Chemistry Books

Book SynopsisComplemented by an estimating tool spreadsheet based on a fixed set of chemicals to assist in risk estimations, Probability of Ignition of a Released Flammable Mass converts a best guess to a calculated value based on available information and current technology.Table of ContentsFORWARD XI 1 INTRODUCTION 1 1.1 Objectives 1 1.2 Motivation for this Book 1 1.2.1 A Brief History of Fire Protection 2 1.2.2 The Development of Risk-Based Approaches to Flammables Management 3 1.2.3 Difficulties in Developing Ignition Probability Prediction Methods 4 1.2.4 Missing Variables 5 1.2.5 Summary of Industry Needs and Path Forward 5 1.2.6 Applications for This Book 6 1.2.7 Limitations in Applying the Approaches in This Book 7 1.3 Ignition Probability Overview 8 1.3.1 Theoretical Basis for Ignition 8 1.3.2 Key Ignition Factors Related to the Properties of the Fuel, and Available Surrogates that can be Used for Developing Probability of Ignition Predictions 13 1.3.3 Key Ignition Factors Related to the Release Source 19 1.3.4 Key Ignition Factors Related to the External Environment After the Release 27 1.4 Control of Ignition Sources 30 1.4.1 Ignition Source Management 30 1.4.2 Minimization of Release 33 1.5 Vapor Cloud Explosion Probability Overview 33 1.6 Detonation Overview 35 1.6.1 Detonation Using a Strong Ignition Source 35 1.6.2 Deflagration-to-Detonation Transition 35 1.6.3 Buncefield 35 1.7 Other Ignition Topics - Hydrogen 36 1.7.1 Ignition Mechanisms 36 1.7.2 Other Hydrogen Ignition Topics 37 2 ESTIMATION METHODS 39 2.1 Introduction 39 2.1.1 Event Tree 39 2.1.2 Failure Frequency Data for Use in Event Trees 41 2.1.3 Quantification of the Event Tree 41 2.2 Factors Influencing the Probability of Immediate Ignition 41 2.2.1 Temperature of Release Relative to the Autoignition Temperature 42 2.2.2 Minimum Ignition Energy (MIE) of Material Being Released 42 2.2.3 Pyrophoricity of Released Material 44 2.2.4 Pressure/Velocity of Discharge 44 2.2.5 Droplet Size 45 2.2.6 Presence of Particulates 46 2.2.7 Configuration/Orientation of Equipment Near/At the Point of Release 46 2.2.8 Temperature of Release (as it relates to its effect on MIE) 46 2.2.9 Phase of Release (API RBI) 47 2.2.10 Flash Point and Release Rate (TNO) 47 2.3 Factors Influencing the Probability of Delayed Ignition 47 2.3.1 Strength and Numbers of Ignition Sources 47 2.3.2 Duration of Exposure 51 2.3.3 Release Rate/Amount 51 2.3.4 Material Being Released 53 2.3.5 Release Phase/Flash Point/Boiling Point 53 2.3.6 Distance from Point of Release to Ignition Source 54 2.3.7 Meteorology 54 2.3.8 Events Originating Indoors 54 2.4 Factors Influencing the Probability of Explosion, Given Delayed Ignition 57 2.5 Potential Interdependence of Variables 57 2.6 Summary of Variables Used in Each Analysis Level 58 2.7 Basic (Level 1) Probability of Ignition Algorithms 59 2.7.1 Level 1 Algorithm for Probability of Immediate Ignition 59 2.7.2 Level 1 Algorithm for Probability of Delayed Ignition 60 2.8 Level 2 Probability of Ignition Algorithms 61 2.8.1 Level 2 Algorithm for Probability of Immediate Ignition 61 2.8.2 Level 2 Algorithm for Probability of Delayed Ignition 62 2.9 Advanced (Level 3) Probability of Ignition Algorithms 67 2.9.1 Level 3 Algorithm for Probability of Immediate Ignition 67 2.9.2 Level 3 Algorithm for Probability of Delayed Ignition 67 2.10 Developing Inputs When Chemical Properties Are Not Available 69 2.10.1 Estimating Input Properties of Chemicals Not in the Pick List 69 2.10.2 Estimating the Properties of Flammable Mixtures 71 2.11 Worked Example 73 2.11.1 Problem Statement 73 2.11.2 Level 1 Analysis 74 2.11.3 Level 2 Analysis 75 2.11.4 Level 3 Analysis 76 2.12 Application of the Models to a Study with Multiple Ignition Sources 77 3 TECHNICAL BACKGROUND AND DATA SOURCES 78 3.1 Introduction and Summary 78 3.2 Government-driven studies 82 3.2.1 Rew et al. 82 3.2.2 Bevi Risk Assessment Manual (TNO Purple Book) 91 3.2.3 HSE / Crossthwaite, et al. 95 3.2.4 HSE/Thyer 95 3.2.5 HSE/Gummer and Hawksworth - Hydrogen 97 3.2.6 Cawley/U.S. Bureau of Mines 98 3.2.7 Canvey 99 3.2.8 Witcofski (NASA) Liquid Hydrogen 100 3.3 Information Developed by Industry Groups 100 3.3.1 Cox/Lees/Ang 100 3.3.2 E&P Forum 103 3.3.3 API RBI 103 3.3.4 API RP 2216 108 3.3.5 IEEE 109 3.3.6 UK Energy Institute 110 3.4 Information Developed in Academia 113 3.4.1 Ronza, et al. 113 3.4.2 Offshore Explosions (Loughborough) 116 3.4.3 Srekl and Golob 116 3.4.4 Duarte et al. 117 3.4.5 Swain - Ignition of Hydrogen 118 3.4.6 Dryer et al. – Hydrogen and Light Hydrocarbons 118 3.4.7 Britton – Silanes and Chlorosilanes 119 3.4.8 Pesce et al. 120 3.5 Information Developed by Individual Companies 121 3.5.1 Spouge 121 3.5.2 Moosemiller 122 3.5.3 Johnson – Humans as Electrostatic Ignition Sources 123 3.5.4 Jallais – Hydrogen 125 3.5.5 Zalosh – Hydrogen 125 3.5.6 Smith - Pipelines 127 3.6 Studies Specific to Ignition of Sprays 128 3.6.1 Lee et al. 128 3.6.2 Babrauskas 130 3.7 Case Histories 131 3.7.1 Britton - External Ignition Events 131 3.7.2 Pratt - Gas Well and Pipeline Blowouts 132 3.7.3 Gummer and Hawksworth – Hydrogen Events 133 4 ADDITIONAL EXAMPLES 136 4.1 Introduction to Examples, and Potential “Lessons Learned” 136 4.1.1 “Reality” vs. Predictions 136 4.1.2 “Conservatism” – Does it Exist? 137 4.1.3 Cases where the Model may not be Appropriate or the Results Misinterpreted 138 4.1.4 Summary of Worked Examples 139 4.2 Worked Examples (based on other CCPS books) 140 4.2.1 “Vapor Cloud Explosion Hazard Assessment of a Storage Site” 140 4.2.2 “Open Field Release of Propane” 145 4.2.3 “Release from Pipeline” 149 4.3 Worked Examples (chemical and petrochemical plants) 152 4.3.1 “Ethylene Tubing Failure” 152 4.3.2 “Benzene Pipe Rupture” 154 4.3.3 “Spill from Methyl Ethyl Ketone Tank” 155 4.3.4 “Indoor Puncture of MEK Tote” 158 4.3.5 “Elevated Release” 161 4.4 Worked Examples (oil refineries) 164 4.4.1 “Gasoline Release from a Sight Glass” 164 4.4.2 “Overfilling a Gasoline Storage Tank” 168 4.4.3 “Overfilling a Propane Bullet” 170 4.4.4 “Hydrogen Release from a Sight Glass” 172 4.5 Worked Examples (Unusual Cases) 174 4.5.1 “Indoor Acid Spill - Ventilation Model” 174 4.5.2 “Release of Ammonia” 179 4.6 Worked Examples (‘Out of Scope’ Cases) 180 4.6.1 “Release of Gas from an Offshore Platform Separator” 180 4.6.2 “Dust Ignition” 183 4.7 Worked Examples of the Benefits of Plant Modifications and Design Changes 186 4.7.1 “Ignition by Hot Surfaces” 186 4.7.2 Release Prevention 189 4.7.3 Duration of Exposure 189 4.7.4 Benefit of Improved Ventilation of Indoor Releases – Continuation of “Indoor Acid Spill” Example 192 5 SOFTWARE ILLUSTRATION 194 5.1 Explanation and Instructions for Software Tool 194 5.2 Opening the Software Tool 194 5.3 General Inputs and Outputs 195 5.4 Level 1 Inputs 196 5.5 Level 2 Analyses 198 5.6 Level 3 Analyses 200 5.7 Explosion Probability 200 5.8 Illustrations of Software Use 201 5.8.1 “Vapor Cloud Explosion Hazard Assessment of a Storage Site” (example from Section 4.2.1) 201 5.8.2 “Open Field Release of Propane” (example from Section 4.2.2) 204 APPENDIX A. CHEMICAL PROPERTY DATA 207 APPENDIX B. OTHER MODELS FOR CONSIDERATION 213

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Book SynopsisComprehensive coverage on the growing science and technology of producing ethanol from the world's abundant cellulosic biomass The inevitable decline in petroleum reserves and its impact on gasoline prices, combined with climate change concerns, have contributed to current interest in renewable fuels.Table of ContentsPreface xvii Part 1 Introduction to Cellulosic Ethanol 1 1 Renewable Fuels 3 1.1 Introduction 3 1.2 Renewable Energy 6 1.3 Biofuels 7 1.4 Renewable Energy in the United States 14 1.5 Renewable Fuel Legislature in the United States 20 References 25 2 Bioethanol as a Transportation Fuel 29 2.1 Introduction — History of Bioethanol as a Transportation Fuel 29 2.2 Alcohol Fuels 31 2.3 Fuel Characteristics of Ethanol 31 2.4 Corn and Sugarcane Ethanol 34 2.5 Advantages of Cellulosic Ethanol 35 References 40 3 Feedstocks for Cellulosic Ethanol Production 43 3.1 Introduction 43 3.2 Cellulosic Ethanol Feedstock Types 46 3.3 Potential of Agricultural Wastes 46 3.4 Major Crop Residue Feedstock 50 3.5 Forestry Residue, Logging and Mill Residue 68 3.6 Grass Feedstocks 70 3.7 Purpose-Grown Trees as Feedstock 92 3.8 Municipal and Other Waste as Feedstock for Cellulosic Ethanol 101 References 108 Part 2 Aqueous Phase Biomass Hydrolysis Route 131 4 Challenges in Aqueous-Phase Biomass Hydrolysis Route: Recalcitrance 133 4.1 Introduction – Two Ways to Produce Cellulosic Ethanol 133 4.2 Challenges in Aqueous-Phase Biomass Hydrolysis 134 4.3 Structure of Plant Cells and Lignocellulosic Biomass 135 4.4 Major Components of Lignocellulosic Biomass 137 4.5 Cellulose Recalcitrance 140 References 143 5 Pretreatment of Lignocellulosic Biomass 147 5.1 Introduction 147 5.2 Different Categories of Pretreatment Methods 150 5.3 Physical Pretreatment 150 5.4 Physicochemical Pretreatment 153 5.5 Chemical Pretreatment 177 5.6 Biological Pretreatment 190 5.7 Conclusion 191 References 197 6 Enzymatic Hydrolysis of Cellulose and Hemicellulose 219 6.1 Introduction 219 6.2 Enzymatic Actions on Lignocellulosic Biomass 220 6.3 Enzymatic Hydrolysis of Cellulose 221 6.4 Enzymatic Hydrolysis of Hemicellulose 233 6.5 Future Directions in Enzymatic Cellulose Hydrolysis Research 237 References 239 7 Acid Hydrolysis of Cellulose and Hemicellulose 247 7.1 Introduction 247 7.2 Concentrated Acid Hydrolysis 248 7.3 Dilute Acid Hydrolysis 252 7.4 Ionic Liquid-Based Direct Acid Hydrolysis 262 7.5 Solid Acid Hydrolysis 269 References 275 8 Fermentation I – Microorganisms 283 8.1 Introduction 283 8.2 Detoxification of Lignocellulosic Hydrolyzate 284 8.3 Separate Hydrolysis and Fermentation (SHF) 288 8.4 Microorganisms Used in the Fermentation 288 8.5 Fermentation Using Yeasts 289 8.6 Fermentation Using Bacteria 294 8.7 Simultaneous Saccharification and Fermentation (SSF) 300 8.8 Immobilization of Yeast 317 References 322 9 Fermentation II – Fermenter Configuration and Design 339 9.1 Introduction 339 9.2 Batch Fermentation 340 9.2.1 Examples of Batch Fermentation 340 9.3 Fed-Batch Fermentation 340 9.4 Continuous Fermentation 346 9.5 New Directions in Fermenter Configuration and Design 352 References 353 10 Separation and Uses of Lignin 357 10.1 Introduction 357 10.2 Structure of Lignin 359 10.3 Separation of Lignin in the Cellulosic Ethanol Process 360 10.4 Physical and Chemical Properties of Lignin 363 10.5 Applications of Lignin 365 10.5.1 Lignin-Based Phenol Formaldehyde Resins 365 References 373 Part 3 Biomass Gasification Route 381 11 Biomass Pyrolysis and Gasifier Designs 383 11.1 Introduction 383 11.2 Chemistry of the Conversion of Biomass to Syngas 384 11.3 Classifications of Biomass Gasifiers 387 11.4 Fixed-Bed Gasifier 388 11.5 Fluidized-Bed Gasifier 389 11.6 Bubbling Fluidized-Bed (BFB) Gasifier 390 11.7 Circulating Fluidized-Bed (CFB) Gasifier 392 11.8 Allothermal Dual Fluidized-Bed (DFB) Gasifier 392 11.9 Entrained-Flow Gasifier 395 11.10 Syngas Cleaning 396 11.11 Tar Control and Treatment Methods 403 References 403 12 Conversion of Syngas to Ethanol Using Microorganisms 407 12.1 Introduction 407 12.2 Metabolic Pathways 410 12.3 Microorganisms Used in Syngas Fermentation 414 12.4 Biochemical Reactions in Syngas Fermentation 414 12.5 The Effects of Operation Parameters on Ethanol Yield 416 12.6 Syngas Fermentation Reactors 424 12.7 Industrial-Scale Syngas Fermentation and Commercialization 426 References 427 13 Conversion of Syngas to Ethanol Using Chemical Catalysts 433 13.1 Introduction 433 13.2 Homogeneous Catalysts 434 13.3 Introduction to Heterogeneous Catalysts 437 13.4 Heterogeneous Catalyst Types 437 13.5 Rhodium-Based Catalysts 438 13.6 Copper-Based Modified Methanol Synthesis Catalysts 449 13.7 Modified Fischer-Tropsch-Type Catalysts 455 13.8 Molybdenum-Based Catalysts 456 13.9 Catalyst Selection 459 References 461 Part 4 Processing of Cellulosic Ethanol 467 14 Distillation of Ethanol 469 14.1 Introduction 469 14.2 Distillation of the Beer 470 14.3 How Distillation Works 470 14.4 Conventional Ethanol Distillation System 472 14.5 Steam Generation for Distillation Process 475 14.6 Studies on Development of Hybrid Systems for Ethanol Distillation 476 References 479 15 Dehydration to Fuel Grade Ethanol 481 15.1 Introduction 481 15.2 Dehydration Methods 482 15.3 Adsorption Method 482 15.4 Azeotropic Distillation Method 488 15.5 Extractive Distillation Methods 491 15.6 Membrane-Based Pervaporation Methods 494 15.7 Other Dehydration Methods 498 15.8 Comparisons of Common Dehydration Methods 498 References 500 Part 5 Fuel Ethanol Standards and Process Evaluation 507 16 Fuel Ethanol Standards, Testing and Blending 509 16.1 Introduction 509 16.2 Fuel Grade Ethanol Standards in the United States 510 16.3 Quality Assurance and Test Methods 514 16.4 European Fuel Ethanol Standards 517 16.5 Material Safety Data Sheet (MSDS) for Denatured Fuel Ethanol 518 16.6 Gasoline Ethanol Blends 520 16.7 Engine Performance Using Gasoline Ethanol Blends 524 References 528 17 Techno-Economic Analysis and Future of Cellulosic Ethanol 531 17.1 Introduction 531 17.2 Techno-Economic Aspects of Biomass Hydrolysis Process 532 17.3 Techno-Economic Aspects of Biomass Gasification Process 533 17.4 Comparison of Biomass Hydrolysis and Gasification Processes 539 17.5 Some Cellulosic Plants around the World 540 17.6 Challenges in Cellulosic Ethanol 550 17.7 Future Prospects of Cellulosic Ethanol 553 References 554 Appendix 1 557 Index

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Book SynopsisThis book describes methods and procedures for preparing PET radiopharmaceuticals, and highlights new methods for conducting radiochemical reactions with carbon-11 (C11) and fluorine-18 (F18), which are two of the most commonly used radionuclides in positron emission tomography (PET) imaging. Provides reliable methods for radiochemical syntheses and reactions, including all essential information to duplicate the procedure Eliminates the time-consuming process of searching journal articles and extracting pertinent details from lengthy experimental sections or supporting information Focuses on an emerging and important area for pharmaceutical and medical applications Encompasses technical, regulatory, and application aspects Includes solid-phase radiochemistry, transition-metal catalyzed radiochemistry, microfluidics, click chemistry, green radiochemistry and new strategies for radiopharmaceutical quality controlTable of ContentsContributors xi Editorial Preface xvii Abbreviations xix PART I FLUORINE-18 LABELED RADIOPHARMACEUTICALS 1 1. Synthesis of (−)-[18F]Flubatine ([18F]FLBT) 3Megan N. Stewart, Brian G. Hockley, and Peter J. H. Scott 2. Synthesis of [18F]-(−)Fluoroethoxy Benzovesamicol ([18F]FEOBV) 13Brian G. Hockley, Megan N. Stewart, and Peter J. H. Scott 3. Synthesis of [18F]Fluoromethylcholine ([18F]FCH) via [18F]Fluoromethyl Tosylate 21Melissa E. Rodnick, Allen F. Brooks, Brian G. Hockley, Bradford D. Henderson, and Peter J. H. Scott 4. Radiosynthesis of [18F]Flotegatide ([18F]RGD-K5) 29Hartmuth C. Kolb, Fanrong Mu, Umesh Gangadharmath, Vani P. Mocharla, Zhihong Zhu, Ashok Chaudhary, and Joseph C. Walsh 5. Synthesis of 3-[18F]Fluoro-5-(2-Pyridinylethynyl) Benzonitrile ([18F]FPEB) 41Steven H. Liang, Daniel L. Yokell, Raul N. Jackson, Peter A. Rice, Eli Livni, David Alagille, Gilles Tamagnan, Thomas Lee Collier, and Neil Vasdev 6. Radiosynthesis of 2′-Deoxy-2′-[18F]Fluoro-5-Methyl-1-β-d-Arabinofuranosyluracil ([18F]FMAU) 53Kai Chen and Peter S. Conti PART II CARBON-11 LABELED RADIOPHARMACEUTICALS 63 7. Synthesis of N-[11C]Methyl-4-Piperidinyl Propionate ([11C]PMP) 65Xia Shao and Peter J. H. Scott 8. Synthesis of 1-(2,4-Dichlorophenyl)-4-Cyano-5-(4-[11C]methoxyphenyl)-N-(Piperidin-1-yl)-1H-Pyrazole-3-Carboxamide ([11C]OMAR) 73Xia Shao, Keunsam Jang, and Peter J. H. Scott 9. Synthesis of Carbon-11 Labeled (+)-4-Propyl-3,4,4a,5,6,10b-Hexahydro-2H-Naphtho[1,2-b][1,4]Oxazin-9-Ol ([11C]-(+)-PHNO) 81Christophe Plisson, Joaquim Ramada-Magalhaes, and Jan Passchier 10. Synthesis of (R)-[N-Methyl-11C]PK11195 93Vítor H. Alves, Antero J. Abrunhosa, and Miguel Castelo-Branco PART III OTHER RADIOPHARMACEUTICALS 103 11. Synthesis of Oxygen-15 Water ([15O]H2O) 105David W. Dick and G. Leonard Watkins PART IV NEW METHODS FOR THE SYNTHESIS AND QUALITY CONTROL OF RADIOPHARMACEUTICALS 115 12. Direct, Nucleophilic Radiosynthesis of [18F]Trifluoroethyl Tosylate 117Patrick J. Riss, Waqas Rafique, and Franklin I. Aigbirhio 13. Synthesis of [18F]N-Methyl Lansoprazole via Generation of a [18F]Trifluoromethyl Group 123Allen F. Brooks, Melissa E. Rodnick, Garret M. Carpenter, and Peter J. H. Scott 14. [18F]Fluorination of (Mesityl)(Aryl)Iodonium Salts 129Naoko Ichiishi, Allen F. Brooks, Joseph J. Topczewski, Melissa E. Rodnick, Melanie S. Sanford, and Peter J. H. Scott 15. Pd(IV)-Mediated Fluorination of Arenes with [18F]F– for PET Imaging 139Nathan J. Schauer, Stephen M. Carlin, Hong Ren, and Jacob M. Hooker 16. Silicon Fluoride Acceptors (SIFAs) for Peptide and Protein Labeling with 18F 149Ralf Schirrmacher, Alexey Kostikov, Carmen Wängler, Klaus Jurkschat, Vadim Bernard-Gauthier, Esther Schirrmacher, and Björn Wängler 17. Solid Phase Synthesis of [18F]-2-Fluoro-2-Deoxy-d-Glucose: A Resin-Linker-Vector (RLV) Approach 163Lynda J. Brown, Imtiaz Khan, Harry J. Wadsworth, Alexander Jackson, Nianchun Ma, Nicolas Millot, Sue M. Champion, Denis R. Bouvet, Alex M. Gibson, and Richard C. D. Brown 18. Production and Reaction of [11C]Carbon Disulfide for the Synthesis of [11C]Dithiocarbamates 177Philip W. Miller 19. One-Pot, Direct Incorporation of [11CO2] into Carbamates 185Christian K. Moseley and Jacob M. Hooker 20. Radiosynthesis of [11C]Carboxamides via Reaction of [11C]CO2 Captured by a Cu(I)-Based Catalyst System with Boronic Acid Ester Precursors 197Patrick J. Riss, Shuiyu Lu, Sanjay Telu, Franklin I. Aigbirhio, and Victor W. Pike 21. Ethanol as a Solvent for Carbon-11 Radiochemistry 207Xia Shao, Maria V. Fawaz, Keunsam Jang, and Peter J. H. Scott 22. Synthesis and Applications of [11C]Hydrogen Cyanide 233Xia Shao, Melissa E. Rodnick, Allen F. Brooks, and Peter J. H. Scott 23. Determination of Radiochemical Purity and Radiochemical Identity of [13N]NH3 Using Thin Layer Chromatography 241Peter A. Rice and Daniel L. Yokell Appendix 1: Supplier Information 247 Index 253

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Book SynopsisThe newfound stability of carbenes has led to their development as catalysts and ligands for metal complexes of vast potential, including biomolecule labeling and surface modification of materials.Trade Review“Overall I think that this book is generally well presented and free of obvious mistakes. I very much like the fact that there is consistency in structure throughout each chapter, indicating that the editorial process has been thorough. In particular, the conclusion and outlook sections provide a valuable summary of the state-of-the-art in each area, and how the future is foreseen.” (Applied Organometallic Chemistry, 10 October 2014) Table of ContentsPreface PART 1: PROPERTIES AND REACTIONS OF CARBENES 1 Carbene Stability S. Gronert and R. M. O’Ferrall 2 Stable Carbenes J. P. Moerdyk and C. W. Bielawski 3 Acid-Base Chemistry of Carbenes A. M. O’Donoghue and R. S. Massey 4 Computational Methods for the Study of Carbenes and their Excited States H. L. Luk, S. Vyas, and C. M. Hadad 5 Dynamics in Carbene Reactions D. Merrer, K. Houk, and L. Xu 6 Ultrafast Kinetics of Carbene Reactions G. Burdzinski and M. S. Platz 7 Tunneling in the Reactions of Carbenes and Oxacarbenes D. Gerbig and P. R. Schreiner 8 Carbodicarbenes G. Frenking and R. Tonner 9 Catalytic Reactions with N-Mesityl Substituted N-Heterocyclic Carbenes J. Mahatthananchai and J. W. Bode 10 Supramolecular Carbene Chemistry U. Brinker, J.-L. Mieusset, and M. G. Rosenberg PART 2: METAL CARBENES 11 Modern Lithium Carbenoid Chemistry V. Capriati 12 Rhodium Carbenes H. Davies and B. Parr 13 Ruthenium Carbenes S. T. Diver and J. M. French 14 Nucleophilic Carbenes of the Chromium Triad Z. J. Tonzetich 15 Cobalt-Mediated Carbene Transfer Reactions X. Cui and X. P. Zhang 16 Gold Carbenes L. Zhang

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Book SynopsisThis Dictionary provides over 75,000 entries covering all areas of chemistry, such as Chemical Biology, Biochemistry, Biotechnology, and Nanochemistry, plus relevant terms in related spheres of expertise. In order to prepare this Second Edition, the First Edition was completely revised, and over 35,000 new terms were added.Table of ContentsPreface and Notes on the Use of This Dictionary v Prologo y notas sobre el uso de este diccionario vi Acknowledgments vii Reconocimientos viii English to Spanish / Inglés a Espanol A - Z 3 - 482 Greek Letters 485 Espanol a Ingles / Spanish to English A - Z 489 - 970

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Book SynopsisCovering fundamentals and new developments in phytotherapy, this book combines pharmaceutical sciences and chemistry with clinical issues. Helps readers better understand phytotherapy and learn the fundamentals of and how to analyze phytotherapeutic agents Discusses phytotherapy in modern medicine, chemoprevention of disease, and alternatives to western medicines for specific diseases Chapters summarizes the uses and applications of phytomedicines, by type like Chinese, Greco-Arab, Indian, European, and Ayurvedic Includes international regulatory perspectives and discusses emerging regulations for various established and emerging marketsTable of ContentsList of Contributors xvii Preface xxi 1 Phytotherapies—Past, Present, and Future 1Iqbal Ramzan and George Q. Li 1.1 Overview of Phytotherapy 1 1.2 Preclinical Research on Phytotherapies 3 1.3 Clinical Research on Phytotherapies 6 1.4 Safety of Phytotherapies 8 1.5 Profile of Research in Complementary Medicine 9 1.6 Summary and Future Directions 12 References 12 2 Quality Control and Quality Assurance of Phytomedicines: Key Considerations, Methods, and Analytical Challenges 18Wai‐Ping Yau, Cheong Hian Goh, and Hwee‐Ling Koh 2.1 Introduction 18 2.2 Key Considerations in QC/QA of Phytomedicines 20 2.3 Methods for QC/QA of Phytomedicines 27 2.4 Challenges 37 2.5 Conclusions 40 References 40 3 Preclinical (In Vivo) and Laboratory (In Vitro) Evidence of Phytomedicine Efficacy 49Mohi Iqbal Mohammed Abdul and Tom Hsun‐Wei Huang 3.1 Introduction to Development of Drugs from Nature 49 3.2 Use of In Vitro and in Vivo Models in Herb Drug Research: Learning Thus Far 50 3.3 Cardiovascular‐ and Stroke‐Related Diseases: In Vitro and In Vivo Focus 53 3.4 Conclusions 60 References 61 4 Clinical Efficacy Trials with Natural Products and Herbal Medicines 65Christina L. Nance 4.1 Introduction 65 4.2 Trials in Various Disease States 66 4.3 Natural Product: Green Tea 73 4.4 EGCG Clinical Trials 75 4.5 Human Clinical Study: EGCG and HIV‐1 Infection 78 4.6 Conclusion 80 References 80 5 Novel Formulations and Drug Delivery Systems for Phytotherapies 89Shengpeng Wang, Meiwan Chen, Qi (Tony) Zhou, and Hak‐Kim Chan 5.1 Limitations of Conventional Formulations for Herbal Medicines 89 5.2 Crucial Issues of Developing Novel Delivery Systems for Herbal Medicines 91 5.3 Novel Delivery Systems of Herbal Medicines 93 5.4 Summary 96 References 97 6 Phytotherapies Used by Indigenous Populations 101Bradley S. Simpson and Susan J. Semple 6.1 Introduction 101 6.2 Phytotherapies of Indigenous Australians 103 6.3 Challenges of a Changing Environment 114 6.4 Conclusions 117 References 118 7 Phytotherapies from Traditional Chinese Medicine 122Michael Rieder 7.1 Traditional Chinese Medicine 122 7.2 Key Concepts in Traditional Chinese Medicine 124 7.3 Herbal Medicine and Traditional Chinese Medicine 126 7.4 Issues in the Development of Phytotherapy from Traditional Chinese Medicine 130 7.5 Phytotherapies Developed from Traditional Chinese Medicine 131 7.6 Huang Qin Tang and the Development of PHY906 134 7.7 Ginseng 136 7.8 Moving Forward 138 References 138 8 Integrating Traditional Greco‐Arab and Islamic Diet and Herbal Medicines in Research and Clinical Practice 142Bashar Saad 8.1 Introduction 142 8.2 Food Therapy in Greco‐Arab and Islamic Medicine 147 8.3 Medicinal Plants 157 References 177 9 Evolution of Herbal Medicines in Europe and its Relationship with Modern Medicine 183Elizabeth M. Williamson and Kelvin Chan 9.1 Background 183 9.2 Historical Perspective 184 9.3 European Herbal Medicine: Relationship with Modern Medicine 194 9.4 Summary 194 References 196 10 Chemical Classification and Chemistry of Phytotherapeutics Constituents 199Pei H. Cui and Colin C. Duke 10.1 Introduction 199 10.2 Phytochemicals 201 10.3 Other Phytochemicals 215 10.4 Medicinal Effects Relating to Dietary Intake 217 10.5 Natural Products as Leads for Drug Development 223 10.6 Summary 230 References 230 11 Therapeutic Potential of Ginsenosides in Management of Atherosclerosis 236Xiao‐Jing Zhang, Huanxing Su, Yi-Tao Wang, and Jian-Bo Wan 11.1 Introduction 236 11.2 Chemical Diversity of Ginsenosides and Distribution 238 11.3 Anti‐Atherosclerotic Effects of Ginsenosides 240 11.4 Underlying Mechanisms of Ginsenosides Against Atherosclerosis 244 11.5 Conclusions and Future Perspectives 258 Acknowledgments 258 References 258 12 Phytotherapy Pharmacophores for Major Cellular Drug Targets 268Jennifer A. Ong, Paul W. Groundwater, and David E. Hibbs 12.1 Introduction 268 12.2 What is a Pharmacophore? 269 12.3 Pharmacophore Models of Cardiovascular Drugs 270 12.4 Pharmacophore Models for Anticancer Drugs 285 12.5 Pharmacophore Models for Anti‐Inflammatory Drugs 290 12.6 Pharmacophore Models for Anti‐Infective Drugs 297 12.7 Pharmacophore Models for Neurological Drugs 299 12.8 Pharmacophore Models for Miscellaneous Drugs 305 12.9 Conclusions 309 References 309 13 Use of Kava as a Phytotherapeutic Agent and Kava‐Related Hepatotoxicity 312Dong Fu and Iqbal Ramzan 13.1 Introduction 312 13.2 Active Components in Kava 313 13.3 Therapeutic Applications of Kava 314 13.4 Pharmacology of Kava 314 13.5 Side Effects of Kava 317 13.6 Hepatotoxicity of Kava 318 13.7 Summary and Future Challenges 322 References 323 14 Phytotherapies as New Drug Sources: Gossypol and Curcumin 330Vivian Wan Yu Liao, Rajeshwar Narlawar, David E. Hibbs, and Paul W. Groundwater 14.1 Botanical Sources of Gossypol and Curcumin 330 14.2 Stereoisomerism, Tautomerism, and Reactivity 332 14.3 Biological Activity of Gossypol and its Analogues 337 14.4 Biological Activity of Curcumin and its Analogues 346 References 360 15 Phytotherapies for the Management of Obesity and Diabetes 370Michel Rapinski and Alain Cuerrier 15.1 Introduction 370 15.2 Plants from the North American Pharmacopoeia 372 15.3 Pharmacological Screening: Providing Empirical Evidence for Phytotherapies 379 15.4 Community‐Based Participation: Developing Phytotherapies from Traditional Knowledge 385 15.5 Conclusions 387 References 387 16 Phytotherapeutics for Cancer Therapy 394Daniel M.‐Y. Sze, Hao Liu, Maureen V. Boost, Raimond Wong, and Stephen Sagar 16.1 Introduction 394 16.2 Anticancer Phytotherapeutics With NK Enhancement 395 16.3 Conclusions 423 References 425 17 Phytomedicines for Fatty Liver Disease and Functional Gastrointestinal Conditions 429George Q. Li, Moon‐Sun Kim, Fangming Jin, and Jun‐Lae Cho 17.1 Introduction 429 17.2 Phytomedicines for FLD 430 17.3 Phytomedicines for IBS 439 17.4 Phytomedicines for Constipation 444 17.5 Summary and Future Perspectives 448 References 448 18 Phytomedicines for Inflammatory Conditions 464Sigrun Chrubasik‐Hausmann 18.1 Traditional Medicines for Inflammatory Conditions in Europe 464 18.2 Twenty‐First‐Century Update on Paids 465 18.3 Oral Extracts from Salix Species 465 18.4 Oral Extracts from Harpagophytum procumbens 468 18.5 Oral Avocado–Soybean Unsaponifiables 469 18.6 Oral Extracts From Tripterygium wilfordii 473 18.7 Oral Paids Containing Unsaturated Fatty Acids 475 18.8 Other Oral Paids 476 18.9 Topical Paids 477 References 478 19 Phytotherapies for Infectious Diseases: Are These Really Useful? 483Gail B. Mahady, Gabrielle Escalante, Pooja Mikkilineni, Laura J. Mahady, Temitope O. Lawal, and Bolanle A. Adeniyi The History of Medicine 483 19.1 Introduction 484 19.2 Historical Precedent for Natural Products as Antimicrobial Drugs 486 19.3 Are Phytotherapies Useful for the Treatment of Infectious Diseases? 487 19.4 Naturally Occurring Compounds that may Reduce Zoonosis 495 19.5 Synergistic and Additive Effects with Antibiotics 496 19.6 New Emerging Infectious Diseases and those with no Known Treatments 496 19.7 SARS 497 19.8 Reducing MRSA Carriage 498 19.9 Conclusions 499 References 500 20 Phytomedicines for CNS Disorders: Safety Issues for use with Antiepileptic Drugs 504Sophia Yui Kau Fong, Rosina Yau Mok, Qiong Gao, Yin Cheong Wong, and Zhong Zuo 20.1 Introduction 504 20.2 Methodology of Systematic Literature Search 506 20.3 Pharmacokinetic Interactions 506 20.4 Pharmacodynamic Interactions 512 20.5 Conclusions 524 References 524 21 Phytotherapies: Drug Interactions in Cancer 536Andrew J. McLachlan and Stephen J. Clarke 21.1 Introduction 536 21.2 Use of Herbal and Complementary Medicines by People Living with Cancer 537 21.3 Mechanisms of Phytotherapy–Drug Interactions 538 21.4 Selected Examples of Phytotherapy Medicines that have the Potential to Cause Drug Interactions in Cancer 540 21.5 Future Perspectives: Need for Evidence and Advice to Cancer Patients and Physicians 546 21.6 Conclusions 547 Acknowledgments 547 Conflict of Interest 547 References 547 22 Quality Use of Medicines: Considerations in Phytotherapy 554Lynn Weekes 22.1 Introduction 554 22.2 Relevance of Qum for Herbal Medicines 556 22.3 Use of Phytotherapies by Consumers 558 22.4 Consumer Attitudes and Beliefs about Herbal Medicines 559 22.5 Applying the Qum Framework to Phytotherapies 561 22.6 Building Blocks for Quality Use of Herbal Medicines 566 22.7 Conclusion 570 References 570 23 Intellectual Property and Patent Issues with Phytotherapy Products 573Gint Silins, Jennifer Tan, and Kelvin Chan 23.1 Introduction 573 23.2 IP Rights—Phyto‐Industry 575 23.3 Brief Overview of Patents and the Patenting Process 578 23.4 Other Types of IP Rights 585 23.5 Patenting Trends for Phytotherapeutics 587 23.6 Traditional Knowledge and IP Rights 587 Disclaimer 589 References 590 24 International Regulatory Status of Phytotherapies 593Ernest V. Linek 24.1 Introduction 593 24.2 Specific Country Regulations 596 24.3 Future of Phytotherapies: World Health Organization (WHO) 631 Further Reading 634 Index 635

