Assessment Issues—SVFs 434 11.15 Recapitulation and Synthesis: Factors Affecting Fiber Dosimetry and Toxicity 436 11.16 Discussion 438 11.17 Conclusions 439 Acknowledgments 440 Acronyms 440 References 441 12 Carbon Monoxide 455 12.1 Introduction 455 12.2 CO Exposure and Dosimetry 456 12.3 Mechanisms of CO Toxicity 458 12.4 Populations at Risk of Health Effects Due to CO Exposure 459 12.5 Potential Risks for Pregnant Women, Fetuses, and Newborn Children 460 12.6 Historical Regulatory Background 460 12.7 Health Effects of CO 461 12.8 Exposure and Relationship to COHb Concentrations 465 12.9 Neurotoxicological and Behavioral Effects 470 12.10 Fetal Developmental and Perinatal Effects 471 12.11 CO as a Risk Factor in Cardiovascular Disease Development 472 12.12 Summary and Conclusions 472 References 474 13 Chromium 487 13.1 Introduction 487 13.2 Exposure 488 13.3 Chromium Uptake and Metabolism 492 13.4 Toxicological Effects 494 13.5 Mechanisms of Chromium Toxicity and Carcinogenicity 500 References 503 14 Diesel Exhaust and Lung Cancer Risk 515 14.1 Historical Overview 515 14.2 Composition of Diesel Engine Exhaust 517 14.3 Environmental Exposures to Diesel Exhaust 520 14.4 Cancer 521 14.5 Conclusions 528 Acknowledgments 529 References 530 15 Endocrine‐Disrupting Chemicals 535 15.1 Introduction 535 15.2 Modes of Action 536 15.3 Selected Disease Endpoints 542 15.4 Conclusion 547 References 548 16 Formaldehyde and Other Saturated Aldehydes 555 16.1 Background 555 16.2 Single‐Exposure Health Effects 570 16.3 Effects of Multiple Exposures 580 References 597 17 Lead and Compounds 627 17.1 Introduction 627 17.2 Physical/Chemical Properties and Behavior of PB and its Compounds 628 17.3 Lead in the Environment and Human Exposure 631 17.4 Lead Absorption 634 17.5 Distribution 639 17.6 Kinetics 642 17.7 Biomarkers 648 17.8 Health Effects 651 17.9 Mechanisms Underlying Lead Toxicity 658 17.10 Treatment of Lead Toxicity 661 17.11 Summation 663 References 663 18 Mercury 677 18.1 Introduction 677 18.2 Chemistry 678 18.3 Sources 678 18.4 Environmental Exposures 679 18.5 Kinetics and Metabolism 682 18.6 Absorption 682 18.7 Distribution 683 18.8 Elimination 684 18.9 Health Effects 685 18.10 Prevention 688 References 689 19 Cardiopulmonary Effects of Nanomaterials 695 19.1 Introduction 695 19.2 Nanoparticles: Scope and Toxicity 696 19.3 Lessons Learned 697 19.4 Particle Characterization 698 19.5 Relevant Exposure Scenario 698 19.6 NP Exposure 699 19.7 Cardiovascular Effects Following Pulmonary NP Exposure 700 19.8 Types of NP in Common Usage 701 19.9 Case Study: Subchronic Effects of Inhaled Nickel Nanoparticles on the Progression of Atherosclerosis in a Hyperlipidemic Mouse Model 709 19.10 Human Data 710 19.11 Future Studies 710 19.12 Summary 710 References 711 20 Nitrogen Oxides 721 20.1 Introduction 721 20.2 Sources of NOx 723 20.3 Nitrogen Dioxide 725 20.4 Nitric Oxide 753 20.5 Nitric/Nitrous Acid 756 20.6 Inorganic Nitrates 757 20.7 Summary and Conclusions 759 References 761 21 Ozone 783 21.1 Introduction 783 21.2 Background on Exposures and Health‐Related Effects 787 21.3 Effects of Short‐Term Exposures to Ozone in Humans 790 21.4 Factors Affecting Responsiveness in Humans 805 21.5 Mechanistic Studies in Laboratory Animals 807 21.6 Studies of Populations Exposed to Ozone in Ambient Air 808 21.7 Effects Observed in Studies in Laboratory Animals 816 21.8 Effects of Other Pollutants on Responses to Ozone 821 21.9 Effects of Multiday and Ambient Episode Exposures 824 21.10 Cumulative Effects of Ambient Ozone Exposures 826 21.11 Controlled Laboratory Exposure Studies: Animal Responses 829 21.12 Standards and Exposure Guidelines 833 21.13 Summary and Conclusions 835 Acknowledgments 837 References 838 22 Pesticides 855 22.1 Uses of Pesticides 855 22.2 History of Pesticides 856 22.3 Exposure to Pesticides 857 22.4 Acute Poisoning with Pesticides 858 22.5 Toxicity of Pesticides 859 22.6 Pesticides as Endocrine Disruptors 867 22.7 Pesticides and Developmental Neurotoxicity 868 22.8 Legislative Framework 868 22.9 Conclusion 870 Acknowledgment 870 References 870 23 Radon and Lung