Chemistry Books

Book SynopsisIncreasing the potency of therapeutic compounds, while limiting side-effects, is a common goal in medicinal chemistry. Ligands that effectively bind metal ions and also include specific features to enhance targeting, reporting, and overall efficacy are driving innovation in areas of disease diagnosis and therapy.Table of ContentsAbout the Editor xiii List of Contributors xv 1 Introduction to Ligand Design in Medicinal Inorganic Chemistry 1 Michael R. Jones, Dustin Duncan, and Tim Storr References 7 2 Platinum-Based Anticancer Agents 9 Alice V. Klein and Trevor W. Hambley 2.1 Introduction 9 2.2 The advent of platinum-based anticancer agents 9 2.3 Strategies for overcoming the limitations of cisplatin 11 2.4 The influence of ligands on the physicochemical properties of platinum anticancer complexes 11 2.4.1 Lipophilicity 11 2.4.2 Reactivity 13 2.4.3 Rate of reduction 14 2.5 Ligands for enhancing the anticancer activity of platinum complexes 15 2.5.1 Ligands for improving DNA affinity 15 2.5.2 Ligands for inhibiting enzymes 17 2.6 Ligands for enhancing the tumour selectivity of platinum complexes 20 2.6.1 Ligands for targeting transporters 21 2.6.2 Ligands for targeting receptors 22 2.6.3 Ligands for targeting the EPR effect 28 2.6.4 Ligands for targeting bone cancer 33 2.7 Ligands for photoactivatable platinum complexes 35 2.8 Conclusions 36 References 37 3 Coordination Chemistry and Ligand Design in the Development of Metal Based Radiopharmaceuticals 47 Eszter Boros, Bernadette V. Marquez, Oluwatayo F. Ikotun, Suzanne E. Lapi, and Cara L. Ferreira 3.1 Introduction 47 3.1.1 Metals in nuclear medicine 48 3.1.2 The importance of coordination chemistry 49 3.1.3 Overview 50 3.2 General metal based radiopharmaceutical design 50 3.2.1 Choice of radionuclide 50 3.2.2 Production of the radiometal starting materials 51 3.2.3 Ligand and chelate design consideration 51 3.3 Survey of the coordination chemistry of radiometals applicable to nuclear medicine 53 3.3.1 Technetium 53 3.3.2 Rhenium 56 3.3.3 Gallium 57 3.3.4 Indium 60 3.3.5 Yttrium and lanthanides 61 3.3.6 Copper 62 3.3.7 Zirconium 65 3.3.8 Scandium 66 3.3.9 Cobalt 68 3.4 Conclusions 71 References 71 4 Ligand Design in d-Block Optical Imaging Agents and Sensors 81 Mike Coogan 4.1 Summary and scope 81 4.2 Introduction 82 4.2.1 Criteria for biological imaging optical probes 82 4.3 Overview of transition-metal optical probes in biomedicinal applications 83 4.3.1 Common families of transition metal probes 83 4.4 Ligand design for controlling photophysics 87 4.4.1 Photophysical processes in transition metal optical imaging agents and sensors 87 4.4.2 Photophysically active ligand families – tuning electronic levels 87 4.4.3 Ligands which control photophysics through indirect effects 90 4.4.4 Transition metal optical probes with carbonyl ligands 90 4.5 Ligand design for controlling stability 91 4.6 Ligand design for controlling transport and localisation 91 4.6.1 Passive diffusion 91 4.6.2 Active transport 92 4.7 Ligand design for controlling distribution 92 4.7.1 Mitochondrial-targeting probes 92 4.7.2 Nuclear-targeting probes 93 4.7.3 Bioconjugation 94 4.8 Selected examples of ligand design for important individual probes 101 4.8.1 A pH-sensitive ligand to control Ir luminescence 101 4.8.2 Dimeric NHC ligands for gold cyclophanes 102 4.9 Transition metal probes incorporating or capable of more than one imaging mode 103 4.9.1 Bimodal MRI/optical probes 103 4.9.2 Bimodal radio/optical probes 104 4.9.3 Bimodal IR/optical probes 106 4.10 Conclusions and prospects 106 Abbreviations 108 References 108 5 Luminescent Lanthanoid Probes 113 Edward S. O’Neill and Elizabeth J. New 5.1 Introduction 113 5.2 Luminescent probes 114 5.3 The lanthanoids – an overview 116 5.4 Photophysical properties of luminescent lanthanoid complexes 116 5.4.1 The need for a sensitiser 117 5.5 The suitability of lanthanoid complexes as luminescent probes 119 5.6 Modulating chemical properties by ligand design 120 5.6.1 Chemical stability 120 5.6.2 Photophysical properties 122 5.6.3 Analyte response 123 5.7 Modulating biological properties by ligand design 129 5.7.1 Cellular uptake 129 5.7.2 Localisation to desired region of the cell 131 5.7.3 Maintenance of cellular homeostasis 135 5.8 Concluding remarks 138 Acknowledgement 138 References 138 6 Metal Complexes of Carbohydrate-targeted Ligands in Medicinal Inorganic Chemistry 145 Yuji Mikata and Michael Gottschaldt 6.1 Introduction 145 6.2 Radioactive metal complexes bearing a carbohydrate moiety 147 6.3 MRI contrast agents utilizing metal complexes bearing carbohydrate moieties 150 6.4 Fluorescent complexes with carbohydrate-conjugated functions 153 6.5 Carbohydrate-attached photosensitizers for photodynamic therapy (PDT) 157 6.6 Carbohydrate-based metal complexes exhibiting anticancer activity 161 6.7 Carbohydrate-appended metallic nanoparticles, quantum dots, electrodes and surfaces 165 6.8 Concluding remarks 167 References 168 7 Design of Schiff Base-derived Ligands: Applications in Therapeutics and Medical Diagnosis 175 Rafael Pinto Vieira and Heloisa Beraldo 7.1 Introduction 175 7.2 Design of thiosemicarbazones and hydrazones as drug candidates for cancer chemotherapy 176 7.3 Design of bis(thiosemicarbazone) ligands 184 7.3.1 Bis(thiosemicarbazones) and their metal complexes as anticancer agents 184 7.3.2 Design of bis(thiosemicarbazones) as ligands for copper(II) complexes with potential applications in medical diagnosis 186 7.3.3 Design of functionalized bis(thiosemicarbazone) ligands to target selected biological processes 189 7.4 Design of Schiff base-derived ligands as anti-parasitic drug candidates: Applications in the therapeutics of chagas disease 193 7.5 Concluding remarks 197 References 197 8 Metal-based Antimalarial Agents 205 Maribel Navarro and Christophe Biot 8.1 Background 205 8.2 Standard antimalarial chemotherapy 208 8.2.1 Quinoline-based antimalarials 208 8.2.2 Quinoline-based antimalarials target 209 8.2.3 Other standard antimalarial therapies 210 8.3 Metal complexes in malaria 212 8.3.1 Chloroquine as an inter-ligand in the design of metal-based antimalarial agents 212 8.3.2 Chloroquine as an intra-ligand in the design of metal-based antimalarial agents 214 8.3.3 Trioxaquines as a ligand in the design of metal-based antimalarial agents 218 8.3.4 Other standard antimalarial drugs and diverse ligands used in the design of metal-based antimalarial agents 218 8.4 Conclusion 220 Acknowledgements 221 References 221 9 Therapeutic Gold Compounds 227 Susan J. Berners-Price and Peter J. Barnard 9.1 Introduction 227 9.2 Antiarthritic gold drugs 229 9.2.1 Gold (I) thiolates 229 9.2.2 Gold (I) phosphines 229 9.2.3 Design of specific enzyme inhibitors 230 9.3 Gold complexes as anticancer agents 231 9.3.1 Gold(I) compounds 231 9.3.2 Gold (III) compounds 241 9.4 Gold complexes as antiparasitic agents 244 9.4.1 Metal drug synergism 245 9.4.2 Emerging parasite drug targets for gold compounds 245 9.5 Concluding remarks: Design of gold complexes that target specific proteins 246 Acknowledgements 248 References 248 10 Ligand Design to Target and Modulate Metal–Protein Interactions in Neurodegenerative Diseases 257 Michael W. Beck, Amit S. Pithadia, Alaina S. DeToma, Kyle J. Korshavn, and Mi Hee Lim 10.1 Introduction 257 10.1.1 Metals in the brain 257 10.1.2 Aberrant metal–protein interactions 259 10.1.3 Oxidative stress 260 10.2 Neurodegenerative diseases 261 10.2.1 Alzheimer’s disease (AD) 261 10.2.2 Parkinson’s disease (PD) 261 10.2.3 Prion disease 261 10.2.4 Huntington’s disease (HD) 264 10.2.5 Amyotrophic lateral sclerosis (ALS) 264 10.3 