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Book SynopsisThe Chemistry of Food Additives and Preservatives is an up-to-date reference guide on the range of different types of additives (both natural and synthetic) used in the food industry today. It looks at the processes involved in inputting additives and preservatives to foods, and the mechanisms and methods used.Table of ContentsPreface ix Introduction x List of Abbreviations xiii 1 Antioxidants and Radical Scavengers 1 1.1 Chemistry of free radicals and antioxidants 1 1.2 Types of antioxidants 4 1.3 Efficacy of different antioxidants 7 1.4 Action mechanisms of antioxidants 9 1.5 Structure–activity relationship of antioxidants 11 1.6 Factors affecting antioxidant activity 14 1.7 Quality assessment of dietary antioxidants 15 1.8 How safe are food antioxidants? 23 1.9 Summary 25 References 25 Further reading 31 2 Emulsifiers 33 2.1 Mechanisms of food emulsifiers 33 2.2 The role of emulsifiers in foods 35 2.3 Classification of emulsifiers 37 2.4 Types of food emulsifiers 38 2.5 Quality and analysis of food emulsifiers 58 2.6 Foods containing emulsifiers 60 References 62 Further reading 64 3 Stabilisers, Gums, Thickeners and Gelling Agents as Food Additives 67 3.1 Introduction to stabilisers, thickeners and gelling agents 67 3.2 Polysaccharides 68 3.3 Protein-based food stabilisers 77 3.4 Quality control of food stabilisers and thickeners 78 3.5 Analytical methods 78 References 80 Further reading 82 4 Sweeteners 83 4.1 Introduction to sweeteners 83 4.2 Properties of sweeteners 84 4.3 Intense sweeteners in foods 86 4.4 Bulk food sweeteners 92 4.5 Quality assurance and quality control 95 4.6 Analytical methods 98 References 98 Further reading 100 5 Fragrances, Flavouring Agents and Enhancers 102 5.1 Introduction to flavours and flavouring agents 102 5.2 Classification of food flavourings 103 5.3 Chemistry of food flavourings 105 5.4 Quality control of flavour compounds 119 5.5 Analytical methods for the analysis of food flavourings 120 References 121 Further reading 124 6 Food Acids and Acidity Regulators 125 6.1 What are food acids and acid regulators? 125 6.2 Types of food acids 126 6.3 Uses of food acids 128 References 129 Further reading 130 7 Food Colour and Colour Retention Agents 131 7.1 Why add colourants to foods? 131 7.2 Classification of food colourants 131 7.3 Overview of colourants 133 7.4 Chemistry of food colourants 143 7.5 Extraction from natural sources 143 7.6 Quality assurance of food colourants 144 7.7 Analytical methods 145 References 145 8 Flour Treatment/Improving Agents 148 8.1 What are flour treatment/improving agents? 148 8.2 Flour maturing agents 148 8.3 Flour bleaching agents 151 8.4 Flour processing agents 154 References 154 9 Anticaking Agents 155 9.1 The caking phenomena 155 9.2 Mechanisms of caking 156 9.3 Classification of anticaking agents 159 9.4 Anticaking agents in use 159 References 160 Further reading 161 10 Humectants 162 10.1 Humectants and moisture control 162 10.2 Classification of humectants 162 References 166 11 Antifoaming Agents 167 11.1 Sources of foam in food processing 167 11.2 Properties of antifoaming agents 168 11.3 Mechanisms of antifoaming and foam destabilisation 168 11.4 Synthetic defoamers 168 11.5 Natural defoamers 170 References 171 12 Minerals and Mineral Salts 172 12.1 The importance of minerals and mineral salts 172 12.2 Inorganic mineral salts 173 12.3 Organic mineral salts 175 References 176 13 Dietary Supplements 177 13.1 Introduction to dietary supplements 177 13.2 Classification of vitamins 178 13.3 Vitamin A (retinols) 179 13.4 Vitamin D (calciferol) 189 13.5 Vitamin E 194 13.6 Vitamin K 196 13.7 Vitamin B 199 13.8 Vitamin C (L-ascorbic acid) 210 13.9 Conclusions 212 References 213 14 Glazing Agents 218 14.1 Introduction to glazing agents 218 14.2 Mineral hydrocarbon glazes 218 14.3 Chemistry of MHCs 220 14.4 Conclusion 222 References 223 15 Preservatives 224 15.1 Preservatives: Past, present and future 224 15.2 Natural food preservatives 226 15.3 Traditional food preservation methods 231 15.4 Artificial preservative agents 232 15.5 Modern food preservation techniques 235 15.6 Safety concerns of food preservatives 237 15.7 Analytical methods for the determination of preservative residues 238 15.8 Conclusions 238 References 238 Further reading 243 16 Nutraceuticals and Functional Foods 244 16.1 What are nutraceuticals? 244 16.2 Classification of nutraceuticals 245 16.3 Mechanisms of action 246 16.4 Conclusion 253 References 254 Further reading 257 17 Nutritional Genomics: Nutrigenetics and Nutrigenomics 258 17.1 Nutrition and gene expression 258 17.2 Nutrigenetic areas of application 260 17.3 Analytical methods for nutrigenetical food functions 268 17.4 Conclusion 270 References 270 18 Probiotic Foods and Dietary Supplements 274 18.1 Microbial gut flora activity 274 18.2 Probiotics and nutrition 275 18.3 Probiotics and health 275 18.4 Safety and stability of probiotics 277 18.5 Suitable dietary carriers for probiotics 278 18.6 Assessment of probiotics in foodstuffs and supplements 279 18.7 Conclusions 280 References 281 19 Prebiotics 285 19.1 Prebiotics and health 285 19.2 Factors that influence the activity and effectiveness of prebiotics 286 19.3 Types of oligosaccharides 286 19.4 Quality assessment of prebiotics 289 19.5 Conclusions 290 References 290 20 Synbiotics 291 20.1 Synbiotic foods and health 291 20.2 Health benefits of synbiotics 292 20.3 Mechanism of action of synbiotics 293 20.4 The future of synbotic foods 294 References 294 21 Microencapsulation and Bioencapsulation 295 21.1 Introduction to microencapsulation and bioencapsulation 295 21.2 Commonly used food-grade microcapsules 297 21.3 Methods of food microencapsulation 303 21.4 Microencapsulation for food colourants 307 21.5 Bioencapsulation for probiotics 309 21.6 Conclusions 310 References 310 General Conclusions 314 Index 315

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Book SynopsisDescribes new state-of-the-science tools and their contribution to industrial R&D With contributions from leading international experts in the field, this book explains how scanning probe microscopy is used in industry, resulting in improved product formulation, enhanced processes, better quality control and assurance, and new business opportunities. Readers will learn about the use of scanning probe microscopy to support R&D efforts in the semiconductor, chemical, personal care product, biomaterial, pharmaceutical, and food science industries, among others. Scanning Probe Microscopy in Industrial Applications emphasizes nanomechanical characterization using scanning probe microscopy. The first half of the book is dedicated to a general overview of nanomechanical characterization methods, offering a complete practical tutorial for readers who are new to the topic. Several chapters include worked examples of useful calculations such as using Hertz mechanicTable of ContentsContributors List xiii Preface xv Acknowledgments xix 1. Overview of Atomic Force Microscopy 1 Dalia G. Yablon 1.1 A Word on Nomenclature 2 1.2 Atomic Force Microscopy—The Appeal to Industrial R&D 2 1.3 Mechanical Properties 5 1.4 Overview of AFM Operation 6 1.5 Nanomechanical Methods Surveyed in Book 11 1.6 Industries Represented 13 Acknowledgments 14 References 14 2. Understanding the Tip–Sample Contact: An Overview of Contact Mechanics from the Macro- to the Nanoscale 15 Tevis D. B. Jacobs, C. Mathew Mate, Kevin T. Turner, and Robert W. Carpick 2.1 Hertz Equations for Elastic Contact 15 2.2 Adhesive Contacts 22 2.3 Further Extensions of Continuum Contact Mechanics Models 29 2.4 Thin Films 34 2.5 Tangential Forces 37 2.6 Application of Continuum Mechanics to Nanoscale Contacts 42 Acknowledgments 44 Appendix 2A Surface Energy and Work of Adhesion 44 References 45 3. Understanding Surface Forces Using Static and Dynamic Approach–Retraction Curves 49 Sudharsan Balasubramaniam, Daniel Kiracofe, and Arvind Raman 3.1 Tip–Sample Interaction Forces 53 3.2 Static F–Z Curves 58 3.3 Dynamic Amplitude/Phase–Distance Curves 69 3.4 Brief Guide to VEDA Simulations 78 3.5 Conclusions 90 Glossary 91 References 93 4. Phase Imaging 95 Dalia G. Yablon and Greg Haugstad 4.1 Introduction 95 4.2 Bistability: Attractive and Repulsive Mode 97 4.3 Complications in Phase Quantification 107 References 113 5. Dynamic Contact AFM Methods for Nanomechanical Properties 115 Donna C. Hurley and Jason P. Killgore 5.1 Introduction 115 5.2 Force Modulation Microscopy (FMM) 121 5.3 Contact Resonance (CR) Techniques 125 5.4 Comparison of FMM and CR-FM 136 5.5 Other Dynamic Contact Approaches 138 5.6 Summary and Conclusions 140 Acknowledgments 141 Appendix 5A Data Analysis Procedure for Contact Resonance Spectroscopy Measurements 141 References 145 6. Guide to Best Practices for AFM Users 150 Greg Haugstad 6.1 Force–Distance Measurements—Instrumental Sources of Nonideality 151 6.2 Force–Distance Measurements—Physical Sources of Nonideality 157 References 161 7. Nanoindentation Measurements of Mechanical Properties of Very Thin Films and Nanostructured Materials at High Spatial Resolution 162 Steve J. Bull 7.1 Introduction 162 7.2 Bulk Materials 163 7.3 Coatings 176 7.4 Conclusions 188 Acknowledgments 188 References 188 8. Scanning Probe Microscopy for Critical Measurements in the Semiconductor Industry 190 Johann Foucher 8.1 Introduction 190 8.2 Critical Dimension in the Semiconductor Industry 191 8.3 CD Metrology Techniques for Production 192 8.4 Obtaining Accurate CD in the Semiconductor Industry 194 8.5 Hybrid Metrology as a Final Solution to Overcome CD-AFM, CD-SEM, and Scatterometry Intrinsic Limitations 203 8.6 Conclusion 208 References 208 9. Atomic Force Microscopy of Polymers 210 Andy H. Tsou and Dalia G. Yablon 9.1 Introduction 210 9.2 Tapping Phase AFM 213 9.3 Nanoindentation 217 9.4 Force Modulation 218 9.5 Pulsed Force Imaging 219 9.6 Force–Volume AFM 220 9.7 HarmoniX and Peak Force QNM Imaging 222 9.8 Summary 227 References 229 10. Unraveling Links between Food Structure and Function with Probe Microscopy 232 A. Patrick Gunning and Victor J. Morris 10.1 Introduction 232 10.2 Gels and Thickeners: Molecular Networks 236 10.3 Emulsions and Foams: Protein–Surfactant Competition 238 10.4 Interfacial Structure and Digestion: Designer Interfaces 241 10.5 Force Spectroscopy: Model Emulsions 244 10.6 Force Spectroscopy: Origins of Bioactivity 247 10.7 Conclusions 248 References 249 11. Microcantilever Sensors for Petrochemical Applications 251 Alan M. Schilowitz 11.1 Introduction 251 11.2 Background 252 11.3 Applications 257 11.4 Conclusion 266 References 267 12. Applications of Scanning Probe Methods in Cosmetic Science 270 Gustavo S. Luengo and Anthony Galliano 12.1 Introduction 270 12.2 Substrates of Cosmetics 271 12.3 Mechanical Properties and Modifications by Cosmetic Products 274 12.4 Scanning Probe Technologies Adapted to Cosmetic Science 275 12.5 Conclusions 285 References 285 13. Applications of Scanning Probe Microscopy and Nanomechanical Analysis in Pharmaceutical Development 287 Matthew S. Lamm 13.1 Introduction 287 13.2 Applications of SPM Imaging 288 13.3 SPM as a Screening Tool 291 13.4 Applications of Nanoindentation 293 13.5 Conclusion 299 Acknowledgments 299 References 300 14. Comparative Nanomechanical Study of Multiharmonic Force Microscopy and Nanoindentation on Low Dielectric Constant Materials 302 Katharine Walz, Robin King, Willi Volksen, Geraud Dubois, Jane Frommer, and Kumar Virwani 14.1 Introduction 302 14.2 Experimental 308 14.3 Results and Discussions 311 14.4 Conclusions 319 Acknowledgments 320 References 320 15. Nanomechanical Characterization of Biomaterial Surfaces: Polymer Coatings That Elute Drugs 323 Klaus Wormuth and Greg Haugstad 15.1 Introduction 323 15.2 Materials and Methods 325 15.3 Dexamethasone in PBMA or PBMA–PLMA Polymer Blends 327 15.4 Simvastatin in PEO–PBT Copolymers 337 15.5 Concluding Comments 340 Acknowledgments 341 References 341 Index 342

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Book SynopsisAlthough these reactions have been studied for a long time, cycloaddition chemistry makes frequent and considerable advances that requires chemists to keep constantly up-to-date with the practices and state-of-the-art.Table of ContentsPREFACE ix CONTRIBUTORS xi PART I [2+1] CYCLOADDITION 1 [2+1]-TYPE CYCLOPROPANATION REACTIONS 1 Akio Kamimura 2 N1 UNIT TRANSFER REACTION TO C__C DOUBLE BONDS 67 Satoshi Minakata, Youhei Takeda, and Kensuke Kiyokawa PART II [2+2] CYCLOADDITION 3 LEWIS BASE CATALYZED ASYMMETRIC FORMAL [2þ2] CYCLOADDITIONS 89 Andrew D. Smith, James Douglas, Louis C. Morrill, and Edward Richmond PART III [2+2] AND [4+2]/[2+2] CYCLOADDITION 4 CATALYTIC [2þ2] CYCLOADDITION OF SILYL ENOL ETHERS 115 Yosuke Yamaoka and Kiyosei Takasu PART IV [3+2] CYCLOADDITION 5 [3þ2] CYCLOADDITION OF a,b-UNSATURATED METAL–CARBENE COMPLEXES 135 Ryukichi Takagi and Manabu Abe 6 GEOMETRY-CONTROLLED CYCLOADDITION OF C-ALKOXYCARBONYL NITRONES: SYNTHETIC STUDIES ON NONPROTEINOGENIC AMINO ACIDS 151 Osamu Tamura 7 RECENT ADVANCES IN CATALYTIC ASYMMETRIC 1,3-DIPOLAR CYCLOADDITIONS OF AZOMETHINE IMINES, NITRILE OXIDES, DIAZOALKANES, AND CARBONYL YLIDES 175 Hiroyuki Suga and Kennosuke Itoh 8 CONDENSATION OF PRIMARY NITRO COMPOUNDS TO ISOXAZOLE DERIVATIVES: STOICHIOMETRIC TO CATALYTIC 205 Francesco De Sarlo and Fabrizio Machetti 9 CARBAMOYLNITRILE OXIDE AND INVERSE ELECTRON-DEMAND 1,3-DIPOLAR CYCLOADDITION 223 Nagatoshi Nishiwaki and Haruyasu Asahara PART V [3+2], [3+3], AND [4+2] CYCLOADDITION 10 CYCLOADDITION REACTIONS OF SMALL RINGS 241 Steven D. R. Christie and Hayley T. A. Watson PART VI [3+2] AND [5+1] CYCLOADDITION 11 DEVELOPMENT OF NEW METHODS FOR THE CONSTRUCTION OF HETEROCYCLES BASED ON CYCLOADDITION REACTION OF 1,3-DIPOLES 263 Yutaka Ukaji and Takahiro Soeta PART VII [3+3] CYCLOADDITION 12 A FORMAL [3þ3] CYCLOADDITION APPROACH TO NATURAL PRODUCT SYNTHESIS 283 Jun Deng, Xiao-Na Wang, and Richard P. Hsung PART VIII [4+2] CYCLOADDITION 13 [4þ2] CYCLOADDITION CHEMISTRY OF SUBSTITUTED FURANS 355 Scott Bur and Albert Padwa 14 SYNTHESIS OF SUBSTITUTED OLIGOACENES VIA DIELS–ALDER REACTIONS AND SUBSTITUENT EFFECTS ON MOLECULAR STRUCTURE, PACKING ARRANGEMENT, AND SOLID-STATE OPTICAL PROPERTIES 407 Chitoshi Kitamura 15 CYCLOREVERSION APPROACH FOR PREPARATION OF LARGE p-CONJUGATED COMPOUNDS 429 Hidemitsu Uno PART IX [4+2]/[3+2] CYCLOADDITION 16 TANDEM [4þ2]/[3þ2] CYCLOADDITIONS 471 Ramil Y. Baiazitov and Scott E. Denmark PART X [5+1] CYCLOADDITION 17 TRANSITION METAL-CATALYZED OR -MEDIATED [5þ1] CYCLOADDITIONS 551 Xu-Fei Fu and Zhi-Xiang Yu PART XI [4+3] CYCLOADDITION 18 [4þ3] CYCLOADDITIONS OF ENOLSILANE DERIVATIVES 565 Sarah Y. Y. Lam and Pauline Chiu 19 APPLICATION OF THE [4þ3] CYCLOADDITION REACTION TO THE SYNTHESIS OF NATURAL PRODUCTS 599 Darin E. Jones and Michael Harmata PART XII [5+2] CYCLOADDITION 20 RECENT DEVELOPMENTS IN THE [5þ2] CYCLOADDITION 631 Hervé Clavier and Hélène Pellissier INDEX 655

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Book SynopsisBy guiding in the application of techniques and tools for predicting ADMET outcomes in drug candidates, Predictive ADMET offers a road map for drug discovery scientists to generate effective and safe drugs for unmet medical needs.Trade Review“In conclusion, this volume fulfills its promise of being a very useful tool for guidance and diagnosis on ADMET matters, and I would recommend it to any scientist in the field.” (ChemMedChem, 1 June 2015) Table of ContentsPreface ix Contributors xi I Introduction to the Current Scientific, Clinical, and Social Environment of Drug Discovery and Development 1 Current Social, Clinical, and Scientific Environment of Pharmaceutical R&D 3Laszlo Urban, Jean-Pierre Valentin, Kenneth I Kaitin, and Jianling Wang 2 Polypharmacology and Adverse Bioactivity Profiles Predict Potential Toxicity and Drug-related ADRs 23Teresa Kaserer, Veronika Temml, and Daniela Schuster II Intelligent Integration and Extrapolation of Admet Data 3 ADMET Diagnosis Models 49Bernard Faller, Suzanne Skolnik, and Jianling Wang 4 PATH (Probe ADME and Test Hypotheses): A Useful Approach Enabling Hypothesis-driven ADME Optimization 63Leslie Bell, Suzanne Skolnik, and Dallas Bednarczyk 5 PK-MATRIX—A Permeability: Intrinsic Clearance System for Prediction, Classification, and Profiling of Pharmacokinetics and Drug–drug Interactions 89Urban Fagerholm 6 Maximizing the Power of a Local Model for ADMET-property Prediction 103Sebastien Ronseaux, Jeremy Beck, and Clayton Springer 7 Chemoinformatic and Chemogenomic Approach to ADMET 125Virginie Y. Martiny, Ilza Pajeva, Michael Wiese, Andrew M. Davis, and Maria A. Miteva 8 Multiparameter Optimization of ADMET for Drug Design 145Matthew D. Segall and Edmund J. Champness 9 PBPK: Integrating In Vitro and In Silico Data in Physiologically Based Models 167Hannah M. Jones and Neil Parrott 10 Emerging Full Mechanistic Physiologically Based Modeling 189Kiyohiko Sugano 11 Pharmacokinetic/Pharmacodynamic Modeling in Drug Discovery: A Translational Tool to Optimize Discovery Compounds Toward the Ideal Target-specific Profile 211Patricia Schroeder III Assessment and Mitigation of Critical Clinically Relevant Admet Risks in Drug Discovery and Development 12 In Vitro–In Silico Tools to Predict Pharmacokinetics of Poorly Soluble Drug Compounds 235Christian Wagner and Jennifer B. Dressman 13 Evaluation of the Collective Impact of Passive Permeability and Active Transport on In Vivo Blood-brain Barrier and Gastrointestinal Drug Absorption 263Donna A. Volpe, Hong Shen, and Praveen V. Balimane 14 Integrated Assessment of Drug Clearance and Cross-Species Scalability 291Kevin Beaumont, James R. Gosset, and Chris E. Keefer 15 Practical Anticipation of Human Efficacious Doses and Pharmacokinetics using Preclinical In Vitro and In Vivo Data 319Tycho Heimbach, Rakesh Gollen, and Handan He 16 Management and Mitigation of Human Drug–drug Interaction Risks in the Drug Discovery and Development Phases 353Heidi J. Einolf and Imad Hanna 17 Integrated Assessment and Clinical Translation of In Vitro Off-target Safety Pharmacology Risks 397Patrick Y. Muller and Christian F. Trendelenburg 18 Integrated Risk Assessment of Cardiovascular Safety in Drug Discovery 407Gül Erdemli and Ruth L. Martin 19 Drug-induced Hepatotoxicity: Advances in Preclinical Predictive Strategies and Tools 433Donna M. Dambach 20 Carcinogenicity and Teratogenicity Assessment 467Hans-Jörg Martus, David Beckman, and Lutz Mueller 21 Nephrotoxicity: Development of Biomarkers for Preclinical and Clinical Application 491Frank Dieterle and Estelle Marrer IV Success Stories and Lessons Learned 22 Early Intervention with Formulation Strategies for Multidimensional Problems to Optimize for Success 507Stephanie Dodd, Christina Capacci-Daniel, Christopher Towler, Riccardo Panicucci, and Keith Hoffmaster 23 Cytochrome P450-mediated Drug Interaction and Cardiovascular Safety: The Seldane to Allegra Transformation 523F. Peter Guengerich 24 Clinical Toxicity Profile of VEGF Inhibitors 535Mark P. S. Sie and Ferry A. L. M. Eskens 25 Cardiomyopathy: Drug Induced and Predisposed 555Shirley A. Aguirre and Eileen R. Blasi 26 Safety Management by Pharmacokinetic Considerations: Ranibizumab (Lucentis) and Bevacizumab (Avastin) 569Nicole H. Siegel and Manju L. Subramanian Index 583

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Book SynopsisIdeal as a graduate textbook, this title is aimed at helping design effective biomaterials,taking into account the complex interactions that occur at the interface when a synthetic material is inserted into a living system. Surface reactivity, biochemistry,substrates, cleaning, preparation, and coatings are presented, with numerous case studies and applications throughout. Highlights include: Starts with concepts and works up to real-life applications such as implantable devices, medical devices, prosthetics, and drug delivery technology Addresses surface reactivity, requirements for surface coating, cleaning and preparation techniques, and characterization Discusses the biological response to coatings Addresses biomaterial-tissue interaction Incorporates nanomechanical properties and processing strategies Table of ContentsChapter 1. Introduction to Biomaterials 1.1 Introduction 1.2 Summary Chapter 2. Tissue Interaction with Biomaterials 2.1 Introduction 2.2 Protein adsorption and Cell adhesion 2.3 Cell Migration 2.4 Controlled Cell Deposition 2.5 Extracellular Matrix 2.6 Biomineralization Chapter 3. Host Response of Implanted Biomaterials 3.1 Immune Response to Implanted Biomaterials 3.2 Transplant Immunology 3.3 Biocomaptibility Chapter 4. Fundamentals of Surface Modification 4.1 Introduction 4.2 Surface Properties of Biomaterials 4.3 Surface modifications 4.4 Applications Chapter 5. Multi Length Scale Hierarchy in Natural Materials 5.1 Introduction 5.2 Multi Length-scale Hierarchy 5.3 Human Bone 5.4 Turtle shell 5.5 Wood 5.6 Silk 5.7 Nacre 5.8 Gecko-feet 5.9 Lotus Leaf Chapter 6. Superhydrophobic Surfaces 6.1 Introduction 6.2 Surfaces and superhydrophobicity in nature 6.3 Classification of surfaces 6.4 Mechanics and nature of wetting 6.5 Fabrication of artificial superhydrophobic surfaces 6.6 Preparation of metallic superhydrophobic surfaces 6.7 Controlled wettability surfaces (CWS) 6.8 Conclusions Chapter 7. Surface Engineering and Modification for Biomedical Applications 7.1 Corrosion of Biomaterials and Need for Surface Coating for Biomedical Applications 7.2 Surface Reactivity and Body Cell Response 7.3 Key Requirements of Surface Coating 7.4 Key Biomaterial Substrates 7.5 Surface Preparation and Cleaning Techniques 7.6 Surface Engineering and Coating Techniques 7.7 Coatings for Biomedical Applications 7.8. Biosurface Characterization Chapter 8. Laser Engineering of Surface Structures 8.1 Introduction 8.2 Laser processing of biomaterials 8.3 Laser-based prototyping methods 8.4 Ultrafast laser pulses 8.5 Neural implants 8.6 Ophthalmic implants 8.7 Laser fabrication of cardiovascular devices 8.8 Laser-fabricated nanoscale materials 8.9 Two photon polymerization 8.10 Microneedle fabrication 8.11 Conclusions Chapter 9. Processing and Nanomechanical Properties of Hydroxyapatite-Nanotube Biocomposite 9.1 Introduction 9.2 Processing of HA-Carbon Nanotube Composites 9.3 Fracture Toughness and Tribological Properties of HA-Carbon Nanotube Composites 9.4 Adhesion of Bone Forming Cells on HA-CNT Surface 9.5 Biomechanical Compatibility at Bone/Coated Implant Interface 9.6 HA-Boron Nitride Nano Tube (BNNT) Composites 9.7 HA-TiO2 Nanotube Composites 9.8 Summary Chapter 10. Applications of Biomaterials 10.1 Multi-scale hierarchy in natural Bone 10.2 Coronary Stents 10.3 Medical Devices 10.4 Drug Delivery Chapter 11. Nanosafety, Nanosocietal and Nanoethical Issues 11.1 Governmental Environment and Health Safety Organization Protocols 11.2 Related Safety Hazards 11.3 Approach to Developing Safety Protocol for Laboratory Environment 11.4 Tendency of Nanoparticles 11.5 Current Capability of Nanoparticle Filters