Cancer 877 23.1 Introduction 877 23.2 History of Radon and Decay Product Measurement 880 23.3 Indoor Measurements of 222RN 881 23.4 Outdoor Measurements of 222RN 882 23.5 Measurement of 222RN Decay Products 884 23.6 Groundwater as a Source of Indoor 222RN 885 23.7 220RN (Thoron) the Other Radon 887 23.8 Radon Epidemiology in Underground Mines and Lung Cancer Risk 888 23.9 Residential Radon Epidemiology Lung Cancer Models and Lung Cancer Risk 890 23.10 Lung Dosimetry 892 23.11 Regulations and Guidelines for 222RN Exposure 897 23.12 Radon and Smoking 898 23.13 Childhood 222RN Exposure 899 23.14 Other Natural Background Exposure 902 23.15 Summary 903 Glossary 903 References 905 24 Secondhand Tobacco Smoke 911 24.1 Introduction 911 24.2 Exposure to Secondhand Smoke (SHS) 912 24.3 Health Effects of Involuntary Smoking 917 24.4 Control of Exposure to Secondhand Smoke 921 24.5 Summary 922 References 923 25 Sulfur Oxides (SOx): SO2, H2SO4, NH4HSO4, and (NH4)2SO4 927 25.1 Introduction 927 25.2 Sources and Exposures 928 25.3 Health Effects of So2 932 25.4 Long‐Term Multi‐Pollutant Effects Studies 939 25.5 Exposures to and Health Effects of Acidic Aerosols 942 25.6 Ambient Air Quality Standard 960 25.7 Who Guidelines 960 25.8 Overall Discussion 961 25.9 Conclusions 962 Acknowledgment 962 References 962 26 World Trade Center (WTC) Dust 973 26.1 Introduction 973 26.2 Post‐Collapse Human Inhalation Exposures to WTC Dusts 974 26.3 Potential Dosimetry of WTC Dusts 978 26.4 Associations Between WTC Dust Inhalation and Health Effects 980 26.5 Studies of Biologic Responses to WTC Dusts 986 26.6 Possible Roles of Minor Mass Components as Causal Factors for Observed Health Effects 991 26.7 Roles of Major Mass Components as Potential Causal Factors for Observed Health Effects 992 26.8 Conclusions 993 Acknowledgments 995 References 995 Index 999

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Book SynopsisOutlines recent advances in the field of polar organometallic chemistry, particularly in the context of the emergent areas of synergic and cooperative species. Polar Organometallic Reagents provides a critical overview of developments in the field of modern polar organometallic chemistry. With a particular focus on the emergent area of synergic heterometallic reagents, this timely volume describes our attempts to understand recently developed polar organometallics and their application in a range of new directions. Contributions from leading researchers present new synthetic work and discuss recent advances in characterization techniques, synthetic applications, and mechanistic understanding of heterometallic complexes. In-depth chapters provide detailed information on fundamental, structural, and theoretical aspects of polar organometallic chemistry while articulating the need and rationale for the advent of new reagents. Topics include alkali and alkaline earthTable of ContentsPreface xi List of Contributors xv Acknowledgements xvii 1 The Road to Aromatic Functionalization by Mixed-metal Ate Chemistry 1 Masanori Shigeno, Andrew J. Peel, Andrew E. H. Wheatley, and Yoshinori Kondo 1.1 Introduction 1 1.2 Deprotonation of Aromatics 2 1.2.1 Monometallic Bases 2 1.2.2 Bimetallic Bases 7 1.2.2.1 Group 1/1 Reagents 7 1.2.2.2 Group 1/2 Reagents 11 1.3 Aromatic Ate Complex Chemistry: Metal/Halogen Exchange 13 1.3.1 Introduction 13 1.3.2 Zincates 13 1.3.3 Cuprates 17 1.3.4 Solid-phase Synthesis 24 1.4 Deprotonation Using Ate Complexes 25 1.4.1 Introduction 25 1.4.2 Zincates 26 1.4.3 Cadmates 29 1.4.4 Aluminates 30 1.4.5 Cuprates 32 1.4.6 Argentates 39 1.5 Concluding Remarks 41 References 42 2 Structural Evidence for Synergistic Bimetallic Main Group Bases 49 Robert E. Mulvey and Stuart D. Robertson 2.1 General Introduction 49 2.2 Homometallic Bases 51 2.2.1 Carbanionic Lithium Reagents 51 2.2.2 Heavier Carbanionic Alkali Metal Reagents 56 2.2.3 Alkali Metal Amides 58 2.3 Heterometallic Bases 60 2.3.1 Heteroalkali Metal Bases 60 2.3.2 Alkali Metal Magnesiate Chemistry 64 2.3.3 Early Signs of Synergistic Behaviour in Zincate Chemistry 64 2.3.4 Lithium TMP–Zincate Chemistry 66 2.3.5 