Ligand design to target and modulate metal–protein interactions 265 10.3.1 Metal chelating compounds 267 10.3.2 Small molecules designed for metal–protein complexes 269 10.3.3 Other relevant compounds 272 10.3.4 Naturally occurring molecules 273 10.4 Conclusions 274 Abbreviations 275 References 276 11 Rational Design of Copper and Iron Chelators to Treat Wilson’s Disease and Hemochromatosis 287 Christelle Gateau, Elisabeth Mintz, and Pascale Delangle 11.1 Introduction 287 11.2 Chelating agents 288 11.2.1 Thermodynamic parameters 288 11.2.2 Principles of coordination chemistry applied to chelation therapy 289 11.2.3 Examples of classical chelating agents 290 11.3 Modern medicinal inorganic chemistry and chelation therapy 291 11.4 Iron overload 292 11.4.1 Iron distribution and homeostasis 292 11.4.2 Iron overload diseases 294 11.4.3 Fe3+ chelators 295 11.4.4 Current developments 296 11.5 Copper overload in Wilson’s disease 299 11.5.1 Copper metabolism 299 11.5.2 Copper homeostasis 300 11.5.3 Wilson’s disease 303 11.6 Current developments in copper overload treatments 304 11.6.1 From Cu homeostasis understanding to the rational design of drugs 304 11.6.2 Cu+ chelating units inspired from proteins involved in Cu homeostasis 305 11.6.3 Cu+ chelators inspired from metallochaperones 306 11.6.4 Cysteine-rich compounds inspired from metallothioneins 307 11.6.5 Liver-targeting: the ASGP-R 308 11.6.6 Two glycoconjugates that release high affinity Cu chelators in hepatocytes 308 11.7 Conclusion 311 Acknowledgments 312 References 312 12 MRI Contrast Agents 321 Célia S. Bonnet and Éva Tóth 12.1 Introduction to MRI contrast agents 321 12.2 Ligand optimization to increase relaxivity 323 12.2.1 Hydration number 324 12.2.2 Optimization of water exchange kinetics via rational ligand design 325 12.2.3 Optimization of the rotational dynamics via rational ligand design: Size and flexibility 329 12.3 Ligand design for CEST agents 332 12.3.1 Application of paramagnetic ions – PARACEST 333 12.4 Ligand design for responsive probes 333 12.4.1 Probes responsive to pH 334 12.4.2 Probes responsive to physiological cations 338 12.4.3 Probes responsive to enzymes 344 12.5 Conclusions 348 Abbreviations 348 References 348 13 Photoactivatable Metal Complexes and Their Use in Biology and Medicine 355 Tara R. deBoer-Maggard and Pradip K. Mascharak 13.1 Introduction 355 13.2 Cisplatin-inspired photoactivatable chemotherapeutics 358 13.3 Metal-based photosensitizers in photodynamic therapy 360 13.4 Photoinduced interactions of coordination complexes with DNA 362 13.4.1 Photocleavage of DNA with coordination complexes 362 13.4.2 Photoactivatable complexes as antisense agents 364 13.5 Photoactivatable metal complexes that release small bioactive molecules 367 13.6 Conclusion 371 References 372 14 Metalloprotein Inhibitors 375 David P. Martin, David T. Puerta, and Seth M. Cohen 14.1 Metal binding groups in metalloprotein inhibitor design 375 14.2 Thiols, carboxylates, phosphates, and hydroxamates 379 14.3 MBGs related to hydroxamic acids 382 14.4 MBGs related to carboxylic acids 387 14.5 MBGs related to thiols 391 14.6 Amine, alcohol, and carbonyl MBGs 393 14.7 Other MBGs 395 14.8 Conclusion 399 References 401 15 Ruthenium Anticancer Compounds with Biologically-derived Ligands 405 Changhua Mu and Charles J. Walsby 15.1 Introduction 405 15.1.1 Simple coordination complexes 406 15.1.2 Ruthenium(III) complexes with heterocyclic N-donor and/or DMSO ligands 406 15.1.3 Ruthenium(II) arene complexes 408 15.1.4 Polypyridyl complexes 410 15.1.5 Other ruthenium anticancer compounds 411 15.2 Amino acids and amino acid-containing ligands 411 15.3 Peptides and peptide-functionalized ligands 413 15.4 Coordinated proteins as ligands 416 15.5 Carbohydrate-based ligands 419 15.6 Purine, nucleoside, and oligonucleotide ligands 422 15.7 Other selected ruthenium complexes with biological ligands 424 15.7.1 steroids 424 15.7.2 Curcumin – an example of a natural product ligand 425 15.8 Conclusion 426 References 426 Index 439

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Book SynopsisPhycotoxins are a diverse group of poisonous substances produced by certain seaweed and algae in marine and fresh waters and are important to the scientific community for many reasons, the most obvious being that they pose food safety issues which requires a large investment to regularly monitor the presence of these compounds in foods.Table of ContentsList of contributors vii Preface xiii 1 Analysis of marine toxins: gaps on food safety control of marine toxins 1Paz Otero and Carmen Alfonso 2 Pharmacology of ciguatoxins 23Carmen Vale, Álvaro Antelo and Víctor Martín 3 Chemistry of pinnatoxins 49Phillip Mabe and Armen Zakarian 4 Chemistry and analysis of PSP toxins 69Ana Botana and Verónica Rey López 5 Chemistry of palytoxin and its analogues 85Patrizia Ciminiello, Carmela Dell’Aversano and Martino Forino 6 Pharmacology of palytoxins and ostreocins 113M. Carmen Louzao, María Fraga and Natalia Vilarin˜ o 7 Recent insights into anatoxin-a chemical synthesis, biomolecular targets, mechanisms of action and LC-MS detection 137Custódia Fonseca, Manuel Aureliano, Feras Abbas and Ambrose Furey 8 Therapeutics of marine toxins 181Eva Alonso and Juan A. Rubiolo 9 Marine toxins as modulators of apoptosis 203Amparo Alfonso, Andrea Fernández-Araujo and Mercedes R. Vieytes 10 Cyanobacterial toxins 225Vitor Vasconcelos, Pedro Leão and Alexandre Campos 11 Marine toxins and climate change: the case of PSP from cyanobacteria in coastal lagoons 239Antonella Lugliè, Silvia Pulina, Milena Bruno, Bachisio Mario Padedda, Cecilia Teodora Satta, and Nicola Sechi 12 Microalgae as a source of nutraceuticals 255Sushanta Kumar Saha, Edward McHugh, Patrick Murray and Daniel J. Walsh 13 The marine origin of drugs 293André Horta, Celso Alves, Susete Pinteus and Rui Pedrosa 14 Pharmacology of cylindrospermopsin 317Juan A. Rubiolo, Diego Alberto Fernández, Henar López and M. Carmen Louzao 15 Pharmacology of the cyclic imines 343 Natalia Vilarinõ, Sara F. Ferreiro, Andrés Crespo and José Gil 16 Diversity of organic structures of marine microbial origin with drug potential 361Marcel Jaspars, Rainer Ebel and Hai Deng 17 Polyketides as a source of chemical diversity 381Tanya Beletskaya, Catherine Collins and Patrick Murray 18 Ichthyotoxins 407John W. La Claire II and Schonna R. Manning 19 Pathological clues of phycotoxin ingestion 463Manuel Cifuentes, Andrés Crespo and Roberto Bermúdez Index 513

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Book SynopsisEnsuring safe and plentiful supplies of potable water (both now and for future generations) and developing sustainable treatment processes for wastewater are among the world's greatest engineering challenges. However, sustainability requires investment of money, time and knowledge. Some parts of the world are already working towards this goal but many nations have neither the political will nor the resources to tackle even basic provision and sanitation. Combining theory and practice from the developing and developed worlds with high- and low-tech, high- and low-cost solutions, this book discusses fundamental and advanced aspects of water engineering and includes: water resource issues including climate change, water scarcity, economic and financial aspects requirements for sustainable water systems fundamentals of treatment and process design industrial water use and wastewater treatment sustainable effluent disposalTable of ContentsPreface xi Abbreviations xiii Glossary xvii 1 Water Crisis 1 1.1 Water Resource Issues 6 1.1.1 Water Footprint 8 1.2 Climate Change and Its Influence on Global