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Book SynopsisA timely, accessible survey of the multidisciplinary field of bioanalytical chemistry Provides an all in one approach for both beginners and experts, from a broad range of backgrounds, covering introductions, theory, advanced concepts and diverse applications for each method Each chapter progresses from basic concepts to applications involving real samples Includes three new chapters on Biomimetic Materials, Lab-on-Chip, and Analytical Methods Contains end-of-chapter problems and an appendix with selected answers Table of ContentsPreface to Second Edition xix Preface to First Edition xxi Acknowledgments xxiii 1. Quantitative Instrumental Measurements 1 1.1. Introduction 1 1.2. Optical Measurements 2 1.2.1. UV-Visible Absorbance 3 1.2.2. Turbidimetry (Light-Scattering) 5 1.2.3. Fluorescence 5 1.2.4. Chemiluminescence and Bioluminescence 7 1.3. Electrochemical Measurements 8 1.3.1. Potentiometry 10 1.3.2. Amperometry 10 1.3.3. Impedimetry 11 1.4. Radiochemical Measurements 12 1.4.1. Scintillation Counting 12 1.4.2. Geiger Counting 12 1.5. Surface Plasmon Resonance 13 1.6. Calorimetry 14 1.6.1. Differential Scanning Calorimetry (DSC) 15 1.6.2. Isothermal Titration Calorimetry (ITC) 16 1.7. Automation: Microplates, Multiwell Liquid Dispensers and Microplate Readers 16 1.8. Calibration of Instrumental Measurements 18 1.8.1. External Standards 18 1.8.2. Internal Standards 19 1.8.3. Standard Additions 20 1.9. Quantitative and Semi-Quantitative Measurements 21 1.9.1. Exact Concentration 21 1.9.2. Positive or Negative Result 21 Suggested Reading 22 Problems 22 2. Spectroscopic Methods for the Quantitation of Classes of Biomolecules 23 2.1. Introduction 23 2.2. Total Protein 24 2.2.1. Lowry Method 24 2.2.2. Smith (BCA) Method 24 2.2.3. Bradford Method 26 2.2.4. Ninhydrin-Based Assay 27 2.2.5. Other Protein Quantitation Methods 28 2.3. Total DNA 31 2.3.1. Diaminobenzoic Acid (DABA) Method 32 2.3.2. Diphenylamine (DPA) Method 32 2.3.3. Other Fluorimetric Methods 33 2.4. Total RNA 34 2.5. Total Carbohydrate 35 2.5.1. Ferricyanide Method 35 2.5.2. Phenol-Sulfuric Acid Method 36 2.5.3. 2-Aminothiophenol Method 36 2.5.4. Purpald Assay for Bacterial Polysaccharides 37 2.6. Free Fatty Acids 37 References 38 Problems 39 3. Enzymes 41 3.1. Introduction 41 3.2. Enzyme Nomenclature 42 3.3. Enzyme Commission Numbers 43 3.4. Enzymes in Bioanalytical Chemistry 45 3.5. Enzyme Kinetics 46 3.5.1. Simple One-Substrate Enzyme Kinetics 48 3.5.2. Experimental Determination of Michaelis-Menten Parameters 50 3.5.2.1. Eadie-Hofstee Method 50 3.5.2.2. Hanes Method 50 3.5.2.3. Lineweaver-Burk Method 51 3.5.2.4. Cornish-Bowden-Eisenthal Method 52 3.5.3. Comparison of Methods for the Determination of KM Values 52 3.5.4. One-Substrate, Two-Product Enzyme Kinetics 54 3.5.5. Two-Substrate Enzyme Kinetics 54 3.5.6. Examples of Enzyme-Catalyzed Reactions and their Treatment 56 3.5.7. Curve Fitting for Enzyme Kinetic Data 57 3.6. Enzyme Activators 58 3.7. Enzyme Inhibitors 59 3.7.1. Competitive Inhibition 60 3.7.2. Noncompetitive Inhibition 60 3.7.3. Uncompetitive Inhibition 62 3.8. Enzyme Units and Concentrations 62 Suggested Reading 64 References 64 Problems 64 4. Quantitation of Enzymes and Their Substrates 67 4.1. Introduction 67 4.2. Substrate Depletion or Product Accumulation 68 4.3. Direct and Coupled Measurements 69 4.4. Classification of Methods 71 4.5. Instrumental Methods 73 4.5.1. Optical Detection 73 4.5.1.1. Absorbance 73 4.5.1.2. Fluorescence 75 4.5.1.3. Luminescence 77 4.5.1.4. Nephelometry 79 4.5.2. Electrochemical Detection 79 4.5.2.1. Amperometry 79 4.5.2.2. Potentiometry 80 4.5.2.3. Conductimetry 80 4.5.3. Other Detection Methods 81 4.5.3.1. Radiochemical 81 4.5.3.2. Manometry 81 4.5.3.3. Calorimetry 82 4.6. High-Throughput Assays for Enzymes and Inhibitors 82 4.7. Assays for Enzymatic Reporter Gene Products 84 4.8. Practical Considerations for Enzymatic Assays 85 Suggested Reading 86 References 86 Problems 87 5. Immobilized Enzymes 90 5.1. Introduction 90 5.2. Immobilization Methods 90 5.2.1. Nonpolymerizing Covalent Immobilization 91 5.2.1.1. Controlled-Pore Glass 92 5.2.1.2. Polysaccharides 93 5.2.1.3. Polyacrylamide 95 5.2.1.4. Acidic Supports 95 5.2.1.5. Anhydride Groups 96 5.2.1.6. Thiol Groups 97 5.2.2. Crosslinking with Bifunctional Reagents 97 5.2.3. Adsorption 98 5.2.4. Entrapment 99 5.2.5. Microencapsulation 100 5.3. Properties of Immobilized Enzymes 101 5.4. Immobilized Enzyme Reactors 107 5.5. Theoretical Treatment of Packed-Bed Enzyme Reactors 109 Suggested Reading 113 References 113 Problems 114 6. Antibodies 117 6.1. Introduction 117 6.2. Structural and Functional Properties of Antibodies 118 6.3. Polyclonal and Monoclonal Antibodies 121 6.4. Antibody-Antigen Interactions 122 6.5. Analytical Applications of Secondary Antibody-Antigen Interactions 124 6.5.1. Agglutination Reactions 124 6.5.2. Precipitation Reactions 126 Suggested Reading 129 References 129 Problems 129 7. Quantitative Immunoassays with Labels 131 7.1. Introduction 131 7.2. Labeling Reactions 132 7.3. Heterogeneous Immunoassays 134 7.3.1. Labeled-Antibody Methods 136 7.3.2. Labeled-Ligand Assays 136 7.3.3. Radioisotopes 139 7.3.4. Fluorophores 139 7.3.4.1. Indirect Fluorescence 140 7.3.4.2. Competitive Fluorescence 140 7.3.4.3. Sandwich Fluorescence 140 7.3.4.4. Fluorescence Excitation Transfer 140 7.3.4.5. Time-Resolved Fluorescence 141 7.3.5. Quantum Dots 142 7.3.6. Chemiluminescent Labels 143 7.3.7. Enzyme Labels 145 7.3.8. Lateral Flow Immunoassay 148 7.4. Homogeneous Immunoassays 149 7.4.1. Fluorescent Labels 149 7.4.1.1. Enhancement Fluorescence 149 7.4.1.2. Direct Quenching Fluorescence 150 7.4.1.3. Indirect Quenching Fluorescence 150 7.4.1.4. Fluorescence Polarization Immunoassay 151 7.4.1.5. Fluorescence Excitation Transfer 151 7.4.2. Enzyme Labels 152 7.4.2.1. Enzyme-Multiplied Immunoassay Technique 152 7.4.2.2. Substrate-Labelled Fluorescein Immunoassay 153 7.4.2.3. Apoenzyme Reactivation Immunoassay 153 7.4.2.4. Cloned Enzyme Donor Immunoassay 154 7.4.2.5. Enzyme Inhibitory Homogeneous Immunoassay 154 7.5. Evaluation of New Immunoassay Methods 155 Suggested Reading 160 References 160 Problems 161 8. Biosensors 166 8.1. Introduction 166 8.2. Biosensor Diversity and Classification 169 8.3. Recognition Agents 171 8.3.1. Natural Recognition Agents 171 8.3.2. Artificial Recognition Agents 172 8.4. Response of Enzyme-Based Biosensors 175 8.5. Examples of Biosensor Configurations 178 8.5.1. Ferrocene-Mediated Amperometric Glucose Sensor 178 8.5.2. Potentiometric Biosensor for Phenyl Acetate 180 8.5.3. Evanescent-Wave Fluorescence Biosensor for Bungarotoxin 181 8.5.4. Optical Biosensor for Glucose Based on Fluorescence Resonance Energy Transfer 183 8.5.5. Piezoelectric Sensor for Nucleic Acid Detection 184 8.5.6. Enzyme Thermistors 186 8.5.7. Fluorescence Sensor for Nitroaromatic Explosives Based on a Molecularly Imprinted Polymer 187 8.5.8. Immunosensor Microwell Arrays from Gold Compact Disks 188 8.5.9. Nanoparticle-Enhanced Detection of Thrombin by SPR 190 8.5.10. Environmental BOD and Toxicity Biosensors Based on Viable Cells 192 8.5.11. Detection of Viruses using a Surface Acoustic Wave (SAW) Biosensor 193 8.5.12. MEMS Microcantilever Biosensor for Virus Detection 196 8.5.13. DNA Microarrays 198 8.6. Evaluation of Biosensor Perfomance 201 8.7. In Vivo Applications of Biosensors 202 8.7.1. Biocompatible Materials 203 8.7.2. Physiological Environment of the Human Body 203 8.7.3. The Artificial Pancreas 205 8.7.4. An Enzymatic Fuel Cell as a Component of an Implanted Biosensing System 205 8.7.5. Other Examples of Implantable Biosensors 206 Suggested Reading 207 References 207 Problems 209 9. Directed Evolution for the Design of Macromolecular Reagents 210 9.1. Introduction 210 9.2. Rational Design and Directed Evolution 211 9.3. Generation of Genetic Diversity 214 9.3.1. Polymerase Chain Reaction and Error-Prone PCR 215 9.3.2. DNA Shuffling 217 9.4. Linking Genotype and Phenotype 217 9.4.1. Cell Expression and Cell Surface Display (In vivo) 218 9.4.2. Phage Display (In vivo) 218 9.4.3. Ribosome Display (In vitro) 219 9.4.4. mRNA-Peptide Fusion (In vitro) 220 9.4.5. Microcompartmentalization (In vitro) 220 9.5. Identification and Selection of Successful Variants 221 9.5.1. Identification of Successful Variants Based on Binding Properties 222 9.5.2. Identification of Successful Variants Based on Catalytic Activity 222 9.6. Examples of Directed Evolution Experiments 224 9.6.1. Directed Evolution of Galactose Oxidase 224 9.6.2. α-Hemolysin Evolution 225 Suggested Reading 226 References 226 Problems 227 10. Image-Based Bioanalysis 229 10.1. Introduction 229 10.2. Magnification and Resolution 230 10.3. Optical Microscopy 231 10.3.1. The Compound Light Microscope 231 10.3.2. The Confocal Microscope 231 10.3.3. Sample Preparation 232 10.3.4. General and Selective Stains 233 10.3.5. Fluorescence In situ Hybridization 234 10.3.6. Green Fluorescent Protein and its Analogues 234 10.4. Electron Microscopy 234 10.4.1. Principles and Instrumentation 234 10.4.2. Sample Preparation 235 10.4.3. Transmission Electron Microscopy (TEM) 236 10.4.4. Scanning Electron Microscopy (SEM) 236 10.5. Scanning Tunneling Microscopy 237 10.5.1. Principles and Instrumentation 237 10.5.2. Biological Applications 237 10.6. Atomic Force Microscopy (AFM) 237 10.6.1. Cantilevers and Operational Modes 237 10.6.2. Samples and Substrates 239 10.6.3. Biological Applications 239 10.6.4. Four-Dimensional (4D) Scanning 240 10.7. Scanning Electrochemical Microscopy (SECM) 240 10.7.1. Principles and Instrumentation 240 10.7.2. Samples and Substrates 241 10.7.3. Biological Applications 241 Suggested Reading 242 References 242 Problems 243 11. Principles of Electrophoresis 244 11.1. Introduction 244 11.2. Electrophoretic Support Media 248 11.2.1. Paper 248 11.2.2. Starch Gels 249 11.2.3. Polyacrylamide Gels 250 11.2.4. Agarose Gels 254 11.2.5. Polyacrylamide-Agarose Gels 254 11.3. Effect of Experimental Conditions Onelectrophoretic Separations 254 11.4. Electric Field Strength Gradients 255 11.5. Pulsed Field Gel Electrophoresis (PFGE) 256 11.6. Detection of Proteins and Nucleic Acids After Electrophoretic Separation 258 11.6.1. Stains and Dyes 258 11.6.2. Detection of Enzymes by Substrate Staining 260 11.6.3. The Southern Blot 260 11.6.4. The Northern Blot 262 11.6.5. The Western Blot 262 11.6.6. Detection of DNA Fragments on Membranes with DNA Probes 263 Suggested Reading 265 References 266 Problems 266 12. Applications of Zone Electrophoresis 268 12.1. Introduction 268 12.2. Determination of Protein Net Charge and Molecular Weight Using PAGE 268 12.3. Determination of Protein Subunit Composition and Subunit Molecular Weights 270 12.4. Molecular Weight of DNA by Agarose Gel Electrophoresis 272 12.5. Identification of Isoenzymes 273 12.6. Diagnosis of Genetic (Inherited) Disorders 274 12.7. DNA Fingerprinting and Restriction Fragment Length Polymorphism 275 12.8. DNA Sequencing with the Maxam-Gilbert Method 279 12.9. Immunoelectrophoresis 282 Suggested Reading 287 References 287 Problems 288 13. Isoelectric Focusing and 2D Electrophoresis 290 13.1. Introduction 290 13.2. Carrier Ampholytes 291 13.3. Modern IEF with Carrier Ampholytes 293 13.4. Immobilized pH Gradients (IPGs) 296 13.5. Two-Dimensional Electrophoresis 299 13.6. Difference Gel Electrophoresis (DIGE) 301 Suggested Reading 303 References 303 Problems 304 14. Capillary Electrophoresis 306 14.1. Introduction 306 14.2. Electroosmosis 307 14.3. Elution of Sample Components 308 14.4. Sample Introduction 309 14.5. Detectors for Capillary Electrophoresis 310 14.5.1. Laser-Induced Fluorescence Detection 311 14.5.2. Mass Spectrometric Detection 313 14.5.3. Amperometric Detection 315 14.5.4. Radiochemical Detection 318 14.6. Capillary Polyacrylamide Gel Electrophoresis (C-PAGE) 319 14.7. Capillary Isoelectric Focusing (CIEF) 321 Suggested Reading 322 References 323 Problems 323 15. Centrifugation Methods 325 15.1. Introduction 325 15.2. Sedimentation and Relative Centrifugal g Force 325 15.3. Centrifugal Forces in Different Rotor Types 327 15.3.1. Swinging-Bucket Rotors 327 15.3.2. Fixed-Angle Rotors 328 15.3.3. Vertical Rotors 328 15.4. Clearing Factor (K) 329 15.5. Density Gradients 330 15.5.1. Materials Used to Generate a Gradient 331 15.5.2. Constructing Pre-Formed and Self-Generated Gradients 331 15.5.3. Redistribution of the Gradient in Fixed-Angle and Vertical Rotors 333 15.6. Types of Centrifugation Techniques 333 15.6.1. Differential Centrifugation 334 15.6.2. Rate-Zonal Centrifugation 334 15.6.3. Isopycnic Centrifugation 336 15.7. Harvesting Samples 336 15.8. Analytical Ultracentrifugation 336 15.8.1. Instrumentation 337 15.8.2. Sedimentation Velocity Analysis 338 15.8.3. Sedimentation Equilibrium Analysis 341 15.9. Selected Examples 342 15.9.1. Analytical Ultracentrifugation for Quaternary Structure Elucidation 342 15.9.2. Isolation of Retroviruses by Self-Generated Gradients 343 15.9.3. Isolation of Lipoproteins from Human Plasma 344 15.9.4. Centrifugal Microfluidic Analysis 344 Suggested Reading 346 References 346 Problems 347 16.Chromatography of Biomolecules 349 16.1. Introduction 349 16.2. Units and Definitions 350 16.3. Plate Theory of Chromatography 350 16.4. Rate Theory of Chromatography 351 16.5. Size Exclusion (Gel Filtration) Chromatography 353 16.6. Stationary Phases For Size Exclusion Chromatography 358 16.6.1. Particulate Gels 358 16.6.2. Monolithic Stationary Phases 360 16.7. Affinity Chromatography 360 16.7.1. Immobilization of Affinity Ligands 362 16.7.2. Elution Methods 364 16.7.3. Determination of Association Constants by High Performance Affinity Chromatography 364 16.8. Ion-exchange Chromatography 368 16.8.1. Retention Model for Ion-Exchange Chromatography of Polyelectrolytes 369 16.8.2. Further Advances in Ion-Exchange Chromatography 374 Suggested Reading 374 References 374 Problems 375 17. Mass Spectrometry of Biomolecules 377 17.1. Introduction 377 17.2. Basic Description of the Instrumentation 379 17.2.1. Soft Ionization Sources 379 17.2.1.1. Fast Atom/Ion Bombardment (FAB) 380 17.2.1.2. Electrospray Ionization (ESI) 380 17.2.1.3. Matrix-Assisted Laser Desorption/Ionization (MALDI) 381 17.2.2. Mass Analyzers 382 17.2.3. Detectors 385 17.3. Interpretation of Mass Spectra 386 17.4. Biomolecule Molecular Weight Determination 388 17.5. Protein Identification 392 17.6. Protein-Peptide Sequencing 393 17.7. Nucleic Acid Applications 397 17.8. Bacterial Mass Spectrometry 398 17.9. Mass Spectrometry Imaging 399 Suggested Reading 401 References 401 Problems 402 18. Micro-TAS, Lab-on-a-Chip, and Microarray Devices 404 18.1. Introduction 404 18.2. Device Fabrication Materials and Methods 405 18.3. Microfluidics 405 18.3.1. Fluid Transport 405 18.3.2. Valves and Reservoirs 406 18.3.3. Mixing and Sample Separation 406 18.4. Detectors 407 18.5. Examples of Bioanalytical Devices 407 18.5.1. DNA Separation Using a Nanofence Array Microfluidic Device 408 18.5.2. Two Dimensional Electrophoresis on a Microfluidic Chip 409 18.5.3. Microfluidic Antibody Capture for Single-Cell Proteomics 410 18.5.4. Multiplexed PCR Amplification and DNA Detection on a Microfluidic Chip 410 18.5.5. Silicone Protein Separation Chip Based on a Grafted Ion-Exchange Polymer 411 18.5.6. Circular, Biofunctionalized PEG Microchannels for Cell Adhesion Studies 411 Suggested Reading 412 References 412 Problems 413 19. Validation of New Bioanalytical Methods 414 19.1. Introduction 414 19.2. Precision and Accuracy 415 19.3. Mean and Variance 416 19.4. Relative Standard Deviation and Other Precision Estimators 417 19.4.1. Distribution of Errors and Confidence Limits 418 19.4.2. Linear Regression and Calibration 419 19.4.3. Precision Profiles 420 19.4.4. Limit of Quantitiation and Detection 421 19.4.5. Linearizing Sigmoidal Curves (Four-Parameter Log-Logit Model) 422 19.4.6. Effective Dose Method 423 19.5. Estimation of Accuracy 424 19.5.1. Standardization 424 19.5.2. Matrix Effects 425 19.5.2.1. Recovery 425 19.5.2.2. Parallelism 426 19.5.3. Interferences 426 19.6. Qualitative (Screening) Assays 427 19.6.1. Figures of Merit for Qualitative (Screening) Assays 427 19.7. Examples of Validation Procedures 428 19.7.1. Validation of a Qualitative Antibiotic Susceptibility Test 428 19.7.2. Measurement of Plasma Homocysteine by Fluorescence Polarization Immunoassay (FPIA) Methodology 429 19.7.3. Determination of Enzymatic Activity of β-Galactosidase 433 19.7.4. Establishment of a Cutoff Value for Semi-Quantitative Assays for Cannabinoids 434 Suggested Reading 435 References 436 Answers to Selected Problems 437 Index 449

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Book SynopsisThis textbook introduces chemistry and chemical engineering students to molecular descriptions of thermodynamics, chemical systems, and biomolecules. Equips students with the ability to apply the method to their own systems, as today''s research is microscopic and molecular and articles are written in that language Provides ample illustrations and tables to describe rather difficult concepts Makes use of plots (charts) to help students understand the mathematics necessary for the contents Includes practice problems and answers Table of ContentsPreface xiii Acknowledgments xvii About the Companion Website xix Symbols and Constants xxi 1 Introduction 1 1.1 Classical Thermodynamics and Statistical Thermodynamics 1 1.2 Examples of Results Obtained from Statistical Thermodynamics 2 1.2.1 Heat Capacity of Gas of Diatomic Molecules 2 1.2.2 Heat Capacity of a Solid 3 1.2.3 Blackbody Radiation 3 1.2.4 Adsorption 4 1.2.5 Helix–Coil Transition 5 1.2.6 Boltzmann Factor 6 1.3 Practices of Notation 6 2 Review of Probability Theory 9 2.1 Probability 9 2.2 Discrete Distributions 11 2.2.1 Binomial Distribution 12 2.2.2 Poisson Distribution 13 2.2.3 Multinomial Distribution 14 2.3 Continuous Distributions 15 2.3.1 Uniform Distribution 19 2.3.2 Exponential Distribution 19 2.3.3 Normal Distribution 21 2.3.4 Distribution of a Dihedral Angle 21 2.4 Means and Variances 22 2.4.1 Discrete Distributions 22 2.4.2 Continuous Distributions 26 2.4.3 Central Limit Theorem 27 2.5 Uncertainty 28 Problems 31 3 Energy and Interactions 35 3.1 Kinetic Energy and Potential Energy of Atoms and Ions 35 3.1.1 Kinetic Energy 35 3.1.2 Gravitational Potential 36 3.1.3 Ion in an Electric Field 36 3.1.4 Total Energy of Atoms and Ions 37 3.2 Kinetic Energy and Potential Energy of Diatomic Molecules 37 3.2.1 Kinetic Energy (Translation, Rotation, Vibration) 37 3.2.2 Dipolar Potential 42 3.2.2.1 Potential of a Permanent Dipole 42 3.2.2.2 Potential of an Induced Dipole 44 3.3 Kinetic Energy of Polyatomic Molecules 46 3.3.1 Linear Polyatomic Molecule 46 3.3.2 Nonlinear Polyatomic Molecule 48 3.4 Interactions Between Molecules 50 3.4.1 Excluded-Volume Interaction 52 3.4.2 Coulomb Interaction 52 3.4.3 Dipole–Dipole Interaction 53 3.4.4 van der Waals Interaction 54 3.4.5 Lennard-Jones Potential 55 3.5 Energy as an Extensive Property 57 3.6 Kinetic Energy of a Gas Molecule in Quantum Mechanics 58 3.6.1 Quantization of Translational Energy 58 3.6.2 Quantization of Rotational Energy 61 3.6.3 Quantization of Vibrational Energy 63 3.6.4 Electronic Energy Levels 65 3.6.5 Comparison of Energy Level Spacings 66 Problems 67 4 Statistical Mechanics 69 4.1 Basic Assumptions, Microcanonical Ensembles, and Canonical Ensembles 69 4.1.1 Basic Assumptions 69 4.1.2 Microcanonical Ensembles 73 4.1.3 Canonical Ensembles 75 4.2 Probability Distribution in Canonical Ensembles and Partition Functions 77 4.2.1 Probability Distribution 77 4.2.2 Partition Function for a System with Discrete States 79 4.2.3 Partition Function for a System with Continuous States 81 4.2.4 Energy Levels and States 83 4.3 Internal Energy 88 4.4 Identification of 𝛽 89 4.5 Equipartition Law 91 4.6 Other Thermodynamic Functions 93 4.7 Another View of Entropy 97 4.8 Fluctuations of Energy 99 4.9 Grand Canonical Ensembles 100 4.10 Cumulants of Energy 107 Problems 110 5 Canonical Ensemble of Gas Molecules 113 5.1 Velocity of Gas Molecules 113 5.2 Heat Capacity of a Classical Gas 116 5.2.1 Point Mass 117 5.2.2 Rigid Dumbbell 117 5.2.3 Elastic Dumbbell 118 5.3 Heat Capacity of a Quantum-Mechanical Gas 120 5.3.1 General Formulas 120 5.3.2 Translation 122 5.3.3 Rotation 124 5.3.4 Vibration 127 5.3.5 Comparison with Classical Models 128 5.4 Distribution of Rotational Energy Levels 129 5.5 Conformations of a Molecule 130 Problems 132 6 Indistinguishable Particles 135 6.1 Distinguishable Particles and Indistinguishable Particles 135 6.2 Partition Function of Indistinguishable Particles 137 6.2.1 System of Distinguishable Particles 137 6.2.2 System of Indistinguishable Particles 137 6.3 Condition of Nondegeneracy 142 6.4 Significance of Division by N! 144 6.4.1 Gas in a Two-Part Box 144 6.4.2 Chemical Potential 145 6.4.3 Mixture of Two Gases 146 6.5 Indistinguishability and Center-of-Mass Movement 147 6.6 Open System of Gas 147 Problems 149 7 Imperfect Gas 153 7.1 Virial Expansion 153 7.2 Molecular Expression of Interaction in the Canonical Ensemble 157 7.3 Second Virial Coefficients in Different Models 164 7.3.1 Hard-Core Repulsion Only 164 7.3.2 Square-well Potential 165 7.3.3 Lennard-Jones Potential 167 7.4 Joule–Thomson Effect 167 Problems 171 8 Rubber Elasticity 175 8.1 Rubber 175 8.2 Polymer Chain in One Dimension 176 8.3 Polymer Chain in Three Dimensions 180 8.4 Network of Springs 184 Problems 185 9 Law of Mass Action 189 9.1 Reaction of Two Monatomic Molecules 190 9.2 Decomposition of Homonuclear Diatomic Molecules 193 9.3 Isomerization 195 9.4 Method of the Steepest Descent 197 Problems 198 10 Adsorption 201 10.1 Adsorption Phenomena 201 10.2 Langmuir Isotherm 202 10.3 BET Isotherm 206 10.4 Dissociative Adsorption 211 10.5 Interaction Between Adsorbed Molecules 213 Problems 213 11 Ising Model 217 11.1 Model 217 11.2 Partition Function 220 11.2.1 One-Dimensional Ising Model 220 11.2.2 Calculating Statistical Averages 221 11.2.2.1 Average Number of Up Spins 222 11.2.2.2 Average of the Number of Spin Alterations (Number of Domains – 1) 222 11.2.2.3 Domain Size 223 11.2.2.4 Size of a Domain of Uniform Spins 223 11.2.3 A Few Examples of 1D Ising Model 223 11.2.3.1 Linear Ising Model, N = 3 223 11.2.3.2 Ring Ising Model, N = 3 225 11.2.3.3 Ring Ising Model, N = 4 225 11.3 Mean-FieldTheories 226 11.3.1 Bragg–Williams (B–W) Approximation 227 11.3.2 Flory–Huggins (F–H) Approximation 231 11.3.3 Approximation by a Mean-Field (MF) Theory 235 11.4 Exact Solution of 1D Ising Model 236 11.4.1 General Formula 236 11.4.2 Large-N Approximation 239 11.4.3 Exact Partition Function for Arbitrary N 241 11.4.4 Ring Ising Model, Arbitrary N 244 11.4.5 Comparison of the Exact Results with Those of Mean-Field Approximations 245 11.5 Variations of the Ising Model 247 11.5.1 System of Uniform Spins 247 11.5.2 Random Local Fields of Opposite Directions 249 11.5.3 Dilute Local Fields 252 Problems 254 12 Helical Polymer 263 12.1 Helix-Forming Polymer 263 12.2 Optical Rotation and Circular Dichroism 266 12.3 Pristine Poly(n-hexyl isocyanate) 267 12.4 Variations to the Helical Polymer 271 12.4.1 Copolymer of Chiral and Achiral Isocyanate Monomers 272 12.4.2 Copolymer of R- and S-Enantiomers of Isocyanate 274 Problems 274 13 Helix–Coil Transition 277 13.1 Historical Background 277 13.2 Polypeptides 281 13.3 Zimm–Bragg Model 283 Problems 289 14 Regular Solutions 291 14.1 Binary Mixture of Equal-Size Molecules 291 14.1.1 Free Energy of Mixing 291 14.1.2 Derivatives of the Free Energy of Mixing 296 14.1.3 Phase Separation 300 14.2 Binary Mixture of Molecules of Different Sizes 304 Problems 312 Appendix A Mathematics 315 A.1 Hyperbolic Functions 315 A.2 Series 317 A.3 Binomial Theorem and Trinomial Theorem 317 A.4 Stirling’s formula 318 A.5 Integrals 318 A.6 Error Functions 318 A.7 Gamma Functions 319 References 321 Index 325

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Book SynopsisPresenting a clear, neutral analysis of the key plastic-related issues, Environmental Impacts of Plastics focuses on three key areas: plastics industry, post-consumer fate of plastics on land and in the oceans, and toxicity of plastics.Trade Review“Plastics and environmental sustainability is a fine book, packed with informative data and well worth reading . . . Overall, I enjoyed this book a great deal.” (Chemistry in Australia, 1 December 2015)Table of ContentsPreface xiii Acknowledgments xvii List of Plastic Materials xix 1 The Anthropocene 1 1.1 Energy Futures 6 1.1.1 Fossil Fuel Energy 8 1.1.1.1 Oil 8 1.1.1.2 Coal 9 1.1.1.3 Gas 10 1.1.1.4 Nuclear Energy 11 1.1.2 Renewable Energy 12 1.1.2.1 Wind Energy 12 1.1.2.2 Solar Energy 13 1.1.2.3 Solar Biomass Energy 13 1.2 Materials Demand in the Future 14 1.2.1 Materials of Construction 15 1.2.2 Metal Resources 16 1.2.3 Critical Materials 18 1.2.4 Plastic Materials 19 1.3 Environmental Pollution 22 1.3.1 Classifying Pollution Impacts 23 1.3.2 Climate Change and Global Warming 24 References 27 2 A Sustainability Primer 31 2.1 The Precautionary Principle 33 2.1.1 Objectives in Sustainability 35 2.2 Microeconomics of Sustainability: The Business Enterprise 36 2.3 Models on Implementing Sustainability 38 2.4 Life Cycle Analysis 41 2.5 The Emerging Paradigm and the Plastics Industry 44 2.5.1 Examples from Plastics Industry 47 2.5.1.1 Using the Minimum Energy Needed to Manufacture Products 47 2.5.1.2 Using the Energy Mix with a Minimal Environmental Footprint 47 2.5.1.3 Recovering Waste Process Energy for Reuse 48 2.5.1.4 Using Only as Much Material as Is Needed to Ensure Functionality 48 2.5.1.5 Using More of Renewable and Recycled Raw Materials 48 2.5.1.6 Reusing and Recycling Postuse Products 49 2.5.1.7 Minimizing Externalities at Source: Green Chemistry 49 2.5.1.8 Avoiding Toxic Components and Potential Hazards Associated with Products and Processes 50 2.5.1.9 Converting the Pollutants into Resources 50 References 51 3 An Introduction to Plastics 55 3.1 Polymer Molecules 56 3.1.1 Size of Polymer Molecules 57 3.2 Consequences of Long-Chain Molecular Architecture 59 3.2.1 Molecular Weight of Chain Molecules 59 3.2.2 Tacticity 61 3.2.3 Partially Crystalline Plastics 62 3.2.4 Chain Branching and Cross-Linking 63 3.2.5 Glass Transition Temperature 66 3.3 Synthesis of Polymers 67 3.3.1 Addition or Chain Growth Reaction 68 3.3.2 Condensation or Step Growth Reaction 69 3.3.3 Copolymers 72 3.4 Testing of Polymers 72 3.4.1 Tensile Properties 73 3.4.2 Thermal Properties: DSC (Differential Scanning Calorimetry) 74 3.4.3 Thermal Properties: TGA 76 3.5 Common Plastics 76 3.5.1 Polyethylenes 77 3.5.2 Polypropylenes 78 3.5.3 Polystyrene 78 3.5.4 Poly(vinyl chloride) 80 References 81 4 Plastic Products 83 4.1 Plastics: The Miracle Material 84 4.2 Plastic Production, Use, and Disposal 88 4.2.1 From Resin to Products 90 4.2.1.1 Resin Manufacture 90 4.2.1.2 Compounding 90 4.2.1.3 Processing into Product 91 4.3 Processing Methods for Common Thermoplastics 91 4.3.1 Injection Molding 91 4.3.2 Extrusion 95 4.3.3 Blow Molding 95 4.4 The Environmental Footprint of Plastics 97 4.4.1 Energy Considerations in Resin Manufacture 98 4.4.2 Atmospheric Emissions from Plastics Industry 101 4.5 Plastics Additives 103 4.5.1 Fillers for Plastics 106 4.5.2 Plasticizers in PVC 106 4.6 Biopolymer or Bio-Derived Plastics 107 4.6.1 Bio-Based Plastics and Sustainability 109 4.6.2 Emerging Bio-Based Plastics 111 4.6.2.1 Bio-PE 112 4.6.2.2 Bio-PET 112 4.6.2.3 PLA 113 4.6.2.4 Poly(Hydroxyalkanoates) 115 4.6.2.5 Bio-Based Thermosets: PU 116 References 116 5 Societal Benefits of Plastics 121 5.1 Transportation Applications of Plastics 122 5.1.1 Passenger Cars 122 5.1.2 Air and Sea Transport 124 5.2 Benefits from Plastic Packaging 126 5.2.1 Waste Reduction 129 5.2.2 Chemical and Microbial Protection 130 5.3 Plastics in Agriculture 131 5.4 Building Industry Applications 132 5.4.1 Pipes, Conduit, and Cladding 133 5.4.2 Extruded PVC Cladding and Window Frames 134 5.4.3 Foam Insulation 135 5.4.4 Wood–Plastic Composites 137 5.5 Original Equipment Manufacture (OEM) 138 5.6 Using Plastics Sustainably 139 References 140 6 Degradation of Plastics in the Environment 145 6.1 Defining Degradability 146 6.2 Chemistry of Light-Induced Degradation 147 6.2.1 Light-Initiated Photo-Oxidation in PE and PP 150 6.2.2 Embrittlement and Fragmentation 152 6.2.3 Temperature and Humidity Effects on Degradation 154 6.2.4 Wavelength-Dependent Photodamage 155 6.2.5 Testing Plastics for Photodegradability 157 6.3 Enhanced Photodegradable Polyolefins 160 6.3.1 Effects of Photodegradation on Biodegradation 162 6.4 Biodegradation of Polymers 163 6.4.1 Terminology and Definitions 165 6.4.2 Biodegradable Plastics 168 6.4.3 Testing Readily Biodegradable Plastics 170 6.5 Biodegradability of Common Polymers 173 6.5.1 Additives that Enhance Degradation in Common Polymers 175 6.5.2 Degradable Plastics and Sustainable Development 176 References 178 7 Endocrine Disruptor Chemicals 185 7.1 Endocrine Disruptor Chemicals Used in Plastics Industry 187 7.2 BPA {2,2-Bis(4-Hydroxyphenyl)Propane} 187 7.2.1 Exposure to BPA 190 7.2.2 Effects of Exposure to BPA 192 7.2.3 Dose–Response Relationships of BPA 194 7.2.4 Safe Levels of BPA 194 7.2.5 Contrary Viewpoint on BPA 196 7.2.6 Environmental Sustainability and BPA 197 7.3 Phthalate Plasticizers 198 7.3.1 Exposure to Phthalates 201 7.3.2 Toxicity of Phthalates 203 7.3.3 Environmental Sustainability and Phthalates 203 7.4 Polybrominated Diphenyl Ethers (PBDEs) 204 7.4.1 Toxicity of PBDEs 207 7.4.2 Environmental Sustainability and PBDE 208 7.5 Alkylphenols and Their Ethoxylates (APE) 209 7.6 EDCs and PET Bottles 209 References 212 8 Plastics and Health Impacts 227 8.1 Packaging versus the Contents 228 8.1.1 Packaging Milk in HDPE 230 8.1.2 Overpackaging 232 8.2 Package–Food Interactions 233 8.2.1 Oxygen and Water Permeability 234 8.2.2 Additive Migration and Toxicity 236 8.2.3 Residual Monomer in Packaging Resin 240 8.2.4 Scalping of Flavor Components 240 8.3 Styrene and Expanded Polystyrene Food Service Materials 242 8.3.1 Exposure to Styrene from Packaging 244 8.3.2 Leachate from PET Bottles 244 8.4 Ranking Common Plastics 245 8.4.1 PVC 248 References 249 9 Managing Plastic Waste 255 9.1 Recovery of Waste 258 9.1.1 Material Recycling 261 9.1.2 Feedstock Recovery 261 9.1.3 Energy Recovery 261 9.2 Pyrolysis of Plastic Waste for Feedstock Recovery 261 9.2.1 Direct Thermolysis 261 9.2.2 Hydrogenation or hydrocracking 264 9.2.3 Gasification 265 9.2.3.1 Thermal Gasification 265 9.2.3.2 Plasma Arc Gasification 266 9.2.4 Feedstock Recycling 267 9.2.5 Landfilling 271 9.2.6 Plastics Waste Incineration 272 9.2.7 Biological Recovery Technologies 274 9.3 Sustainable Waste Management Choices 275 9.4 Mechanical Recycling of Plastics 278 9.4.1 Recycling: A Sustainable Choice 281 9.5 Recycling Bottles: Beverage Bottles and Jugs 282 9.5.1 Bottle-to-Bottle Recycling 282 9.5.2 Open-Loop Recycling 284 9.5.3 Recycling of HDPE 285 9.6 Designing for Recyclability 285 References 286 10 Plastics in the Oceans 295 10.1 Origins of Plastics in the Ocean 297 10.2 Weathering of Plastics in the Ocean Environment 299 10.2.1 Beach (Supralittoral) Zone 300 10.2.2 Surface Water Zone 301 10.2.3 Deep Water and Sediment Zones 301 10.2.3.1 Comparison of the Weathering Rates in Different Zones 301 10.3 Microplastic Debris 304 10.3.1 Primary and Secondary Microplastics 305 10.3.2 Persistent Organic Pollutant in Microplastics 307 10.3.3 Ingestion of Microplastics by Marine Species 309 10.4 Ocean Litter and Sustainability 310 References 311 Index 319

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Book SynopsisIncluding chemical, synthetic, and cross-disciplinary approaches; this book includes the necessary techniques and technologies to help readers better understand polymers for polymer electrolyte membrane (PEM) fuel cells.Table of ContentsPreface ix Acknowledgments xi 1 Introduction 1 1.1 Principles of Fuel Cells 1 1.2 Types of Fuel Cells 3 1.2.1 AFC 3 1.2.2 PAFC 6 1.2.3 MCFC 7 1.2.4 SOFC 8 1.2.5 PEMFC 11 1.2.6 DMFC 12 1.3 Applications 14 1.3.1 Stationary Power 15 1.3.2 Propulsion of Vehicles 15 1.3.3 Portable Applications 17 1.4 Needs of Fundamental Materials for PEM Fuel Cells 17 1.4.1 Membranes 17 1.4.2 Electrodes 18 1.4.3 Polymeric Materials as Components of Fuel Cell Catalytic System 20 1.4.4 Bipolar Plates 21 1.5 Membranes for PEM Fuel Cells 22 1.5.1 Proton Exchange Membranes 22 1.5.2 PEMs for DMFCs 29 1.5.3 Anion Exchange Membranes (AEMs) 34 1.5.4 Organic–Inorganic Composites 35 1.6 Testing of PEMs 36 References 36 2 Fluoropolymers for Proton Exchange Membranes 50 2.1 Introduction 50 2.2 Perfluorosulfonic Acid Resins 51 2.2.1 PFSA Polymers with Long Side Chains 53 2.2.2 PFSA Polymers with Short Side Chains 55 2.2.3 Sulfonimide Membranes 58 2.3 Partially Fluorinated Polymers 59 2.3.1 Partially Fluorinated Aromatic Polymers 59 2.3.2 Partially Fluorinated Graft Copolymers 67 2.4 Durability of Fluoropolymers for Proton Exchange Membranes 75 2.5 Composite Membranes Based on Fluoropolymers 82 2.5.1 Reinforcement by a Polymer 83 2.5.2 Organic–Inorganic Composite Membranes 83 2.5.3 Nafion®/Sulfonated Polymers 85 2.5.4 Multilayer Membranes 85 2.5.5 Semi-IPN Membranes 86 References 87 3 Nonfluorinated Polymers for Proton Exchange Membranes 102 3.1 Introduction 102 3.2 Sulfonated Polyimides 103 3.2.1 Synthesis of Sulfonated Polyimides 104 3.2.2 Structure and Properties of Sulfonated Polyimide 116 3.2.3 Modification of Sulfonated Polyimides 127 3.2.4 Fuel Cell Performance and Stability of sPI Membranes 136 3.3 Sulfonated Poly(ether ether ketone) 141 3.3.1 Synthesis of sPEEK 142 3.3.2 Structure and Properties 146 3.3.3 Modification of sPEEK Membranes 153 3.4 Sulfonated Polysulfone and Poly(ether sulfone) 160 3.4.1 Polysulfones and Poly(ether sulfone) 160 3.4.2 Sulfonation and Phosphonation of Polysulfones and Poly(ether sulfone)s 162 3.4.3 Poly(arylene thioether sulfone)s 180 3.5 Sulfonated Polyphosphazenes 181 3.5.1 Synthesis of Sulfonated Polyphosphazenes 184 3.5.2 Phenylphosphonic Acid-Functionalized Polyphosphazenes 187 3.5.3 Polyphosphazenes with Sulfonimide Side Groups 188 3.5.4 Modification of Sulfonated Polyphosphazenes 190 3.5.5 Polyphosphazene Membranes for PEMFCs 192 3.5.6 Polyphosphazene Membranes for DMFCs 193 3.6 Sulfonated Polybenzimidazole 194 3.7 Sulfonated Poly(phenylene oxide) 198 3.7.1 Sulfonated PPO for PEMs 198 3.7.2 Modification of sPPO 202 3.7.3 Fuel Cell Performances of sPPO Membranes 210 References 212 4 Anhydrous Proton-Conducting Polymers for High-Temperature PEMFCs 241 4.1 Introduction 241 4.2 Phosphoric Acid-Impregnated Polybenzimidazole Membranes 242 4.2.1 Synthesis of PBIs 243 4.2.2 Membrane Fabrication of PBIs 256 4.2.3 Structure and Properties of PBIs 259 4.2.4 Modification of PBIs 268 4.2.5 Composite Membranes of PBIs 271 4.2.6 Fuel Cell Technologies 272 References 276 5 Anion Exchange Membranes for Alkaline Fuel Cells 293 5.1 Introduction 293 5.2 Anion Exchange Membranes for Alkaline Fuel Cells 296 5.2.1 Heterogeneous Membranes 296 5.2.2 Interpenetrating Polymer Network 303 5.2.3 Homogeneous Membranes 304 5.3 Structure and Properties of AEMs 329 5.3.1 General Properties of AEMs 329 5.3.2 Properties of the Ionic Groups 331 5.3.3 Transport Mechanisms in AEMs 332 5.3.4 Stability of Alkaline AEMs 335 5.3.5 Examples of Chemical Stability of Ammonium Groups Toward OH- Attack 338 5.4 Application of AEMs 340 References 345 6 Polymers for New Types of Fuel Cells 360 6.1 Direct Liquid-Feed Fuel Cells 360 6.1.1 Introduction 360 6.1.2 Direct Liquid-Feed Fuels 361 6.1.3 Carbon-Free Fuels 369 6.2 Microbial Fuel Cells 373 6.2.1 Introduction 373 6.2.2 Materials of Construction 377 6.2.3 Outlook and Application of MFCs 379 6.3 Microfuel Cells 380 6.3.1 Introduction 380 6.3.2 Different Types of Microfuel Cells 382 6.3.3 Commercial Developments of Microfuel Cells 392 References 395 Index 407

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Book SynopsisThe highly successful Fieser & Fieser series has provided several generations of professional chemists and students with an timely survey of the reagent literature. Providing an up-to-date, A-to-Z listing of reagents cited in synthetic literature, Fiesers'' Reagents for Organic Synthesis, Volume 27 encompasses chemical literature from the end of 2009 to the end of 2011. Listed by common name, each entry feature a concise description, illustrations of chemical reactions, selected examples of applications, how to make it or buy it, what it is good for, and where to find complete details.Table of ContentsPreface vii Foreword ix General Abbreviations xi Reference Abbreviations xv Reagents 1 Author Index 527 Subject Index 618

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Book SynopsisAllylic boron compounds have gained a prominent position as a truly practical class of synthetic reagents in the past twenty-five years. Their main application as a method for the stereoselective synthesis of homoallylic alcohols by allyl-transfer to carbonyl compounds is essentially unmatched. In this process, a new carbon-carbon bond is formed, and up to two new stereogenic centers are created in a predictably controlled manner. Highly effective and general enantioselective variants are available, with countless applications in the total syntheses of polyacetate and polypropionate natural products. Furthermore, the residual allylic unit can be manipulated through a number of different transformations such as oxidative cleavage, olefin metathesis, hydrometalations, and many others. The discovery of Lewis and Brønsted acid catalyzed manifolds recently, has opened new doors for further development of this important reaction. This book provides an up-to-date, comprehensive survey of tTable of ContentsFOREWORD vii PREFACE ix ALLYLBORATION OF CARBONYL COMPOUNDS Dennis G. Hall and Hugo Lachance 1 INDEX 581