Sodium TMP–Zincate Chemistry 73 2.3.6 Lithium Chloride (Turbo Charged) TMP–Zinc Chemistry 78 2.3.7 Indirect TMP Zincation 79 2.3.8 Alkali Metal Group 13 Ates 80 2.3.9 Bimetallic Complexes Without an Alkali Metal Component 85 2.4 Outlook 91 References 91 3 Turbo Charging Group 2 Reagents for Metathesis, Metalation, and Catalysis 97 Michael S. Hill, Anne-Frédérique Pécharman, and Andrew S. S. Wilson 3.1 Introduction and Historical Context: Monometallic s-block Reagents and Their Utility 97 3.2 Heterobimetallic Reagents for Selective Metalation 100 3.2.1 Ate Complexes and Superbases 100 3.2.2 Lithium, Sodium, Potassium Magnesiates, MMgX3 101 3.2.3 Salt Effects and Magnesiate Formation 107 3.2.3.1 ‘Turbo-Grignards’ for Selective Metalation 108 3.2.3.2 Turbo–Hauser Bases 112 3.2.4 Ate Complexes of the Heavier Alkaline Earth Elements Ca, Sr, and Ba 114 3.2.4.1 Alkyl Calciate, Strontiate, and Bariate Derivatives, MM′R3 (M = Li, Na, K; M′ = Ca, Sr, Ba; R = alkyl) 115 3.2.4.2 Alkoxo and Aryloxo Calciate, Strontiate, and Bariate Derivatives, MM′ (OR/Ar)3 (M = Li, Na, K; M′ = Ca, Sr, Ba) 115 3.2.4.3 Amido Calciate, Strontiate, and Bariate Derivatives, MM′(OR/Ar)3 (M = Li, Na, K; M′ = Ca, Sr, Ba) 116 3.3 Homogeneous Catalysis by s-block Reagents 117 3.4 Outlook: Turbo Charging the Turbo Reagents and Prospects for Catalysis 120 References 121 4 Mechanisms in Heterobimetallic Reactivity: Experimental and Computational Insights for Catalyst Design in Small Molecule Activation and Polymer Synthesis 133 Frances N. Singer and Antoine Buchard 4.1 Introduction and Scope of the Chapter 133 4.2 Small Molecule Activation and Catalysis 135 4.2.1 Hydrogen Activation 135 4.2.2 Dinitrogen Activation 147 4.2.3 CO2 Activation 150 4.3 Polymerization Catalysis 152 4.3.1 Olefin polymerization 152 4.3.1.1 Metallocene-based Heterobimetallic Catalysts 154 4.3.1.2 Constrained Geometries Heterobimetallic Catalysts 159 4.3.1.3 Late Transition Metal Heterobimetallic Catalysts 164 4.3.2 Ring-opening Polymerization 171 4.3.2.1 ROP M1–O–M2 Heterobimetallic Catalysts 174 4.3.2.2 Other Heterobimetallic Catalysts for ROP 178 4.3.3 Ring-opening Copolymerization of Epoxides and Carbon Dioxide 181 4.3.3.1 Mechanistic Insight into Homobimetallic Catalysts 183 4.3.3.2 ROCOP Heterobimetallic Catalysts 186 4.4 Conclusion 192 References 193 5 Cationic Compounds of Group 13 Elements: Entry Point to the p-block for Modern Lewis Acid Reagents 201 Sanjay Singh, Mamta Bhandari, Sandeep Rawat, and Sharanappa Nembenna 5.1 Introduction 201 5.2 General Considerations 202 5.2.1 Classification of Cationic Group 13 Complexes 202 5.2.2 General Methods for the Syntheses of Cationic Group 13 Complexes 203 5.2.3 Characteristics of Counter-anions and Solvents 204 5.2.4 Quantification of LA of Cationic Group 13 Complexes 205 5.2.4.1 Experimental Methods to Quantify Lewis Acidity 206 5.2.4.2 Computational Approaches to Determine Lewis Acidity 207 5.3 Recent Developments in Cationic Group 13 Complexes 209 5.3.1 Advances in the Synthesis and Characterization of Borocations 209 5.3.1.1 Borinium Cations: Two-coordinate Cationic Boron Complexes 209 5.3.1.2 Borenium Cations: Three-coordinate Cationic Boron Complexes 211 5.3.1.3 Borenium Cations Stabilized by NHC and MIC as Neutral C-donor Ligand 212 5.3.1.4 Phosphine-coordinated Borenium Cations 217 5.3.1.5 Borenium Cations Coordinated with N-donor Ligands 218 5.3.1.6 Boronium Cations: Four-coordinate Cationic Boron Complexes 220 5.3.1.7 Miscellaneous Borocations 223 5.3.2 Advances in the Synthesis and Characterization of Aluminium Cations 223 5.3.2.1 Organoaluminium Cations 224 5.3.2.2 Aluminium Cations Supported by N,N′-donor Monoanionic Bidentate Ligands 230 5.3.2.3 An Aluminium Cationic Complex Supported by a Neutral Bidentate N,N′-donor Ligand 232 5.3.2.4 Miscellaneous Aluminium Cations that Appeared Since 2010 232 5.3.3 Advances in the Synthesis and Characterization of Heavier Group 13 (Ga, In, and Tl) Cations 235 5.3.3.1 Low Oxidation State Univalent Heavier Group 13 Cations (Ga, In, and Tl) 239 5.4 Recent Advancements in Catalytic Applications of Cationic Group 13 