Water Resources 9 1.3 Protection and Enhancement of Natural Watershed and Aquifer Environments 12 1.4 Water Engineering for Sustainable Coastal and Offshore Environments 12 1.5 Endangering World Peace and Security 13 1.6 Awareness among Decision Makers and the Public across the World 15 1.7 Criteria for Sustainable Water Management 16 1.8 Water Scarcity and Millennium Development Goals 18 1.9 Lack of Access to Clean Drinking Water and Sanitation 19 1.10 Fragmentation of Water Management 20 1.11 Economics and Financial Aspects 22 1.11.1 Water Treatment and Distribution 24 1.11.2 Wastewater Treatment, Collection and Disposal 27 1.12 Legal Aspects 28 References 30 2 Requirements for the Sustainability of Water Systems 35 2.1 History of Water Distribution and Wastewater Collection 38 2.2 Integrated Water Management 40 2.3 Sewerage Treatment and Urban Pollution Management 44 2.4 Conventional Water Supply 45 2.4.1 Features 49 2.4.2 Capacity and Pressure Requirements 50 2.4.3 Design and Hydraulic Analysis of Distribution System 52 2.4.4 Unsustainable Characteristics 55 2.4.5 Sustainable Approach 64 2.5 Conventional Wastewater Collection Systems 71 2.5.1 Features 71 2.5.2 Unsustainable Characteristics 77 2.5.3 Sustainable Approach 79 References 80 3 Water Quality Issues 83 3.1 Water-Related Diseases 84 3.1.1 Transmission Vectors 85 3.1.2 Field Testing and Monitoring 85 3.1.3 Village-Level Monitoring 89 3.2 Selection Options for Water Supply Source 89 3.2.1 Spring Capping 91 3.2.2 Simple Tube Wells 93 3.2.3 Hand Pumps 95 3.2.4 Rainwater Harvesting 95 3.2.5 Fog and Dew Harvesting 98 3.2.6 Snow Harvesting 99 3.3 On-Site Sanitation 99 3.3.1 Latrines 99 3.3.2 Septic Tanks 103 3.3.3 Aqua Privies 103 3.3.4 Oxidation Pond Treatment Systems 103 3.3.5 Storm Drainage 105 3.4 Water Quality Characteristics of Potable Drinking Water and Wastewater Effluents 110 3.4.1 Physical Parameters 110 3.4.2 Chemical Parameters 113 3.4.3 Solids in Water 127 3.4.4 Biological Parameters 139 3.5 Standards and Consents 147 3.5.1 Potable Water Standards 147 3.5.2 Wastewater Effluent Standards 148 3.6 Kinetics of Biochemical Oxygen Demand 149 3.7 Water Management for Wildlife Conservation 149 3.8 Water-Quality Deterioration 152 References 153 4 Fundamentals of Treatment and Process Design, and Sustainability 163 4.1 History of Water and Wastewater Treatment Regulatory Issues across the World 164 4.1.1 Low-Tech versus Hi-Tech 165 4.1.2 Low Cost versus High Cost 167 4.2 Design Principles for Sustainable Treatment Systems 168 4.2.1 Low Carbon 168 4.2.2 Low Energy 168 4.2.3 Low Chemical Use 172 4.2.4 Modelling of Treatment Processes to Attain Sustainability 172 4.2.5 Operation, Management, Financial, Socio-Economic Aspect 173 4.3 Preliminary and Primary Treatment 174 4.3.1 Screening 174 4.3.2 Coarse-Solid Reduction 174 4.3.3 Grease Removal Chamber 174 4.3.4 Flow Equalization 177 4.3.5 Mixing and Flocculation 177 4.3.6 Sedimentation 180 4.3.7 Flotation 183 4.4 Secondary Treatment 185 4.4.1 Biological Treatment 185 4.4.2 Vermifiltration 202 4.4.3 Chemical Treatment 202 4.5 Tertiary Treatment 203 4.5.1 Filtration 203 4.5.2 Activated Carbon Treatment 205 4.5.3 Ion Exchange 206 4.5.4 Forward and Reverse Osmosis, Membrane Filtration, Membrane Bioreactor, Membrane Distillation, and Electro Dialysis 206 4.5.5 Air Stripping 207 4.5.6 Disinfection and Fluoridation 209 4.5.7 Removal of Specific Constituents 211 4.6 Emerging Technologies 211 4.6.1 Nanotechnology applied for Water Purification 212 4.6.2 Photocatalysis 212 4.6.3 Evaporation 214 4.6.4 Incineration 214 4.6.5 Sono-Photo-Fenton Process 214 4.7 Residual Management 215 4.7.1 Thickening 216 4.7.2 Drying 216 4.7.3 Stabilization 216 4.7.4 Digestion 217 4.7.5 Composting 217 4.7.6 Dewatering 218 4.7.7 Incineration 218 4.7.8 Remediation of Contaminants in Subsurface 219 4.8 Portable Water Purification Kit 220 4.9 Requirements of Electrical, Instrumentation and Mechanical Equipment in Water and Wastewater Treatment to Achieve Sustainability 220 4.9.1 Electrical Equipment and Energy Requirement 221 4.9.2 Piping and Instrumentation 223 4.9.3 Mechanical Equipment Requirements and Related Issues 224 4.9.4 Systems and Operational Issues 224 4.9.5 Real-Time Control 225 4.9.6 Indicators of Sustainable Performance; Systems Approach for Sustainability Assessment of Water Infrastructure 225 4.9.7 Troubleshooting 226 4.9.8 Operational Checks for the STP 228 4.9.9 Design, Construction and Engineering Checks for the WWTP 228 4.9.10 Odour Management 228 References 232 5 Sustainable Industrial Water Use and Wastewater Treatment 237 5.1 Sustainable Principles in Industrial Water Use and Wastewater Treatment 237 5.1.1 Industries with High Dissolved Solids 240 5.1.2 Industries/Activities with High Inorganic Content 242 5.2 Industries with Low Dissolved Solids 282 5.2.1 Industries with Low Amounts of Inorganic Materials 282 5.2.2 Industries Dealing with Low Dissolved Organic Material 284 References 292 6 Sustainable Effluent Disposal 297 6.1 Dissolved Oxygen Sag Curves, Mass Balance Calculations and Basic River Models 299 6.2 Disposal Options and Impact on Environment 302 6.2.1 Ocean Disposal 304 6.2.2 Disposal into Fresh Water Bodies 306 6.2.3 On-Land Disposal 308 6.3 Sustainable Reuse Options and Practice 310 6.3.1 Toilet Flushing 317 6.3.2 Floor Washing 317 6.3.3 Sustainable Wastewater Irrigation 317 6.3.4 Nonpotable Industrial Use 320 References 326 7 Sustainable Construction of Water Structures 331 7.1 Sustainable Construction – Principles 333 7.1.1 Green Building 337 7.1.2 Cementless Construction 339 7.1.3 Choosing Eco-Friendly Construction Material 340 7.1.4 Energy Saving during Construction 341 7.1.5 Precautions to be Taken during Construction to save Energy during Operations 343 7.2 Intake Structures 343 7.3 Treatment Plants 344 7.4 Water Storage and Distribution Systems 344 7.5 Wastewater Collection and Disposal System 348 References 350 8 Safety Issues in Sustainable Water Management 353 8.1 Health, Safety and Sustainability 356 8.2 Safety of Consumer versus Operator 359 8.3 Safety of People and Animals other than Consumers and Operators 370 8.4 Safety Issues during Construction 377 8.4.1 Electrical Protective Devices 380 8.5 Chemical Handling and Storage 380 8.5.1 Chlorine 382 8.5.2 Herbicides/Pesticides 383 8.6 Safety during Water/Wastewater Treatment Plant Operation 383 8.6.1 Work-Permit System 398 8.7 Disaster Management 398 References 400 Index 405

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Book SynopsisRecycling carbon-dioxide at the source would not only go a long way towards minimizing the emissions, but would also motivate industry leaders to take the positive approach for CO2 reuse.Table of ContentsPreface xi Acknowledgments xvii Contributors xix 1. Perspectives and State of the Art in Producing Solar Fuels and Chemicals from CO2 1Gabriele Centi and Siglinda Perathoner 1.1 Introduction 1.2 Solar Fuels and Chemicals From CO2 8 1.3 Toward Artificial Leaves 16 1.4 Conclusions 19 Acknowledgments 20 References 20 2. Transformation of Carbon Dioxide to Useable Products Through Free Radical-Induced Reactions 25G. R. Dey 2.1 Introduction 25 2.2 Chemical Reduction of CO2 29 2.3 Conclusions 46 Acknowledgments 46 References 46 3. Synthesis of Useful Compounds from CO2 51Boxun Hu and Steven L. Suib 3.1 Introduction 51 3.2 Photochemical Reduction 53 3.3 Electrochemical Reduction 55 3.4 Electrocatalytic Reduction 57 3.5 CO2 Hydrogenation 71 3.6 CO2 Reforming 84 3.7 Prospects in CO2 Reduction 86 Acknowledgments 86 References 86 4. Hydrogenation of Carbon Dioxide to Liquid Fuels 99Muthu Kumaran Gnanamani, Gary Jacobs, Venkat Ramana Rao