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Book SynopsisPolymers are increasingly finding applications in the areas of energy storage and conversion. This book assimilates these advances in the form of a comprehensive text that includes the synthesis and properties of a large number of polymer systems for applications in the areas of lithium batteries, photovoltaics, solar cells, etc.Table of ContentsPreface ix List of Contributors xi 1 High Performance Polymer Hydrogel based Materials for Fuel Cells 1 1.1 Introduction 1 1.2 Hydrogel Electrolyte 3 1.3 Poly(vinyl alcohol) Hydrogel 4 Summary 19 References 20 2 PVAc Based Polymer Blend Electrolytes for Lithium Batteries 27 2.1 Introduction 27 Conclusion 49 References 49 3 Lithium Polymer Batteries Based on Ionic Liquids 53 3.1 Lithium Batteries 54 3.2 Lithium Polymer Batteries Containing Ionic Liquids 61 Battery Performance 88 Glossary 94 References 96 4 Organic Quantum Dots Grown by Molecular Layer Deposition for Photovoltaics 103 4.1 Introduction 104 4.2 Molecular Layer Deposition 105 4.3 Concept of Solar Cells with Organic Quantum Dots 107 4.4 Polymer Multiple Quantum Dots 110 4.5 Molecular Multiple Quantum Dots 120 4.6 Waveguide-Type Solar Cells 127 4.7 Summary 135 References 135 5 Solvent Effects in Polymer Based Organic Photovoltaics 137 5.1 Introduction 137 5.2 Solar Cell Device Structure and Prepartion 139 5.3 Spin-Coating of Active Layer 141 5.4 Influence of Solvent on Morphology 143 5.5 Residual Solvent 152 5.6 Summary 156 Acknowledgment 157 References 157 6 Polymer-Inorganic Hybrid Solar Cells 163 6.1 Introduction 163 6.2 Hybrid Conjugated Polymer-Inorganic Semiconductor Composites 173 6.3 Conclusion 185 References 191 7 Semiconducting Polymer-based Bulk Heterojunction Solar Cells 199 7.1 Introduction 199 7.2 Optical Properties of Semiconducting Polymers 200 7.3 Electrical Properties of Semiconducting Polymers 206 7.4 Mechanical Properties Polymer Solar Cells 208 7.5 Processing of Polymers 210 7.6 State-of-the-art of the Technology 212 References 213 8 Energy Gas Storage in Porous Polymers 215 8.1 Introduction 216 8.2 Microporous Organic Polymers 217 8.3 Characterization of MOPs 239 Conclusion 242 List of Abbreviation 242 References 243

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Book SynopsisThis unique and comprehensive book covers all the recent physical, chemical, and mechanical advancements in encapsulation nanotechnologies. Encapsulation is prevalent in the evolutionary processes of nature, where nature protects the materials from the environment by engulfing them in a suitable shell.Table of ContentsPreface xiii List of Contributors xvii 1 Copper Encapsulation of Multi-Walled Carbon Nanotubes 1 1.1 Introduction 2 1.2 Preparation of Copper Encapsulated CNTs 3 References 37 2 Novel Nanocomposites: Intercalation of Ionically Conductive Polymers into Molybdic Acid 41 2.1 Introduction 41 2.2 Experimental 47 2.3 Intercalation into Molybdic Acid 48 2.4 Preparation of Polymer-Lithium Complexes 49 2.5 Instrumentation 50 2.6 Results and Discussion 51 2.7 Conclusions 68 References 68 3 Fluid-Bed Technology for Encapsulation and Coating Purposes 71 3.1 Introduction 71 3.2 Principles of Fluidization 74 3.3 Classification of Powders 78 3.4 Fluidized Bed Coaters 80 3.5 Fluid-Bed Coating and Encapsulation Processes 88 3.6 The Design, Optimization and Scale-Up of the Coating Process and the Apparatus 94 3.7 Numerical Modeling of Fluid-Bed Coating 97 References 101 4 Use of Electrospinning for Encapsulation 107 4.1 Introduction 107 4.2 Electrospun Structures for the Encapsulation of Bioactive Substances in the Food Area 112 4.3 Electrospun Encapsulation Structures for Biomedical Applications 117 4.4 Other Uses of Electrospinning for Encapsulation 124 4.5 Outlook and Conclusions 129 References 130 5 Microencapsulation by Interfacial Polymerization 137 5.1 Introduction 137 5.2 Generalities 141 5.3 Encapsulation by Heterophase Polymerization 144 5.4 Microencapsulation by Polyaddition & Polycondensation Interfacial 148 5.5 Microencapsulation by In Situ Polymerization 158 5.6 Conclusion 166 References 167 6 Encapsulation of Silica Particles by a Thin Shell of Poly(Methyl) Methacrylate 175 6.1 Introduction 176 6.2 Synthesis of Silica (Nano)Particles and Their Surface Modification 178 6.3 Encapsulation of Silica Particles in a Thin PMMA Shell 181 6.4 Summary 198 References 199 7 Organic Thin-Film Transistors with Solution-Processed Encapsulation 203 7.1 Introduction 203 7.2 Environment-Induced Degradations of OTFTs 205 7.3 Encapsulation of OTFTs 209 7.4 Summary and Outlook 221 References 221 8 Tunable Encapsulation Property of Amphiphilic Polymer Based on Hyperbranched Polyethylenimine 225 8.1 Introduction 226 8.2 Synthesis of PEI-CAMs 228 8.3 Unimolecularity versus Aggregate of PEI-CAMs 230 8.4 Host–Guest Chemistry of PEI-CAMs 231 8.5 Charge Selective Encapsulation and Separation 233 8.6 Recognition and Separation of Anionic–Anionic Mixtures by Core Engineering of a CAM 239 8.7 Modulation of the Guest Release of a CAM 247 8.8 Concluding Remarks 250 Acknowledgements 251 References 251 9 Polymer Layers by Initiated CVD for Thin Film Gas Barrier Encapsulation 255 9.1 Introduction 256 9.2 Initiated CVD Polymerization 258 9.3 Coating by Initiated CVD 268 9.4 Advantages of iCVD in Hybrid Multilayer Gas Barriers 272 9.5 Specific Requirements for the Use in Hybrid Multilayers 276 9.6 Multilayer Gas Barriers Containing Polymers by iCVD 281 9.7 Upscaling and Utilization 285 References 287 10 Polymeric Hollow Particles for Encapsulation of Chemical Molecules 291 10.1 Introduction 292 10.2 Colloidosome Approach 295 10.3 Internal Phase Separation/Precipitation Approach 299 10.4 Self-Assembly of Amphiphilic Copolymers (Copolymer Vesicles) 305 10.4.1 From Amphiphilic Copolymers 306 10.5 Layer-by-Layer (L-b-L) Deposition 310 10.6 Unimolecular Micelles Approach 315 10.7 Heterophase Polymerization 319 10.8 Key Design Features for Applications of Hollow Polymer Particles 332 10.9 Conclusions 340 References 341 11 Protic Ionic Liquids Confinement in Macro, Meso and Microporous Materials for Proton Conduction 347 11.1 Introduction 348 11.2 Structure and Properties of Materials for Proton Conduction 351 11.3 Encapsulation Procedures and Proton Conduction Performance 365 11.4 New Activities and Development Trends 383 References 386 12 Encapsulation Methods with Supercritical Carbon Dioxide: Basis and Applications 391 12.1 Introduction 391 12.2 Supercritical Fluids – Properties 392 12.3 Particle Engineering and Encapsulation with Supercritical Fluids 394 References 419 Index 425

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Book SynopsisDesigned for practitioners of organic synthesis, this book helps chemists understand and take advantage of rearrangement reactions to enhance the synthesis of useful chemical compounds. The book discusses synthetic applications for natural products, medicinal compounds, functional materials, and physical organic chemistry.Trade Review"a valuable teaching resource to those engaged in mentoring of advanced undergraduates and postgraduates........an accessible entry to the subject area for all students and practitioners of the art. Highly recommended." (Angewandte Chemie 2016)Table of ContentsLIST OF CONTRIBUTORS xvii PREFACE xxi PART 1 1,2-MIGRATIONS 1 1 Pinacol and Semipinacol Rearrangements in Total Synthesis 3 1.1 Introduction 3 1.2 Pinacol Reaction 4 1.3 Semipinacol Rearrangement 15 1.4 Conclusion 30 References 32 2 Baeyer–Villiger (BV) Oxidation/Rearrangement in Organic Synthesis 35 2.1 Introduction 35 2.2 Mechanism 35 2.3 Synthetic Applications 37 2.4 Summary and Outlook 55 References 55 3 The Wolff Rearrangement: Tactics, Strategies and Recent Applications in Organic Synthesis 59 3.1 Introduction 59 3.2 Tactics and Strategies via the Wolff Rearrangement 60 3.3 Mechanistic Features and Selectivity Issues of the Wolff Rearrangement 63 3.4 Preparation of α-Diazocarbonyl Compounds 64 3.5 Recent Synthetic Applications of the Wolff Rearrangement 67 3.6 Conclusion and Outlook 80 References 81 4 Alkyl and Acyl Azide Rearrangements 85 4.1 Introduction 85 4.2 Alkyl Azide Rearrangements 86 4.3 Acyl Azide Rearrangements 98 4.4 Hofmann Rearrangement 102 4.5 Lossen Rearrangement 104 4.6 Conclusion 107 References 108 5 Beckmann Rearrangements and Fragmentations in Organic Synthesis 111 5.1 Introduction 111 5.2 Strategic Planning: A Historical Perspective 118 5.3 Recent Applications Toward the Synthesis of Natural Products 121 5.4 Access to Diverse Scaffolds via the Beckmann Reaction 129 5.4.1 Diterpene Hydrocarbons 129 5.5 Formation of Heterocyclic Scaffolds 136 5.6 Synthesis of Functional Groups 140 5.7 Summary and Outlook 144 References 145 6 Brook Rearrangement 151 6.1 Introduction 151 6.2 Mechanism 152 6.3 Methods for Generation of α-Silyl Alkoxides 153 6.4 Synthetic Reactions Using Brook Rearrangements in the Reactions of Acylsilanes with Nucleophiles 154 6.5 Synthetic Reactions Using Brook Rearrangements Triggered by Deprotonation of α-Silyl Alcohols 166 6.6 Synthetic Reactions Using Brook Rearrangements Triggered by Addition of Silylmetallic Reagents 169 6.7 Synthetic Reactions Using Brook Rearrangements in β-Silyl Alkoxides Generated via Regioselective β-Ring-Opening of α, β-Epoxysilanes by a Nucleophile 172 6.8 Synthetic Reactions Using Brook Rearrangements in α-Silyl Alkoxides Generated by a Base-Induced Ring-Opening of alpha;, β-Epoxysilanes 173 6.9 Conclusion 176 References 178 PART II 1,2-MIGRATIONS VIA THREE-MEMBERED RINGS 183 7 The Quasi-Favorskii Rearrangement 185 7.1 Introduction 185 7.2 Retrons of the Quasi-Favorskii Rearrangement 191 7.3 Mechanistic Considerations in the Quasi-Favorskii Rearrangement 192 7.4 The Preparation of Substrates for the Quasi-Favorskii Rearrangement 193 7.5 Applications of the Quasi-Favorskii Rearrangement in Synthesis 199 7.6 Conclusions and Prospects 220 Acknowledgments 222 References 222 8 The Ramberg–Bäcklund Reaction 227 8.1 Introduction 227 8.2 Methods to Synthesize Sulfones as RBR Precursors 229 8.3 Variations of the RBR 231 8.4 Mechanistic Evaluation of the RBR 233 8.5 Strategic Considerations Relevant to the Use of the RBR in Synthesis 234 8.6 Utility, Scope, and Limitations of the RBR 236 8.7 Recent Applications of the RBR in the Synthesis of Complex Target Structures 246 8.7.1 Fawcettidine 246 8.8 Concluding Remarks 254 Acknowledgments 256 References 256 9 Applications of Di-л-Methane and Related Rearrangement Reactions in Chemical Synthesis 261 9.1 Introduction: The Basic Process and its Variants 261 9.2 Mechanistic Features and Competing Reactions 265 9.3 Structural Requirements of Substrates and Matters of Regio- and Stereochemistry 271 9.4 Synthetic Routes to Substrates and Applications in Synthesis 277 9.5 Outlook 284 References 285 PARTIII 1,3-TRANSPOSITIONS 289 10 Payne Rearrangement 291 10.1 Background on the Payne Rearrangement 291 10.2 Synthetic Applications of 2,3-Epoxy Alcohols 295 10.3 Utilization of the Payne Rearrangement for the Preparation of Fluorine-Containing Compounds 307 10.4 Conclusion 317 References 318 11 Vinylcyclopropane–Cyclopentene Rearrangement 323 11.1 Introduction 323 11.2 Thermal VCP–CP Rearrangement 324 11.3 Acid-Mediated VCP–CP Rearrangement 328 11.4 Mechanisms 330 11.5 Heteroatom-Containing Analogues of the VCP–CP Rearrangement 334 11.6 Applications in Synthesis 336 11.7 Photochemical VCP–CP Rearrangement 340 11.8 Metal-Catalyzed VCP–CP Rearrangement 346 11.9 Heteroatom Variants of the Metal-Catalyzed VCP–CP Rearrangement 354 11.10 Summary and Outlook 359 References 360 12 Ferrier Carbocyclization Reaction 363 12.1 Introduction 363 12.2 General Discussion and Mechanistic Features 365 12.3 Synthetic Strategies Based on the Ferrier Carbocyclization Reaction 373 12.4 Methodologies for Assembling the Ferrier Carbocyclization Reaction Substrates 377 12.5 Applications of the Ferrier Carbocyclization Reaction in Natural Product Synthesis 380 12.6 Conclusion 397 References 398 PARTIV [3,3]- AND [2,3]-SIGMATROPIC REARRANGEMENTS 401 13 The Claisen Rearrangement 403 13.1 Introduction 403 13.2 Strategic Planning for the Claisen Rearrangement Reaction 407 13.3 Mechanistic Features of the Claisen Rearrangement Reaction 409 13.4 Methodologies for Synthesis of Claisen Rearrangement Substrates 417 13.5 Applications of the Claisen Rearrangement Reaction in Target-Oriented Synthesis 421 13.6 Conclusions 426 References 427 14 [3,3]-Sigmatropic Rearrangements with Heteroatom–Heteroatom Bonds 431 14.1 Introduction 431 14.2 [3,3]-Sigmatropic Rearrangements of N–O Bonds 434 14.3 [3,3]-Sigmatropic Rearrangements of N–N Bonds 445 14.4 [3,3]-Rearrangements of N–N Bond Fragments that Eliminate N2 451 14.5 Summary 454 References 455 15 [2,3]-Rearrangements of Ammonium Zwitterions 459 15.1 Introduction 459 15.2 [2,3]-Meisenheimer Rearrangement of Amine N-Oxides 460 15.3 [2,3]-Stevens Rearrangement of Ammonium Ylides 479 15.4 Conclusion and Outlook 492 References 493 16 Oxonium Ylide Rearrangements in Synthesis 497 16.1 Introduction 497 16.2 Applications in Synthesis: Oxonium Ylide [2,3]-Sigmatropic Rearrangements 507 16.3 Applications in Synthesis: Oxonium Ylide [1,2]-Stevens Rearrangements 528 16.4 Concluding Remarks 535 References 536 17 The [2,3]-Wittig Rearrangement 539 17.1 Introduction 539 17.2 [2,3]-Wittig Rearrangement of Allyl Propargyl Ethers 541 17.3 Factors Determining [2,3]-Wittig Versus [1,2]-Wittig Rearrangement 544 17.4 Acyclic [2,3]-Wittig Rearrangement of Propargyl-Allyl Ethers 547 17.5 [2,3]-Wittig–Still Rearrangement 552 17.6 Asymmetric [2,3]-Wittig Rearrangement 554 17.7 Aza-[2,3]-Wittig Rearrangement 555 17.8 Other Wittig Rearrangements and Miscellaneous 560 17.9 Conclusion 565 References 565 18 The Mislow–Evans Rearrangement 569 18.1 Introduction 569 Part 1 Mechanistic Aspects and the [2,3] Nature of the Rearrangement 571 18.2 Configurational Lability of Allylic Sulfoxides 571 18.3 Deuterium Labeling to Track [2,3] Pathway 573 18.4 Transition State Features 573 18.5 Equilibrium Between Sulfoxide and Sulfenate 576 18.6 Chirality Transfer 579 Part 2 Synthetic Considerations and Applications 580 18.7 Alkene Stereoselectivity 580 18.8 Diastereoface Selectivity in the Rearrangement 583 18.9 Epimerizations via Mislow–Evans Rearrangement Sequences 591 18.10 Vinyl Anion Synthons Accessible via Mislow–Evans Rearrangement 593 18.11 Sequential Processes Incorporating the Mislow–Evans Rearrangement 598 18.12 Heteroatom [2,3]-Rearrangement Variants 614 18.13 [2,3]-Rearrangements of Propargyl and Allenyl Sulfenates and Sulfoxides 620 18.14 Conclusion 622 References 622 PART V IPSO REARRANGEMENTS 627 19 Smiles Rearrangements 629 19.1 Introduction 629 19.2 Scope and Mechanistic Features 632 19.3 Application of Smiles Rearrangements 635 19.4 Conclusion 657 References 658 20 Pummerer-Type Reactions as Powerful Tools in Organic Synthesis 661 20.1 Introduction 661 20.2 Classical Pummerer Reaction 662 20.3 Vinylogous Pummerer Reaction 674 20.4 Interrupted and Additive Pummerer Reactions 680 20.5 Connective Pummerer Reaction 687 20.6 Pummerer Rearrangement in Multiple-Reaction Processes 693 20.7 Other Pummerer Rearrangements 696 20.8 Summary and Outlook 700 References 700 INDEX 703

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Book SynopsisEdited by leading researchers and technologists, Non-Destructive Evaluation of Corrosion is the only book to discuss the interdisciplinary topic of non-destructive evaluation of degradation of materials due to environment.Table of ContentsList of Contributors ix Foreword xi Preface xiv 1 Nondestructive Testing: An Overview of Techniques and Application for Quality Evaluation 1B. Venkatraman and Baldev Raj 2 Corrosion: An Overview of Types, Mechanism, and Requisites of Evaluation 56U. Kamachi Mudali, J. Jayaraj, R.K. Singh Raman and Baldev Raj 3 Nondestructive Evaluation of Corrosion: Case Studies I 75Paritosh Nanekar, N. Jothilakshmi and Baldev Raj 4 NDE Methods for Monitoring Corrosion and Corrosion‐assisted Cracking: Case Studies II 101B.P.C. Rao and Baldev Raj 5 Lock‐in Thermography for the Wide Area Detection of Paint Degradation and Incipient Corrosion 122R. Jones, M. Lo, M. Dorman, A. Bowler, D. Roles and S.A. Wade 6 Electrochemical Impedance Spectroscopy for Nondestructive Evaluation of Corrosion Processes 160V.S. Raja 7 Electrochemical Noise as Nondestructive Evaluation Technique for Understanding and Monitoring Corrosion 198Girija Suresh, U. Kamachi Mudali and Baldev Raj 8 Evaluation of Cracking and Spallation of Oxide Scales by Acoustic Emission 245M.B. Venkataraman, Prabhakar Singh and R.K. Singh Raman 9 Nondestructive Testing and Corrosion Monitoring 261Alec Groysman Index 410

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Book SynopsisA clear explanation of the cause, diagnosis, and treatment of diabetes Written for a broad range of readers, including students, researchers, policymakers, health care providers, and diabetes patients and caregivers, this book explains the underlying biochemistry and physiology of diabetes mellitus.Trade Review“I think that it would be of most use to young diabetologists and chemical pathologists early in their training to ensure that they understand the foundations and principles of the condition they are seeing every day.” (Diabetes Update, 1 October 2013) “Without doubt, this is an interesting and unique book with major merits. It succeeds in closing a gap not filled by other books and in giving fresh insights into biochemistry.” (ChemMedChem, 1 August 2013) Table of ContentsPREFACE xvii 1 DIABETES MELLITUS: A PANDEMIC IN THE MAKING 1 Diabetes Prevalence and Cost in the United States 2 A Dire Prediction Based on Alarming Data 2 The Increase of Diabetes in Youths 4 The Cost 6 Diabetes Prevalence and Cost Worldwide 7 A Worldwide Epidemic 7 Numbers of Cases of Diabetes 7 Cost 7 Obesity and Overweight; Another Epidemic in the United States 9 A Parallel Pandemic 9 Definitions of Overweight and Obesity 9 Overweight and Obesity among Adults in the United States 9 Obesity and Overweight among Children and Adolescents in the United States 12 Overweight and Obesity Worldwide 14 Overweight and Obesity Globally in Adults 14 Overweight and Obesity in Children 16 The Relationship Between Obesity and Diabetes 16 Projects and Questions 18 Glossary 18 References 19 2 AN EARLY HISTORY OF DIABETES MELLITUS 23 Translation 24 More simply stated 24 The Ebers Papyrus 24 Neandertals 25 Hippocrates, Aretaeus, and Demetrius 25 Galen 26 Sushruta 27 Ibn Sina (Avicenna) 28 The Yellow Emperor 29 Japanese Medicine 29 Paracelsus (Philippus Aureolus Theophrastus Bombastus von Hohenheim) 30 Thomas Willis 31 Johann Conrad Brunner 31 Matthew Dobson 31 John Rollo and William Cruickshane 32 Thomas Cawley 33 Michel Eugene Chevreul 34 Claude Bernard 34 Paul Langerhans (Edouard Laguesse and Eugene L. Opie) 35 Oscar Minkowski and Josef von Mering 36 Advances in Sugar (Glucose) Determinations 37 Earliest Approaches—Taste and Fermentation 37 Evaporation of Urine to Yield Sugar Crystals 38 Moore’s Test 38 Trommer’s Test 39 Barreswil and Fehling’s Solutions 39 Frederick Pavy 40 Benedict’s Solution 40 Folin–Wu Determination of Blood Glucose 41 Banting, Best, and MacLeod 43 Leonard Thompson 44 John Jacob Abel 45 Frederick Sanger 45 Pedro Cuatrecasas 48 Questions and Crossword Puzzle 50 References 52 3 A PRIMER: GLUCOSE METABOLISM 55 Prolog 55 The Carbohydrates and their Function 56 Digestion and Absorption of Carbohydrates 57 Salivary and Pancreatic Amylase 57 Disaccharidases 58 Absorption 59 Overview of Glucose Metabolism 60 Adenosine 5 -Triphosphate (ATP) 61 Glucose Metabolism 63 Glucose Transport into Cells 63 Phosphorylation of Glucose 64 Introduction to Glycogen Synthesis and Hydrolysis 65 Beautiful Concepts 65 Glycogen Synthesis 66 Uridine Bisphosphate Glucose (UBP-Glucose) 67 Glycogen Synthase 67 Branching Enzyme 69 Glycogenolysis 69 Debranching Enzyme 70 Glycogen Phosphorylase 71 Phosphoglucomutase 71 Glucose 6-Phosphatase 72 α(1 → 4)-Glucosidase 72 Synchronization of Glycogenesis and Glycogenolysis (A Beautiful Pathway) 72 Dephosphorylation 73 Effectors 73 Glycolysis (Glycolytic Pathway) 75 Phosphoglucose Isomerase 75 Phosphofructokinase 76 Aldolase 76 Triose Phosphate Isomerase 76 Glyceraldehyde 3-Phosphate Dehydrogenase 77 Erythrocyte Bisphosphoglyceromutase and Bisphosphoglycerate Phosphatase 77 3-Phosphoglycerate Kinase 78 Phosphoglyceromutase 78 Enolase 78 Pyruvate Kinase 78 Lactate Dehydrogenase 79 Tricarboxylic Acid Cycle 80 The Coenzymes: Nicotinamide Adenine Dinucleotide (NAD+) and Flavin Adenine Dinucleotide (FADH) 81 Steps in the Tricarboxylic Acid Cycle 83 Pyruvate Dehydrogenase; Acetyl CoA 83 Pyruvate Decarboxylase 84 Dihydrolipoyl Transacetylase 85 Dihydrolipoyl Dehydrogenase 86 Citrate Synthase 86 Aconitase 86 Isocitrate Dehydrogenase 87 α-Ketoglutarate Dehydrogenase 87 Succinate Dehydrogenase 88 Fumarase 89 l-Malate Dehydrogenase 89 Pyruvate Carboxylase 89 Glycolysis 90 Tricarboxylic Acid Cycle 90 Sum Total of Glycolysis and Tricarboxylic Acid Cycle 90 Summary 90 The Electron Transport System and Oxidative Phosphorylation 91 Steps in the Electron Transport System 92 Oxidative Phosphorylation (ATP Synthase) 95 Shuttles 97 Glycerol 3-Phosphate Shuttle 97 Malate–Aspartate Shuttle 97 Moles ATP Produced by Oxidative Phosphorylation from 1 mol of Glucose 97 The Phosphogluconate Oxidative Cycle 98 Steps in The Phosphogluconate Oxidative Cycle 99 Glucose 6-Phosphate Dehydrogenase; Lactonase 99 Transaldolase 101 Transketolase 101 The Fate of Glyceraldehyde 3-phosphate 101 Uronic Acid Pathway 103 Hexosamine Biosynthesis Pathway 104 The Steps of Gluconeogenesis 105 Conclusions 108 Questions 108 Glossary 109 4 REGULATION OF GLUCOSE METABOLISM 113 Insulin 114 Structure 114 Transport and Secretion of Insulin 114 Insulin Signaling Pathways 118 Akt Pathway 119 GLUT4 Translocation 120 Insulin-Stimulated Glycogenesis 121 Insulin-Stimulated Inhibition of Gluconeogenesis 123 Insulin-Stimulated Protein Synthesis 123 Insulin-Stimulated Lipogenesis (Fatty Acid Synthesis) 124 Insulin-Inhibited Lipolysis (Fatty Acid Hydrolysis) 124 Scaffold Proteins 125 The Incretin Hormones (Incretins) 128 Amylin 131 Other Hormones 133 Glucagon 133 Epinephrine 135 Somatotropin (Growth Hormone) 137 Somatostatin (SST) 139 Cortisol 140 Adrenocorticotropin 142 Thyroid Hormones 143 Insulin-Like Growth Factor (IGF) 146 Fibroblast Growth Factor 19 146 Adenosine 5 -Monophosphate-Activated Protein Kinase 147 Glossary 149 References 150 5 GLUCOSE METABOLISM GONE WRONG 153 Pancreatic β-Cell Mass 156 Glucose Transport and Hexokinase 158 Glycogen Synthesis and Breakdown 160 Glycogen Cycling 161 Gluconeogenesis and Glycogenolysis 164 Glycolysis, Glucose Oxidation, and Pyruvate Dehydrogenase 166 Mitochondrial Defects 169 Tricarboxylic Acid Pathway and Oxidative Phosphorylation 169 Hexosamine Biosynthesis Pathway 174 Techniques Used in the Investigations 175 Hyperinsulinemic-Euglycemic Clamp 175 Vastus Lateralis Muscle Biopsy 176 Glossary 176 References 177 6 CLASSIFICATION SYSTEM FOR DIABETES MELLITUS 183 T1D 184 Latent Autoimmune Diabetes (LADA) or Type 1.5 184 T2D 187 Hybrid 187 Idiopathic Diabetes (T1b) 187 Secondary 187 Genetic Defects of β-islet Function 188 Mody 188 Other Genetic Defects of the β-cell 189 Genetic Defects in Insulin Action 189 Diseases of the Exocrine Pancreas 190 Endocrinopathies 190 Drug or Chemically Caused Diabetes 190 Infections 191 Uncommon Forms of Immune-Mediated Diseases 191 Other Genetic Syndromes Sometimes Associated With Diabetes 192 Prediabetes 192 Gestational Diabetes Mellitus (GDM) 193 Statistical Risk Classes 194 Metabolic Syndrome 195 Glossary 197 References 198 7 DIAGNOSIS OF DIABETES MELLITUS 201 PART 1: Establishing a Normal Range 201 The Concept of Normal and Abnormal Populations 201 The Probability Factor in Diagnosing Disease 203 Probability of Disease and Prevalence 203 The Normal Range 204 Assay Sensitivity and Specificity 205 Relationships Among Sensitivity, Specificity, Prevalence, Predictability, and Normal Range 207 Exercise 208 How Does One Choose a Normal Range? 209 Truthfulness (Efficiency) 209 Non-gaussian Distribution 210 The Effect of Reproducibility on Sensitivity and Specificity 210 Severity of Disease and Assay Results 211 Parallel and Series Multiparameter Testing 212 Exercise 213 Example 215 Example 216 References 216 PART 2: Modern Techniques for the Quantitation of Glucose 216 Methods of Historical Interest 216 Modern-day Methods of Measuring Glucose 218 Glucose OxidasePeroxidaseChromogen 218 HexokinaseNADP 220 Exercise 221 Glycated Hemoglobin 221 Specimen Collection 223 Exercise 225 The Gold Standard 225 Instrumentation 226 References 229 PART 3: Symptoms and Tools for the Diagnosis of Diabetes Mellitus 230 The Symptoms of Diabetes Mellitus 231 Individuals Who Should be Tested for Diabetes 231 Tools for the Diagnosis of Diabetes 233 Urinary Glucose 233 Fasting Blood Glucose 233 Oral Glucose Tolerance Test 234 HbA1c 235 Cut Points for the Diagnosis of Diabetes 237 Diagnosis of Diabetes Using FBG, 2-h PG, or HbA1c 239 Diagnosis of Gestational Diabetes Mellitus 239 Autoimmune Antibodies as Predictors for T1D And LADA 241 Glossary 245 References 246 8 COMPLICATIONS OF DIABETES MELLITUS AND THEIR PATHOPHYSIOLOGY 249 The Complications of Diabetes Mellitus 249 Retinopathy and Other Eye Complications 249 Neuropathy and Related Conditions 252 Nephropathy, Diabetic Kidney Disease (DKD), and End-Stage Renal Disease 254 Cardiovascular Disease (CVD), Hypertension, Coronary Heart Disease or Coronary Artery Disease (CHD), Cerebrovascular Accident (CVA), Pathophysiology of CVD: Endothelial Dysfunction 258 The Pathophysiology of CVD: Endothelium Dysfunction 260 Diabetic Ketoacidosis (DKA) 265 Hyperglycemic Hyperosmolar Non-Ketotic Syndrome 266 Hypoglycemia 266 Infections 267 Alzheimer’s Disease or Alzheimer Disease (AD) 269 Diabetes and Cancer 270 Pathophysiology of Diabetic Complications 272 Glycation 272 Sorbitol Accumulation 275 Reactive Oxygen Species (ROS) in Diabetes 275 Glossary 278 References 278 9 HEREDITARY TRANSMISSION OF DIABETES MELLITUS 283 Inheritance of T1D in Monozygotic and Dizygotic Twins 284 Pairwise and Probandwise Concordance in T1D 284 Pairwise and Probandwise Concordance in T2D 286 Diabetes in Offspring of One or Two Diabetic Conjugal (Biological) Parents 288 Diabetes in Siblings of Diabetics 289 Summary 289 The Genetic Component of Diabetes Mellitus 290 The Major Histocompatibility Complex Proteins or Human Lymphocyte Antigens and Disease 290 Online Mendelian Inheritance in Man 293 HLA Nomenclature 294 HLas and Diabetes Mellitus 295 T1D and Class II Genes 295 T1D and Class I Genes 297 Non-HLA T1D Promoting Alleles 298 Genetics of T2D 298 T1D and Environment 306 Enteroviruses (Coxsackie B Virus) 308 Rubella Virus (German Measles) 309 Mumps Virus 310 Cytomegalovirus 310 Retrovirus 310 Reovirus and Rotavirus 310 Epstein–Barr Virus 311 Viruses that Need More Evidence for the Assumption that They Promote T1D in Humans 311 Viruses That Produce T1D in Animals but so Far no Evidence in Humans 311 Other Environmental Factors 312 Early Exposure to Cow’s Milk as Opposed to Breast Milk 312 Vitamin D 313 Summary 314 Genes and Obesity 314 The FTO Gene 315 The KLF14 Gene 316 Projects 317 Glossary 317 References 318 10 TREATMENT 323 PART 1: Medicinal Treatment 323 Insulin (Early Treatment) 323 It is Not Your Father’s Insulin Any More Modern-Day Human Insulin 326 Genetically Engineered Insulin Derivatives 327 Other Modes of Delivering Insulin: Tablets or Capsules, Inhalable Insulin and Nasal Spray Insulin 330 Closed-Loop Insulin Delivery (Artificial Pancreas) 330 Islet Transplantation and Stem Cell Therapy 331 Antidiabetic Oral Drugs 332 Sulfonylureas 332 Biguanides 333 Thiazolidinediones 335 Incretin-Based Inhibitors 335 Exenatide 337 Liraglutide 337 Albiglutide and Taspoglutide (Long-Acting Release) 337 Sitagliptin, Vildagliptin, and Saxagliptin 337 Amylin Derivatives (Pramlintide) 339 Glucokinase Activators (GKA): Potential Anti Diabetic Compounds 340 α-Glucosidase Inhibitors 341 Other New Strategies that are in the Clinical Trials Phase 342 SGLT2 Inhibitors 342 11β-Hydroxysteroid Dehydrogenase Type 1 Inhibitors 342 References 343 PART 2: Prevention, Delay and Management 345 Prevention and Delay 345 Exercise 346 Evidence 347 Diet 349 Biochemistry of the Beneficial Effects of Exercise 349 Gastric Bypass Surgery (A Cure for T2D?) 350 Project 352 Glossary 352 References 352 POSTSCRIPT 355 The Future 355 APPENDIX A 357 General Assembly 358 The White House 359 APPENDIX B 361 Problems 361 INDEX 377