Complexes 241 5.4.1 Borocation in Catalysis 241 5.4.1.1 Cationic Boron Complexes in Catalysis 241 5.4.1.2 Hydroboration Reaction 241 5.4.1.3 Hydrosilylation Reaction 243 5.4.1.4 Hydrogenation Reaction 244 5.4.1.5 Use of Chiral NHC 246 5.4.1.6 Use of Chiral Borane 247 5.4.2 Cationic Al Complexes in Catalysis 248 5.4.2.1 Hydroboration Reaction 248 5.4.2.2 Cyanosilylation Reaction 250 5.4.2.3 Hydrosilylation Reaction 252 5.4.2.4 Hydroamination Reaction 254 5.4.2.5 ROP of rac-Lactide, Epoxides and ε-Caprolactone 255 5.4.3 Cationic Heavier Group 13 Complexes in Catalysis 256 5.4.3.1 Cationic Gallium Complexes in Catalysis 256 5.4.3.2 Activation of Alcohols 257 5.4.3.3 Olefin Epoxidation in Water 257 5.4.3.4 Transfer Hydrogenation of Alkene 258 5.4.3.5 Hydroarylation Reaction 258 5.4.3.6 Cycloisomerization of Enyne 260 5.4.3.7 Tandem Carbonyl–Olefin Metathesis 260 5.4.3.8 Polymerization of Propylene Oxide and Isobutylene 261 5.4.3.9 Cationic Indium and Thallium Complexes in Catalysis 262 5.4.3.10 Coupling of Epoxides and Lactones 262 5.4.3.11 ROP of Epoxides, Lactide, and ε-Caprolactone 262 5.5 Concluding Remarks 264 References 265 6 Recent Development in the Solution Structural Chemistry of Main Group Organometallics 271 Alistair M. Broughton, Leonie J. Bole, Andrew E. H. Wheatley, and Eva Hevia 6.1 Introduction 271 6.2 Monometallic Systems 273 6.2.1 Introduction 273 6.2.2 Organo(s-block Metal) Aggregation and Reactivity 273 6.2.3 DOSY on s-block Organometallics 280 6.2.3.1 Development and Early Applications 280 6.2.3.2 Recent Refinements to Diffusion Techniques 283 6.3 Heteropolymetallic Systems 287 6.3.1 Introduction 287 6.3.2 s/s-block Systems 287 6.3.2.1 Alkali Metal/Magnesium 287 6.3.2.2 Turbo–Hauser Chemistry 289 6.3.3 s/p-block Systems 291 6.3.3.1 Lithium/Aluminium Chemistry and Trans-metal-trapping 291 6.3.3.2 Alkali Metal/Gallium Systems 293 6.3.4 s/d-block Systems 294 6.3.4.1 Lithium/Cadmium 294 6.3.4.2 Lithium/Copper 295 6.3.4.3 Alkali Metal/Zinc 302 6.3.4.4 Magnesium/Zinc 308 6.4 Concluding Remarks 311 References 312 7 Chemistry of Boryl Anions: Recent Developments 317 Makoto Yamashita 7.1 Introduction 317 7.2 Boryl Anions as a Salt of Alkali Metals 317 7.2.1 Early Examples of Base-stabilized Boryl Anions and Borylcopper Species 317 7.2.2 Diaminoboryl Anions as a Lithium Salt 318 7.2.3 Base-stabilized Boryl Anion with π-delocalization 321 7.2.3.1 Lewis Base-stabilized Borole Anion 321 7.2.3.2 Carbene-stabilized Boryl Anion 322 7.2.3.3 Stabilization with Cyanide 323 7.2.3.4 Metal-substituted Boryl Anion 325 7.3 Boryl Anions as a Salt of Magnesium, Zinc, and Copper as Relatives of Carbanions 325 7.3.1 Transmetalation of Boryllithium to Magnesium, Copper, and Zinc to Form Borylmetals 325 7.3.2 Transmetalation of Diborane(4) to Magnesium and Zinc to Form Borylmetals 329 7.4 Application of Borylcopper and Borylzinc Species for Synthetic Organic Chemistry 330 7.5 Summary 332 References 333 8 Novel Chemical Transformations in Organic Synthesis with Ate Complexes 337 Keiichi Hirano and Masanobu Uchiyama 8.1 Introduction 337 8.2 Ate Complexes 337 8.3 Di-anion-type Zincate 338 8.3.1 Mono-anion-type Zincates and Di-anion-type Zincates 338 8.3.2 Highly Bulky Di-anion-type Zincate: Li2[Znt-Bu4] 339 8.3.2.1 Halogen–Zinc Exchange in the Presence of Proton Sources 339 8.3.2.2 Anionic Polymerization in Water 340 8.3.3 Cross-coupling Reaction via C–O Bond Cleavage 340 8.4 Heteroleptic Zinc Ate Complexes 342 8.4.1 Deprotonative Metalation of Aromatic C–H Bonds 342 8.4.1.1 Amidozincate Base: Li[(TMP)ZnR2] 343 8.4.1.2 Amidoaluminate Base: Li[(TMP)Ali-Bu3] 343 8.4.1.3 Amidocuprate Base: Li2[(TMP)Cu(CN)R] 345 8.4.2 Hydridozincate: M[HZnMe2] 346 8.4.3 Silylzincates 348 8.4.3.1 Silylzincation of Alkynes 349 8.4.3.2 Silylzincation of Alkynes via Si–B Activation 350 8.4.3.3 Silylzincation of Alkenes (1): Synthesis of Allylsilanes 350 8.4.3.4 Silylzincation of Alkenes (2): Synthesis of Alkylsilanes 350 8.4.4 Perfluoroalkylzincates Li[RFZnMeCl] and RFZnR 350 8.4.5 Design of Boryl Anion Equivalents and Applications in Synthetic Chemistry 354 8.4.5.1 Borylzincate: M[(pinB)ZnEt2] 355 8.4.5.2 Trans-Diboration of Alkynes via pseudo-Intramolecular Activation 357 8.4.5.3 Trans-Alkynylboration of Alkynes 360 8.5 Conclusion 360 References 362 9 Isolable Alkenylcopper Compounds: Synthesis, Structure, and Reaction Chemistry 365 Liang Liu, Chao Wang, and Zhenfeng Xi 9.1 Introduction 365 9.2 Well-defined Alkenylcopper Compounds 365 9.2.1 Mono-alkenyl Organocopper Compounds with Intramolecular Coordination 366 9.2.2 Mono-alkenyl Organocopper Compounds Stabilized by N-heterocyclic Carbene 367 9.2.3 Butadienyl Copper Compounds 369 9.3 Summary 379 References 380 Index 383