Pendyala, Wenping Ma, and Burtron H. Davis 4.1 Introduction 99 4.2 Methanation of Carbon Dioxide 100 4.3 Methanol and Higher Alcohol Synthesis by CO2 Hydrogenation 102 4.4 Hydrocarbons Through Modified Fischer-Tropsch Synthesis 105 4.5 Conclusions 114 References 115 5. Direct Synthesis of Organic Carbonates from CO2 and Alcohols Using Heterogeneous Oxide Catalysts 119Yoshinao Nakagawa, Masayoshi Honda, and Keiichi Tomishige 5.1 Introduction 120 5.2 Ceria-Based Catalysts 122 5.3 Zirconia-Based Catalysts 137 5.4 Other Metal Oxide Catalysts 145 5.5 Conclusions and Outlook 145 References 146 6. High-Solar-Efficiency Utilization of CO2: the STEP (Solar Thermal Electrochemical Production) of Energetic Molecules 149Stuart Licht 6.1 Introduction 149 6.2 Solar Thermal Electrochemical Production of Energetic Molecules: an Overview 151 6.3 Demonstrated STEP Processes 165 6.4 STEP Constraints 180 6.5 Conclusions 186 Acknowledgments 186 References 186 7. Electrocatalytic Reduction of CO2 in Methanol Medium 191M. Murugananthan, S. Kaneco, H. Katsumata, T. Suzuki and M. Kumaravel 7.1 Introduction 191 7.2 Electrocatalytic Reduction of CO2 in Methanol Medium 193 7.3 Mechanisms of CO2 Reduction in Nonaqueous Protic (CH3OH) Medium 210 7.4 Conclusions 211 References 213 8. Synthetic Fuel Production from the Catalytic Thermochemical Conversion of Carbon Dioxide 215Navadol Laosiripojana, Kajornsak Faungnawakij, and Suttichai Assabumrungrat 8.1 Introduction 215 8.2 General Aspects of CO2 Reforming 218 8.3 Catalyst Selection for CO2 Reforming Reaction 221 8.4 Reactor Technology for Dry Reforming 228 8.5 Conversion of Synthesis Gas to Synthetic Fuels 230 8.6 Conclusions 239 Acknowledgments 240 References 240 9. Fuel Production from Photocatalytic Reduction of CO2 with Water Using TiO2-Based Nanocomposites 245Ying Li 9.1 Introduction 245 9.2 CO2 Photoreduction: Principles and Challenges 246 9.3 TiO2-Based Photocatalysts for CO2 Photoreduction: Material Innovations 247 9.4 Photocatalysis Experiments 254 9.5 CO2 Photoreduction Activity 255 9.6 Reaction Mechanism and Factors Influencing Catalytic Activity 259 9.7 Conclusions and Future Research Recommendations 265References 265 10. Photocatalytic Reduction of CO2 to Hydrocarbons Using Carbon-Based AgBr Nanocomposites Under Visible Light 269Mudar Abou Asi, Chun He, Qiong Zhang, Zuocheng Xu, Jingling Yang, Linfei Zhu, Yanling Huang, Ya Xiong, and Dong Shu 10.1 Introduction 269 10.2 Mechanism of Photocatalytic Reduction for CO2 270 10.3 Carbon Dioxide Reduction 271 10.4 AgBr Nanocomposites 274 10.5 Conclusions 283 Acknowledgments 283 References 284 11. Use of Carbon Dioxide in Enhanced Oil Recovery and Carbon Capture and Sequestration 287Suguru Uemura, Shohji Tsushima, and Shuichiro Hirai 11.1 Introduction 287 11.2 Enhanced Oil Recovery 288 11.3 Carbon Capture and Sequestration 294 11.4 Future Tasks 298 11.5 Summary 298 References 298 Index 301

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Book SynopsisThe Organometallic Chemistry of N-heterocyclic Carbenes describes various aspects of N-heterocyclic Carbenes (NHCs) and their transition metal complexes at an entry level suitable for advanced undergraduate students and above. The book starts with a historical overview on the quest for carbenes and their complexes. Subsequently, unique properties, reactivities and nomenclature of the four classical NHCs derived from imidazoline, imidazole, benzimidazole and 1,2,4-triazole are elaborated. General and historically relevant synthetic aspects for NHCs, their precursors and complexes are then explained. The book continues with coverage on the preparation and characteristics of selected NHC complexes containing the most common metals in this area, i.e. Ni, Pd, Pt, Ag, Cu, Au, Ru, Rh and Ir. The book concludes with an overview and outlook on the development of various non-classical NHCs beyond the four classical types. Topics covered include: StabilizationTable of ContentsForeword ix Preface x List of Abbreviations and Definitions xii 1 General Introduction 1 1.1 Definition of Carbenes 1 1.2 Historical Overview of Carbenes, N-Heterocyclic Carbenes, and Their Complexes 3 1.2.1 The Quest for Free Stable Carbenes 3 1.2.2 The Quest for Carbene Complexes 11 References 15 2 General Properties of Classical NHCs and Their Complexes 17 2.1 Stabilization in NHCs (Push-Pull Effect) 19 2.2 Backbone Differences and Their Implications 20 2.3 Dimerization of Carbenes 22 2.4 Nomenclature of N-Heterocyclic Carbenes 25 2.5 Electronic Properties of NHCs and Different Electronic Parameters 29 2.5.1 Tolman’s Electronic Parameter (TEP) and Related Carbonyl Based Systems 29 2.5.2 Lever’s Electronic Parameter (LEP) 36 2.5.3 Huynh’s Electronic Parameter (HEP) 38 2.6 Steric Properties of NHCs 42 2.7 Structural Diversity of NHC Ligands and Their Complexes 45 2.7.1 Donor-Functionalized NHCs 45 2.7.2 Multidentate NHCs 46 2.7.3 Pincer-Type NHC Ligands 47 2.7.4 Tripodal and Macrocyclic Ligands 48 References 49 3 Synthetic Aspects 52 3.1 General Routes to Azolium Salts as NHC Precursors 52 3.1.1 N-Alkylation of Neutral Azoles 52 3.1.2 Multicomponent Condensation Reactions 55 3.1.3 Cyclization of Diamines 58 3.1.4 Cyclization of Formamidines 64 3.2 General Routes to Free NHCs 66 3.2.1 NHCs via Deprotonation of Azolium Salts 68 3.2.2 NHCs via Reduction of Thiones 71 3.2.3 NHCs via α-Elimination of Small Molecules 73 3.3 General Synthetic Routes to NHC Complexes 74 3.3.1 Coordination of Free NHCs 76 3.3.2 Cleavage of Electron-Rich Entetramines by Transition Metals 78 3.3.3 In Situ Deprotonation of Azolium Salts in the Presence of Transition Metals 78 3.3.4 Carbene Transfer Routes 81 3.3.5 Oxidative Addition of an Azolium Salt to a Low-Valent Metal Complex 83 3.3.6 Metal-Template Synthesis Using Isocyanide Complexes as Precursors 85 3.3.7 NHC Complexes by Small Molecule Elimination 89 3.3.8 NHC Complexes by Protonation/Alkylation of Azolyl Complexes 93 References 95 4 Group 10 Metal(0)-NHC Complexes 99 4.1 Nickel(0)-NHC Complexes 99 4.1.1 Reactions of Enetetramines and Free NHCs 99 4.1.2 Reduction of Nickel(II)-NHC Complexes 106 4.2 Palladium(0)-NHC Complexes 107 4.2.1 Reactions of Free NHCs 107 4.2.2 Reduction of Palladium(II)-NHC Complexes 112 4.3 Platinum(0)-NHC Complexes 115 4.3.1 Homoleptic Complexes 115 4.3.2 Heteroleptic Complexes 117 References 120 5 Group 10 Metal(II)-NHC Complexes 122 5.1 Nickel(II)-NHC Complexes 122 5.1.1 Cleavage of Enetetramines and the Free Carbene Route 122 5.1.2 In Situ Deprotonation of Azolium Salts with Basic Metal Salts 124 5.1.3 The Silver-Carbene Transfer Route 127 5.2 Palladium(II)-NHC Complexes 129 5.2.1 Cleavage of Entetramines and the Free Carbene Route 130 5.2.2 In Situ Deprotonation of Azolium Salts with External Base 133 5.2.3 The “Palladium Acetate” Route 135 5.2.4 The Silver-Carbene Transfer Route 139 5.2.5 Isomers of Bis(NHC) Palladium(II) Complexes 143 5.3 Platinum(II)-NHC Complexes 150 5.3.1 Cleavage of Entetramines 151 5.3.2 Cyclization of Isocyanide Complexes 152 5.3.3 The Oxidative Addition Route 153 5.3.4 The Free Carbene Route 157 5.3.5 In Situ Deprotonation of Azolium Salts with External Base 159 5.3.6 In Situ Deprotonation with Basic Platinum Precursors 162 5.3.7 Carbene Transfer Reactions 164 References 168 6 Group 11 Metal-NHC Complexes 171 6.1 Copper(I)-NHC Complexes 171 6.1.1 The Free Carbene Route 171 6.1.2 Alkylation of Copper-Azolate Complexes 172 6.1.3 In Situ Deprotonation with External Base 173 6.1.4 In Situ Deprotonation with Basic Copper Precursors 177 6.1.5 The Silver Carbene Transfer Route 180 6.1.6 The Copper Powder Route 182 6.2 Silver(I)-NHC Complexes 183 6.2.1 The Free Carbene