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Book SynopsisGeneral, Organic and Biological Chemistry, 4th Edition has been written for students preparing for careers in health-related fields such as nursing, dental hygiene, nutrition, medical technology and occupational therapy. It is also suited for students majoring in other fields where it is important to have an understanding of the basics of chemistry. An integrated approach is employed in which related general chemistry, organic chemistry, and biochemistry topics are presented in adjacent chapters. This approach helps students see the strong connections that exist between these three branches of chemistry, and allows instructors to discuss these, interrelationships while the material is still fresh in students'' minds.Table of Contentschapter 1 Science and Measurements 1 1.1 The Scientific Method 2 HealthLink Science and Medicine5 1.2 Matter and Energy 5 1.3 Units of Measurement 9 1.4 Scientific Notation, SI and Metric Prefixes 13 1.5 Measurements and Significant Figures 15 HealthLink Body Mass Index 18 HealthLink Body Temperature 21 1.6 Conversion Factors and the Factor Label Method 22 1.7 Density, Specific Gravity, and Specific Heat 25 HealthLink Making Weight 28 1.8 Measurements in General Chemistry,Organic Chemistry, and Biochemistry 29 chapter 2 A toms and Elements 42 2.1 Atoms 44 2.2 Elements 46 2.3 Trace Elements 48 2.4 Atomic Number and Mass Number 51 HealthLink Stable Isotopes and Drug Testing 53 2.5 Periodic Table 54 HealthLink Lead 58 2.6 The Mole 59 2.7 The Arrangement of Electrons 62 BiochemistryLink Bioluminescence 67 2.8 Radioactive Isotopes 68 2.9 Radioisotopes in Medicine 71 HealthLink Radioisotopes for Sale 79 HealthLink CT and MRI Imaging 79 chapter 3 Compounds 88 3.1 Ions 90 3.2 The Octet Rule 93 BiochemistryLink Ionophores and Biological Ion Transport 95 3.3 Ionic Compounds 96 HealthLink Pass the Salt, Please 100 3.4 Covalent Bonds 101 3.5 Molecules 103 HealthLink Dental Fillings 105 3.6 Formula Weight, Molecular Weight,and Molar Mass 105 HealthLink Nitric Oxide 108 chapter 4 An Introduct ion to Organic Compounds 116 4.1 Structural Formulas 118 4.2 Polar Covalent Bonds, Shape, and Polarity 123 HealthLink Prion Diseases 128 4.3 Noncovalent Interactions 130 4.4 Families of Organic Compounds 132 BiochemistryLink Ethylene, a Plant Hormone 134 HealthLink Sunscreens 139 chapter 5 Reactions 150 5.1 Chemical Equations 152 5.2 Reaction Types 156 5.3 Reactions Involving Water 158 5.4 Oxidation and Reduction 161 HealthLink Antiseptics and Oxidation 166 5.5 Mole and Mass Relationships in Reactions 167 5.6 Calculating the Yield of a Reaction 171 5.7 Free Energy and Reaction Rate 174 HealthLink Carbonic Anhydrase 177 chapter 6 Gases, Solutions,Colloids, and Suspensions 190 6.1 Gases and Pressure 192 HealthLink Blood Pressure 196 6.2 The Gas Laws 197 6.3 Partial Pressure 202 HealthLink Breathing 203 6.4 Solutions 204 6.5 Precipitation Reactions 207 6.6 Solubility of Gases in Water 209 6.7 Organic and Biochemical Compounds 212 HealthLink Prodrugs 215 6.8 Concentration 216 6.9 Dilution 221 6.10 Colloids and Suspensions 222 HealthLink Saliva 224 6.11 Diffusion and Osmosis 225 HealthLink Diffusion and the Kidneys 227 chapter 7 Acids, Bases, and Equilibrium 238 7.1 Acids and Bases 240 7.2 Brønsted–Lowry Acids and Bases 241 7.3 Equilibrium 243 7.4 Le Châtelier’s Principle 246 BiochemistryLink Diving Mammals, Oxygen, and Myoglobin 249 7.5 Ionization of Water 250 7.6 The pH Scale 251 7.7 Acid and Base Strength 254 BiochemistryLink Plants as pH Indicators 257 7.8 Neutralizing Acids and Bases 257 7.9 Effect of pH on Acid and Conjugate Base Concentrations 259 7.10 Buffers 261 BiochemistryLink The Henderson–Hasselbalch Equation 262 7.11 Maintaining the pH of Blood Serum 263 chapter 8 Organic Reactions 1—Hydrocarbons,Carboxylic Acids,Amines, and Related Compounds 276 8.1 Alkanes 278 8.2 Constitutional Isomers 282 8.3 Conformations 284 8.4 Cycloalkanes 285 8.5 Alkenes, Alkynes, and Aromatic Compounds 287 8.6 Reactions of Hydrocarbons 291 8.7 Carboxylic Acids 297 8.8 Phenols 299 HealthLink A Chili Pepper Painkiller 300 8.9 Carboxylic Acids and Phenols as Weak Organic Acids 301 8.10 Preparing Esters 304 HealthLink Alpha Hydroxy Acids 306 8.11 Amines 307 HealthLink Adrenaline and Related Compounds 310 8.12 Amines as Weak Organic Bases 311 8.13 Amides 313 HealthLink Biofilms 315 BiochemistryLink A Cure for Fleas 316 chapter 9 Organic Reactions 2—Alcohols, Ethers, Aldehydes, and Ketones 334 9.1 Alcohols, Ethers, and Related Compounds 336 9.2 Preparation 339 9.3 Reactions 341 9.4 Aldehydes and Ketones 344 9.5 Oxidation of Aldehydes 347 HealthLink Aldehyde Dehydrogenase 349 9.6 Reduction of Aldehydes and Ketones 349 HealthLink Protective Enzymes 351 9.7 Reactions of Alcohols with Aldehydes and Ketones 352 HealthLink Drugs in the Environment 354 chapter 10 Carbohydrates 370 10.1 Monosaccharides 372 10.2 Stereoisomers 374 10.3 Important Monosaccharides and Monosaccharide Derivatives 381 10.4 Reactions of Monosaccharides 384 10.5 Monosaccharides in Their Cyclic Form 386 10.6 Oligosaccharides 390 HealthLink Natural and Artificial Sweeteners 397 HealthLink Stevia 400 10.7 Polysaccharides 401 chapter 11 Lipids and Membranes 420 11.1 Fatty Acids 422 HealthLink Omega-3 Fatty Acids 426 11.2 Waxes 427 11.3 Triglycerides 429 HealthLink Trans Fats 435 HealthLink Olestra 436 11.4 Phospholipids and Glycolipids 437 11.5 Steroids 441 HealthLink Anabolic Steroids 445 11.6 Eicosanoids 445 11.7 Membranes 447 chapter 12 Peptides, Proteins, and Enzymes 458 12.1 Amino Acids 460 12.2 The Peptide Bond 464 12.3 Peptides, Proteins, and pH 468 12.4 Protein Structure 469 BiochemistryLink Hemoglobin, a Globular Protein, and Collagen, a Fibrous Protein 475 HealthLink Immunotherapy 476 12.5 Denaturation 477 12.6 Enzymes 478 12.7 Control of Enzyme-Catalyzed Reactions 482 HealthLink Tamiflu and Relenza as Enzyme Inhibitors 486 HealthLink Proteins in Medicine 489 chapter 13 Nucleic Acids 498 13.1 Nucleic Acid Building Blocks 500 13.2 Nucleoside Di- and Triphosphates, Cyclic Nucleotides 505 13.3 Polynucleotides 506 13.4 DNA Structure 509 13.5 Denaturation 512 13.6 Nucleic Acids and Information Flow 514 13.7 DNA Replication 515 13.8 Transcription and RNA 517 HealthLink Lupus 519 13.9 Translation 520 13.10 Control of Gene Expression 522 HealthLink RNA Interference 524 13.11 Mutation 524 13.12 Recombinant DNA 525 BiochemistryLink Glowing Cats 528 13.13 DNA Fingerprinting 529 chapter 14 Metabolism 540 14.1 Metabolic Pathways, Energy, and Coupled Reactions 542 14.2 Overview of Metabolism 543 14.3 Digestion 548 14.4 Glycolysis 551 14.5 Gluconeogenesis 556 14.6 Glycogen Metabolism 558 14.7 Citric Acid Cycle 560 14.8 Electron Transport Chain and Oxidative Phosphorylation 562 HealthLink Brown Fat 566 14.9 Lipid Metabolism 566 14.10 Amino Acid Metabolism 571 Appendix A Important Families of Organic Compounds 582 Appendix B Naming Ions, Ionic Compounds, Binary Molecules, and Organic Compounds 584 Appendix C Answers to Odd-Numbered Problems 591 Appendix D Glossary 639 Index I-1

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Book SynopsisThis volume in the venerable Organic Reactions series contains three chapters focusing on the introduction or the removal of nitrogen from organic compounds. The first chapter features a classic chemical reaction for introducing nitrogen into organic compounds, namely the Schmidt Reaction. The second chapter highlights a less-well-known yet fascinating transformation that introduces nitrogen into organic compounds, The Neber Rearrangement. The third chapter describes an unusual class of reactions that involve the loss of small molecular fragments from a ring, where separate carbon atoms unite to form alkenes.Table of ContentsCHAPTER PAGE 1. THE SCHMIDT REACTION Aaron Wrobleski, Thomas C. Coombs, Chan Woo Huh, Sze-Wan Li, and Jeffrey Aub´e 1 2. THE NEBER REARRANGEMENT William F. Berkowitz 321 3. TWOFOLD EXTRUSION REACTIONS Lynn James Guziec and Frank S. Guziec, Jr 411 CUMULATIVE CHAPTER TITLES BY VOLUME 551 AUTHOR INDEX, VOLUMES 1–78 567 CHAPTER AND TOPIC INDEX, VOLUMES 1–78 573

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Book SynopsisIn the wake of rapid advances in genetic technologies, new products continue to be developed to help improve human health and quality of life.Table of ContentsList of Contributors xi Part I Case Study 1 1 Bacillus and the Story of Protein Secretion and Production 3Giulia Barbieri, Anthony Calabria, Gopal Chotani, and Eugenio Ferrari 1.1 Bacillus as a Production Host: Introduction and Historical Account 3 1.2 The Building of a Production Strain: Genetic Tools for B. subtilis Manipulation 5 1.2.1 Promoters 5 1.2.2 Vectors for Building a Production Strain 6 1.2.3 B. subtilis Competent Cell Transformation 7 1.2.4 Protoplasts-Mediated Manipulations 9 1.2.5 Genetics by Electroporation 9 1.3 B. subtilis Secretion Systemand Heterologous Protein Production 9 1.3.1 Bacillus Fermentation and Recovery of Industrial Enzyme 11 1.3.2 Fermentation Stoichiometry 12 1.3.3 Fermentor Kinetics and Outputs 14 1.3.4 Downstream Processing 17 1.4 Summary 21 References 21 2 New Expression Systems for GPCRs 29Dimitra Gialama, Fragiskos N. Kolisis, and Georgios Skretas 2.1 Introduction 29 2.2 Recombinant GPCR Production – Traditional Approaches for Achieving High-Level Production 39 2.3 Engineered Expression Systems for GPCR Production 42 2.3.1 Bacteria 42 2.3.2 Yeasts 48 2.3.3 Insect Cells 51 2.3.4 Mammalian Cells 54 2.3.5 Transgenic Animals 54 2.3.6 Cell-Free Systems 56 2.4 Conclusion 57 References 58 3 Glycosylation 71Maureen Spearman, Erika Lattová, Hélène Perreault, andMichael Butler 3.1 Introduction 71 3.2 Types of Glycosylation 72 3.2.1 N-linked Glycans 72 3.2.2 O-linked Glycans 74 3.3 Factors Affecting Glycosylation 76 3.3.1 Nutrient Depletion 76 3.3.2 Fed-batch Cultures and Supplements 79 3.3.3 Specific Culture Supplements 80 3.3.4 Ammonia 82 3.3.5 pH 82 3.3.6 Oxygen 83 3.3.7 Host Cell Systems 83 3.3.8 Other Factors 85 3.4 Modification of Glycosylation 86 3.4.1 siRNA and Gene Knockout/Knockin 86 3.4.2 Glycoprotein Processing Inhibitors and In Vitro Modification of Glycans 88 3.5 Glycosylation Analysis 89 3.5.1 Release of Glycans from Glycoproteins 90 3.5.2 Derivatization of Glycans 91 3.6 Methods of Analysis 91 3.6.1 Lectin Arrays 91 3.6.2 Liquid Chromatography 93 3.6.2.1 HILIC Analysis 93 3.6.2.2 Reversed Phase (RP) and Porous Graphitic Carbon (PGC) Chromatography 95 3.6.2.3 Weak Anion Exchange (WAX) HPLC Analysis 96 3.6.2.4 High pH Anion Exchange Chromatography with Pulsed Amperometric Detection (HPAEC-PAD) 96 3.6.3 Capillary Electrophoresis (CE) 97 3.6.4 Fluorophore-assisted Carbohydrate Electrophoresis (FACE) and CGE-LIF 99 3.6.5 Mass Spectrometry (MS) 100 3.6.5.1 Ionization 100 3.6.5.2 Derivatization Techniques Used for MS Analysis of Glycans 102 3.6.5.3 Fragmentation of Carbohydrates 103 3.7 Conclusion 109 References 109 Part II Bioreactors 131 4 Bioreactors for StemCell and Mammalian Cell Cultivation 133Ana Fernandes-Platzgummer, Sara M. Badenes, Cláudia L. da Silva, and JoaquimM. S. Cabral 4.1 Overview of (Mammalian and Stem) Cell Culture Engineering 133 4.1.1 Cell Products for Therapeutics 134 4.1.2 Cell as a Product: Stem Cells 136 4.2 Bioprocess Characterization 140 4.2.1 Cell Cultivation Methods 140 4.2.2 Cell Metabolism 141 4.2.3 Culture Medium Design 143 4.2.4 Culture Parameters 144 4.2.5 Culture Modes 145 4.3 Cell Culture Systems 147 4.3.1 Static Culture Systems 147 4.3.2 Roller Bottles 150 4.3.3 Spinner Flask 150 4.3.4 Airlift Bioreactor 151 4.3.5 Fixed/Fluidized-Bed Bioreactor 152 4.3.6 Wave Bioreactor 152 4.3.7 Rotating-Wall Vessel Bioreactor 154 4.3.8 Stirred Tank Bioreactor 155 4.3.8.1 Agitation/Shear Stress 156 4.4 Cell Culture Modeling 157 4.5 Case Studies 159 4.5.1 Antibody Production in Bioreactor Systems 159 4.5.2 mESC Expansion on Microcarriers in a Stirred Tank Bioreactor 161 4.6 Concluding Remarks 162 List of Symbols 163 References 164 5 Model-Based Technologies Enabling Optimal Bioreactor Performance 175Rimvydas Simutis, Marco Jenzsch, and Andreas Lübbert 5.1 Introduction 175 5.2 Basics 176 5.2.1 Balances 176 5.2.2 Model Identification 177 5.2.3 Model-Based Process Optimization 178 5.3 Examples 180 5.3.1 Model-Based State Estimation 180 5.3.1.1 Static Model Approach 180 5.3.1.2 Dynamic Alternatives 183 5.3.2 Optimizing Open Loop-Controlled Cultivations 184 5.3.2.1 Robust Cultivation Profiles 184 5.3.2.2 Evolutionary Modeling Approach 188 5.3.3 Optimization by Model-Aided Feedback Control 190 5.3.3.1 Improving the Basic Control 190 5.3.3.2 Optimizing the Amount of Soluble Product 190 5.3.4 CO2-Removal in Large-Scale Cell Cultures 194 5.4 Conclusion 197 References 198 6 Monitoring and Control of Bioreactor: Basic Concepts and Recent Advances 201James Gomes, Viki Chopda, and Anurag S. Rathore 6.1 Introduction 201 6.2 Challenges in Bioprocess Control 202 6.2.1 Process Dynamics and Modeling 202 6.2.2 Limits of Hardware and Software andTheir Integration 203 6.2.3 Regulatory Aspects 204 6.3 Basic Elements of Bioprocess Control 205 6.3.1 Bioprocess Monitoring 205 6.3.2 Parameter Estimators 205 6.3.3 Bioprocess Modeling 206 6.4 Current Practices in Bioprocess Control 208 6.4.1 PID Control 208 6.4.2 Model-Based Control 209 6.4.3 Adaptive Control 211 6.4.4 Nonlinear Control 214 6.5 Intelligent Control Systems 217 6.5.1 Fuzzy Control 217 6.5.2 Neural Control 219 6.5.3 Statistical Process Control 222 6.5.4 Integrated and Plant-Wide Bioprocess Control 224 6.5.5 Metabolic Control 225 6.6 Summary 226 6.7 Future Perspectives 227 Acknowledgments 227 References 227 Part III Host Strain Technologies 239 7 Metabolic Engineering for Biocatalyst Robustness to Organic Inhibitors 241Liam Royce and Laura R. Jarboe 7.1 Introduction 241 7.2 Mechanisms of Inhibition 243 7.3 Mechanisms of Tolerance 245 7.4 Membrane Engineering 246 7.5 Evolutionary and Metagenomic Strategies for Increasing Tolerance 251 7.6 Reverse Engineering of Improved Strains 254 7.7 Concluding Remarks 255 Acknowledgments 255 References 255 Index 267

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Book SynopsisThis General, Organic and Biochemistry text has been written for students preparing for careers in health-related fields such as nursing, dental hygiene, nutrition, medical technology and occupational therapy. It is also suited for students majoring in other fields where it is important to have an understanding of the basics of chemistry.Table of ContentsCHAPTER 1 SCIENCE AND MEASUREMENTS 1 1.1 The Scientific Method 2 1.2 Matter and Energy 5 1.3 Units of Measurement 9 1.4 Scientific Notation, SI and Metric Prefixes 13 1.5 Measurements and Significant Figures 15 1.6 Conversion Factors and the Factor Label Method 22 1.7 Density, Specific Gravity, and Specific Heat 25 1.8 Measurements in General Chemistry, Organic Chemistry, and Biochemistry 29 CHAPTER 2 ATOMS AND 2.1 Atoms 44 2.2 Elements 46 2.3 Trace Elements 48 2.4 Atomic Number and Mass Number 51 2.5 Periodic Table 54 2.6 The Mole 59 2.7 The Arrangement of Electrons 62 2.8 Radioactive Isotopes 68 2.9 Radioisotopes in Medicine 71 CHAPTER 3 COMPOUNDS 88 3.1 Ions 90 3.2 The Octet Rule 93 3.3 Ionic Compounds 96 3.4 Covalent Bonds 101 3.5 Molecules 103 3.6 Formula Weight, Molecular Weight, and Molar Mass 105 CHAPTER 4 AN INTRODUCTION TO ORGANIC COMPOUNDS 116 4.1 Structural Formulas 118 4.2 Polar Covalent Bonds, Shape, and Polarity 123 4.3 Noncovalent Interactions 130 4.4 Families of Organic Compounds 132 CHAPTER 5 REACTIONS 150 5.1 Chemical Equations 152 5.2 Reaction Types 156 5.3 Reactions Involving Water 158 5.4 Oxidation and Reduction 161 5.5 Mole and Mass Relationships in Reactions 167 5.6 Calculating the Yield of a Reaction 171 5.7 Free Energy and Reaction Rate 174 CHAPTER 6 GASES, SOLUTIONS, COLLOIDS, AND SUSPENSIONS 190 6.1 Gases and Pressure 192 6.2 The Gas Laws 197 6.3 Partial Pressure 202 6.4 Solutions 204 6.5 Precipitation Reactions 207 6.6 Solubility of Gases in Water 209 6.7 Organic and Biochemical Compounds 212 6.8 Concentration 216 6.9 Dilution 221 6.10 Colloids and Suspensions 222 6.11 Diffusion and Osmosis 225 CHAPTER 7 ACIDS, BASES, AND EQUILIBRIUM 238 7.1 Acids and Bases 240 7.2 Brønsted–Lowry Acids and Bases 241 7.3 Equilibrium 243 7.4 Le Châtelier’s Principle 246 7.5 Ionization of Water 250 7.6 The pH Scale 251 7.7 Acid and Base Strength 254 7.8 Neutralizing Acids and Bases 257 7.9 Effect of pH on Acid and Conjugate Base Concentrations 259 7.10 Buffers 261 7.11 Maintaining the pH of Blood Serum 263 CHAPTER 8 ORGANIC REACTIONS 1—HYDROCARBONS, CARBOXYLIC ACIDS, AMINES, AND RELATED COMPOUNDS 276 8.1 Alkanes 278 8.2 Constitutional Isomers 282 8.3 Conformations 284 8.4 Cycloalkanes 285 8.5 Alkenes, Alkynes, and Aromatic Compounds 287 8.6 Reactions of Hydrocarbons 291 8.7 Carboxylic Acids 297 8.8 Phenols 299 8.9 Carboxylic Acids and Phenols as Weak Organic Acids 301 8.10 Preparing Esters 304 8.11 Amines 307 8.12 Amines as Weak Organic Bases 311 8.13 Amides 313 ORGANIC REACTIONS 2—ALCOHOLS, ETHERS,ALDEHYDES, AND KETONES 334 9.1 Alcohols, Ethers, and Related Compounds 336 9.2 Preparation 339 9.3 Reactions 341 9.4 Aldehydes and Ketones 344 9.5 Oxidation of Aldehydes 347 9.6 Reduction of Aldehydes and Ketones 349 9.7 Reactions of Alcohols with Aldehydes and Ketones 352 CHAPTER 10 CARBOHYDRATES 370 10.1 Monosaccharides 372 10.2 Stereoisomers 374 10.3 Important Monosaccharides and Monosaccharide Derivatives 381 10.4 Reactions of Monosaccharides 384 10.5 Monosaccharides in Their Cyclic Form 386 10.6 Oligosaccharides 390 10.7 Polysaccharides 401 CHAPTER 11 LIPIDS AND MEMBRANES 420 11.1 Fatty Acids 422 11.2 Waxes 427 11.3 Triglycerides 429 11.4 Phospholipids and Glycolipids 437 11.5 Steroids 441 11.6 Eicosanoids 445 11.7 Membranes 447 CHAPTER 12 PEPTIDES, PROTEINS, AND ENZYMES 458 12.1 Amino Acids 460 12.2 The Peptide Bond 464 12.3 Peptides, Proteins, and pH 468 12.4 Protein Structure 469 12.5 Denaturation 477 12.6 Enzymes 478 12.7 Control of Enzyme-Catalyzed Reactions 482 CHAPTER 13 NUCLEIC ACIDS 498 13.1 Nucleic Acid Building Blocks 500 13.2 Nucleoside Di- and Triphosphates, Cyclic Nucleotides 505 13.3 Polynucleotides 506 13.4 DNA Structure 509 13.5 Denaturation 512 13.6 Nucleic Acids and Information Flow 514 13.7 DNA Replication 515 13.8 Transcription and RNA 517 13.9 Translation 520 13.10 Control of Gene Expression 522 13.11 Mutation 524 13.12 Recombinant DNA 525 13.13 DNA Fingerprinting 529 CHAPTER 14 METABOLISM 540 14.1 Metabolic Pathways, Energy, and Coupled Reactions 542 14.2 Overview of Metabolism 543 14.3 Digestion 548 14.4 Glycolysis 551 14.5 Gluconeogenesis 556 14.6 Glycogen Metabolism 558 14.7 Citric Acid Cycle 560 14.8 Electron Transport Chain and Oxidative Phosphorylation 562 14.9 Lipid Metabolism 566 14.10 Amino Acid Metabolism 571 Appendix A Important Families of Organic Compounds 582 Appendix B Naming Ions, Ionic Compounds, Binary Molecules, and Organic Compounds 584 Appendix C Answers to Odd-Numbered Problems 591 Appendix D Glossary 639 Index I

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Book SynopsisThe Second Edition features new problems that engage readers in contemporary reactor design Highly praised by instructors, students, and chemical engineers, Introduction to Chemical Engineering Kinetics & Reactor Design has been extensively revised and updated in this Second Edition. The text continues to offer a solid background in chemical reaction kinetics as well as in material and energy balances, preparing readers with the foundation necessary for success in the design of chemical reactors. Moreover, it reflects not only the basic engineering science, but also the mathematical tools used by today's engineers to solve problems associated with the design of chemical reactors. Introduction to Chemical Engineering Kinetics & Reactor Design enables readers to progressively build their knowledge and skills by applying the laws of conservation of mass and energy to increasingly more difficult challenges in reactor design. The first oneTable of ContentsPreface ix Preface to the First Edition xi 1. Stoichiometric Coefficients and Reaction Progress Variables 1 1.0 Introduction 1 1.1 Basic Stoichiometric Concepts 2 Literature Citation 3 2. Thermodynamics of Chemical Reactions 4 2.0 Introduction 4 2.1 Chemical Potentials and Standard States 4 2.2 Energy Effects Associated with Chemical Reactions 5 2.3 Sources of Thermochemical Data 7 2.4 The Equilibrium Constant and its Relation to ΔG0 7 2.5 Effects of Temperature and Pressure Changes on the Equilibrium Constant 8 2.6 Determination of Equilibrium Compositions 9 2.7 Effects of Reaction Conditions on Equilibrium Yields 11 2.8 Heterogeneous Reactions 12 2.9 Equilibrium Treatment of Simultaneous Reactions 12 2.10 Supplementary Reading References 15 Literature Citations 15 Problems 15 3. Basic Concepts in Chemical Kinetics: Determination of the Reaction Rate Expression 22 3.0 Introduction 22 3.1 Mathematical Characterization of Simple Reaction Systems 25 3.2 Experimental Aspects of Kinetic Studies 29 3.3 Techniques for the Interpretation of Kinetic Data 34 Literature Citations 53 Problems 54 4. Basic Concepts in Chemical Kinetics: Molecular Interpretations of Kinetic Phenomena 72 4.0 Introduction 72 4.1 Reaction Mechanisms 73 4.2 Chain Reactions 83 4.3 Molecular Theories of Chemical Kinetics 93 Literature Citations 103 Problems 104 5. Chemical Systems Involving Multiple Reactions 117 5.0 Introduction 117 5.1 Reversible Reactions 117 5.2 Parallel or Competitive Reactions 125 5.3 Series or Consecutive Reactions: Irreversible Series Reactions 133 5.4 Complex Reactions 137 Literature Citations 142 Problems 142 6. Elements of Heterogeneous Catalysis 152 6.0 Introduction 152 6.1 Adsorption Phenomena 153 6.2 Adsorption Isotherms 156 6.3 Reaction Rate Expressions for Heterogeneous Catalytic Reactions 160 6.4 Physical Characterization of Heterogeneous Catalysts 170 6.5 Catalyst Preparation, Fabrication, and Activation 174 6.6 Poisoning and Deactivation of Catalysts 177 Literature Citations 178 Problems 179 7. Liquid Phase Reactions 189 7.0 Introduction 189 7.1 Electrostatic Effects in Liquid Solution 191 7.2 Pressure Effects on Reactions in Liquid Solution 192 7.3 Homogeneous Catalysis in Liquid Solution 193 7.4 Correlation Methods for Kinetic Data: Linear Free Energy Relations 202 Literature Citations 207 Problems 207 8. Basic Concepts in Reactor Design and Ideal Reactor Models 216 8.0 Introduction 216 8.1 Design Analysis for Batch Reactors 225 8.2 Design of Tubular Reactors 228 8.3 Continuous Flow Stirred-Tank Reactors 234 8.4 Reactor Networks Composed of Combinations of Ideal Continuous Flow Stirred-Tank Reactors and Plug Flow Reactors 254 8.5 Summary of Fundamental Design Relations: Comparison of Isothermal Stirred-Tank and Plug Flow Reactors 256 8.6 Semibatch or Semiflow Reactors 256 Literature Citations 259 Problems 259 9. Selectivity and Optimization Considerations in the Design of Isothermal Reactors 273 9.0 Introduction 273 9.1 Competitive (Parallel) Reactions 274 9.2 Consecutive (Series) Reactions: A →k1→ B →k2→ C →k3→ D 278 9.3 Competitive Consecutive Reactions 283 9.4 Reactor Design for Autocatalytic Reactions 290 Literature Citations 294 Problems 294 10. Temperature and Energy Effects in Chemical Reactors 305 10.0 Introduction 305 10.1 The Energy Balance as Applied to Chemical Reactors 305 10.2 The Ideal Well-Stirred Batch Reactor 307 10.3 The Ideal Continuous Flow Stirred-Tank Reactor 311 10.4 Temperature and Energy Considerations in Tubular Reactors 314 10.5 Autothermal Operation of Reactors 317 10.6 Stable Operating Conditions in Stirred Tank Reactors 320 10.7 Selection of Optimum Reactor Temperature Profiles: Thermodynamic and Selectivity Considerations 324 Literature Citations 327 Problems 328 11. Deviations from Ideal Flow Conditions 337 11.0 Introduction 337 11.1 Residence Time Distribution Functions, F(t) and dF(t) 337 11.2 Conversion Levels in Nonideal Flow Reactors 352 11.3 General Comments and Rules of Thumb 358 Literature Citations 359 Problems 359 12. Reactor Design for Heterogeneous Catalytic Reactions 371 12.0 Introduction 371 12.1 Commercially Significant Types of Heterogeneous Catalytic Reactors 371 12.2 Mass Transport Processes within Porous Catalysts 376 12.3 Diffusion and Reaction in Porous Catalysts 380 12.4 Mass Transfer Between the Bulk Fluid and External Surfaces of Solid Catalysts 406 12.5 Heat Transfer Between the Bulk Fluid and External Surfaces of Solid Catalysts 413 12.6 Global Reaction Rates 416 12.7 Design of Fixed Bed Reactors 418 12.8 Design of Fluidized Bed Catalytic Reactors 437 Literature Citations 439 Problems 441 13. Basic and Applied Aspects of Biochemical Transformations and Bioreactors 451 13.0 Introduction 451 13.1 Growth Cycles of Microorganisms: Batch Operation of Bioreactors 452 13.2 Principles and Special Considerations for Bioreactor Design 472 13.3 Commercial Scale Applications of Bioreactors in Chemical and Environmental Engineering 495 Literature Citations 516 Problems 517 Appendix A. Fugacity Coefficient Chart 527 Appendix B. Nomenclature 528 Appendix C. Supplementary References 535 Author Index 537 Subject Index 545

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Book SynopsisThis book provides readers with a one-stop entry into the chemistry of varied hybrids and applications, from a molecular synthetic standpoint Describes introduction and effect of organic structures on specific support components (carbon-based materials, proteins, metals, and polymers). Chapters cover hot topics including nanodiamonds, nanocrystals, metal-organic frameworks, peptide bioconjugates, and chemoselective protein modification Describes analytical techniques, with pros and cons, to validate synthetic strategies Edited by internationally-recognized chemists from different backgrounds (synthetic polymer chemistry, inorganic surfaces and particles, and synthetic organic chemistry) to pull together diverse perspectives and approachesTable of ContentsPreface vii Contributors ix 1 COVALENT ORGANIC FUNCTIONALIZATION AND CHARACTERIZATION OF CARBON NANOTUBES 1 Cécilia Ménard-Moyon 2 FUNCTIONALIZED GRAPHENES 36 Iban Azcarate, David Lachkar, Emmanuel Lacôte, Jennifer Lesage de la Haye, and Anne-Laure Vallet 3 NANODIAMONDS: EMERGENCE OF FUNCTIONALIZED DIAMONDOIDS AND THEIR UNIQUE APPLICATIONS 69 Maria A. Gunawan, Paul Kahl, Didier Poinsot, Bruno Domenichini, Peter R. Schreiner, Andrey A. Fokin, and Jean-Cyrille Hierso 4 TITANIA-BASED HYBRID MATERIALS: FROM MOLECULAR PRECURSORS TO THE CONTROLLED DESIGN OF HIERARCHICAL HYBRID MATERIALS 114 Laurence Rozes, Loïc D’Arras, Chloé Hoffman, François Potier, Niki Halttunen, and Lionel Nicole 5 FUNCTIONALIZATION OF ZIRCONIUM OXIDE SURFACES 168 Marc Petit and Julien Monot 6 FUNCTIONAL METAL–ORGANIC FRAMEWORKS: SYNTHESIS AND REACTIVITY 200 Flavien L. Morel, Xiaoying Xu, Marco Ranocchiari, and Jeroen A. van Bokhoven 7 SURFACE CHEMISTRY OF COLLOIDAL SEMICONDUCTOR NANOCRYSTALS: ORGANIC, INORGANIC, AND HYBRID 233 Richard Brutchey, Zeger Hens, and Maksym V. Kovalenko 8 COVALENT ORGANIC FUNCTIONALIZATION OF NUCLEIC ACIDS 272 Michel Arthur and Mélanie Etheve-Quelquejeu 9 CHEMOSELECTIVE PROTEIN MODIFICATIONS: METHODS AND APPLICATIONS FOR THE FUNCTIONALIZATION OF VIRAL CAPSIDS 299 Divya Agrawal and Christian P. R. Hackenberger 10 CYCLODEXTRINS–METAL HYBRIDS 349 Maxime Guitet, Mickaël Ménand, and Matthieu Sollogoub 11 POST-FUNCTIONALIZATION OF POLYMERS VIA ORTHOGONAL LIGATION CHEMISTRY 395 Anja S. Goldmann, M. Glassner, Andrew J. Inglis, and Christopher Barner-Kowollik 12 POLYMER–PROTEIN/PEPTIDE BIOCONJUGATES 466 Paul Wilson, Julien Nicolas, and David M. Haddleton 13 HYBRID MATERIALS BUILT FROM (PHOSPHORUS) DENDRIMERS 503 Anne-Marie Caminade, Beatrice Delavaux-Nicot, and Jean-Pierre Majoral Index

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Book SynopsisAn excellent, unique, and up-to-date reference book on polyoxymethylene, its compounds, and nanocomposites, specifically dealing with synthesis, characterization, processing, morphology, and applications Polyoxymethylene Handbook: Structure, Properties, Applications, and Their Nanocomposites summarizes many of the state-of-the-art technological and research accomplishments in the area of polyoxymethylene (POM). It discusses in length the polymerization and manufacture of polyoxymethylene and various types of additives, as well as the structure and crystallization behavior of POM and its thermal, physical, mechanical, flame retardant, chemical, electrical, and optical properties. The environmental impact of POM is also addressed. The 15 chapters in the handbook are written by prominent researchers from industry, academia, and government/private research laboratories across the globe. Because so few books have ever been published on polyoxymethylene, the haTable of ContentsPreface xiii 1 Polyoxymethylene: State of Art, New Challenges and Opportunities 1 Sigrid Luft l and Visakh. P.M. 1.1 Scope 2 1.2 History 2 1.3 Commercial Significance 7 References 13 2 Polymerization and Manufacture of Polyoxymethylene 21 Johannes Karl Fink 2.1 Introduction 21 2.2 Monomers 22 2.3 Comonomers 25 2.4 Polymerization and Fabrication 28 2.5 Special Additives 44 References 46 3 Polyoxymethylene Additives 53 Emmanuel Richaud 3.1 Introduction 53 3.2 Antioxidants 54 3.3 Compounds Reacting with Secondary Reaction Products 59 3.4 UV Stabilization 60 3.5 Impact Modifier 65 3.6 Nucleating Agent 67 3.7 Pigments and Dyes 72 3.8 Flame Retardants 75 3.9 Antistatic Agents 79 3.10 Lubricating Agents 80 3.11 Fillers 82 3.12 Processing Aids 90 References 91 Appendix 3.1: List of Stabilizers 100 4 Polyoxymethylene Processing 107 Kinga Pielichowska 4.1 Introduction 107 4.2 Injection Molding 109 4.3 Melt Extrusion 116 4.4 Solid-State Extrusion 118 4.5 Extrusion Assisted by Supercritical Carbon Dioxide 120 4.6 Blow Molding 121 4.7 Others Methods 123 4.8 Highly Oriented Products 132 4.9 Recycling of Production Waste 136 4.10 Finishing and Machining of POM 138 4.11 Conclusions 141 References 142 5 Polyoxymethylene Applications 153 Lidia Tokarz, Slawomir Pawlowski and Michal Kedzierski 5.1 Introduction 153 5.2 Automotive Industry, Mechanical Engineering 156 5.3 Electrical and Electronic Industry, Fancy Goods 157 5.4 Medical Applications 158 5.5 Future Trends 160 References 160 6 Structure and Morphology of Polyoxymethylene 163 Maria Raimo 6.1 Introduction 163 6.2 Crystalline Structure of POM: Orthorhombic and Hexagonal Phases 165 6.3 Crystal Structure Determination 170 6.4 Morphology of Orthorhombic and Hexagonal POM 173 6.5 Morphology of Rubber-Modified POM 179 6.6 Structure-Properties Relationships 181 References 186 7 Crystal Structure and Crystallization Behavior of POM and its Microscopically-Viewed Relation with the Physical and Thermal Properties on the Basis of X-ray Scattering, Vibrational Spectroscopy and Lattice Dynamical Theory 193 Kohji Tashiro 7.1 Introduction 194 7.2 Crystal Structure Analysis of POM 195 7.3 Vibrational Spectra of POM 204 7.4 Structural Evolution in Isothermal Crystallization 207 7.5 Microscopically-Viewed Mechanical Property of POM 216 7.6 Conclusions 223 Acknowledgements 224 References 224 8 Physical Properties of Polyoxymethylene 227 Johannes Karl Fink 8.1 Introduction 227 8.2 Density 228 8.3 Hardness 230 8.4 Heat Capacity 231 8.5 Melt Flow 231 8.6 Water Absorption 235 8.7 Gas Permeability 236 8.8 Specific Absorption 238 References 239 9 POM Mechanical Properties 241 Fahmi Bedoui and Bruno Fayolle 9.1 Short Term Properties 242 9.2 Long-Term Properties 249 9.3 Conclusion 252 Acknowledgement 253 References 253 10 Thermal Properties and Flammability of Polyoxymethylene 257 Vasiliki-Maria Archodoulaki and Sigrid Luft l 10.1 Glass Transition and Melting Temperature 257 10.2 Coefficient of Linear Thermal Expansion 260 10.3 Thermal Conductivity and Specific Heat 260 10.4 HDT and Vicat 261 10.5 Thermo-Oxidative Degradation Behavior and Aging 261 10.6 Testing of Long-Term Heat Aging 266 10.7 Flammability 267 10.8 Hot Sterilization 270 References 271 11 Chemical Resistance of Polyoxymethylene 277 Sigrid Luft l and Emmanuel Richaud 11.1 Intoduction 277 11.2 Degradation and Oxidation Mechanisms in POM 278 11.3 Resistance to Chemicals 283 References 295 12 The Electrical Response of Polyoxymethylene (POM) 301 D.A. Wasylyshyn 12.1 Introduction 301 12.2 Interactions between POM and Electromagnetic Waves 302 12.3 Interactions between POM and Arc Plasma 313 References 318 13 Electrical and Optical Properties of Polyoxymethylene 321 Natamai Subramanian Muralisrinivasan 13.1 Introduction 321 13.2 Electrical Properties 322 13.3 Optical Properties 327 References 329 14 Nanocomposites of Polyoxymethylene 331 Agnieszka Leszczyñska and Krzysztof Pielichowski 14.1 Introduction 331 14.2 Preparation and Structure of POM Nanocomposites with Different Nanoadditives 332 14.3 Properties of Polyoxymethylene-Based Nanocomposites 347 14.4 POM Blends as Matrices in Nanocomposite Materials 376 14.5 POM Nanostructures - Electrospun POM Nanofibers 381 14.6 Applications of POM-Based Nanocomposites and Future Trends 385 14.7 Conclusions 386 List of acronyms 387 References 388 15 Future, Environmental Impact and Suppliers 399 Takashi Iwamoto and Junzo Masamoto 15.1 Introduction 400 15.2 Developments and Specialty Resins 400 15.3 Safety (Regulation and Approvals) 421 15.4 Environmental Impact 424 15.5 Suppliers and Commercial Grades 426 15.6 Future 426 References 432 Index 435