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Book SynopsisOffers a comprehensive guide to the isolation, properties and applications of chitin and chitosan Chitin and Chitosan: Properties and Applications presents a comprehensive review of the isolation, properties and applications of chitin and chitosan. These promising biomaterials have the potential to be broadly applied and there is a growing market for these biopolymers in areas such as medical and pharmaceutical, packaging, agricultural, textile, cosmetics, nanoparticles and more. The authors noted experts in the field explore the isolation, characterization and the physical and chemical properties of chitin and chitosan. They also examine their properties such as hydrogels, immunomodulation and biotechnology, antimicrobial activity and chemical enzymatic modifications. The book offers an analysis of the myriad medical and pharmaceutical applications as well as a review of applications in other areas. In addition, the authors discuss regulations, marketsTable of ContentsList of Contributors xvii Series Preface xxi Preface xxiii 1 Sources of Chitin and Chitosan and their Isolation 1Leen Bastiaens, Lise Soetemans, Els D’Hondt, and Kathy Elst 1.1 Chitin and Chitosan 2 1.1.1 Chemical Structure 2 1.1.2 Different Crystalline Forms of Chitin 2 1.2 Sources of Chitin and Chitosan 5 1.2.1 Sources of Chitin 5 1.2.2 Sources for Chitosan 10 1.3 Isolation of Chitin 11 1.3.1 Technology Principles 11 1.3.2 Isolation of Chitin from Crustaceans 13 1.3.3 Isolation of Chitin from Insects 16 1.3.4 Isolation of Chitin from Other Biomass Types 16 1.4 Production of Chitosan 19 1.4.1 Conversion of Chitin to Chitosan 19 1.4.2 Chitosan Extracted from Fungi 24 1.5 Towards Commercial Applications 25 1.6 Outlook 28 References 28 2 Methods of Isolating Chitin from Sponges (Porifera) 35Sonia Żółtowska, Christine Klinger, Iaroslav Petrenko, Marcin Wysokowski, Yvonne Joseph, Teofil Jesionowski, and Hermann Ehrlich 2.1 Introduction 35 2.2 Brief Overview of Classical Methods of Isolating Chitin from Invertebrates 38 2.3 The Modern Approach to Chitin Isolation from Sponges 40 2.3.1 Methods of Isolating Chitin from Glass Sponges (Hexactinellida) 41 2.3.2 Methods of Isolating Chitin from Demosponges (Demospongiae) 43 2.4 Prospective Applications of Poriferan Chitin 49 2.4.1 Poriferan Chitin and Modern Bioinspired Materials Science 49 2.4.2 Chitinous 3D Scaffolds of Sponge Origin for Tissue Engineering 51 2.5 Outlook 54 Acknowledgment 54 References 54 3 Physicochemical Properties of Chitosan and its Degradation Products 61Karolina Gzyra‐Jagieła, Bożenna Pęczek, Maria Wiśniewska‐Wrona, and Natalia Gutowska 3.1 Physicochemical Properties of Chitosan 62 3.1.1 Determination of Molar Mass 62 3.1.2 Determination of the Deacetylation Degree 67 3.1.3 Determination of Dynamic Viscosity 70 3.1.4 Determination of Nitrogen 70 3.1.5 Determination of Ash Content 71 3.1.6 Determination of Heavy Metal Content 71 3.1.7 Determination of Water Retention Value (WRV) 72 3.1.8 Determination of Solubility in Hydrochloric Acid 72 3.1.9 Determination of Water Content 72 3.1.10 Determination of Protein Content 73 3.1.11 Quantitative Determination of Chitosan by Ninhydrin 73 3.2 Products of Degradation and their Application 74 3.3 Outlook 77 References 77 4 New Developments in the Analysis of Partially Acetylated Chitosan Polymers and Oligomers 81Stefan Cord‐Landwehr, Anna Niehues, Jasper Wattjes, and Bruno M. Moerschbacher 4.1 Introduction 82 4.2 Chitosan Oligomers 83 4.2.1 