Route 183 6.2.2 In Situ Deprotonation with Basic Silver Precursors 186 6.2.3 Silver-Carbene Transfer Reactions 192 6.3 Gold(I)-NHC Complexes 194 6.3.1 Cleavage of Enetetramines 194 6.3.2 Protonation/Alkylation of Azolato Complexes 194 6.3.3 The Free Carbene Route 196 6.3.4 The Silver-Carbene Transfer Route 200 6.3.5 Ligand Redistribution and Autoionization of Gold(I) NHC Complexes 210 6.4 Gold(III)-NHC Complexes 212 References 218 7 Ruthenium, Rhodium, and Iridium Metal-NHC Complexes 220 7.1 Ruthenium(II)-NHC Complexes 220 7.1.1 Cleavage of Enetetramines and the Free Carbene Route 220 7.1.2 In Situ α-Elimination 227 7.1.3 In Situ Deprotonation of Azolium Salts 228 7.1.4 The Silver-Carbene Transfer Route 230 7.2 Rhodium(I)- and Rhodium(III)-NHC Complexes 232 7.2.1 Cleavage of Enetetramines and the Free Carbene Route 232 7.2.2 In Situ Deprotonation of Azolium Salts 238 7.2.3 The Silver-Carbene Transfer Route 243 7.3 Iridium(I)- and Iridium(III) NHC Complexes 245 7.3.1 Cleavage of Enetetramines and the Free Carbene Route 245 7.3.2 In Situ α-Elimination 250 7.3.3 In Situ Deprotonation of Azolium Salts 251 7.3.4 The Silver-Carbene Transfer Route 256 References 261 8 Beyond Classical N-heterocyclic Carbenes I 263 8.1 N,S-Heterocyclic Carbenes (NSHCs) 263 8.2 N,O-Heterocyclic Carbenes (NOHCs) 270 8.3 Expanded Six-Membered NHCs 277 8.4 Expanded Seven- and Eight-Membered NHCs 282 8.5 Expanded Diamidocarbenes (DAC) 287 References 291 9 Beyond Classical N-heterocyclic Carbenes II 293 9.1 Abnormal Imidazolin-4/5-ylidenes (aNHC) 294 9.2 Mesoionic 1,2,3-Triazolin-5-ylidenes (MIC) 303 9.3 Pyrazolin-3/5-ylidenes (Pyry) and Indazolin-3-ylidenes (Indy) 310 9.3.1 Pyrazolin-3/5-ylidenes 310 9.3.2 Indazolin-3-ylidenes 317 9.4 Cyclic (Alkyl)(Amino)Carbenes (CAACs) Or Pyrrolidin-2-ylidenes 320 9.5 Remote N-Heterocyclic Carbenes (rNHC) 324 9.5.1 Pyridin-3/4-ylidenes 324 9.5.2 Pyrazolin-4-ylidenes 326 References 328 Index 330

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Book SynopsisThe most comprehensive and thorough reference work available for petroleum engineers of all levels. Finally, there is a one-stop reference book for the petroleum engineer which offers practical, easy-to-understand responses to complicated technical questions. This is a must-have for any engineer or non-engineer working in the petroleum industry, anyone studying petroleum engineering, or any reference library. Written by one of the most well-known and prolific petroleum engineering writers who has ever lived, this modern classic is sure to become a staple of any engineer's library and a handy reference in the field. Whether open on your desk, on the hood of your truck at the well, or on an offshore platform, this is the only book available that covers the petroleum engineer's rules of thumb that have been compiled over decades. Some of these rules, until now, have been unspoken but everyone knows, while others are meant to help guide the engineer through some of the more recent brTable of ContentsPreface xv About the Author xxi Abrasion 1 Absorption 3 Acid Gas Removal 5 Acid Gas Scrubbing 9 Acid Number 11 Acid Rain 13 Acid-Base Catalysts 15 Acidity and Alkalinity 17 Acidizing 19 Adsorption 21 Adsorption Isotherm 23 Adulteration 25 Air Emissions 27 Alcohol Blended Fuels 29 Alcohols 31 Alicyclic Hydrocarbons 33 Aliphatic Hydrocarbons 35 Alloys – Composition 37 Amine Absorber 39 Amine Condenser 41 Amine Washing 43 Ammonia 45 Aniline Point 47 Anticline 49 Antoine Equation 51 API Gravity 53 Aromatic Hydrocarbons 59 Asphalt Manufacture 61 Asphaltene Constituents 63 Associated Natural Gas 65 Atmospheric Equivalent Boiling Point 67 Auto-ignition Temperature 69 Barrel 71 Baumé Gravity 73 Benchmark Crude Oil 75 Bernoulli’s Principle 77 Biomass and Biofuels 79 Bitumen 83 Bituminous Rock and Bituminous Sand 85 Black Acids 87 Black Oil 89 Blending and Mixing 91 Boiling Point and Boiling Range 95 Brine 97 Bubble Point and Bubble Point Pressure 99 Bureau of Mines Correlation Index 101 Calorific Value 103 Capillary Forces 105 Capillary Number 107 Capillary Pressure 109 Carbon Monoxide and Carbon Dioxide 111 Carbon Number and Possible Isomers 113 Carbonate Reservoir 115 Carbonate Washing and Water Washing 117 Catalyst Pore Diameter 119 Catalytic Materials 121 Catalytic Reforming 123 Cementation Value 125 Cetane Index 127 Characterization Factor 129 Chemical Reaction Rates 131 Chemicals Reactive with Water 133 Chemometrics 135 Clausius Equation and Clausius-Clapeyron Equation 137 Coal – General Properties 139 Coke Yield from Conradson Carbon 141 Common Acronyms 143 Common Names of Selected Chemical Compounds 145 Common Unit Conversions 147 Commonly Used Constants 149 Compressibility 151 Coning 153 Conversion Charts 155 Conversion Factors 157 Correlation Index 163 Corrosion 165 Corrosion – Fuel Ash 167 Corrosion – Naphthenic Acid 169 Cricondenbar 171 Cricondentherm 173 Critical Properties 175 Critical Temperatures of Gases 177 Crude Oil – Assay 179 Crude Oil – Classification 181 Crude Oil – Desalting 183 Crude Oil – Distillation 185 Crude Oil – Fractional Composition 187 Crude Oil – Hydrotreating 189 Crude Oil – Molecular Composition 191 Crude Oil – Primary Recovery 193 Crude Oil – Recovery 195 Crude Oil – Refining 197 Crude Oil – Residua 201 Crude Oil – Sampling and Analysis 203 Crude Oil – Secondary Recovery 205 Crude Oil – Tertiary Recovery 207 Crude Oil from Tight Formations 209 Darcy and Non-Darcy Flow in Porous Media 211 Darcy’s Law 213 Decimal Multipliers for SI Prefixes 215 Decline Curve Evaluation 217 Delivery Point 219 Density, Specific Gravity, and API Gravity 221 Density-Boiling Point Constant 223 Determining Depreciation 225 Dew Point Temperature and Pressure 227 Dielectric Constant 229 Dielectric Loss and Power Factor 231 Diesel Index 233 Dipole Moment 235 Distillation 237 Distillation – Flooding 239 Distillation – Gap-Overlap 241 Drilling Fluid 243 Drilling Fluid Additives 245 E85 Fuel 247 Embrittlement 249 Embrittlement – Hydrogen 251 Emulsion 253 Enhanced Oil Recovery 255 Environmental Regulations 259 Evaporation 261 Expansion and Contraction of Solids 263 Explosive Limits 265 Fire Point 267 Fischer-Tropsch Chemistry 269 Flammability and Flammability Limits 271 Flash Point 273 Flow Through Porous Media 275 Fluid Catalytic Cracking – Chemistry 277 Fluid Flow Fundamentals 279 Fluid Flow Through Permeable Media 281 Fluid Flow 289 Fluid Saturation 291 Foamy Oil 293 Formation Volume Factor 295 Fouling 297 Fracturing Fluids 299 Fuel Oil 303 Functional Groups 305 Fundamental Physical Constants 309 Gas Deviation Factor 311 Gas Formation Volume Factor 313 Gas Laws 315 Gas Processing – Hydrogen Sulfide Conversion 319 Gas Processing – Metal Oxide Processes 321 Gas Processing – Olamine Processes 323 Gas Processing – Sweetening 325 Gas Processing – Absorption and Adsorption Processes 327 Gas Processing – Acid Gas Removal 329 Gas Processing – Carbonate and Water Washing Processes 331 Gas Processing – Catalytic Oxidation Processes 333 Gas Processing - Fractionation 335 Gas Processing – Gas-Oil Separation 337 Gas Processing – Liquids Removal 339 Gas Processing – Metal Oxide Processes 341 Gas Processing – Methanol-Based Processes 343 Gas Processing – Molecular Sieve Processes 345 Gas Processing – Nitrogen Removal 347 Gas Processing – Physical Solvent Processes 349 Gas Processing – Plant Schematic and Products 351 Gas Processing – Processes and Process Selection 353 Gas Processing – Water Removal 361 Gas Solubility 363 Gas-Condensate Reservoirs 365 Gaseous Fuels 367 Gaseous Hydrocarbons – General Properties 369 Gasification – Chemistry 371 Gasification – Refinery Resids 373 Gas-Liquid Solubility 