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Book SynopsisLearn how to design and implement successful aeration control systems Combining principles and practices from mechanical, electrical, and environmental engineering, this book enables you to analyze, design, implement, and test automatic wastewater aeration control systems and processes. It brings together all the process requirements, mechanical equipment operations, instrumentation and controls, carefully explaining how all of these elements are integrated into successful aeration control systems. Moreover, Aeration Control System Design features a host of practical, state-of-the-technology tools for determining energy and process improvements, payback calculations, system commissioning, and more. Author Thomas E. Jenkins has three decades of hands-on experience in every phase of aeration control systems design and implementation. He presents not only the most current theory and technology, but also practical tips and techniques that can only be gained bTable of ContentsPreface xiAcknowledgments xiiiList of Figures xvList of Tables xxi1 Introduction 11.1 Basic Concepts and Objectives 21.2 Safety 91.3 The Importance of an Integrated Approach 101.4 Importance of Operator Involvement 131.5 The Benefits of Successful Aeration Process Automation 14Example Problems 192 Initial System Assessment 212.1 Define Current Operations 242.2 Evaluate Process and Equipment 372.3 Benchmark Performance 402.4 Estimate Potential Energy Savings and Performance Improvement 422.5 Prepare Report 45Example Problems 473 Aeration Processes 493.1 Process Fundamentals 493.2 Loading Variations and Their Implications 683.3 Process Limitations and Their Impact on Control Systems 70Example Problems 744 Mechanical and Diffused Aeration Systems 774.1 Oxygen Transfer Basics 784.2 Types of Aerators 874.3 Savings Determinations 106Example Problems 1115 Blowers and Blower Control 1135.1 Common Application and Selection Concerns 1145.2 Positive Displacement Blowers and Control Characteristics 1345.3 Dynamic Blowers 143Example Problems 1576 Piping Systems 1616.1 Design Considerations 1626.2 Pressure Drop 1786.3 Control Valve Selection 182Example Problems 1877 Instrumentation 1917.1 Common Characteristics and Electrical Design Considerations 1927.2 Pressure 2027.3 Temperature 2057.4 Flow 2097.5 Analytic Instruments 2167.6 Motor Monitoring and Electrical Measurements 2247.7 Miscellaneous 226Example Problems 2308 Final Control Elements 2338.1 Valve Operators 2348.2 Guide Vanes 2388.3 Motor Basics 2398.4 Motor Control 2478.5 Variable Frequency Drives 251Example Problems 2599 Control Loops and Algorithms 2619.1 Control Fundamentals 2649.2 Dissolved Oxygen Control 2809.3 Aeration Basin Air Flow Control 2879.4 Pressure Control 2889.5 Most-Open-Valve Control 2919.6 Blower Control and Coordination 2939.7 Control Loop Timing Considerations 3029.8 Miscellaneous Controls 303Example Problems 30510 Control Components 30910.1 Programmable Logic Controllers 31010.2 Distributed Control Systems 32310.3 Human Machine Interfaces 32310.4 Control Panel Design Considerations 328Example Problems 33011 Documentation 33311.1 Specification Considerations 33511.2 Data Lists 33811.3 Process and Instrumentation Diagrams 34111.4 Ladder and Loop Diagrams 34211.5 One-Line Diagrams 34411.6 Installation Drawings 34511.7 Loop Descriptions 34711.8 Operation and Maintenance Manuals 348Example Problems 34912 Commissioning 35112.1 Inspection 35412.2 Testing 35712.3 Tuning 36112.4 Training 36512.5 Measurement and Verification of Results 368Example Problems 36913 Summary 37113.1 Review of Integrated Design Procedure 37113.2 Potential Problem Areas 37413.3 Benefits 375Example Problems 375Appendix A: Example Problem Solutions 377Appendix B: List of Equations and Variables 447Bibliography 485Index 487

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Book SynopsisHIGH THROUGHPUT ANALYSIS FOR FOOD SAFETY MEETS FSMA REQUIREMENTS WITH THE LATEST ADVANCES IN HIGH-THROUGHPUT SCREENING High-Throughput Analysis for Food Safety addresses the fundamental concepts involved in the rapid screening for contaminants, including residual veterinary drugs, proteins, metals, hormones, pesticides, and adulterants. Addressing the need forand requirements ofrapid screening tests, the book includes discussions of regulations and compliance issues from perspectives of both domestic and global industry and government contributors. The latest developments and most common techniques are focused on, with an emphasis on the applicability of both stand-alone mass spectrometry methods and coupled techniques. Beginning with a review of high-throughput analysis basics, the authors conduct a full exploration of mass spectrometry applications allowing readers to: Survey GC-MS, LC-MS, stand-alone MS, and tandem MS methods in foodanalysis and coTable of ContentsPreface xi Contributors xiii Chapter 1 Introduction: Basic Principles of Assays to be Covered, Sample Handling, And Sample Processing 1 Wanlong Zhou, Eugene Y. Chang, and Perry G. Wang 1.1 Introduction 1 1.1.1 Current Situation and Challenges of Food Safety and Regulations 1 1.1.2 Residues and Matrices of Food Analysis and High-Throughput Analysis 2 1.1.3 Food Safety Classifications 3 1.1.4 “High Throughput” Definition 3 1.1.5 Scope of the Book 4 1.2 Advanced Sample Preparation Techniques 5 1.2.1 Automation of Weighing and Preparing Standard Solutions 5 1.2.2 QuEChERS 6 1.2.3 Swedish Extraction Technique (SweEt) and Other Fast Sample Preparation Methods 6 1.2.4 Turbulent Flow Chromatography 7 1.2.5 Pressurized Liquid Extraction 7 1.2.6 Automated 96- and 384-Well Formatted Sample Preparation as well as Automated SPE Workstations 8 1.2.7 Solid-Phase Microextraction 8 1.2.8 Microextraction by Packed Sorbent 9 1.2.9 Liquid Extraction Surface Analysis 9 1.2.10 Headspace GC 10 1.2.11 Summary 10 1.3 Future Perspectives 10 Acknowledgment 11 References 11 Chapter 2 Survey Of Mass Spectrometry-Based High-Throughput Methods In Food Analysis 15 Lukas Vaclavik, Tomas Cajka, Wanlong Zhou, and Perry G. Wang 2.1 Introduction 15 2.2 Techniques Employing Chromatographic Separation 15 2.2.1 Gas Chromatography–Mass Spectrometry 15 2.2.2 Liquid Chromatography–Mass Spectrometry 21 2.3 Direct Techniques 30 2.3.1 Matrix-Assisted Laser Desorption/Ionization-Mass Spectrometry 30 2.3.2 Headspace (Solid-Phase Microextraction)-Mass Spectrometry E-Nose 37 2.3.3 Ambient Desorption/Ionization-Mass Spectrometry 38 2.4 Concluding Remarks 62 Acknowledgments 62 References 63 Chapter 3 Quality Systems, Quality Control Guidelines and Standards, Method Validation, and Ongoing Analytical Quality Control 73 David Galsworthy and Stewart Reynolds 3.1 Introduction 73 3.1.1 Quality System Design 73 3.1.2 Procedures 74 3.1.3 Roles and Responsibilities 74 3.1.4 Quality Manual 74 3.1.5 Document Control 74 3.1.6 Control of Records 75 3.1.7 Audits 75 3.1.8 Validation of Methodology 75 3.1.9 Staff Competency 75 3.1.10 Internal Quality Control 76 3.1.11 Method Performance Criteria 76 3.2 Qualitative Screening Methods 76 3.2.1 Selectivity of Mass Spectrometry-Based Methods 78 3.2.2 Confirmatory Methods 78 3.2.3 Validation of Qualitative Screening Multiresidue Methods for Pesticide Residues in Foods 79 3.3 Elements of the Analytical Workflow 80 3.3.1 Sample Preparation 80 3.3.2 Effects of Sample Processing 81 3.3.3 Extraction Efficiency 81 3.4 Initial Method Validation 81 3.5 Ongoing Analytical Quality Control 86 3.5.1 Internal Quality Control 86 3.5.2 Proficiency Testing 86 3.6 Validation of Qualitative Screening Multiresidue Methods for Veterinary Drug Residues in Foods 87 3.6.1 EU Legislation Covering Method Validation for Veterinary Drug Screening 87 3.6.2 Determination of Specificity/Selectivity and Detection Capability (CCβ) Using the Classical Approach 88 3.6.3 Establishment of a Cutoff Level and Calculation of CCβ 88 3.6.4 Determination of the Applicability 89 3.7 Conclusions 90 References 90 Chapter 4 Deliberate Chemical Contamination and Processing Contamination 93 Stephen Lock 4.1 Introduction 93 4.2 Heat-Induced Food Processing Contaminants 97 4.3 Packaging Migrants 101 4.4 Malicious Contamination of Food 105 References 111 Chapter 5 Multiresidual Determination Of 295 Pesticides And Chemical Pollutants In Animal Fat By Gel Permeation Chromatography (Gpc) Cleanup Coupled With Gc–Ms/Ms, Gc–Nci-Ms, And Lc–Ms/Ms 117 Yan-Zhong Cao, Yong-Ming Liu, Na Wang, Xin-Xin Ji, Cui-Cui Yao, Xiang Li, Li-Li Shi, Qiao-Ying Chang, Chun-Lin Fan, and Guo-Fang Pang 5.1 Introduction 117 5.1.1 Persistent Organic Pollutants 118 5.1.2 Polycyclic Aromatic Hydrocarbons 119 5.1.3 Polychlorinated Biphenyls 119 5.1.4 Phthalate Esters 120 5.1.5 Multiclass and Multiresidue Analyses 120 5.2 Experiment 122 5.2.1 Instruments 122 5.2.2 Reagents 122 5.2.3 Preparation of Standard Solutions 122 5.2.4 Sample Preparation 123 5.2.5 Analytical Methods 124 5.2.6 Qualitative and Quantitative Determination 136 5.3 Results and Discussion 136 5.3.1 Selection of GPC Cleanup Conditions 136 5.3.2 Selection of Extraction Solvent 138 5.3.3 Comparison of Sample Extraction Methods 150 5.3.4 Comparison of Sample Cleanup 151 5.3.5 Linear Range, LOD, and LOQ 152 5.3.6 Recoveries and Precisions 152 5.3.7 Actual Sample Analysis 157 5.4 Conclusions 161 References 162 Chapter 6 Ultrahigh-Performance Liquid Chromatography Coupled With High-Resolution Mass Spectrometry: A Reliable Tool For Analysis Of Veterinary Drugs In Food 167 María del Mar Aguilera-Luiz, Roberto Romero-González,Patricia Plaza-Bolaños, José Luis Martínez Vidal,and Antonia Garrido Frenich 6.1 Introduction 167 6.2 Veterinary Drug Legislation 168 6.3 Analytical Techniques for VD Residue Analysis 172 6.3.1 Chromatographic Separation 174 6.3.2 High-Resolution Mass Spectrometers 175 6.4 Food Control Applications 181 6.4.1 Screening Applications 181 6.4.2 Confirmation and Quantification Methods 191 6.4.3 Comparison Studies 195 6.5 Conclusions and Future Trends 201 Acknowledgments 202 References 203 Chapter 7 A Role For High-Resolution Mass Spectrometry In The High-Throughput Analysis And Identification Of Veterinary Medicinal Product Residues And Of Their Metabolites In Foods Of Animal Origin 213 Eric Verdon, Dominique Hurtaud-Pessel,and Jagadeshwar-Reddy Thota 7.1 Introduction 213 7.2 Issues Associated with Veterinary Drug Residues and European Regulations 215 7.3 Choosing a Strategy: Targeted or Nontargeted Analysis? 216 7.3.1 Targeted Analysis Using HRMS 218 7.3.2 Nontargeted Analysis Using HRMS: Screening for Unknown Compounds 219 7.4 Application Number 1: Identification of Brilliant Green and its Metabolites in Fish under High-Resolution Mass Spectral Conditions (Targeted and Nontargeted Approaches) 220 7.5 Application Number 2: Targeted and Nontargeted Screening Approaches for the Identification of Antimicrobial Residues in Meat 223 7.6 Conclusions 227 References 227 Chapter 8 High-Throughput Analysis of Mycotoxins 231 Marta Vaclavikova, Lukas Vaclavik, and Tomas Cajka 8.1 Introduction 231 8.1.1 Legislation and Regulatory Limits 231 8.1.2 Emerging Mycotoxins 237 8.1.3 Analysis of Mycotoxins in the High-Throughput Environment 238 8.2 Sample Preparation 239 8.2.1 Sampling 240 8.2.2 Matrices of Interest 240 8.2.3 Extraction of Mycotoxins 241 8.2.4 Purification of Sample Extracts 246 8.3 Separation and Detection of Mycotoxins 247 8.3.1 Liquid Chromatography–Mass Spectrometry-Based Methods 248 8.3.2 High-Resolution Mass Spectrometry in Mycotoxins Analysis 250 8.4 No-Separation Mass Spectrometry-Based Methods 252 8.4.1 Matrix-Assisted Laser Desorption Ionization–Mass Spectrometry 252 8.4.2 Ambient Ionization Mass Spectrometry 253 8.4.3 Ion Mobility Spectrometry 254 8.4.4 Immunochemical Methods 256 8.5 Conclusions 259 Acknowledgments 259 References 259 Index 267

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Book SynopsisSustainable Energy Conversion for Electricity and Coproducts Comprehensive and a fundamental approach to the study of sustainable fuel conversion for the generation of electricity and for coproducing synthetic fuels and chemicals Both electricity and chemicals are critical to maintain our modern way of life; however, environmental impacts have to be factored in to sustain this type of lifestyle. Sustainable Energy Conversion for Electricity and Coproducts provides a unified, comprehensive, and a fundamental approach to the study of sustainable fuel conversion in order to generate electricity and optionally coproduce synthetic fuels and chemicals. The book starts with an introduction to energy systems and describes the various forms of energy sources: natural gas, petroleum, coal, biomass, and other renewables and nuclear. Their distribution is discussed in order to emphasize the uneven availability and finiteness of some of these resources. Each topic in Table of ContentsPreface xi About the Book xiv About the Author xv 1 Introduction to Energy Systems 1 1.1 Energy Sources and Distribution of Resources 2 1.1.1 Fossil Fuels 2 1.1.2 Nuclear 16 1.1.3 Renewables 17 1.2 Energy and the Environment 21 1.2.1 Criteria and Other Air Pollutants 22 1.2.2 Carbon Dioxide Emissions, Capture, and Storage 26 1.2.3 Water Usage 28 1.3 Holistic Approach 29 1.3.1 Supply Chain and Life Cycle Assessment 29 1.4 Conclusions 31 References 31 2 Thermodynamics 33 2.1 First Law 34 2.1.1 Application to a Combustor 36 2.1.2 Efficiency Based on First Law 45 2.2 Second Law 46 2.2.1 Quality Destruction and Entropy Generation 51 2.2.2 Second Law Analysis 53 2.2.3 First and Second Law Efficiencies 57 2.3 Combustion and Gibbs Free Energy Minimization 58 2.4 Nonideal Behavior 60 2.4.1 Gas Phase 60 2.4.2 Vapor–Liquid Phases 62 References 64 3 Fluid Flow Equipment 66 3.1 Fundamentals of Fluid Flow 66 3.1.1 Flow Regimes 67 3.1.2 Extended Bernoulli Equation 68 3.2 Single-Phase Incompressible Flow 69 3.2.1 Pressure Drop in Pipes 69 3.2.2 Pressure Drop in Fittings 70 3.3 Single-Phase Compressible Flow 71 3.3.1 Pressure Drop in Pipes and Fittings 72 3.3.2 Choked Flow 72 3.4 Two-Phase Fluid Flow 72 3.4.1 Gas–Liquid Flow Regimes 73 3.4.2 Pressure Drop in Pipes and Fittings 74 3.4.3 Droplet Separation 74 3.5 Solid Fluid Systems 77 3.5.1 Flow Regimes 77 3.5.2 Pressure Drop 78 3.5.3 Pneumatic Conveying 80 3.6 Fluid Velocity in Pipes 80 3.7 Turbomachinery 81 3.7.1 Pumps 81 3.7.2 Compressors 90 3.7.3 Fans and Blowers 97 3.7.4 Expansion Turbines 98 References 99 4 Heat Transfer Equipment 101 4.1 Fundamentals of Heat Transfer 101 4.1.1 Conduction 102 4.1.2 Convection 103 4.1.3 Radiation 112 4.2 Heat Exchange Equipment 117 4.2.1 Shell and Tube Heat Exchangers 118 4.2.2 Plate Heat Exchangers 124 4.2.3 Air-Cooled Exchangers 127 4.2.4 Heat Recovery Steam Generators (HRSGs) 128 4.2.5 Boilers and Fired Heaters 129 References 130 5 Mass Transfer and Chemical Reaction Equipment 131 5.1 Fundamentals of Mass Transfer 131 5.1.1 Molecular Diffusion 132 5.1.2 Convective Transport 133 5.1.3 Adsorption 134 5.2 Gas–Liquid Systems 135 5.2.1 Types of Mass Transfer Operations 135 5.2.2 Types of Columns 144 5.2.3 Column Sizing 146 5.2.4 Column Diameter and Pressure Drop 157 5.3 Fluid–Solid Systems 159 5.3.1 Adsorbers 159 5.3.2 Catalytic Reactors 162 References 167 6 Prime Movers 169 6.1 Gas Turbines 170 6.1.1 Principles of Operation 171 6.1.2 Combustor and Air Emissions 176 6.1.3 Start-Up and Load Control 177 6.1.4 Performance Characteristics 177 6.1.5 Fuel Types 179 6.1.6 Technology Developments 182 6.2 Steam Turbines 185 6.2.1 Principles of Operation 185 6.2.2 Load Control 186 6.2.3 Performance Characteristics 187 6.2.4 Technology Developments 189 6.3 Reciprocating Internal Combustion Engines 190 6.3.1 Principles of Operation 190 6.3.2 Air Emissions 193 6.3.3 Start-up 193 6.3.4 Performance Characteristics 194 6.3.5 Fuel Types 194 6.4 Hydraulic Turbines 195 6.4.1 Process Industry Applications 195 6.4.2 Hydroelectric Power Plant Applications 196 References 196 7 Systems Analysis 198 7.1 Design Basis 198 7.1.1 Fuel or Feedstock Specifications 200 7.1.2 Mode of Heat Rejection 200 7.1.3 Ambient Conditions 200 7.1.4 Other Site-Specific Considerations 201 7.1.5 Environmental Emissions Criteria 202 7.1.6 Capacity Factor 203 7.1.7 Off-Design Requirements 204 7.2 System Configuration 205 7.3 Exergy and Pinch Analyses 207 7.3.1 Exergy Analysis 207 7.3.2 Pinch Analysis 208 7.4 Process Flow Diagrams 212 7.5 Dynamic Simulation and Process Control 215 7.5.1 Dynamic Simulation 215 7.5.2 Automatic Process Control 219 7.6 Cost Estimation and Economics 220 7.6.1 Total Plant Cost 220 7.6.2 Economic Analysis 225 7.7 Life Cycle Assessment 227 References 228 8 Rankine Cycle Systems 230 8.1 Basic Rankine Cycle 231 8.2 Addition of Superheating 233 8.3 Addition of Reheat 236 8.4 Addition of Economizer and Regenerative Feedwater Heating 238 8.5 Supercritical Rankine Cycle 241 8.6 The Steam Cycle 241 8.7 Coal-Fired Power Generation 244 8.7.1 Coal-Fired Boilers 244 8.7.2 Emissions and Control 245 8.7.3 Description of a Large Supercritical Steam Rankine Cycle 251 8.8 Plant-Derived Biomass-Fired Power Generation 255 8.8.1 Feedstock Characteristics 255 8.8.2 Biomass-Fired Boilers 256 8.8.3 Cofiring Biomass in Coal-Fired Boilers 256 8.8.4 Emissions 257 8.9 Municipal Solid Waste Fired Power Generation 258 8.9.1 MSW-Fired Boilers 258 8.9.2 Emissions Control 259 8.10 Low-Temperature Cycles 260 8.10.1 Organic Rankine Cycle (ORC) 260 References 262 9 Brayton–Rankine Combined Cycle Systems 264 9.1 Combined Cycle 264 9.1.1 Gas Turbine Cycles for Combined Cycles 265 9.1.2 Steam Cycles for Combined Cycles 266 9.2 Natural Gas-Fueled Plants 267 9.2.1 Description of a Large Combined Cycle 267 9.2.2 No X Control 272 9.2.3 CO and Volatile Organic Compounds Control 272 9.2.4 CO 2 Emissions Control 273 9.2.5 Characteristics of Combined Cycles 276 9.3 Coal and Biomass Fueled Plants 279 9.3.1 Gasification 280 9.3.2 Gasifier Feedstocks 282 9.3.3 Key Technologies in IGCC Systems 283 9.3.4 Description of an IGCC 287 9.3.5 Advantages of an IGCC 291 9.3.6 Economies of Scale and Biomass Gasification 291 9.4 Indirectly Fired Cycle 291 References 294 10 Coproduction and Cogeneration 296 10.1 Types of Coproducts and Synergy in Coproduction 297 10.2 Syngas Generation for Coproduction 298 10.2.1 Gasifiers 298 10.2.2 Reformers 299 10.2.3 Shift Reactors 300 10.3 Syngas Conversion to Some Key Coproducts 302 10.3.1 Methanol 302 10.3.2 Urea 305 10.3.3 Fischer–Tropsch Liquids 309 10.4 Hydrogen Coproduction from Coal and Biomass 315 10.4.1 Current Technology Plant 315 10.4.2 Advanced Technology Plant 318 10.5 Combined Heat and Power 322 10.5.1 LiBr Absorption Refrigeration 325 References 328 11 Advanced Systems 330 11.1 High Temperature Membrane Separators 330 11.1.1 Ceramic Membranes 331 11.1.2 Application of Membranes to Air Separation 333 11.1.3 Application of Membranes to H 2 Separation 334 11.2 Fuel Cells 334 11.2.1 Basic Electrochemistry and Transport Phenomena 337 11.2.2 Real Fuel Cell Behavior 339 11.2.3 Overall Cell Performance 342 11.2.4 A Fuel Cell Power Generation System 345 11.2.5 Major Fuel Cell Type Characteristics 347 11.2.6 Hybrid Cycles 351 11.2.7 A Coal-Fueled Hybrid System 354 11.3 Chemical Looping 354 11.4 Magnetohydrodynamics 356 References 357 12 Renewables and Nuclear 359 12.1 Wind 360 12.1.1 Wind Resources and Plant Siting 361 12.1.2 Key Equipment 363 12.1.3 Economics 364 12.1.4 Environmental Issues 365 12.2 Solar 365 12.2.1 Solar Resources and Plant Siting 366 12.2.2 Key Equipment 366 12.2.3 Economics 368 12.2.4 Environmental Issues 369 12.3 Geothermal 371 12.3.1 Geothermal Resources and Plant Siting 371 12.3.2 Key Equipment 372 12.3.3 Economics 376 12.3.4 Environmental Issues 377 12.4 Nuclear 378 12.4.1 Nuclear Fuel Resources and Plant Siting 379 12.4.2 Key Equipment 380 12.4.3 Economics 381 12.4.4 Environmental Issues 382 12.5 Electric Grid Stability and Dependence on Fossil Fuels 383 12.5.1 Super and Micro Grids 385 References 385 Appendix: Acronyms and Abbreviations, Symbols and Units 387 Index 396

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Book SynopsisThe Reviews in Computational Chemistry series brings together leading authorities in the field to teach the newcomer and update the expert on topics centered around molecular modeling, such as computer-assisted molecular design (CAMD), quantum chemistry, molecular mechanics and dynamics, and quantitative structure-activity relationships (QSAR). This volume, like those prior to it, features chapters by experts in various fields of computational chemistry. Topics in Volume 28 include: Free-energy Calculations with Metadynamics Polarizable Force Fields for Biomolecular Modeling Modeling Protein Folding Pathways Assessing Structural Predictions of Protein-Protein Recognition Kinetic Monte Carlo Simulation of Electrochemical Systems Reactivity and Dynamics at Liquid Interfaces Table of ContentsPreface xi List of Contributors xv Contributors to Previous Volumes xvii 1. Free-Energy Calculations with Metadynamics: Theory and Practice 1Giovanni Bussi and Davide Branduardi Introduction 1 Molecular Dynamics and Free-Energy Estimation 3 Molecular Dynamics 3 Free-Energy Landscapes 4 A Toy Model: Alanine Dipeptide 6 Biased Sampling 8 Adaptive Biasing with Metadynamics 9 Reweighting 12 Well-Tempered Metadynamics 12 Reweighting 14 Metadynamics How-To 14 The Choice of the CV(s) 15 The Width of the Deposited Gaussian Potential 17 The Deposition Rate of the Gaussian Potential 18 A First Test Run Using Gyration Radius 19 A Better Collective Variable: Φ Dihedral Angle 23 Well-Tempered Metadynamics Using Gyration Radius 24 Well-Tempered Metadynamics Using Dihedral Angle Φ 27 Advanced Collective Variables 28 Path-Based Collective Variables 30 Collective Variables Based on Dimensional Reduction Methods 32 Template-Based Collective Variables 34 Potential Energy as a Collective Variable 35 Improved Variants 36 Multiple Walkers Metadynamics 36 Replica Exchange Metadynamics 37 Bias Exchange Metadynamics 38 Adaptive Gaussians 39 Conclusion 41 Acknowledgments 42 Appendix A: Metadynamics Input Files with PLUMED 42 References 44 2. Polarizable Force Fields for Biomolecular Modeling 51Yue Shi, Pengyu Ren, Michael Schnieders, and Jean-Philip Piquemal Introduction 51 Modeling Polarization Effects 52 Induced Dipole Models 52 Classic Drude Oscillators 54 Fluctuating Charges 54 Recent Developments 55 AMOEBA 55 SIBFA 57 NEMO 58 CHARMM-Drude 58 CHARMM-FQ 59 X-Pol 60 PFF 60 Applications 61 Water Simulations 61 Ion Solvation 62 Small Molecules 63 Proteins 64 Lipids 66 Continuum Solvents for Polarizable Biomolecular Solutes 66 Macromolecular X-ray Crystallography Refinement 67 Prediction of Organic Crystal Structure, Thermodynamics, and Solubility 70 Summary 71 Acknowledgment 71 References 72 3. Modeling Protein Folding Pathways 87Clare-Louise Towse and Valerie Daggett Introduction 87 Outline of this Chapter 90 Protein Simulation Methodology 90 Force Fields, Models and Solvation Approaches 90 Unfolding: The Reverse of Folding 97 Elevated Temperature Unfolding Simulations 100 Biological Relevance of Forced Unfolding 103 Biased or Restrained MD 108 Characterizing Different States 111 Protein Folding and Refolding 115 Folding in Families 118 Conclusions and Outlook 121 Acknowledgment 122 References 122 4. Assessing Structural Predictions of Protein–Protein Recognition: The CAPRI Experiment 137Joël Janin, Shoshana J. Wodak, Marc F. Lensink, and Sameer Velankar Introduction 137 Protein–Protein Docking 138 A Short History of Protein–Protein Docking 138 Major Current Algorithms 141 The CAPRI Experiment 144 Why Do Blind Predictions? 144 Organizing CAPRI 145 The CAPRI Targets 146 Creating a Community 149 Assessing Docking Predictions 150 The CAPRI Evaluation Procedure 150 A Survey of the Results of 12 Years of Blind Predictions on 45 Targets 154 Recent Developments in Modeling Protein–Protein Interaction 160 Modeling Multicomponent Assemblies. The Multiscale Approach 160 Genome-Wide Modeling of Protein–Protein Interaction 161 Engineering Interactions and Predicting Affinity 162 Conclusion 164 Acknowledgments 165 References 165 5. Kinetic Monte Carlo Simulation of Electrochemical Systems 175C. Heath Turner, Zhongtao Zhang, Lev D. Gelb, and Brett I. Dunlap Background 175 Introduction to Kinetic Monte Carlo 176 Electrochemical Relationships 180 Applications 184 Transport in Li-ion Batteries 184 Solid Electrolyte Interphase (SEI) Passive Layer Formation 187 Analysis of Impedance Spectra 189 Electrochemical Dealloying 189 Electrochemical Cells 190 Solid Oxide Fuel Cells 193 Other Electrochemical Systems 197 Conclusions and Future Outlook 198 Acknowledgments 199 References 199 6. Reactivity and Dynamics at Liquid Interfaces 205Ilan Benjamin Introduction 205 Simulation Methodology for Liquid Interfaces 207 Force Fields for Molecular Simulations of Liquid Interfaces 207 Boundary Conditions and the Treatment of Long-Range Forces 210 Statistical Ensembles for Simulating Liquid Interfaces 213 Comments About Monte Carlo Simulations 214 The Neat Interface 214 Density, Fluctuations, and Intrinsic Structure 215 Surface Tension 221 Molecular Structure 223 Dynamics 230 Solutes at Interfaces: Structure and Thermodynamics 235 Solute Density 236 Solute–Solvent Correlations 240 Solute Molecular Orientation 242 Solutes at Interfaces: Electronic Spectroscopy 243 A Brief General Background on Electronic Spectroscopy in the Condensed Phase 243 Experimental Electronic Spectroscopy at Liquid Interfaces 245 Computer Simulations of Electronic Transitions at Interfaces 249 Solutes at Interfaces: Dynamics 253 Solute Vibrational Relaxation at Liquid Interfaces 253 Solute Rotational Relaxation at Liquid Interfaces 258 Solvation Dynamics 263 Summary 269 Reactivity at Liquid Interfaces 270 Introduction 270 Electron Transfer Reactions at Liquid/Liquid Interfaces 271 Nucleophilic Substitution Reactions and Phase Transfer Catalysis (PTC) 277 Conclusions 283 Acknowledgments 284 References 284 7. Computational Techniques in the Study of the Properties of Clathrate Hydrates 315John S. Tse Historical Perspective 315 Structures 317 The van der Waals–Platteeuw Solid Solution Theory 318 Computational Advancements 322 Thermodynamic Modelling 322 Atomistic Simulations 327 Thermodynamic Stability 344 Hydrate Nucleation and Growth 355 Guest Diffusion Through Hydrate Cages 368 Ab Initio Methods 371 Outlook 381 References 382 8. The Quantum Chemistry of Loosely-Bound Electrons 391John M. Herbert Introduction and Overview 391 What Is a Loosely-Bound Electron? 391 Scope of This Review 392 Chemical Significance of Loosely-Bound Electrons 394 Challenges for Theory 400 Terminology and Fundamental Concepts 402 Bound Anions 402 Metastable (Resonance) Anions 415 Quantum Chemistry for Weakly-Bound Anions 425 Gaussian Basis Sets 425 Wave Function Electronic Structure Methods 439 Density Functional Theory 456 Quantum Chemistry for Metastable Anions 471 Maximum Overlap Method 474 Complex Coordinate Rotation 477 Stabilization Methods 483 Concluding Remarks 495 Acknowledgments 495 Appendix A: List of Acronyms 496 References 497 Index 519