Degree of Polymerisation (DP), Fraction and Pattern of Acetylation (FA and PA) 83 4.3 Chitosan Polymers 86 4.3.1 Molecular Weight (MW) / Degree of Polymerisation (DP) and its Dispersity (ÐMW / ÐDP) 86 4.3.2 Fraction of Acetylation (FA) and its Dispersity (ÐFA) 87 4.3.3 Pattern of Acetylation (PA) 89 4.4 Outlook 91 References 92 5 Chitosan‐Based Hydrogels 97Zhengke Wang, Ling Yang, and Wen Fang 5.1 Introduction 97 5.2 Chitosan‐Based Multilayered Hydrogels 98 5.2.1 Periodic Precipitation 99 5.2.2 Alternating Process 100 5.2.3 Induced by Electrical Signals 100 5.2.4 Layer‐by‐Layer (LbL) Assembly 101 5.2.5 Sequential Curing 101 5.3 Chitin/Chitosan Physical Hydrogels Based on Alkali/Urea Solvent System 103 5.3.1 Chitin Hydrogels Based on Alkali/Urea Solvent System 104 5.3.2 Chitosan Hydrogels Based on Alkali/Urea Solvent System 104 5.4 Chitosan‐Based Injectable Hydrogels 108 5.4.1 Physical Association Networks 108 5.4.2 Chemical Association Networks 110 5.4.3 Double‐Network Hydrogels 116 5.5 Chitosan‐Based Self‐Healing Hydrogels 119 5.5.1 Physical Interactions 119 5.5.2 Dynamic Chemical Bonds 121 5.6 Chitosan‐Based Shape Memory Hydrogels 125 5.6.1 Water‐/Solvent‐Triggered Shape Recovery 126 5.6.2 pH‐triggered Shape Recovery 126 5.6.3 Ultrasound Triggered Shape Recovery 126 5.6.4 Self‐Actuated Shape Memory Hydrogels 127 5.6.5 Chitosan‐Based Hydrogels with Triple Shape Memory Effect 127 5.7 Superabsorbent Chitosan‐Based Hydrogels 131 5.7.1 Cross‐Linked Chitosan‐Based Hydrogels 132 5.7.2 Hydrogels by Graft Copolymerization 133 5.7.3 Chitosan‐Based Composite Hydrogels 134 5.7.4 Pure Chitosan‐Based Materials 135 5.8 Outlook 136 References 136 6 Beneficial Health Effects of Chitin and Chitosan 145Liyou Dong, Harry J. Wichers, and Coen Govers 6.1 Immunomodulatory Effects of Chitin and Chitosan as Demonstrated with In Vitro Studies 146 6.2 Beneficial Health Effects Mediated by Chitin and Chitosan as Demonstrated with Animal Studies 149 6.2.1 Immune Modulation 149 6.2.2 Anti‐Pathogenic Effects 155 6.2.3 Anti‐Tumour Effects 157 6.3 Beneficial Health Effects Mediated by Chitin and Chitosan as Demonstrated with Clinical Trials 158 6.3.1 Cholesterol Reduction and CVD Preventive Effects 158 6.3.2 Other Health Effects 160 6.4 Requirements to forward the Field of Study Towards the Beneficial Health Effects of Chitin and Chitosan 163 6.5 Outlook 164 Acknowledgement 164 References 164 7 Antimicrobial Properties of Chitin and Chitosan 169Magdalena Kucharska, Monika Sikora, Kinga Brzoza‐Malczewska, and Monika Owczarek 7.1 Microbiological Activity of Chitosan – The Mechanism of its Antibacterial and Antifungal Activity 169 7.2 The use of Chitin/Chitosan’s Microbiological Activity in Medicine and Pharmacy 171 7.3 Microbiological Activity of Chitosan in the Food Industry 174 7.4 Microbiological Activity of Chitosan in Paper and Textile Industries 176 7.5 Microbiological Activity of Chitosan in Agriculture 177 7.6 Outlook 181 References 181 8 Enzymes for Modification of Chitin and Chitosan 189Gustav Vaaje‐Kolstad, Tina Rise Tuveng, Sophanit Mekasha, and Vincent G.H. Eijsink 8.1 CAZymes in Chitin Degradation and Modification 190 8.1.1 Chitinases 191 8.1.2 β‐N‐acetylhexosaminidases 195 8.1.3 Exo‐β‐glucosaminidases 195 8.1.4 Chitosanases 197 8.1.5 Lytic Polysaccharide Monooxygenases 199 8.1.6 Carbohydrate Esterases 200 8.1.7 Carbohydrate‐Binding Modules 204 8.2 Modular Diversity in Chitinases, Chitosanases and LPMOs 204 8.3 Biological Roles of Chitin‐Active Enzymes 205 8.4 Microbial Degradation and Utilisation of Chitin 208 8.4.1 Chitin Degradation by Serratia marcescens 209 8.4.2 Chitin Degradation by Bacteria in the Bacteroidetes Phylum 211 8.4.3 Chitin Degradation by Thermococcus Kodakarensis 211 8.4.4 Chitin Degradation by Fungi 212 8.5 Biotechnological Perspectives 213 8.6 Biorefining of Chitin‐Rich Biomass 214 8.7 Outlook 216 References 216 9 Chitin and Chitosan as Sources of Bio‐Based Building Blocks and Chemicals 229Malgorzata Kaisler, Lambertus A.M. van den Broek, and Carmen G. Boeriu 9.1 Introduction 230 9.2 Chitin Conversion into Chitosan, Chitooligosaccharides and Monosaccharides 