375 Gas-Oil Ratio 377 Gas-Oil Separation 379 Gasoline – Component Streams 381 Gas-to-Liquids 383 Geological Time Scale 385 Geothermal Gradient 387 Glycol 389 Grease 391 Greek Alphabet 393 Hazardous Chemicals 395 Hazardous Waste 399 Heat Capacity 401 Heat Content of Petroleum Products 403 Heat Exchangers 405 Heat of Combustion of Petroleum Fuels 407 Heat of Combustion of Petroleum Fuels 409 Heat Transfer Coefficient 411 Heat Transfer – Convection and Conduction 413 Heating Value 415 Heavy Feedstock Conversion – Thermal Processes 417 Heterogeneity 419 Heterogeneous Catalysis and Homogeneous Catalysis 421 High-Acid Crudes 423 Hydrate Formation and Prevention 425 Hydraulic Fracturing 427 Hydrocarbon Gases – Physical Constants 429 Hydroconversion 431 Hydrogen Chloride 433 Hydrogen in Refineries 435 Hydrogen Sulfide Conversion 437 Hydrogen Sulfide 439 Hydrogen 441 Hydrostatic Pressure 443 Ideal Gas 445 Improved Oil Recovery Processes 447 Incompatible Chemicals 449 Ionic Liquids 451 Isothermal Compressibility of Oil 453 Kinematic Viscosity 455 Liquefied Petroleum Gas 457 Liquid-Gas Separators 459 Lubricants – Classification 461 Lubricating Oil – Base Stock 463 M85 465 Marx-Langenheim Model 467 Material Balance 469 Mean Density – Gas-Air Mixture 471 Mean Density – Gas-Air Mixture 473 Metals Content and FCC Coke Production 475 Methane 477 Molecular Weight of Petroleum Fractions 479 Naphthenic Acids – Corrosion in Distillation Units 481 Naphthenic Acids – Mitigating Corrosion 483 Naphthenic Acids 485 Natural Gas - Associated 487 Natural Gas – Composition 489 Natural Gas – Compressibility 493 Natural Gas – Measurement 495 Natural Gas – Nonassociated 497 Natural Gas – Properties 499 Natural Gas – Specific Gravity 505 Natural Gas – Phase Behavior 507 Natural Gas – Sweetening 509 Natural Gasoline 511 Nitrogen and Nitrogen Oxide Gases 513 Nonassociated Natural Gas 515 Octane Barrel Yield 517 Octane Number 519 Oil and Gas from Tight Formations 521 Oil and Gas Originally in Place 523 Oil Recovery Factor 525 Oil Shale – General Classification 527 Oilfield Chemicals 529 Olamine Processes 531 Olamine 533 On-Stream Factor 535 Opportunity Crudes 537 Organic Compounds – Physical and Thermochemical Data 539 Organic Solvents 547 Oxygen 549 Ozone 551 Paraffin Hydrocarbons 553 Particle Size Classification 555 Permeability 557 Petrochemicals 559 Petroleum Products – Heat Content 561 Petroleum Products 563 Phase Behavior 567 Polychlorobiphenyls 569 Porosity 573 Prefixes 575 Pressure Conversion 577 Principal Component Analysis 579 Process System 581 Product Blending 583 Production Engineering Units 585 Productivity Index 587 Proppants 589 PVT Properties 591 Rate of Reaction 593 Reactor Types 595 Recovery Methods 597 Refinery Feedstocks – Corrosive Constituents 599 Refinery Gas 601 Refinery Types 603 Refinery Units – Materials of Construction and Operating Conditions 605 Refractive Index and Specific Refraction 607 Relative Density 609 Relative Permeability 611 Relative Volatility 613 Reserves – Estimation 615 Reserves 617 Reservoir Crude Oil 619 Reservoir – Drive Mechanisms 621 Reservoir Pressure 623 Reservoir – Types and Classification 625 Reservoir 627 Resid Upgrading Technologies 629 Resource Estimation 631 Retrograde Condensate Systems 633 Retrograde Condensation 635 Reynolds Number 637 Rock Types 639 SARA Analysis 641 Saturated Steam 643 Saturation 645 Sediments, Reservoirs, and Deposits 647 Separators – Gas-Oil Separation 649 Shale Gas Formation 651 Shale Gas Reservoirs – Variation in Shale Properties 653 Shale Gas – Variations in Composition 655 Shale Oil (Kerogen-Derived Oil) – Variation in Properties 657 Shale Plays – Properties 659 SI – International System of Units 661 Solubility Parameter 667 Solvents 669 Specific Gravity 673 Specific Heat 675 Stress-Corrosion Cracking 677 Sulfur Dioxide 679 Sulfur Material Balance 681 Supercritical Fluids 683 Surface Tension 685 Sweetening Processes 687 Synthesis Gas 689 Tar Sand 691 Test Methods 695 Contents xvii Thermal Conductivity 697 Thermal Cracking Processes 699 Tight Formations 701 Unit Process 703 Vapor Density 705 Vapor Pressure 707 Viscosity 709 Viscosity Index 713 Viscosity of Petroleum Fractions 715 Viscosity-Gravity Constant 717 Volume Flow Rate 719 Volumetric Evaluation 721 Volumetric Factors 723 Water – Boiling Point Variation with Pressure 725 Water –Common Impurities 727 Water – Density and Viscosity in Relation to Temperature 729 Water Saturation 731 Watson Characterization Factor 733 Weights and Measures – Density 735 Weights and Measures – Fuels 737 Weights and Measures - General 739 Well Casing 741 Wellbore Stability Analysis 743 Wettability 745 Wobbe Index 747 Working Gas 749 Bibliography and Information Sources 751

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Book SynopsisBiocatalysts are increasingly used by chemists engaged in fine chemical synthesis within both industry and academia. Today, there exists a huge choice of high-tech enzymes and whole cell biocatalysts, which add enormously to the repertoire of synthetic possibilities.Table of ContentsList of Contributors ix Abbreviations xxi 1 Considerations for the Application of Process Technologies in Laboratory- and Pilot-Scale Biocatalysis for Chemical Synthesis 1 1.1 Introduction 1 1.2 Process Intensification and Proposed Scale-Up Concept 2 1.3 Enabling Technologies 5 1.4 Enhancing Technologies 20 1.5 Conclusion 28 References 28 2 Cytochrome P450 (CYP) Progress in Biocatalysis for Synthetic Organic Chemistry 31 2.1 Introduction 31 2.2 CYP Development 32 2.3 Recent Developments 34 2.4 Conclusion 41 References 41 3 Use of Hydrolases and Related Enzymes for Synthesis 43 3.1 Continuous-Flow Reactor-Based Enzymatic Synthesis of Phosphorylated Compounds on a Large Scale 43 3.2 Deracemization of sec-Alcohols via Enantio-Convergent Hydrolysis of rac-Sulfate Esters 45 3.3 Dynamic Kinetic Resolution of a Primary Amine by an Efficient Bifunctional Pd-CALB Hybrid Catalyst. A Metalloenzyme Mimic for Enhanced Cooperative Catalysis 50 3.4 Highly Efficient DKR of Secondary 1-Phenylethanol Derivatives Using a Low-Cost Solid Super Acid as Racemization Catalyst 53 3.5 Identification of New Biocatalysts for the Enantioselective Conversion of Tertiary Alcohols 58 3.6 Enzyme-Catalyzed Hydrolysis of Bicycloheptane Diester to Monoester 60 3.7 Double Mutant Lipase with Enhanced Activity and Enantioselectivity for Bulky Secondary Alcohols 64 3.8 Stereoselective Synthesis of β-Amino Acids by Hydrolysis of an Aryl-Substituted Dihydropyrimidine by Hydantoinases 68 References 72 4 Non-Redox Lyases and Transferases for C-C, C-O, C-S, and C-N Bond Formation 75 4.1 Regioselective Enzymatic Carboxylation of Phenols and Hydroxystyrenes Employing Co-Factor-Independent Decarboxylases 75 4.2 Stetter Reactions Catalyzed by Thiamine Diphosphate-Dependent Enzymes 81 4.3 Asymmetric Michael-Type Additions of Acetaldehyde to Nitroolefins Catalyzed by 4-Oxalocrotonate Tautomerase (4-OT) Yielding Valuable γ-Nitroaldehydes 85 4.4 Michael-Type Addition of Aldehydes to β-Nitrostyrenes by Whole Cells of Escherichia coli Expressing 4-Oxalocrotonate Tautomerase (4-OT) 91 4.5 Norcoclaurine Synthases for the Biocatalytic Synthesis of Tetrahydroisoquinolines 95 4.6 Streptavidin-Based Artificial Metallo-Annulase for the Enantioselective Synthesis of Dihydroisoquinolones 101 4.7 Regiospecific Benzylation of Tryptophan and Derivatives Catalyzed by a Fungal Dimethylallyl Transferase 102 4.8 Enantioselective Michael Addition of Water Using Rhodococcus Rhodochrous ATCC 17895 106 4.9 Sulfation of Various Compounds by an Arylsulfotransferase from Desulfitobacterium hafniense and Synthesis