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Book SynopsisThe new edition of this book greatly updates and expands the previous edition. It boasts new chapters on the divided wall column and carbon dioxide capture from stack gas, revises the design and control of distillation systems, and explains the use of dynamic simulation to study safety issues in the event of operating failures.Table of ContentsPREFACE TO THE SECOND EDITION xv PREFACE TO THE FIRST EDITION xvii 1 FUNDAMENTALS OF VAPOR–LIQUID–EQUILIBRIUM (VLE) 1 1.1 Vapor Pressure 1 1.2 Binary VLE Phase Diagrams 3 1.3 Physical Property Methods 7 1.4 Relative Volatility 7 1.5 Bubble Point Calculations 8 1.6 Ternary Diagrams 9 1.7 VLE Nonideality 11 1.8 Residue Curves for Ternary Systems 15 1.9 Distillation Boundaries 22 1.10 Conclusions 25 Reference 27 2 ANALYSIS OF DISTILLATION COLUMNS 29 2.1 Design Degrees of Freedom 29 2.2 Binary McCabe–Thiele Method 30 2.2.1 Operating Lines 32 2.2.2 q-Line 33 2.2.3 Stepping Off Trays 35 2.2.4 Effect of Parameters 35 2.2.5 Limiting Conditions 36 2.3 Approximate Multicomponent Methods 36 2.3.1 Fenske Equation for Minimum Number of Trays 37 2.3.2 Underwood Equations for Minimum Reflux Ratio 37 2.4 Conclusions 38 3 SETTING UP A STEADY-STATE SIMULATION 39 3.1 Configuring a New Simulation 39 3.2 Specifying Chemical Components and Physical Properties 46 3.3 Specifying Stream Properties 51 3.4 Specifying Parameters of Equipment 52 3.4.1 Column C1 52 3.4.2 Valves and Pumps 55 3.5 Running the Simulation 57 3.6 Using Design Spec/Vary Function 58 3.7 Finding the Optimum Feed Tray and Minimum Conditions 70 3.7.1 Optimum Feed Tray 70 3.7.2 Minimum Reflux Ratio 71 3.7.3 Minimum Number of Trays 71 3.8 Column Sizing 72 3.8.1 Length 72 3.8.2 Diameter 72 3.9 Conceptual Design 74 3.10 Conclusions 80 4 DISTILLATION ECONOMIC OPTIMIZATION 81 4.1 Heuristic Optimization 81 4.1.1 Set Total Trays to Twice Minimum Number of Trays 81 4.1.2 Set Reflux Ratio to 1.2 Times Minimum Reflux Ratio 83 4.2 Economic Basis 83 4.3 Results 85 4.4 Operating Optimization 87 4.5 Optimum Pressure for Vacuum Columns 92 4.6 Conclusions 94 5 MORE COMPLEX DISTILLATION SYSTEMS 95 5.1 Extractive Distillation 95 5.1.1 Design 99 5.1.2 Simulation Issues 101 5.2 Ethanol Dehydration 105 5.2.1 VLLE Behavior 106 5.2.2 Process Flowsheet Simulation 109 5.2.3 Converging the Flowsheet 112 5.3 Pressure-Swing Azeotropic Distillation 115 5.4 Heat-Integrated Columns 121 5.4.1 Flowsheet 121 5.4.2 Converging for Neat Operation 122 5.5 Conclusions 126 6 STEADY-STATE CALCULATIONS FOR CONTROL STRUCTURE SELECTION 127 6.1 Control Structure Alternatives 127 6.1.1 Dual-Composition Control 127 6.1.2 Single-End Control 128 6.2 Feed Composition Sensitivity Analysis (ZSA) 128 6.3 Temperature Control Tray Selection 129 6.3.1 Summary of Methods 130 6.3.2 Binary Propane/Isobutane System 131 6.3.3 Ternary BTX System 135 6.3.4 Ternary Azeotropic System 139 6.4 Conclusions 144 Reference 144 7 CONVERTING FROM STEADY-STATE TO DYNAMIC SIMULATION 145 7.1 Equipment Sizing 146 7.2 Exporting to Aspen Dynamics 148 7.3 Opening the Dynamic Simulation in Aspen Dynamics 150 7.4 Installing Basic Controllers 152 7.4.1 Reflux 156 7.4.2 Issues 157 7.5 Installing Temperature and Composition Controllers 161 7.5.1 Tray Temperature Control 162 7.5.2 Composition Control 170 7.5.3 Composition/Temperature Cascade Control 170 7.6 Performance Evaluation 172 7.6.1 Installing a Plot 172 7.6.2 Importing Dynamic Results into Matlab 174 7.6.3 Reboiler Heat Input to Feed Ratio 176 7.6.4 Comparison of Temperature Control with Cascade CC/TC 181 7.7 Conclusions 184 8 CONTROL OF MORE COMPLEX COLUMNS 185 8.1 Extractive Distillation Process 185 8.1.1 Design 185 8.1.2 Control Structure 188 8.1.3 Dynamic Performance 191 8.2 Columns with Partial Condensers 191 8.2.1 Total Vapor Distillate 192 8.2.2 Both Vapor and Liquid Distillate Streams 209 8.3 Control of Heat-Integrated Distillation Columns 217 8.3.1 Process Studied 217 8.3.2 Heat Integration Relationships 218 8.3.3 Control Structure 222 8.3.4 Dynamic Performance 223 8.4 Control of Azeotropic Columns/Decanter System 226 8.4.1 Converting to Dynamics and Closing Recycle Loop 227 8.4.2 Installing the Control Structure 228 8.4.3 Performance 233 8.4.4 Numerical Integration Issues 237 8.5 Unusual Control Structure 238 8.5.1 Process Studied 239 8.5.2 Economic Optimum Steady-State Design 242 8.5.3 Control Structure Selection 243 8.5.4 Dynamic Simulation Results 248 8.5.5 Alternative Control Structures 248 8.5.6 Conclusions 254 8.6 Conclusions 255 References 255 9 REACTIVE DISTILLATION 257 9.1 Introduction 257 9.2 Types of Reactive Distillation Systems 258 9.2.1 Single-Feed Reactions 259 9.2.2 Irreversible Reaction with Heavy Product 259 9.2.3 Neat Operation Versus Use of Excess Reactant 260 9.3 TAME Process Basics 263 9.3.1 Prereactor 263 9.3.2 Reactive Column C1 263 9.4 TAME Reaction Kinetics and VLE 266 9.5 Plantwide Control Structure 270 9.6 Conclusions 274 References 274 10 CONTROL OF SIDESTREAM COLUMNS 275 10.1 Liquid Sidestream Column 276 10.1.1 Steady-State Design 276 10.1.2 Dynamic Control 277 10.2 Vapor Sidestream Column 281 10.2.1 Steady-State Design 282 10.2.2 Dynamic Control 282 10.3 Liquid Sidestream Column with Stripper 286 10.3.1 Steady-State Design 286 10.3.2 Dynamic Control 288 10.4 Vapor Sidestream Column with Rectifier 292 10.4.1 Steady-State Design 292 10.4.2 Dynamic Control 293 10.5 Sidestream Purge Column 300 10.5.1 Steady-State Design 300 10.5.2 Dynamic Control 302 10.6 Conclusions 307 11 CONTROL OF PETROLEUM FRACTIONATORS 309 11.1 Petroleum Fractions 310 11.2 Characterization Crude Oil 314 11.3 Steady-State Design of Preflash Column 321 11.4 Control of Preflash Column 328 11.5 Steady-State Design of Pipestill 332 11.5.1 Overview of Steady-State Design 333 11.5.2 Configuring the Pipestill in Aspen Plus 335 11.5.3 Effects of Design Parameters 344 11.6 Control of Pipestill 346 11.7 Conclusions 354 References 354 12 DIVIDED-WALL (PETLYUK) COLUMNS 355 12.1 Introduction 355 12.2 Steady-State Design 357 12.2.1 MultiFrac Model 357 12.2.2 RadFrac Model 366 12.3 Control of the Divided-Wall Column 369 12.3.1 Control Structure 369 12.3.2 Implementation in Aspen Dynamics 373 12.3.3 Dynamic Results 375 12.4 Control of the Conventional Column Process 380 12.4.1 Control Structure 380 12.4.2 Dynamic Results and Comparisons 381 12.5 Conclusions and Discussion 383 References 384 13 DYNAMIC SAFETY ANALYSIS 385 13.1 Introduction 385 13.2 Safety Scenarios 385 13.3 Process Studied 387 13.4 Basic RadFrac Models 387 13.4.1 Constant Duty Model 387 13.4.2 Constant Temperature Model 388 13.4.3 LMTD Model 388 13.4.4 Condensing or Evaporating Medium Models 388 13.4.5 Dynamic Model for Reboiler 388 13.5 RadFrac Model with Explicit Heat-Exchanger Dynamics 389 13.5.1 Column 389 13.5.2 Condenser 390 13.5.3 Reflux Drum 391 13.5.4 Liquid Split 391 13.5.5 Reboiler 391 13.6 Dynamic Simulations 392 13.6.1 Base Case Control Structure 392 13.6.2 Rigorous Case Control Structure 393 13.7 Comparison of Dynamic Responses 394 13.7.1 Condenser Cooling Failure 394 13.7.2 Heat-Input Surge 395 13.8 Other Issues 397 13.9 Conclusions 398 Reference 398 14 CARBON DIOXIDE CAPTURE 399 14.1 Carbon Dioxide Removal in Low-Pressure Air Combustion Power Plants 400 14.1.1 Process Design 400 14.1.2 Simulation Issues 401 14.1.3 Plantwide Control Structure 404 14.1.4 Dynamic Performance 408 14.2 Carbon Dioxide Removal in High-Pressure IGCC Power Plants 412 14.2.1 Design 414 14.2.2 Plantwide Control Structure 414 14.2.3 Dynamic Performance 418 14.3 Conclusions 420 References 421 15 DISTILLATION TURNDOWN 423 15.1 Introduction 423 15.2 Control Problem 424 15.2.1 Two-Temperature Control 425 15.2.2 Valve-Position Control 426 15.2.3 Recycle Control 427 15.3 Process Studied 428 15.4 Dynamic Performance for Ramp Disturbances 431 15.4.1 Two-Temperature Control 431 15.4.2 VPC Control 432 15.4.3 Recycle Control 433 15.4.4 Comparison 434 15.5 Dynamic Performance for Step Disturbances 435 15.5.1 Two-Temperature Control 435 15.5.2 VPC Control 436 15.5.3 Recycle Control 436 15.6 Other Control Structures 439 15.6.1 No Temperature Control 439 15.6.2 Dual Temperature Control 440 15.7 Conclusions 442 References 442 16 PRESSURE-COMPENSATED TEMPERATURE CONTROL IN DISTILLATION COLUMNS 443 16.1 Introduction 443 16.2 Numerical Example Studied 445 16.3 Conventional Control Structure Selection 446 16.4 Temperature/Pressure/Composition Relationships 450 16.5 Implementation in Aspen Dynamics 451 16.6 Comparison of Dynamic Results 452 16.6.1 Feed Flow Rate Disturbances 452 16.6.2 Pressure Disturbances 453 16.7 Conclusions 455 References 456 17 ETHANOL DEHYDRATION 457 17.1 Introduction 457 17.2 Optimization of the Beer Still (Preconcentrator) 459 17.3 Optimization of the Azeotropic and Recovery Columns 460 17.3.1 Optimum Feed Locations 461 17.3.2 Optimum Number of Stages 462 17.4 Optimization of the Entire Process 462 17.5 Cyclohexane Entrainer 466 17.6 Flowsheet Recycle Convergence 466 17.7 Conclusions 467 References 467 18 EXTERNAL RESET FEEDBACK TO PREVENT RESET WINDUP 469 18.1 Introduction 469 18.2 External Reset Feedback Circuit Implementation 471 18.2.1 Generate the Error Signal 472 18.2.2 Multiply by Controller Gain 472 18.2.3 Add the Output of Lag 472 18.2.4 Select Lower Signal 472 18.2.5 Setting up the Lag Block 472 18.3 Flash Tank Example 473 18.3.1 Process and Normal Control Structure 473 18.3.2 Override Control Structure Without External Reset Feedback 474 18.3.3 Override Control Structure with External Reset Feedback 476 18.4 Distillation Column Example 479 18.4.1 Normal Control Structure 479 18.4.2 Normal and Override Controllers Without External Reset 481 18.4.3 Normal and Override Controllers with External Reset Feedback 483 18.5 Conclusions 486 References 486 INDEX 487

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Book SynopsisThe understanding of functional groups is key for the understanding of all organic chemistry. In the tradition of the Patai Series each volume treats all aspects of functional groups. Each volume contains chapters on the theoretical and physicochemical foundations; on analytical aspects; on reaction mechanisms; on applications in synthesis. Depending on the functional group there are additional chapters on industrial use, on medical use, and on human and environmental toxicity issues. The last volume in the series on the topic (Peroxides Vol. 2) was published in 2006. In the eight years since then a lot of developments have taken place, especially in the areas of synthesis, analysis and a better theoretical understanding of the reaction mechanism, all of which are covered here. As with all new volumes, the chapters are first published online in Patai's Chemistry of Functional Groups. Once a volume is completed online, it is then published in print format. The printed book offers Table of ContentsPart 1 1 An introduction to the consequences of spin and bond strength in the chemistry of diatomic oxygen, peroxides, and related species 1 Alexander Greer Alexandru T. Balaban Joel F. Liebman 2 Applications of endoperoxides derived from acenes and singlet oxygen 21 Werner Fudickar Torsten Linker 3 1,1-Dihydroperoxides 87 Chris Schwartz Patrick H. Dussault 4 Peroxide intermediates of oxidation processes: Organic trioxides 125 Sergey L. Khursan 5 Organic tetroxides and mechanism of peroxy radical recombination 197 Sergey L. Khursan 6 1,2-Dioxatrisulfane (thiaperoxide) intermediates in type I and II photooxygenation reactions 231 Edward L. Clennan 7 Sulfoxylic and thiosulfurous acids and their dialkoxy derivatives 265 Sergei V. Makarov Anna S. Makarova Radu Silaghi-Dumitrescu 8 Reactions of metal complexes with singlet oxygen 307 Matthias Selke 9 The chemistry of nitroso oxides 357 Ekaterina M. Chainikova Sergey L. Khursan Rustam L. Safiullin 10 Single-molecule reactive oxygen species detection in photocatalytic reactions 421 Takashi Tachikawa Tetsuro Majima 11 Reactions of peroxides on solid surfaces 437 Rossella Mello Maria Elena Gonzalez Nunez 12 Peroxide explosives 503 Thomas M. Klapotke Thomas Wloka 13 Gas-phase ion chemistry of organic peroxides 531 Shuji Kato Stephen J. Blanksby 14 Quantum chemical studies of carbonyl oxide chemistry in combustion and in the lower atmosphere 585 Keith T. Kuwata 15 Computational treatments of peroxy radicals in combustion and atmospheric reactions 633 Keith T. Kuwata 16 Heteroatom-substituted dioxetanes and their emerging biomedical applications 683 Gregory Nkepang Youngjae You 17 The use of hydrogen peroxide for disinfection and sterilization applications 713 Gerald McDonnell 18 Generation and reactivity of lipid hydroperoxides in biological systems 747 Albert W. Girotti Witold Korytowski 19 [ 18O]-Peroxides: Synthesis and biological applications 769 Paolo Di Mascio Sayuri Miyamoto Marisa H. G. Medeiros Glaucia R. Martinez Jean Cadet 20 Copper peroxide bioinorganic chemistry: From metalloenzymes to bioinspired synthetic systems 805 Isaac Garcia-Bosch Kenneth D. Karlin Subject Index 857

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Book SynopsisPowder diffraction is the mostly widely used crystallographic method, with applications spanning all aspects of structural science. This new volume of International Tables covers all aspects of the technique with over 50 chapters written by experts in the field.

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Book SynopsisThis book addresses the reader to use synergistically the concepts of membranes and sensors materials. It contains insightful contributions from leading scientists working in both the fields. The focus is on the fabrication of smart membranes from sensor materials and related impact on many technologically sophisticated areas such as telemedicine, microfluidics, drug delivery targeting, (bio)separation, labs-on-a-chip, textiles, power storage and release, environment monitoring, agro-food safety, cosmetics, architecture, automotive and so on. This book covers various topics, including the choice of materials and techniques for assembling responsive membranes with ability to transport mass, energy and signals on demand; the reader will find through the book an extensive description of the best techniques used to monitor molecular scale events, which are regarded as responsible for the smartness of multifunctional objects and for the conversion of chemical signals into optical,Table of ContentsPreface Part 1: Sensing Materials for Smart Membranes 1 1 Interfaces Based on Carbon Nanotubes, Ionic Liquids and Polymer Matrices for Sensing and Membrane Separation Applications 3 María Belén Serrano-Santos, Ana Corres Ortega, and Thomas Schäfer 1.1 Introduction 3 1.2 Ionic Liquid-Carbon Nanotubes Composites for Sensing Interfaces 5 1.3 Ionic Liquid Interfaces for Detection and Separation of Gases and Solvents 11 1.4 Ionic Liquid-Polymer Interfaces for Membrane Separation Processes 16 1.5 Conclusions 18 Acknowledgement 19 References 19 2 Photo-Responsive Hydrogels for Adaptive Membranes 21 David Díaz Díaz and Jeremiah A. Johnson 2.1 Introduction 21 2.2 Photo-Responsive Hydrogel Membranes 23 2.3 Photo-Thermally Responsive Hydrogel Membranes 44 2.4 Summary 46 2.5 Acknowledgements 48 Abbreviations 48 References 49 3 Smart Vesicles: Synthesis, Characterization and Applications 53 Jung-Keun Kim, Chang-Soo Lee, and Eunji Lee 3.1 Introduction 53 3.2 Synthesis of Soft Vesicles 54 3.3 Synthesis of Hard Vesicles 64 3.4 Characterization of Vesicular Structures 68 3.5 Stimuli-Responsive Behaviors of Vesicular Structures 72 3.6 Application of Vesicles 78 3.7 Conclusions 91 Acknowledgment 92 References 92 Part 2: Stimuli-Responsive Interfaces 105 4 Computational Modeling of Sensing Membranes and Supramolecular Interactions 107 Giacomo Saielli 4.1 Introduction 107 4.2 Non-covalent Interactions: A Physical and a Chemical View 109 4.3 Physical Interactions 109 4.4 Chemical Interactions 114 4.5 Computational Methods for Supramolecular Interactions 117 4.6 Classical Force Fields 127 4.7 Conclusions 139 References 140 5 Sensing Techniques Involving Thin Films for Studying Biomolecular Interactions and Membrane Fouling Phenomena 145 Gabriela Diaconu and Thomas Schäfer 5.1 Introduction 145 5.2 Quartz Crystal Microbalance with Dissipation Monitoring (QCM-D) 146 5.3 Surface Plasmon Resonance (SPR) 148 5.4 Applications of SPR and QCM-D 151 5.5 Conclusions 159 Acknowledgements 160 References 160 6 Smart Membrane Surfaces: Wettability Amplification and Self-Healing 161 Annarosa Gugliuzza 6.1 Introduction 161 6.2 Basics of surface wettability 162 6.3 Amplified Wettability 164 6.4 Actuation Mechanisms 165 6.5 Self-Powered Liquid Motion 170 6.6 Self-Cleaning Mechanisms 172 6.7 Self-Healing Concepts And Strategies 175 6.8 Repairable Surface Properties 177 6.9 Conclusions and Perspectives 179 References 180 7 Model Bio-Membranes Investigated by AFM and AFS: A Suitable Tool to Unravel Lipid Organization and their Interaction with Proteins 185 Andrea Alessandrini and Paolo Facci 7.1 Introduction 186 7.2 Supported Lipid Bilayers 189 7.3 Atomic Force Microscopy (AFM) and Phase Behavior of Slbs 199 7.4 Atomic Force Spectroscopy (AFS) of Supported Lipid Bilayers 205 7.5 Lipid/Protein Interactions 213 7.6 Conclusions 218 References 218 Part 3: Directed Molecular Separation 227 8 Self-Assembled Nanoporous Membranes for Controlled Drug Release and Bioseparation 229 Dominique Scalarone, Pierangiola Bracco, and Francesco Trotta 8.1 Introduction 229 8.2 General Aspects of Block Copolymer Self-Assembly 231 8.3 Block Copolymer Based Membranes 233 8.4 Fabrication of Nanoporous Membranes Derived from Block Copolymers 234 8.5 Tunability of Surface Properties 242 8.6 Application of Block Copolymer Derived Membranes to Bioseparation and Controlled Drug Release 244 8.7 Conclusion 250 References 250 Abbreviations 253 9 Hybrid Mesoporous Silica for Drug Targeting 255 Luigi Pasqua, Piluso Rosangela, Ilenia Pelaggi, and Catia Morelli 9.1 Introduction 256 9.2 Synthesis and Characterization of Bifunctional Hybrid Mesoporous Silica Nanoparticles Potentially Useful for Drug Targeting 257 9.3 Drug-Loaded Folic-Acid-Grafted Msns Specifically Target FR Expressing Tumour Cells [16] 260 9.4 Conclusion 266 References 268 10 Molecular Recognition-driven Membrane Processes 269 Laura Donato, Rosalinda Mazzei, Catia Algieri, Emma Piacentini, Teresa Poerio, and Lidietta Giorno 10.1 Molecular Imprinting Technique 270 10.2 Affinity Membranes 275 10.3 Cyclodextrins As Molecular Recognition Elements 281 10.4 Zeolite Membranes as Molecular Recognition Devices: Preparation and Characterization 283 10.5 Functionalized Particles-loaded Membranes For Selective Separation Based On Molecular Recognition 287 10.6 Biphasic Enzyme Membrane Systems with Enantioselective Recognition Properties ror Kinetic Resolution 291 10.7 Membrane Surface Modification 292 References 296 Part 4: Membrane Sensors and Challenged Applications 301 11 Electrospun Membranes for Sensors Applications 303 Pierangiola Bracco, Dominique Scalarone, and Francesco Trotta 11.1 Introduction 303 11.2 Basic Principles of Electrospinning 304 11.3 Control of the Electrospinning Process 306 11.4 Application of Electrospun Materials to Ultrasensitive Sensors 311 11.5 Conclusions 329 Abbreviations 330 References 330 12 Smart Sensing Scaffolds 337 Carmelo De Maria, Yudan Whulanza, Giovanni Vozzi, and Arti Ahluwalia 12.1 Introduction 337 12.2 Composite Sensing Biomaterial Preparation 339 12.3 Composite Sensing Biomaterial Characterisation 340 12.4 SWNTs-Based Composite Films Structural Properties 341 12.5 Tensile Properties of SWNTs-Based Composite Films 343 12.6 Electrical Properties of SWNTs-Based Composites Films 348 12.7 Electromechanical Characterisation and Strain-Dependence Measurement 350 12.8 Cell Sensing Scaffolds 352 12.9 Processing of CNT Composite: Microfabrication of Sensing Scaffold 360 12.10 Conclusions 361 References 362 13 Nanostructured Sensing Emulsion Droplets and Particles: Properties and Formulation by Membrane Emulsification 367 Emma Piacentini, Alessandra Imbrogno, and Lidietta Giorno 13.1 Introduction 367 13.2 Emulsions and Emulsification Methods 370 13.3 Senging Particles Produced by Membrane-Based Process 389 13.4 Conclusions 397 References 398 14 Membranes for Ultra-Smart Textiles 401 Annarosa Gugliuzza and Enrico Drioli 14.1 Introduction 401 14.2 Membranes and Comfort 403 14.3 Adaptive Membranes for Smart Textiles 407 14.4 Barrier Functions of Membranes 411 14.5 Membrane Materials for Self-cleaning Function 413 14.6 Interactive Membranes for Wearable Electronics 414 14.7 Conclusions and Prospects 415 References 416

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Book SynopsisThis General, Organic and Biochemistry text has been written for students preparing for careers in health-related fields such as nursing, dental hygiene, nutrition, medical technology and occupational therapy. It is also suited for students majoring in other fields where it is important to have an understanding of the basics of chemistry. An integrated approach is employed in which related general chemistry, organic chemistry, and biochemistry topics are presented in adjacent chapters. This approach helps students see the strong connections that exist between these three branches of chemistry, and allows instructors to discuss these, interrelationships while the material is still fresh in students'' minds.Table of ContentsA Note From the Publisher v Safety in the Laboratory 1 Suggested Equipment 6 Fundamental Laboratory Operations 8 Experiment 1 Measurement 27 Experiment 2 Some Laboratory Techniques 45 Experiment 3 Ions: Role in Nutrition 53 Experiment 4 Paper and Thin Layer Chromatography 69 Experiment 5 Molecules: Organic Compounds 87 Experiment 6 Properties of Water 107 Experiment 7 Chemical Reactions 123 Experiment 8 Stoichiometry: Mole Relationships 139 Experiment 9 Properties of Gases 151 Experiment 10 Acids, Bases, Buffers, and Antacids 169 Experiment 11 Organic Oxygen Compounds 189 Experiment 12 Aspirin and Related Compounds 207 Experiment 13 Organic Nitrogen Compounds 221 Experiment 14 Carbohydrates 233 Experiment 15 Lipids 253 Experiment 16 Proteins 267 Experiment 17 Enzymes 281 Experiment 18 Urine 293 Experiment 19 Nucleosides 305 Experiment 20 DNA and RNA 315 Appendix A Exercise on Chemical Periodicity 327

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Book SynopsisCritical overviews from the front line of ionic liquids research Ionic Liquids Further UnCOILed: Critical Expert Overviews continues the discussion of new processes and developments in ionic liquid technology introduced in the first volume. Written by an international group of key academic and industrial chemists, this next book in the series includes eleven overviews of specific areas of ionic liquid chemistry including: Physicochemical properties of ionic liquids A patent survey Ionic liquid membrane technology Engineering simulations Molecular simulations The goal of this volume is to provide expert overviews that range from applied to theoretical, synthetic to analytical, and biotechnological to electrochemical, while also offering consistent abbreviations of ionic liquids throughout the text. The value of Ionic Liquids Further UnCOILed: Critical Expert Overviews lies in the authorsTable of ContentsCOIL Conferences vii Preface ix Acknowledgements xi Contributors xiii Abbreviations xv 1 Ionic Liquid and Petrochemistry: A Patent Survey 1 Philippe Bonnet, Anne Pigamo, Didier Bernard, and Hélène Olivier-Bourbigou 2 Supercritical Fluids in Ionic Liquids 39 Maaike C. Kroon and Cor J. Peters 3 The Phase Behaviour of 1-Alkyl-3-Methylimidazolium Ionic Liquids 59 Keiko Nishikawa 4 Ionic Liquid Membrane Technology 87 João G. Crespo and Richard D. Noble 5 Engineering Simulations 117 David Rooney and Norfaizah ab Manan 6 Molecular Simulation of Ionic Liquids: Where We Are and the Path Forward 149 Jindal K. Shah and Edward J. Maginn 7 Biocatalytic Reactions in Ionic Liquids 193 Florian Stein and Udo Kragl 8 Ionicity in Ionic Liquids: Origin of Characteristic Properties of Ionic Liquids 217 Masayoshi Watanabe and Hiroyuki Tokuda 9 Dielectric Properties of Ionic Liquids: Achievements So Far and Challenges Remaining 235 Hermann Weingärtner 10 Ionic Liquid Radiation Chemistry 259 James F. Wishart 11 Physicochemical Properties of Ionic Liquids 275 Qing Zhou, Xingmei Lu, Suojiang Zhang, and Liangliang Guo Index 309

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Book SynopsisCritical overviews from the front line of ionic liquids research Ionic Liquids Completely UnCOILed: Critical Expert Overviews concludes the discussion of new processes and developments in ionic liquid technology introduced in the previously published volumes, Ionic Liquids UnCOILed and Ionic Liquids Further UnCOILed. The goal of this volume is to provide expert overviews that range from applied to theoretical, synthetic to structural, and analytical to toxicological. The value of book lies in the authors' expertise, and their willingness to share it with the reader. Written by an international group of chemists, the book presents eleven overviews of specific areas of ionic liquid chemistry including: What is an Ionic Liquid? Molecular modelling Crystallography Chemical engineering of ionic liquid processes Toxicology and Biodegradation Organic reaction mechanisms Edited Table of ContentsContents of “Ionic Liquids UnCOILed” vii Contents of “Ionic Liquids Further UnCOILed” ix COIL Conferences xi Preface xiii Acknowledgements xv Contributors xvii Abbreviations xix 1 What Is an Ionic Liquid? 1 Andrew P. Abbott, Karl Ryder, Peter Licence, and Alasdair W. Taylor 2 N MR Studies of Ionic Liquids 13 Paul M. Bayley, Jan Novak, and Maria Forsyth 3 ‘Unusual Anions’ as Ionic Liquid Constituents 39 Philipp Eiden and Ingo Krossing 4 Investigating the Structure of Ionic Liquids and Ionic Liquid: Molecular Solute Interactions 55 Christopher Hardacre, Claire Mullan, and Tristan G. A. Youngs 5 Molecular Modelling of Ionic Liquids 83 José N. Canongia Lopes, Margarida Costa Gomes, and Agilío A. H. Pádua 6 Chemical Engineering of Ionic Liquid Processes 107 Carolin Meyer, Sebastian Werner, Marco Haumann, and Peter Wasserscheid 7 Vibrational Spectroscopy of Ionic Liquid Surfaces 145 Chariz Peñalber-Johnstone and Steven Baldelli 8 Raman Spectroscopy and the Heterogeneous Liquid Structure in Ionic Liquids 165 Satyen Saha, Takashi Hiroi, Koichi Iwata, and Hiro‐O Hamaguchi 9 (Eco)Toxicology and Biodegradation of Ionic Liquids 189 Stefan Stolte, Marianne Matzke, and Jürgen Arning 10 Ionic Liquids and Organic Reaction Mechanisms 209 Tom Welton 11 Crystallography of Ionic Liquids 231 Neil Winterton Index 535

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Book SynopsisTable of ContentsPreface xxi Companion Website xxiii Biography xxv Solid State Chemistry, an Overview of the Discipline: Chemistry -- Solid State Chemistry -- Materials Chemistry -- Materials Science and Engineering 1 1 Crystal Structures, Crystal Chemistry, Symmetry and Space Groups 7 2 Crystal Defects, Non-stoichiometry and Solid Solutions 119 3 Bonding in Solids 161 4 Synthesis, Processing and Fabrication Methods 221 5 Crystallography and Diffraction Techniques 265 6 Other Characterisation Techniques: Microscopy, Spectroscopy, Thermal Analysis 325 7 Phase Diagrams and Their Interpretation 381 8 Electrical Properties 469 9 Magnetic Properties 563 10 Optical Properties: Luminescence, Lasers and Transparent Conductors 589 11 Heterogeneous Materials, Electroceramics and Impedance Spectroscopy 619 12 Thermal and Thermoelectric Properties 647 13 Functional Materials: Some Important Examples 663 14 Glass 697 15 Structural Materials: Cement, Refractories and Structural Ceramics 743 16 Oxides of the Elements, Their Properties and Uses 771 Appendix A: Interplanar Spacings and Unit Cell Volumes 795 Appendix B: Model Building 797 Appendix C: Geometrical Considerations in Crystal Chemistry 801 Appendix D: The Elements and Some of Their Properties 805 Appendix E: The 32 Crystallographic Point Groups 811 Appendix F: The Arrhenius Equation for Ionic Conductivity 815 Appendix G: A Guide to the Use of Electrode Potentials 819 Further Reading 823 Questions 837 Index 851

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Book SynopsisFocuses on the aggregation of recombinant proteins in bacterial cells in the form of inclusion bodiesand on their use in biotechnological and medical applications The first book devoted specifically to the topic of aggregation in bacteria, Protein Aggregation in Bacteria: Functional and Structural Properties of Inclusion Bodies in Bacterial Cells provides a large overview of protein folding and aggregation, including cell biology and methodological aspects. It summarizes, for the first time in one book, ideas and technical approaches that pave the way for a direct use of inclusion bodies in biotechnological and medical applications. Protein Aggregation in Bacteria covers: Molecular and cellular mechanisms of protein folding, aggregation, and disaggregation in bacteria Physiological importance and consequences of aggregation for the bacterial cell Factors inherent to the protein sequence responsible for aggregation andTable of ContentsContributors vii Preface xi Introduction to the Wiley Series in Protein and Peptide Science xiii 1 Fundamentals of Protein Folding 1 Vladimir N. Uversky 2 Recruiting Unfolding Chaperones to Solubilize Misfolded Recombinant Proteins 63 Rayees U.H. Mattoo and Pierre Goloubinoff 3 Osmolytes as Chemical Chaperones to Use in Protein Biotechnology 77 Ario de Marco 4 Inclusion Bodies in the Study of Amyloid Aggregation 93 Anna Villar-Piqué and Salvador Ventura 5 Protein Aggregation in Unicellular Eukaryotes 117 Marina Caldara, Joris Winderickx, and Vanessa Franssens 6 Structural Properties of Bacterial Inclusion Bodies 151 Antonino Natalello, Diletta Ami, and Silvia Maria Doglia 7 Residue-Specific Structural Studies of Inclusion Bodies 181 Christian Wasmer, Marielle Wälti, Yongli Chen, and Lei Wang 8 Biomedical Applications of Bacterial Inclusion Bodies 203 Imma Ratera, Spela Peternel, Joaquin Seras-Franzoso, Olivia Cano-Garrido, Elena García-Fruitós, Rafael Cubarsí, Esther Vazquez, José Luis Corchero, Escarlata Rodríguez-Carmona, Jaume Veciana, and Antonio Villaverde 9 Aggregation of Recombinant Proteins: Understanding Basic Issues to Overcome Production Bottlenecks 221 Marina Lotti and Loredano Pollegioni 10 Fusion to a Pull-Down Module: Designing Enzymes to Form Biocatalytically Active Insoluble Aggregates 247 Bernd Nidetzky Index 263