232 9.2.1 Chitosan Production 232 9.2.2 Production of Chitooligosaccharides 234 9.2.3 Production of GlcNAc and GlcN from Chitin 235 9.3 Building Blocks for Polymers from Chitin and its Derivatives 238 9.3.1 Furan‐Based Monomers 238 9.3.2 Amino Alcohol and Amino Acid Building Blocks 239 9.4 Outlook 239 Acknowledgement 240 References 240 10 Chemical and Enzymatic Modification of Chitosan to Produce New Functional Materials with Improved Properties 245Carmen G. Boeriu and Lambertus A.M. van den Broek 10.1 Introduction 245 10.2 Functional Chitosan Derivatives by Chemical and Enzymatic Modification 246 10.2.1 Anionic Chitosan Derivatives 248 10.2.2 Hydroxyalkylchitosans 250 10.2.3 Quaternised and Highly Cationic Chitosan Derivatives 250 10.2.4 Hydroxyaryl Chitosan Derivatives 250 10.2.5 Carbohydrate‐Modified Chitosan 251 10.3 Graft Co‐Polymers of Chitosan 251 10.4 Cross‐Linked Chitosan and Chitosan Polymer Networks 254 10.5 Outlook 254 References 255 11 Chitosan‐Based Drug Delivery Systems 259Cristian Peptu, Andra Cristina Humelnicu, Razvan Rotaru, Maria Emiliana Fortuna, Xenia Patras, Mirela Teodorescu, Bogdan Ionel Tamba, and Valeria Harabagiu 11.1 Introduction 260 11.2 Beneficial Effects of Chitosan 261 11.2.1 Interaction with Anionic Drugs 263 11.2.2 Mucoadhesive Properties 263 11.2.3 Transfection Activity 263 11.2.4 Efflux Pump Inhibitory Properties 265 11.2.5 Permeation‐Enhancing Properties 265 11.3 Chitosan—an Active Polymer for Bypassing Biological Barriers 265 11.3.1 Skin Barrier 266 11.3.2 Mucosa Barrier 267 11.3.3 Ophthalmic Barrier 269 11.3.4 Blood–Brain Barrier 270 11.4 Chitosan‐Based DDS Formulations 271 11.4.1 Hydrogels 275 11.4.2 Micro/NPs 275 11.4.3 Nanofibers 275 11.4.4 Scaffolds and Membranes 275 11.5 Outlook 276 Acknowledgment 276 References 276 12 The Application of Chitin and its Derivatives for the Design of Advanced Medical Devices 291Marcin H. Struszczyk, Longina Madej‐Kiełbik, and Dorota Zielińska 12.1 Selection of the Raw Sources: Safety Criteria 291 12.1.1 Aspect of Animal Tissue‐Originated Derivatives 292 12.1.2 General Requirements for Chitinous Biopolymers Applied in Designing Medical Devices 292 12.1.3 Characterisation of the Biopolymer for Application in Wound Dressing Designing 293 12.1.4 Aspect of the Sterilization of the Final Wound Dressing 295 12.2 Types of Wound Dressings Consisting of Chitin‐Derived Biopolymers Available in the Market 297 12.3 Performance and Safety Assessment 297 12.4 New Ideas and Concepts 301 12.5 Risk Acceptance and Design Process Aspects 306 12.6 Outlook 308 Acknowledgements 308 References 308 13 Food Applications of Chitosan and its Derivatives 315Suse Botelho da Silva, Daiana de Souza, and Liziane Dantas Lacerda 13.1 Introduction 315 13.2 Chitosan and its Derivatives as Food Additive 316 13.2.1 Antioxidant 318 13.2.2 Antimicrobial 319 13.2.3 Stabilizer and Thickener 319 13.3 Functional Ingredient and Health Beneficial Effects 320 13.4 Active Packaging 321 13.5 Enzyme Immobilization 331 13.6 Encapsulation and Delivering of Bioactive Ingredients 332 13.7 Adsorption and Chelation of Toxic and Undesirable Compounds 334 13.8 Outlook 339 References 340 14 Potential of Chitosans in the Development of Edible Food Packaging 349Véronique Coma and Artur Bartkowiak 14.1 Potential Limitations for Real Introduction into the Market 350 14.1.1 Generally Recognized as Safe (GRAS) 351 14.1.2 Solubility 351 14.1.3 Source—Origin 352 14.1.4 Structure Variability 352 14.2 Films and Coatings for Food Preservation 353 14.2.1 Definitions and Interests 353 14.2.2 Main Relevant Chitosan‐Based Material Properties 353 14.3 Specific Case of Chitosan Nanoparticles (CSNPs) 357 14.3.1 CSNPs 357 14.3.2 CSNPs in Various Edible Films 358 14.3.3 Antimicrobial Activities of CSNPs in Edible Films 359 14.3.4 Toxicity Studies of CSNPs 360 14.4 Applications to Sensitive Real Food Products 360 14.4.1 Fruits and Vegetables 361 14.4.2 Meat and Meat Products 362 14.4.3 Fish and Seafood Products 362 14.5 Conclusions 364 References 364 15 The Use of Chitosan‐Based Nanoformulations for Controlling Fungi During Storage of Horticultural