of 17β-Estradiol-3-Sulfate 111 4.10 Asymmetric Synthesis of Cyclopropanes and Benzosultams via Enzyme-Catalyzed Carbenoid and Nitrenoid Transfer in E. coli Whole Cells 113 4.11 Biocatalytic Production of Novel Glycolipids 118 4.12 Enzymatic Synthesis of 8-Aza- and 8-Aza-7-Deazapurine 2´-Deoxyribonucleosides 124 4.13 Phenylalanine Ammonia Lyase-Catalyzed Asymmetric Hydroamination for the Synthesis of L-Amino Acids 128 References 130 5 Oxidations 135 5.1 Semi-Preparative-Scale Drug Metabolite Synthesis with Human Flavin Monooxygenases 135 5.2 Biobased Synthesis of Industrially Relevant Nitriles by Selective Oxidative Decarboxylation of Amino Acids by Vanadium Chloroperoxidase 139 5.3 Terminal Oxygenation of Fatty Acids by a CYP153A Fusion Construct Heterologously Expressed in E. coli 142 5.4 Enantioselective Oxidative C-C Bond Formation in Isoquinoline Alkaloids Employing the Berberine Bridge Enzyme 144 5.5 Oxidation of Aldehydes Using Alcohol Dehydrogenases 148 5.6 MAO-Catalyzed Deracemization of Racemic Amines for the Synthesis of Pharmaceutical Building Blocks 150 5.7 Synthesis of (S)-Amines by Chemo-Enzymatic Deracemization Using an (R)-Selective Amine Oxidase 153 5.8 Selective Oxidation of Diols into Lactones under Aerobic Conditions Using a Laccase-TEMPO Catalytic System in Aqueous Medium 156 References 160 6 Reductions 163 6.1 Tetrahydroxynaphthalene Reductase: Broad Substrate Range of an NADPH-Dependent Oxidoreductase Involved in Reductive Asymmetric Naphthol Dearomatization 163 6.2 Chemoenzymatic Synthesis of Diastereo- and Enantiomerically Pure 2,6-Disubstituted Piperidines via Regioselective Monoamination of 1,5-Diketones 167 6.3 Asymmetric Amination of Ketones Employing ω-TAs in Organic Solvents 171 6.4 Stereoselective Synthesis of (R)-Profen Derivatives by the Enoate Reductase YqjM 176 6.5 Productivity Improvement of the Bioreduction of α,β-Unsaturated Aldehydes by Coupling of the In Situ Substrate Feeding Product Removal (SFPR) Strategy with Isolated Enzymes 181 6.6 Reduction of Imines by Recombinant Whole-Cell E. coli Biocatalysts Expressing Imine Reductases (IREDs) 186 References 191 7 Halogenation and Dehalogenation 193 7.1 Site-Directed Mutagenesis Changes the Regioselectivity of the Tryptophan 7-Halogenase PrnA 193 7.2 Controlling Enantioselectivity of Halohydrin Dehalogenase from Arthrobacter sp. Strain AD2, Revealed by Structure-Guided Directed Evolution 197 7.3 Enzymatic Production of Chlorothymol and its Derivatives by Halogenation of the Phenolic Monoterpenes Thymol and Carvacrol with Chloroperoxidase 201 7.4 Halogenation of Non-Activated Fatty Acyl Groups by a Trifunctional Non-Heme Fe(II)-Dependent Halogenase 204 References 211 8 Cascade Reactions 213 8.1 Synthetic Cascades via a Combination of Artificial Metalloenzymes with Monoamine Oxidases (MAO-Ns) 213 8.2 Amination of Primary Alcohols via a Redox-Neutral Biocascade 215 8.3 Biocatalytic Synthesis of a Diketobornane as a Building Block for Bifunctional Camphor Derivatives 218 8.4 Three Enzyme-Catalyzed Redox Cascade for the Production of a Carvo-Lactone 222 8.5 Preparation of Homoallylic Alcohols via a Chemoenzymatic One-Pot Oxidation-Allylation Cascade 226 8.6 Cascade Biotransformations via Enantioselective Reduction, Oxidation, and Hydrolysis: Preparation of (R)-δ-Lactones from 2-Alkylidenecyclopentanones 230 8.7 One-Pot Tandem Enzymatic Reactions for Efficient Biocatalytic Synthesis of D-Fructose-6-Phosphate and Analogs 232 8.8 Efficient One-Pot Tandem Biocatalytic Process for a Valuable Phosphorylated C8 D-Ketose: D-Glycero-D-Altro-2-Octulose 8-Phosphate 239 8.9 Chemoenzymatic Synthesis of (S)-1,2,3,4-Tetrahydroisoquinoline-3-Carboxylic Acid by PAL-Mediated Amination and Pictet-Spengler Cyclization 243 8.10 ω-TA/MAO Cascade for the Regio- and Stereoselective Synthesis of Chiral 2,5-Disubstituted Pyrrolidines 246 References 249 9 Biocatalysis for Industrial Process Development 253 9.1 Efficient Synthesis of (S)-1-(5-Fluoropyrimidin-2-yl)ethylamine Hydrochloride Salt Using an ω-Transaminase Biocatalyst in a Two-Phase System 253 9.2 Preparative-scale Production of a Chiral, Bicyclic Proline Analog Intermediate for Boceprevir 257 9.3 Focused Carbonyl Reductase Screening for Rapid Gram Supply of Highly Enantioenriched Secondary Alcohol Libraries 260 9.4 A Rapid, Inexpensive and Colorimetric High-throughput Assay Format for Screening Commercial Ketoreductase Panels, Providing Indication of Substrate Scope, Co-factor Specificity and Enantioselectivity 266 9.5 Stereoselective Production of (R)-3-quinuclidinol Using Recombinant Escherichia coli Whole Cells Overexpressing 3-Quinuclidinone Reductase and a Co-factor Regeneration System 273 9.6 Preparation of N-Boc-D-Serine Using a Coupled D-Acylase/Racemase Enzyme System 275 9.7 Scale-up of a Biocatalytic Oxidase in a Dynamically Mixed Tubular Flow Reactor 279 References 282 Index 285

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Book SynopsisA practical handbook for chemists needing to incorporate functional groups into organic compounds through the formation of carbon-heteroelement bonds. Each chapter centers on a single type of heteroelement and contains an overview of current synthetic approaches.Table of ContentsPreface ix Acknowledgments xi 1 Introduction to Practical Functional Group Synthesis 1 1.1 General Approaches for Designing Syntheses 1 1.2 New Versions of “Classic” Organic Reactions 6 1.3 Solvent Selection and Solvent‐Free Reactions 7 1.4 Operational Simplicity 11 1.5 Metal‐Catalyzed Transformations 12 1.6 Organocatalysis 16 1.7 Microwave‐ and Ultrasound‐Assisted Chemistry 17 1.8 Sustainability 25 1.9 Asymmetric Synthesis 32 References 33 2 Preparation of Alcohols, Ethers, and Related Compounds 37 2.1 Preparation of Alcohols, Ethers, and Related Compounds through the Formation of Oxygen–Carbon(sp3) Bonds 37 2.2 Preparation of Phenols, Aryl Ethers, and Related Compounds through the Formation of Oxygen–Carbon(sp2) Bonds 57 2.3 Preparation of Vinyl Ethers and Related Compounds through the Formation of Oxygen–Carbon(sp2) Bonds 84 2.4 Preparation of Alkynyl Ethers and Related Compounds through the Formation of Oxygen–Carbon(sp) Bonds 114 References 117 3 Synthesis of Amines, Amides, and Related Compounds 123 Alkylamines 123 3.1 Synthesis of Alkylamines and Related Compounds through Nitrogen–Carbon(sp3) Bond‐Forming Reactions 123 3.2 Synthesis of Arylamines and Related Compounds through Nitrogen–Carbon(sp2) Bond‐Forming Reactions 150 3.3 Synthesis of Vinylamines and Related Compounds through Nitrogen–Carbon(sp2) Bond‐Forming Reactions 191 3.4 Synthesis of Ynamides and Related Compounds through Nitrogen–Carbon(sp) Bond‐Forming Reactions 207 References 213 4 Synthesis of Organophosphines, Phosphonates, and Related Compounds 219 4.1 Introduction to the Synthesis of Organophosphorus Compounds Generated through the Formation of Phosphorus–Carbon Bonds 219 4.2 Synthesis of Alkylphosphines and Related Compounds through the Formation of Phosphorus–Carbon(sp3) Bonds 220 4.3 Synthesis of Arylphosphines and Related Compounds through the Formation of Phosphorus–Carbon(sp2) Bonds 338 4.4 Synthesis of Vinylphosphines and Related Compounds through the Formation of Phosphorus–Carbon(sp2) Bonds 398 4.5 Synthesis of Alkynylphosphines and Related Compounds through the Formation of Phosphorus–Carbon(sp) Bonds 441 References 454 5 Synthesis of Thioethers, Sulfones, and Related Compounds 471 5.1 Synthesis of Thioethers and Related Compounds through the Formation of Sulfur–Carbon(sp3) Bonds 471 5.2 Synthesis of Aryl Thioethers and Related Compounds through the Formation of Sulfur–Carbon(sp2) Bonds 481 5.3 Synthesis of Vinyl Thioethers and Related Compounds through the Formation of Sulfur–Carbon(sp2) Bonds 498 5.4 Synthesis of Thioethers and Related Compounds through the Formation of Sulfur–Carbon(sp) Bonds 506 References 510 6 Synthesis of Organoboronic Acids, Organoboronates, and Related Compounds 515 6.1 Synthesis of Alkylboronates and Related Compounds through the Formation of Boron–Carbon(sp3) Bonds 515 6.2 Synthesis of Arylboronates and Related Compounds through the Formation of Boron–Carbon(sp2) Bonds 526 6.3 Synthesis of Vinylboronates and Related Compounds through the Formation of Boron–Carbon(sp2) Bonds 538 6.4 Synthesis of Alkynylboronates and Related Compounds through the Formation of Boron–Carbon(sp) Bonds 549 References 552 7 Synthesis of Organohalides 557 7.1 Synthesis of Alkyl Halides through the Formation of Halogen–Carbon(sp3) Bonds 557 7.2 Synthesis of Aryl Halides through the Formation of Halogen–Carbon(sp2) Bonds 590 7.3 Synthesis of Vinyl Halides through the Formation of Halogen–Carbon(sp2) Bonds 628 7.4 Synthesis of Alkynyl Halides through the Formation of Halogen–Carbon(sp) Bonds 655 References 670 Index 679