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Book SynopsisWith a focus on structure-property relationships, this book describes how polymer morphology affects properties and how scientists can modify them. The book covers structure development, theory, simulation, and processing; and discusses a broad range of techniques and methods.Table of ContentsPREFACE xiii LIST OF CONTRIBUTORS xv PART I PRINCIPLES AND METHODS OF CHARACTERIZATION 1 1 Overview and Prospects of Polymer Morphology 3 Jerold M. Schultz 1.1 Introductory Remarks 3 1.2 Experimental Avenues of Morphological Research 4 1.2.1 Morphological Characterization: The Enabling of in situ Measurements 4 1.2.2 Morphology–Property Investigation 5 1.2.3 Morphology Development 7 1.3 Modeling and Simulation 8 1.3.1 Self-Generated Fields 9 1.4 Wishful Thinking 11 1.5 Summary 11 References 12 2 X-ray Diffraction from Polymers 14 N. Sanjeeva Murthy 2.1 Introduction 14 2.2 Basic Principles 14 2.3 Instrumentation 16 2.4 Structure Determination 17 2.4.1 Lattice Dimensions 17 2.4.2 Molecular Modeling 18 2.4.3 Rietveld Method 18 2.4.4 Pair Distribution Functions 18 2.5 Phase Analysis 19 2.5.1 Crystallinity Determination 20 2.5.2 Composition Analysis 21 2.6 Crystallite Size and Disorder 21 2.7 Orientation Analysis 22 2.7.1 Crystalline Orientation 22 2.7.2 Uniaxial Orientation 22 2.7.3 Biaxial Orientation 24 2.7.4 Amorphous Orientation 25 2.8 Small-Angle Scattering 25 2.8.1 Central Diffuse Scattering 26 2.8.2 Discrete Reflections from Lamellar Structures 27 2.8.3 Small-Angle Neutron Scattering and Solvent Diffusion 29 2.9 Specialized Measurements 30 2.9.1 In situ Experiments 30 2.9.2 Microbeam Diffraction 31 2.9.3 Grazing Incidence Diffraction 32 2.10 Summary 33 References 33 3 Electron Microscopy of Polymers 37 Goerg H. Michler and Werner Lebek 3.1 Introduction 37 3.2 Microscopic Techniques 37 3.2.1 Scanning Electron Microscopy (SEM) 37 3.2.2 Transmission Electron Microscopy (TEM) 42 3.2.3 Comparison of Different Microscopic Techniques 45 3.2.4 Image Processing and Image Analysis 46 3.3 Sample Preparation 47 3.4 In situ Microscopy 50 References 52 4 Characterization of Polymer Morphology by Scattering Techniques 54 Jean-Michel Guenet 4.1 Introduction 54 4.2 A Short Theoretical Presentation 55 4.2.1 General Expressions 55 4.2.2 The Form Factor 56 4.3 Experimental Aspects 60 4.3.1 The Contrast Factor 60 4.3.2 Experimental Setup 61 4.4 Typical Results 62 4.4.1 Neutrons Experiments: A Contrast Variation Story 62 4.4.2 X-Ray Experiments: A Time-Resolved Story 67 4.5 Concluding Remarks 69 References 69 5 Differential Scanning Calorimetry of Polymers 72 Alejandro J. Müller and Rose Mary Michell 5.1 Introduction to Differential Scanning Calorimetry. Basic Principles and Types of DSC Equipment 72 5.2 Detection of First-Order and Second-Order Transitions by DSC. Applications of Standard DSC Experiments to the Determination of the Glass Transition Temperature and the Melting Temperature of Polymeric Materials 74 5.3 Self-Nucleation 75 5.3.1 Quantification of the Nucleation Efficiency 77 5.4 Thermal Fractionation 78 5.5 Multiphasic Materials: Polymer Blends and Block Copolymers. Fractionated Crystallization and Confinement Effects 81 5.5.1 Blends and Fractionated Crystallization 81 5.5.2 Copolymers 85 5.5.3 Copolymers Versus Blends 87 5.5.4 The Crystallization of Polymers and Copolymers within Nanoporous Templates 88 5.6 Self-Nucleation and the Efficiency Scale to Evaluate Nucleation Power 91 5.6.1 Supernucleation 93 5.7 Determination of Overall Isothermal Crystallization by DSC 95 5.8 Conclusions 95 Acknowledgment 95 References 95 6 Imaging Polymer Morphology using Atomic Force Microscopy 100 Holger Schönherr 6.1 Introduction 100 6.2 Fundamental AFM Techniques 101 6.2.1 Contact Mode AFM 101 6.2.2 Intermittent Contact (Tapping) Mode AFM 104 6.2.3 Further Dynamic AFM Modes 105 6.3 Imaging of Polymer Morphology 107 6.3.1 Single Polymer Chains 107 6.3.2 Crystal Structures 107 6.3.3 Lamellar Crystals 109 6.3.4 Spherulites 109 6.3.5 Multiphase Systems 109 6.3.6 Polymeric Nanostructures 111 6.4 Property Mapping 113 6.4.1 Nanomechanical Properties 113 6.4.2 Scanning Thermal Microscopy 115 References 115 7 FTIR Imaging of Polymeric Materials 118 S. G. Kazarian and K. L. A. Chan 7.1 Introduction 118 7.2 Principles of FTIR Imaging 118 7.3 Sampling Methods 120 7.3.1 Transmission Mode 120 7.3.2 Attenuated Total Reflection (ATR) Mode 121 7.4 Spatial Resolution 122 7.4.1 Transmission FTIR Imaging 123 7.4.2 ATR–FTIR Spectroscopic Imaging 123 7.5 Recent Applications 124 7.5.1 Polymer Blends 124 7.5.2 Polymer Processes 125 7.5.3 Polarized FTIR Imaging for Orientation Studies 126 7.6 Conclusions 127 References 128 8 NMR Analysis of Morphology and Structure of Polymers 131 Takeshi Yamanobe and Hiroki Uehara 8.1 Introduction 131 8.2 Basic Concepts in NMR 131 8.2.1 Principles of NMR 131 8.2.2 Analysis of the Free Induction Decay (FID) 132 8.3 Morphology and Relaxation Behavior of Polyethylene 134 8.3.1 Morphology and Molecular Mobility 134 8.3.2 Lamellar Thickening by Annealing 134 8.3.3 Entanglement in the Amorphous Phase 136 8.4 Morphology and Structure of the Nascent Powders 137 8.4.1 Etching by Fuming Nitric Acid 137 8.4.2 Structural Change by Annealing 138 8.4.3 Nascent Isotactic Polypropylene Powder 139 8.5 Kinetics of Dynamic Process of Polymers 141 8.5.1 Melt Drawing of Polyethylene 141 8.5.2 Crystallization Mechanism of Nylon 46 143 8.5.3 Degree of Curing of Novolac Resins 145 8.6 Conclusions 146 References 146 PART II MORPHOLOGY PROPERTIES AND PROCESSING 151 9 Small-Angle X-ray Scattering for Morphological Analysis of Semicrystalline Polymers 153 Anne Seidlitz and Thomas Thurn-Albrecht 9.1 Introduction 153 9.2 Small-angle X-ray Scattering 153 9.2.1 Typical Experimental Setup 153 9.2.2 Basic Formalism Describing the Relation between Real-Space Structure and Scattering Intensity in a SAXS Experiment 154 9.2.3 Methods of Analysis Used for SAXS on Semicrystalline Polymers 155 9.3 Concluding Remarks 162 Appendix: Calculation of the Model Function KÞ ′′ sim(s) 163 References 163 10 Crystalline Morphology of Homopolymers and Block Copolymers 165 Shuichi Nojima and Hironori Marubayashi 10.1 Introduction 165 10.2 Crystalline Morphology of Homopolymers 165 10.2.1 Crystal Structure 165 10.2.2 Lamellar Morphology 167 10.2.3 Spherulite Structure 168 10.2.4 Crystalline Morphology of Homopolymers Confined in Isolated Nanodomains 168 10.2.5 Crystalline Morphology of Polymer Blends 169 10.3 Crystalline Morphology of Block Copolymers 171 10.3.1 Crystalline Morphology of Weakly Segregated Block Copolymers 172 10.3.2 Crystalline Morphology of Block Copolymers with Glassy Amorphous Blocks 173 10.3.3 Crystalline Morphology of Strongly Segregated Block Copolymers 174 10.3.4 Crystalline Morphology of Double Crystalline Block Copolymers 175 10.4 Concluding Remarks 176 References 176 11 Isothermal Crystallization Kinetics of Polymers 181 Alejandro J. Müller Rose Mary Michell and Arnaldo T. Lorenzo 11.1 Introduction 181 11.2 Crystallization Process 182 11.3 Crystallization Kinetics 182 11.3.1 The Avrami Equation [31] 183 11.3.2 Nucleation and Crystal Growth: Lauritzen–Hofmann Theory 188 11.4 Isothermal Crystallization Kinetics–Morphology Relationship 191 11.4.1 Linear PS-b-PCL versus Miktoarm (PS2)-b-(PCL2) Block Copolymers 191 11.4.2 Crystallization Kinetics and Morphology of PLLA-b-PCL Diblock Copolymers 194 11.4.3 Nucleation and Crystallization Kinetics of Double Crystalline Polyethylene/Polyamide (PE/PA) Blends 196 11.4.4 Crystallization Kinetics of Poly(𝜀-Caprolactone)/Carbon Nanotubes (PCL/CNTs) Blends 200 11.5 Conclusions 201 Acknowledgments 201 References 201 12 Surface-induced Polymer Crystallization 204 Xiaoli Sun and Shouke Yan 12.1 Introduction 204 12.2 Influence of Foreign Surface on the Crystallization Kinetics of Polymers 205 12.3 Influence of Foreign Surface on the Crystal Structure and Morphology of Polymers 205 12.3.1 Crystallization of Thin Polymer Films on Amorphous Foreign Surface 205 12.3.2 Crystallization of Polymer Thin Films on Crystalline Foreign Surface with Special Crystallographic Interaction 209 12.4 Bulk Crystallization of Polymers in Contact with a Foreign Surface 226 12.5 Summary 234 References 235 13 Thermodynamics and Kinetics of Polymer Crystallization 242 Wenbing Hu and Liyun Zha 13.1 Introduction 242 13.2 Thermodynamics of Polymer Crystallization 242 13.3 Crystal Nucleation 247 13.4 Crystal Growth 251 13.5 Crystal Annealing 254 13.6 Summary 255 References 256 14 Self-Assembly and Morphology in Block Copolymer Systems with Specific Interactions 259 Anbazhagan Palanisamy and Qipeng Guo 14.1 Introduction 259 14.2 Block Copolymer Systems with Hydrogen Bonding Interaction in Solid State 260 14.2.1 Diblock Copolymer/Homopolymer Systems 260 14.2.2 Diblock/Triblock Copolymer Systems 264 14.3 Block Copolymer Systems with Hydrogen-Bonding Interaction in Solution 268 14.3.1 Single-Component Block Copolymer Systems 268 14.3.2 Diblock Copolymer/Homopolymer Systems 269 14.3.3 Diblock/Diblock Copolymer Systems 271 14.3.4 Triblock Copolymer Systems 275 14.4 Block Copolymer Systems with Ionic Interaction 275 14.4.1 Diblock Copolymer/Homopolymer Systems 275 14.4.2 Diblock/Triblock Copolymer Systems 276 14.5 Block Copolymer Blends via Metal–Ligand Coordination Bonds 278 14.6 Concluding Remarks 278 References 279 15 Dynamics Simulations of Microphase Separation in Block Copolymers 283 Xuehao He Xuejin Li Peng Chen and Haojun Liang 15.1 Introduction 283 15.2 Polymer Model and Simulation Algorithm 284 15.2.1 Monte Carlo Method 284 15.2.2 Dissipative Particle Dynamics Method 285 15.2.3 Polymeric Self-Consistent Field Theory 286 15.3 Dynamics of Self-Assembly of Block Copolymers 287 15.3.1 Phase Separation of Linear Block Copolymers 287 15.3.2 Self-Assembly of Star Block Copolymers in Melt 287 15.3.3 Self-Assembly of Block Copolymers in Constrained Systems 289 15.3.4 Micellization of Amphiphilic Block Copolymer in Solution 292 15.4 Outlook 294 References 295 16 Morphology Control of Polymer thin Films 299 Jiangang Liu Xinhong Yu Longjian Xue and Yanchun Han 16.1 Wetting 299 16.1.1 Dewetting Mechanisms 300 16.1.2 Dewetting Dynamics 301 16.1.3 Rim Instability 303 16.1.4 Factors Affecting the Stability of Polymer Thin Films 303 16.2 Thin Film of Polymer Blend 304 16.2.1 Fundamentals of Polymer Blends 305 16.2.2 Phase Separation in Thin Polymer Films 306 16.3 The Introduction of Polymer Blend Film in Solar Cells 307 16.3.1 Establish Interpenetrating Network Structure by Controlling Phase Separation 308 16.3.2 Control the Domain Size and Purify of the Domains 310 16.3.3 Adjust the Diffused Structure at the Interface Between Donor and Acceptor 312 16.3.4 Construct the Relationship Between Film Morphology and Device Performance 312 16.4 Summary and Outlook 313 References 313 17 Polymer Surface Topography and Nanomechanical Mapping 317 Hao Liu So Fujinami Dong Wang Ken Nakajima and Toshio Nishi 17.1 Introduction 317 17.2 Contact Mechanics 317 17.2.1 Hertzian Theory (Repulsion between Elastic Bodies) 318 17.2.2 Bradley Model (Interaction between Rigid Bodies) 318 17.2.3 Johnson–Kendall–Roberts (JKR) Model 318 17.2.4 Derjaguin–Muller–Toporov (DMT) Model 319 17.2.5 The JKR–DMT transition and Maugis–Dugdale (MD) Model 319 17.2.6 Adhesion Map 320 17.3 Application of Contact Mechanics to Experimental Data 321 17.3.1 Consideration of Contact Models 321 17.3.2 Force–Distance Curve Conversion 321 17.3.3 Analysis of Load–Indentation Curves 322 17.3.4 Nanomechanical Mapping 322 17.4 Application Examples 323 17.4.1 Effect of Processing Conditions on Morphology and Mechanical Properties of Block Copolymers 323 17.4.2 Measuring the Deformation of Both Ductile and Fragile Polymers 325 17.4.3 Nanorheological AFM on Rubbers 328 17.5 Conclusion 331 References 331 18 Polymer Morphology and Deformation Behavior 335 Masanori Hara 18.1 Introduction 335 18.2 Deformation Behavior of Amorphous Polymers 336 18.2.1 Deformation Behavior of Thin Films 336 18.2.2 Deformation Behavior of Bulk Polymers 338 18.3 Deformation Behavior of Semicrystalline Polymers 339 18.3.1 Deformation of Unoriented Semicrystalline Polymers 341 18.3.2 Strain Hardening and Network Density 341 18.4 Deformation Behavior of Block Copolymers 342 18.4.1 Block Copolymers Based on S and B 343 18.4.2 Block Copolymers Based on E and C (CHE) 345 18.5 Conclusions and Outlook 345 References 346 19 Morphology Development in Immiscible Polymer Blends 348 Ruth Cardinaels and Paula Moldenaers 19.1 Introduction 348 19.2 Morphology Development in Bulk Flow 350 19.2.1 Droplet–Matrix Structures 350 19.2.2 Fibrillar Structures 359 19.2.3 Cocontinuous Structures 361 19.3 Recent Advances in Polymer Blends 363 19.3.1 Immiscible Blends in Confined Flow 363 19.3.2 Blend Compatibilization by Nanoparticles 364 19.4 Conclusions 367 Acknowledgments 368 References 368 20 Processing Structure and Morphology in Polymer Nanocomposites 374 Duraccio Donatella Clara Silvestre Sossio Cimmino Antonella Marra and Marilena Pezzuto 20.1 Overview 374 20.2 Nanoparticles with One Dimension Less Than 100 nm (Layered Silicates) 375 20.3 Nanoparticles with Two Dimensions Less Than 100 nm (Carbon Nanotubes) 377 20.4 Nanoparticles with Three Dimensions Less Than 100 nm (Metal Metal Oxide) 380 20.5 Preparative Methods 382 20.5.1 Solution Processing 382 20.5.2 In situ Polymerization 383 20.5.3 Melt Processing 384 20.5.4 In situ Sol–Gel Technology 384 20.6 Structure and Morphology of Polymer Nanocomposites 385 20.7 Concluding Remarks 388 References 388 21 Morphology and Gas Barrier Properties of Polymer Nanocomposites 397 Abbas Ghanbari Marie-Claude Heuzey Pierre J. Carreau and Minh-Tan Ton-That 21.1 Introduction 397 21.2 Structure of Layered Silicates 397 21.3 Morphologies of Polymer-Layered Silicate Composites 398 21.4 Nanocomposite Preparation Methods 398 21.5 Challenges of Thermal Degradation in Melt Intercalation 400 21.6 Methods for Improving Gas Barrier Properties of Polymers 403 21.7 Polyamide Nanocomposites 405 21.8 Polyolefin Nanocomposites 405 21.9 Pet Nanocomposites 406 21.10 Polylactide Nanocomposites 413 21.11 Conclusions and Perspectives 414 References 415 22 Features on the Development and Stability of Phase Morphology in Complex Multicomponent Polymeric Systems: Main Focus on Processing Aspects 418 Charef Harrats Maria-Beatrice Coltelli and Gabriel Groeninckx 22.1 Introduction 418 22.2 Phase Morphology Development in Polymer Blends 419 22.2.1 Droplet-in-Matrix (Dispersed) Phase Morphology 419 22.2.2 Co-continuous Phase Morphology 419 22.2.3 Phase Morphology in Ternary Blends 420 22.3 Melt Processing of Polymer Blends 423 22.3.1 Morphology Buildup during Processing 423 22.3.2 Effects of Processing Parameters on Phase Morphology 424 22.4 Chemistry Involved in Polymer Blends 426 22.4.1 Effect of the Compatibilizer on Phase Morphology 426 22.4.2 Formation in situ of the Compatibilizer 427 22.4.3 Case of Reactive Ternary Blends 429 22.4.4 Stability of Phase Morphology in Reactively Compatibilized Blends 431 22.4.5 Organoclay-Promoted Phase Morphology 433 22.4.6 Conclusions 435 References 436 INDEX 439

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Book SynopsisOffers a comprehensive overview of different catalytic reactions applied to the activation of chemical bonds. This title covers key C-X classes where carbon is combined with another element: chlorine, fluorine, nitrogen, sulfur, oxygen, hydrogen, and carbon.Table of ContentsPreface Contributor List Chapter 1: Catalysis in C-Cl Activation Zhong-Xia Wang and Wang-Jun Guo Chapter 2: Homogeneous Transition-metal Catalyzed C–F Activation Shang-Dong Yang Chapter 3: Homogeneous Transition-metal Catalzyed C–N Activation Xiao-Bing Wan Chapter 4: Catalytic Carbon-Sulfur Bond Activation and Transformations Zhengkun Yu Chapter 5: Homogeneous Transition-Metal-Catalzyed C–O Bond Activation Da-Gang Yu, Shuang Luo, Fei Zhao, and Zhang-Jie Shi Chapter 6: Homogeneous Transition-Metal-Catalyzed C–H Bond Functionalization Bi-Jie Li and Zhang-Jie Shi Chapter 7: Catalysis in C–C Activation Hu Li and Zhang-Jie Shi

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Book SynopsisIntroduces major catalytic processes including products from the petroleum, chemical, environmental and alternative energy industries. This book provides a description of the fundamentals of catalysis and some of the major catalytic industrial processes used today. It offers a rationale for process designs based on kinetics and thermodynamics.Trade Review"In less than 300 pages it serves as an excellent introduction to these subjects whether for advanced students or those seeking to learn more about these subjects on their own time...Particularly useful are the succinct summaries throughout the book...excellent detail in the table of contents, a detailed index, key references at the end of each chapter, and challenging classroom questions..." (GlobalCatalysis.com, May 2016)Table of ContentsPreface xv Acknowledgments xvii List of Figures xix Nomenclature xxvii Chapter 1 Catalyst Fundamentals of Industrial Catalysis 1 1.1 Introduction 1 1.2 Catalyzed versus Noncatalyzed Reactions 1 1.2.1 Example Reaction: Liquid-Phase Redox Reaction 2 1.2.2 Example Reaction: Gas-Phase Oxidation Reaction 4 1.3 Physical Structure of a Heterogeneous Catalyst 6 1.3.1 Active Catalytic Species 7 1.3.2 Chemical and Textural Promoters 7 1.3.3 Carrier Materials 8 1.3.4 Structure of the Catalyst and Catalytic Reactor 8 1.4 Adsorption and Kinetically Controlled Models for Heterogeneous Catalysis 10 1.4.1 Langmuir Isotherm 11 1.4.2 Reaction Kinetic Models 13 1.4.2.1 Langmuir–Hinshelwood Kinetics for CO Oxidation on Pt 14 1.4.2.2 Mars–van Krevelen Kinetic Mechanism 17 1.4.2.3 Eley–Rideal (E–R) Kinetic Mechanism 18 1.4.2.4 Kinetic versus Empirical Rate Models 18 1.5 Supported Catalysts: Dispersed Model 19 1.5.1 Chemical and Physical Steps Occurring during Heterogeneous Catalysis 19 1.5.2 Reactant Concentration Gradients within the Catalyzed Material 22 1.5.3 The Rate-Limiting Step 22 1.6 Selectivity 24 1.6.1 Examples of Selectivity Calculations for Reactions with Multiple Products 25 1.6.2 Carbon Balance 26 1.6.3 Experimental Methods for Measuring Carbon Balance 27 Questions 27 Bibliography 29 Chapter 2 The Preparation of Catalytic Materials 31 2.1 Introduction 31 2.2 Carrier Materials 32 2.2.1 Al2O3 32 2.2.2 SiO2 34 2.2.3 TiO2 34 2.2.4 Zeolites 35 2.2.5 Carbons 37 2.3 Incorporating the Active Material into the Carrier 37 2.3.1 Impregnation 37 2.3.2 Incipient Wetness or Capillary Impregnation 38 2.3.3 Electrostatic Adsorption 38 2.3.4 Ion Exchange 38 2.3.5 Fixing the Catalytic Species 39 2.3.6 Drying and Calcination 39 2.4 Forming the Final Shape of the Catalyst 40 2.4.1 Powders 40 2.4.1.1 Milling and Sieving 41 2.4.1.2 Spray Drying 42 2.4.2 Pellets, Pills, and Rings 43 2.4.3 Extrudates 43 2.4.4 Granules 44 2.4.5 Monoliths 44 2.5 Catalyst Physical Structure and Its Relationship to Performance 45 2.6 Nomenclature for Dispersed Catalysts 45 Questions 46 Bibliography 46 Chapter 3 Catalyst Characterization 48 3.1 Introduction 48 3.2 Physical Properties of Catalysts 49 3.2.1 Surface Area and Pore Size 49 3.2.1.1 Nitrogen Porosimetry 49 3.2.1.2 Pore Size by Mercury Intrusion 51 3.2.2 Particle Size Distribution of Particulate Catalyst 51 3.2.2.1 Particle Size Distribution 51 3.2.2.2 Mechanical Strength 53 3.2.3 Physical Properties of Environmental Washcoated Monolith Catalysts 54 3.2.3.1 Washcoat Thickness 54 3.2.3.2 Washcoat Adhesion 54 3.3 Chemical and Physical Morphology Structures of Catalytic Materials 54 3.3.1 Elemental Analysis 54 3.3.2 Thermal Gravimetric Analysis and Differential Thermal Analysis 55 3.3.3 The Morphology of Catalytic Materials by Scanning Electron Microscopy 56 3.3.4 Structural Analysis by X-Ray Diffraction 57 3.3.5 Structure and Morphology of Al2O3 Carriers 58 3.3.6 Dispersion or Crystallite Size of Catalytic Species 58 3.3.6.1 Chemisorption 58 3.3.6.2 Transmission Electron Microscopy 61 3.3.7 X-Ray Diffraction 62 3.3.8 Surface Composition of Catalysts by X-Ray Photoelectron Spectroscopy 62 3.3.9 The Bonding Environment of Metal Oxides by Nuclear Magnetic Resonance 64 3.4 Spectroscopy 65 Questions 66 Bibliography 67 Chapter 4 Reaction Rate in Catalytic Reactors 69 4.1 Introduction 69 4.2 Space Velocity, Space Time, and Residence Time 69 4.3 Definition of Reaction Rate 71 4.4 Rate of Surface Kinetics 72 4.4.1 Empirical Power Rate Expressions 72 4.4.2 Experimental Measurement of Empirical Kinetic Parameters 73 4.4.3 Accounting for Chemical Equilibrium in Empirical Rate Expression 77 4.4.4 Special Case for First-Order Isothermal Reaction 77 4.5 Rate of Bulk Mass Transfer 78 4.5.1 Overview of Bulk Mass Transfer Rate 78 4.5.2 Origin of Bulk Mass Transfer Rate Expression 79 4.6 Rate of Pore Diffusion 80 4.6.1 Overview of Pore Diffusion 80 4.6.2 Pore Diffusion Theory 81 4.7 Apparent Activation Energy and the Rate-Limiting Process 82 4.8 Reactor Bed Pressure Drop 83 4.9 Summary 84 Questions 84 Bibliography 87 Chapter 5 Catalyst Deactivation 88 5.1 Introduction 88 5.2 Thermally Induced Deactivation 88 5.2.1 Sintering of the Catalytic Species 89 5.2.2 Sintering of Carrier 92 5.2.3 Catalytic Species–Carrier Interactions 95 5.3 Poisoning 96 5.3.1 Selective Poisoning 96 5.3.2 Nonselective Poisoning or Masking 97 5.4 Coke Formation and Catalyst Regeneration 99 Questions 101 Bibliography 103 Chapter 6 Generating Hydrogen and Synthesis Gas by Catalytic Hydrocarbon Steam Reforming 104 6.1 Introduction 104 6.1.1 Why Steam Reforming with Hydrocarbons? 104 6.2 Large-Scale Industrial Process for Hydrogen Generation 105 6.2.1 General Overview 105 6.2.2 Hydrodesulfurization 106 6.2.3 Hydrogen via Steam Reforming and Partial Oxidation 106 6.2.3.1 Steam Reforming 106 6.2.3.2 Deactivation of Steam Reforming Catalyst 110 6.2.3.3 Pre-reforming 111 6.2.3.4 Partial Oxidation and Autothermal Reforming 111 6.2.4 Water Gas Shift 112 6.2.4.1 Deactivation of Water Gas Shift Catalyst 116 6.2.5 Safety Considerations During Catalyst Removal 116 6.2.6 Other CO Removal Methods 116 6.2.6.1 Pressure Swing Absorption 116 6.2.6.2 Methanation 117 6.2.6.3 Preferential Oxidation of CO 117 6.2.7 Hydrogen Generation for Ammonia Synthesis 119 6.2.8 Hydrogen Generation for Methanol Synthesis 120 6.2.9 Synthesis Gas for Fischer–Tropsch Synthesis 120 6.3 Hydrogen Generation for Fuel Cells 121 6.3.1 New Catalyst and Reactor Designs for the Hydrogen Economy 122 6.3.2 Steam Reforming 123 6.3.3 Water Gas Shift 124 6.3.4 Preferential Oxidation 125 6.3.5 Combustion 125 6.3.6 Autothermal Reforming for Complicated Fuels 126 6.3.7 Steam Reforming of Methanol: Portable Power Applications 126 6.4 Summary 126 Questions 127 Bibliography 128 Chapter 7 Ammonia, Methanol, Fischer–Tropsch Production 129 7.1 Ammonia Synthesis 129 7.1.1 Thermodynamics 129 7.1.2 Reaction Chemistry and Catalyst Design 130 7.1.3 Process Design 132 7.1.4 Catalyst Deactivation 134 7.2 Methanol Synthesis 134 7.2.1 Process Design 136 7.2.1.1 Quench Reactor 136 7.2.1.2 Staged Cooling Reactor 137 7.2.1.3 Tube-Cooled Reactor 137 7.2.1.4 Shell-Cooled Reactor 138 7.2.2 Catalyst Deactivation 139 7.3 Fischer–Tropsch Synthesis 140 7.3.1 Process Design 142 7.3.1.1 Bubble/Slurry-Phase Process 142 7.3.1.2 Packed Bed Process 143 7.3.1.3 Slurry/Loop Reactor (Synthol Process) 143 7.3.2 Catalyst Deactivation 143 Questions 144 Bibliography 145 Chapter 8 Selective Oxidations 146 8.1 Nitric Acid 146 8.1.1 Reaction Chemistry and Catalyst Design 146 8.1.1.1 The Importance of Catalyst Selectivity 147 8.1.1.2 The PtRh Alloy Catalyst 147 8.1.2 Nitric Acid Production Process 148 8.1.3 Catalyst Deactivation 150 8.2 Hydrogen Cyanide 151 8.2.1 HCN Production Process 152 8.2.2 Deactivation 152 8.3 The Claus Process: Oxidation of H2S 154 8.3.1 Clause Process Description 154 8.3.2 Catalyst Deactivation 155 8.4 Sulfuric Acid 155 8.4.1 Sulfuric Acid Production Process 155 8.4.2 Catalyst Deactivation 158 8.5 Ethylene Oxide 159 8.5.1 Catalyst 159 8.5.2 Catalyst Deactivation 160 8.5.3 Ethylene Oxide Production Process 160 8.6 Formaldehyde 160 8.6.1 Low-Methanol Production Process 162 8.6.1.1 Fe+Mo Catalyst 162 8.6.2 High-Methanol Production Process 163 8.6.2.1 Ag Catalyst 164 8.7 Acrylic Acid 164 8.7.1 Acrylic Acid Production Process 164 8.7.2 Acrylic Acid Catalyst 165 8.7.3 Catalyst Deactivation 166 8.8 Maleic Anhydride 166 8.8.1 Catalyst Deactivation 166 8.9 Acrylonitrile 166 8.9.1 Acrylonitrile Production Process 167 8.9.2 Catalyst 168 8.9.3 Deactivation 168 Questions 168 Bibliography 169 Chapter 9 Hydrogenation, Dehydrogenation, and Alkylation 171 9.1 Introduction 171 9.2 Hydrogenation 171 9.2.1 Hydrogenation in Stirred Tank Reactors 171 9.2.2 Kinetics of a Slurry-Phase Hydrogenation Reaction 174 9.2.3 Design Equation for the Continuous Stirred Tank Reactor 176 9.3 Hydrogenation Reactions and Catalysts 177 9.3.1 Hydrogenation of Vegetable Oils for Edible Food Products 177 9.3.2 Hydrogenation of Functional Groups 180 9.3.3 Biomass (Corn Husks) to a Polymer 183 9.3.4 Comparing Base Metal and Precious Metal Catalysts 183 9.4 Dehydrogenation 185 9.5 Alkylation 187 Questions 188 Bibliography 189 Chapter 10 Petroleum Processing 190 10.1 Crude Oil 190 10.2 Distillation 191 10.3 Hydrodemetalization and Hydrodesulfurization 193 10.4 Hydrocarbon Cracking 197 10.4.1 Fluid Catalytic Cracking 197 10.4.2 Hydrocracking 200 10.5 Naphtha Reforming 200 Questions 202 Bibliography 203 Chapter 11 Homogeneous Catalysis and Polymerization Catalysts 205 11.1 Introduction to Homogeneous Catalysis 205 11.2 Hydroformylation: Aldehydes from Olefins 206 11.3 Carboxylation: Acetic Acid Production 208 11.4 Enzymatic Catalysis 209 11.5 Polyolefins 210 11.5.1 Polyethylene 210 11.5.2 Polypropylene 212 Questions 213 Bibliography 213 Chapter 12 Catalytic Treatment from Stationary Sources: Hc, Co, Nox, and O3 215 12.1 Introduction 215 12.2 Catalytic Incineration of Hydrocarbons and Carbon Monoxide 216 12.2.1 Monolith (Honeycomb) Reactors 218 12.2.2 Catalyzed Monolith (Honeycomb) Structures 219 12.2.3 Reactor Sizing 220 12.2.4 Catalyst Deactivation 222 12.2.5 Regeneration of Deactivated Catalysts 224 12.3 Food Processing 225 12.3.1 Catalyst Deactivation 226 12.4 Nitrogen Oxide (NOx) Reduction from Stationary Sources 226 12.4.1 SCR Technology 227 12.4.2 Ozone Abatement in Aircraft Cabin Air 229 12.4.3 Deactivation 229 12.5 CO2 Reduction 230 Questions 231 Bibliography 233 Chapter 13 Catalytic Abatement of Gasoline Engine Emissions 235 13.1 Emissions and Regulations 235 13.1.1 Origins of Emissions 235 13.1.2 Regulations in the United States 236 13.1.3 The Federal Test Procedure for the United States 238 13.2 Catalytic Reactions Occurring During Catalytic Abatement 238 13.3 First-Generation Converters: Oxidation Catalyst 239 13.4 The Failure of Nonprecious Metals: A Summary of Catalyst History 240 13.4.1 Deactivation and Stabilization of Precious Metal Oxidation Catalysts 241 13.5 Supporting the Catalyst in the Exhaust 242 13.5.1 Ceramic Monoliths 242 13.5.2 Metal Monoliths 245 13.6 Preparing the Monolith Catalyst 246 13.7 Rate Control Regimes in Automotive Catalysts 247 13.8 Catalyzed Monolith Nomenclature 248 13.9 Precious Metal Recovery from Catalytic Converters 248 13.10 Monitoring Catalytic Activity in a Monolith 248 13.11 The Failure of the Traditional Beaded (Particulate) Catalysts for Automotive Applications 250 13.12 NOx, CO and HC Reduction: The Three-Way Catalyst 251 13.13 Simulated Aging Methods 255 13.14 Close-Coupled Catalyst 256 13.15 Final Comments 258 Questions 259 Bibliography 261 Chapter 14 Diesel Engine Emission Abatement 262 14.1 Introduction 262 14.1.1 Emissions from Diesel Engines 262 14.1.2 Analytical Procedures for Particulates 264 14.2 Catalytic Technology for Reducing Emissions from Diesel Engines 265 14.2.1 Diesel Oxidation Catalyst 265 14.2.2 Diesel Soot Abatement 266 14.2.3 Controlling NOx in Diesel Engine Exhaust 267 Questions 272 Bibliography 273 Chapter 15 Alternative Energy Sources Using Catalysis: Bioethanol by Fermentation, Biodiesel by Transesterification, and H2-Based Fuel Cells 274 15.1 Introduction: Sources of Non-Fossil Fuel Energy 274 15.2 Sources of Non-Fossil Fuels 276 15.2.1 Biodiesel 276 15.2.1.1 Production Process 276 15.2.2 Bioethanol 277 15.2.2.1 Process for Bioethanol from Corn 278 15.2.3 Lignocellulose Biomass 278 15.2.4 New Sources of Natural Gas and Oil Sands 279 15.3 Fuel Cells 279 15.3.1 Markets for Fuel Cells 281 15.3.1.1 Transportation Applications 281 15.3.1.2 Stationary Applications 282 15.3.1.3 Portable Power Applications 282 15.4 Types of Fuel Cells 283 15.4.1 Low-Temperature PEM Fuel Cell 284 15.4.1.1 Electrochemical Reactions for H2-Fueled Systems 284 15.4.1.2 Mechanistic Principles of the PEM Fuel Cell 286 15.4.1.3 Membrane Electrode Assembly 287 15.4.2 Solid Polymer Membrane 288 15.4.3 PEM Fuel Cells Based on Direct Methanol 289 15.4.4 Alkaline Fuel Cell 290 15.4.5 Phosphoric Acid Fuel Cell 290 15.4.6 Molten Carbonate Fuel Cell 291 15.4.7 Solid Oxide Fuel Cell 293 15.5 The Ideal Hydrogen Economy 293 Questions 294 Bibliography 295 Index 297

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Book SynopsisProviding a roadmap from early to late stages of drug development, this book overviews amorphous solid dispersion technology a leading platform to deliver poorly water soluble drugs, a major hurdle in today s pharmaceutical industry.Table of ContentsContentsContributorsPrefaceChapter 1: Introduction to Amorphous Solid DispersionsGeorge Zografi and Ann NewmanChapter 2: Polymers and SurfactantsPadma Narayan, William W. Porter III, Meinolf Brackhagen, and Christopher TuckerChapter 3: Amorphous Solid Dispersion ScreeningAnn NewmanChapter 4: Solid state Characterization of Amorphous DispersionsFrederick G. VogtChapter 5: Physical Stability and Crystallization InhibitionLynne S. TaylorChapter 6: Solubility and Dissolution Considerations for Amorphous Solid DispersionsGrace A. Ilevbare, Wei Xu, Christopher T. John, James Ormes, Jesse Kuiper, Allen C. Templeton, and Annette BakChapter 7: Translational Development of Amorphous DispersionsPatrick Connelly, Brian Patrick Quinn, Steve Johnston, Philip Bransford, Praveen Mudunuri, Andrey Peresypkin, Majed Fawaz, Setu Roday, Anuj Kuldipkumar, Hong-Ren Wang, Phillip Snyder, Jeff Katstra, Tapan Sanghvi, Bill Rowe, and Patricia HurterChapter 8: Preclinical and Clinical StudiesMarcus E. Brewster, Geert Verreck, Jan Bevernage, Joachim Brouwers, Guy Van den Mooter, and Patrick AugustijnsChapter 9: Spray-Drying and Scale-UpDaniel E. Dobry, Dana M. Settell, and John M. BaumannChapter 10: Hot Melt Extrusion of Amorphous Solid DispersionsKieran Crowley and Andreas GryczkeChapter 11: Formulation Development of Amorphous DispersionsTapan Sanghvi, Jeff Katstra, Brian Patrick Quinn, Hayden Thomas, and Patricia HurterChapter 12: Scientific and Regulatory Considerations in Product DevelopmentAbhay Gupta, Ziyaur Rahmna, and Manssor A. KhanChapter 13: Chapter Patenting Amorphous Solid Dispersions of PharmaceuticalsJeffry A. LindemanChapter 14: Monographs on Polymers and SurfactantsXia Lu, Robert Wenslow, and Ann NewmanAppendix 1Xia Lu, Robert Wenslow, and Ann NewmanAppendix 2: Marketed ProductsAnn Newman

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Book SynopsisA detailed presentation of the physics of electron beam-specimen interactions Electron microscopy is one of the most widely used characterisation techniques in materials science, physics, chemistry, and the life sciences. This book examines the interactions between the electron beam and the specimen, the fundamental starting point for all electron microscopy. Detailed explanations are provided to help reinforce understanding, and new topics at the forefront of current research are presented. It provides readers with a deeper knowledge of the subject, particularly if they intend to simulate electron beam-specimen interactions as part of their research projects. The book covers the vast majority of commonly used electron microscopy techniques. Some of the more advanced topics (annular bright field and dopant atom imaging, atomic resolution chemical analysis, band gap measurements) provide additional value, especially for readers who have access to advanced instrumentatioTable of ContentsPreface ix 1 Introduction 1 1.1 Organisation and Scope of the Book 3 References 8 2 The Monte Carlo Method 9 2.1 Physical Background and Implementation 11 2.1.1 Elastic Scattering By an Atomic Nucleus 11 2.1.2 Inelastic Scattering by Atomic Electrons 18 2.1.3 Implementation of the Monte Carlo Algorithm 23 2.2 Some Applications of the Monte Carlo Method 27 2.2.1 Spatial Resolution and Backscattered Imaging 27 2.2.2 Characteristic X-Ray Generation 34 2.2.3 Cathodoluminescence and Electron Beam Induced Current Microscopy 37 2.3 Further Topics in Monte Carlo Simulations 40 2.3.1 Classical or Quantum Physics? 40 2.3.2 Spin–Orbit Coupling and the Mott Cross-Section 43 2.3.3 Dielectric Model of Stopping Power and Secondary Electron Emission 46 2.4 Summary 49 References 50 3 Multislice Method 53 3.1 Mathematical Treatment of the Multislice Method 56 3.1.1 Specimen Transmission Function 59 3.1.2 Fresnel Propagator Function 66 3.1.3 Objective Lens Contrast Transfer Function and Partial Coherence 71 3.1.4 Implementation of the Multislice Algorithm 76 3.2 Applications of Multislice Simulations 78 3.2.1 HREM Imaging and Electron Crystallography 78 3.2.2 CBED and STEM Applications: Frozen Phonon Model 87 3.3 Further Topics in Multislice Simulation 93 3.3.1 Accuracy of Multislice Algorithms 93 3.3.2 Is the Frozen Phonon Model Physically Realistic? 97 3.4 Summary 102 References 102 4 Bloch Waves 105 4.1 Basic Principles 106 4.1.1 Mathematical Background 106 4.1.2 Application to Two-Beam Theory 111 4.1.3 Phenomenological Modelling of Thermal Diffuse Scattering 116 4.1.4 Bloch States in Zone-Axis Orientations 124 4.2 Applications of Bloch Wave Theory 132 4.2.1 HREM Imaging 132 4.2.2 HAADF Imaging 134 4.2.3 Bloch Wave Scattering By Elastic Strain Fields 144 4.3 Further Topics in Bloch Waves 149 4.3.1 Dopant Atom Imaging in STEM 149 4.3.2 Electron Channelling and Its Uses 156 4.4 Summary 160 References 161 5 Single Electron Inelastic Scattering 165 5.1 Fundamentals of Inelastic Scattering 166 5.1.1 Electron Excitation in a Single Atom by a Plane Wave 166 5.1.2 Mixed Dynamic Form Factor 180 5.1.3 Yoshioka Equations and Inelastic Scattering within a Crystal 189 5.1.4 Coherence in Inelastic Scattering 195 5.2 Fine Structure of The Electron Energy Loss Signal 201 5.2.1 Origin of Fine Structure 201 5.2.2 Core Hole Effects 206 5.2.3 Magnetic Circular Dichroism 209 5.3 Summary 211 References 212 6 Electrodynamic Theory of Inelastic Scattering 215 6.1 Bulk and Surface Energy Loss 216 6.1.1 Energy Loss in an ‘Infinite‘ Solid 216 6.1.2 Phonon Spectroscopy 226 6.1.3 Interface and Surface Contributions 232 6.2 Radiative Phenomena 244 6.2.1 Cerenkov Radiation and Band Gap Measurement 244 6.2.2 Transition Radiation 249 6.3 Simulating Low Energy Loss EELS Spectra 253 6.3.1 Discrete Dipole Approximation (DDA) 253 6.3.2 Boundary Element Method (BEM) 254 6.4 Summary 259 References 259 Appendix A The First Born Approximation and Atom Scattering Factor 263 Appendix B Potential for an ‘Infinite’ Perfect Crystal 267 Appendix C The Transition Matrix Element in the One Electron Approximation 269 Appendix D Bulk Energy Loss in the Retarded Regime 271 Index 275

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Book SynopsisCutting edge high temperature materials include high temperature superconductors and solid oxide fuel cells and have applications in key areas such as energy, transportation and space technologies.Table of ContentsForeword vii Preface ix 1 Introduction to High-Temperature Research 1 2 Basic Design of Laboratory Furnaces 11 3 Temperature Measurements 55 4 Radiation Pyrometry 93 5 Refractory Materials in the Laboratory 129 6 Vacuum in Theory and Practice 177 7 High-Temperature Furnaces and Thermobalances 229 8 The Summing Up 267 Author Index 317 Subject Index 000

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