Commodities 371Silvia Bautista‐Baños, Zormy Nacary Correa‐Pacheco, and Rosa Isela Ventura‐Aguilar 15.1 Introduction 372 15.2 Importance of Fruits and Vegetables 372 15.3 Storage Disorders and Diseases of Horticultural Products 374 15.4 Plant Fungi Inhibition by Chitosan Application 375 15.5 Chitosan Integrated with Other Alternative Methods for Controlling Postharvest Fungi 376 15.6 Chitosan‐Based Formulations 376 15.7 Physiological Response and Quality Retention of Horticultural Commodities to Chitosan Coating Application 376 15.8 Influence of Chitosan Coatings on the Shelf Life of Horticultural Products 378 15.9 Effects of Chitosan Coatings with Additional Compounds on Quality and Microorganisms Development 379 15.10 Integration of Chitosan Nanoparticles into Coating Formulations and their Effects on the Quality of Horticultural Commodities and Development of Microorganisms 384 15.11 Outlook 387 Acknowledgments 387 References 387 16 Chitosan Application in Textile Processing and Fabric Coating 395Thomas Hahn, Leonie Bossog, Tom Hager, Werner Wunderlich, Rudi Breier, Thomas Stegmaier, and Susanne Zibek 16.1 Chitosan in the Textile Industry 396 16.2 Textile Production 398 16.3 General Test Methods 400 16.4 Fibres and Yarns from Chitin and Chitosan 401 16.4.1 Chitin and Chitosan Solubilisation for Spinning Purposes 402 16.4.2 Chitosan Spinning Processes 402 16.4.3 Mechanical Properties of Chitosan Fibres/Yarns 404 16.5 Sizing with Chitosan 406 16.5.1 Miscibility of Chitosan with Other Sizing Agents 407 16.5.2 Viscosity of Chitosan‐Containing Sizing Agents 408 16.5.3 Adhesion and Wetting 410 16.5.4 Mechanical–Physical Properties of Chitosan Films 411 16.5.5 Removal and Processing of Chitosan Sizing after Weaving 412 16.6 Chitosan as a Finishing Agent or Coating 414 16.6.1 Chitosan as a Carrier and Linker 415 16.6.2 Formation of a Durable Finish with Chitosan 416 16.6.3 Chitosan as an Active Agent 417 16.7 Outlook 419 Nomenclature 420 References 421 17 Chitin and Chitosan for Water Purification 429Petrisor Samoila, Andra Cristina Humelnicu, Maria Ignat, Corneliu Cojocaru, and Valeria Harabagiu 17.1 Introduction 430 17.2 Wastewater Treatment by Adsorption 432 17.2.1 Principle of the Adsorption Process 432 17.2.2 Adsorption of Organic Compounds 434 17.2.3 Adsorption of Heavy Metals 437 17.3 Wastewater Treatment by Coagulation/Flocculation 440 17.4 Wastewater Treatment by Membrane Separation 446 17.4.1 Principle of Ultrafiltration Process 446 17.4.2 Fabrication of Ultrafiltration Blend Membranes 448 17.4.3 Chitosan‐Enhanced Ultrafiltration 450 17.5 Outlook 452 Acknowledgement 452 References 453 18 Chitosan for Sensors and Electrochemical Applications 461Suse Botelho da Silva, Guilherme Lopes Batista, and Cristiane Krause Santin 18.1 Introduction 461 18.2 Chitosan: A Biopolymer with Unique Properties 462 18.3 Modification and Preparation of Chitosan‐Based Materials for Electrochemical Applications 463 18.4 The Proton Conductivity of Chitosan 465 18.5 Selected Applications 467 18.5.1 Electrochemical Sensors 467 18.5.2 Spectroscopic Sensors 470 18.5.3 Other Electrochemical Devices 471 18.6 Outlook 472 References 473 19 Marketing and Regulations of Chitin and Chitosan from Insects 477Nathalie Berezina and Antoine Hubert 19.1 Historical Outline 477 19.2 Natural Origins of Chitin 478 19.3 Specificities of Chitin Biopolymer 479 19.4 Differences Among Chitins from Insects and Other Sources 479 19.4.1 Differences of Chemical Compositions of the Cuticles 479 19.4.2 Differences of Physical Assemblies of Chains and Molecules 480 19.5 Extraction and Purification Specificities of Chitins from Insects 480 19.5.1 Different Cuticle Structures and Contents of Insects 480 19.5.2 Chemical Extraction 480 19.5.3 Biological Extraction 481 19.5.4 Characterization and Transformation into Chitosan 481 19.6 Market Opportunities and its Regulations 482 19.6.1 Agriculture Applications 482 19.6.2 Water Treatment Applications 483 19.6.3 Material Applications 483 19.6.4 Biomedical Applications 484 19.7 Outlook 485 References 485 Index 491

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