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Book SynopsisThe challenges faced by environmental scientists today are vast, complex, and multi-faceted. For instance, predicting the fate of an environmental pollutant or understanding ecosystem responses to climate change, necessitate a firm understanding of molecular structure and dynamics of environmental media as well as the components that exist and interact within this media. Furthermore, linking information obtained at the molecular-scale to ecosystem-level processes is a major pursuit of modern environmental research. As such, NMR spectroscopy and its scalability from the molecular-scale to the macroscopic-scale, is facilitating rapid growth in environmental science. In addition, the versatility of NMR spectroscopy has resulted in the development and implementation of different types of NMR techniques to examine the structure of various types of environmental samples, living and non-living, as well as the study of critical environmental processes. This comprTable of ContentsPreface Environmental NMR Part 1: Fundamentals of Environmental NMR 1 Environmental NMR: Solution-state Methods 2 Environmental NMR: Diffusion Ordered Spectroscopy Methods 3 Environmental NMR: Hyphenated Methods 4 Environmental NMR: Solid-state Methods 5 Environmental NMR: High Resolution Magic-angle Spinning 6 Environmental Comprehensive Multi-phase NMR 7 Environmental NMR: Magnetic Resonance Imaging 8 Environmental NMR: Fast Field Cycling Relaxometry 9 Mobile NMR 10 Terrestrial Magnetic Field NMR: Recent Advances Part 2: NMR for Air, Soil and Water 11 Dissolved Organic Matter 12 Atmospheric Organic Matter 13 Soil Organic Matter 14 Chemical Ecology 15 Forest Ecology 16 Biofuels 17 Clay Minerals 18 Soil-water Interactions 19 Metals in The Environment 20 Organic Pollutants in The Environment 21 Soil-plant Atmosphere Continuum Studied by MRI Part 3: NMR and Environmental Metabolomics 22 Environmental Metabolomics 23 Methodology of NMR For Environmental Metabolomics 24 Environmental Metabolomics of Soil Organisms 25 Environmental Metabolomics of Aquatic Organisms 26 Environmental Metabolomics of Microbes 27 Plant Metabolomics

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Book SynopsisAn integrated presentation of the basic science and clinical applications of anticancer agents Aimed at both undergraduate and postgraduate readers, this unique text provides readers with a fully-integrated presentation of all aspects of the science of anticancer drugs, including their chemistry, pharmacology, and clinical applications. After heart disease, cancer is the number one killer worldwide, and the tumor microenvironment is forever changing, creating an ever-greater demand for safer, more effective anticancer agents. In response to that demand, the $100 billion cancer drug market continues to grow, with our increased understanding of cancer leading to new drugs being used clinically almost every year. Anticancer Therapeutics is divided into three sections. Section 1 is an introduction to cancer and therapeutics, and covers the etiology and cellular and molecular basis of cancer. In Section 2, the authors focus on the anticancer agents theTable of ContentsPreface xi Section 1: Introduction 1 1.1 The Global Burden of Cancer 3 References 11 1.2 Cancer Staging and Classification 13 1.2.1 Benign Tumour (or neoplasm) 13 1.2.2 Malignant Tumour (or cancer) 14 1.2.3 Tumour Nomenclature and Classification 14 1.2.4 Cellular Differentiation and Tumour Grade 21 1.2.5 Tumour Invasion and Metastasis 24 1.2.6 Clinical Staging of Cancer 26 References 36 1.3 Cellular and Molecular Basis of Cancer 39 1.3.1 Oncogenes 40 1.3.2 Tumour Suppressor Genes 45 1.3.3 Role of Epigenetics and Gene Promoter Regulation in Tumourigenesis 49 1.3.4 Multistage Tumourigenesis 53 1.3.5 Oncogene Addiction 54 1.3.6 Hallmarks of Cancer 55 1.3.7 Principles of Cancer Treatment 73 References 77 Section 2: The Anticancer Agents 81 2.1 Agents Which Act Directly on DNA 83 2.1.1 Nitrogen Mustards and Nitrosoureas 83 References 96 2.1.2 Temozolomide 98 References 106 2.1.3 Platinum]containing Agents 108 References 118 2.1.4 Gemcitabine 120 References 128 2.1.5 Camptothecin and Its Analogues 128 References 139 2.1.6 Podophyllotoxins 141 References 150 2.1.7 Anthracyclines 151 References 160 2.1.8 Epigenetic Targeting Agents 162 References 177 2.2 Antimetabolites 181 2.2.1 Cytarabine 181 References 183 2.2.2 Methotrexate 184 References 195 2.2.3 5]Fluorouracil 196 References 205 2.2.4 6]Mercaptopurine 206 References 210 2.3 Antimicrotubule Agents 211 2.3.1 Taxanes 211 References 224 2.3.2 Vinca Alkaloids 225 References 231 2.4 Anti]hormonal Agents 233 2.4.1 Bicalutamide 233 References 239 2.4.2 Tamoxifen 240 References 247 2.4.3 Anastrozole 248 References 254 2.5 Kinase Inhibitors 257 2.5.1 Discovery 257 2.5.2 Synthesis 262 2.5.3 Mode of Action 267 2.5.4 Mechanism of Resistance 268 2.5.5 Adverse Drug Reactions 268 References 271 Section 3: The Cancers 275 3.1 Breast Cancer 277 Key points 277 3.1.1 Epidemiology 277 3.1.2 Presentation 279 3.1.3 Diagnosis 282 3.1.4 Staging 283 3.1.5 Treatments 285 References 289 3.2 Colorectal Cancer 293 Key points 293 3.2.1 Epidemiology 293 3.2.2 Presentation 294 3.2.3 Diagnosis 296 3.2.4 Staging 298 3.2.5 Treatments 299 References 303 3.3 Leukaemia 307 Key points 307 3.3.1 Epidemiology 307 3.3.2 Presentation 310 3.3.3 Diagnosis 311 3.3.4 Staging 313 3.3.5 Treatments 314 References 319 3.4 Lung Cancer 323 Key points 323 3.4.1 Epidemiology 323 3.4.2 Presentation 327 3.4.3 Diagnosis 327 3.4.4 Staging 330 3.4.5 Treatments 330 References 337 3.5 Oesophageal Cancer 339 Key points 339 3.5.1 Epidemiology 339 3.5.2 Presentation 340 3.5.3 Diagnosis 341 3.5.4 Staging 344 3.5.5 Treatments 346 References 350 3.6 Ovarian Cancer 353 Key points 353 3.6.1 Epidemiology 353 3.6.2 Presentation 354 3.6.3 Diagnosis 356 3.6.4 Staging 357 3.6.5 Treatments 357 References 363 3.7 Pancreatic Cancer 367 Key points 367 3.7.1 Epidemiology 367 3.7.2 Presentation 368 3.7.3 Diagnosis 370 3.7.4 Staging 371 3.7.5 Treatments 373 References 375 3.8 Prostate Cancer 379 Key points 379 3.8.1 Epidemiology 379 3.8.2 Presentation 381 3.8.3 Diagnosis 382 3.8.4 Staging 384 3.8.5 Treatments 387 References 391 3.9 Skin Cancers 393 Key points 393 3.9.1 Epidemiology 393 3.9.2 Presentation 394 3.9.3 Diagnosis 395 3.9.4 Staging 396 3.9.5 Treatments 399 References 403 3.10 Testicular Cancer 405 Key points 405 3.10.1 Epidemiology 405 3.10.2 Presentation 407 3.10.3 Diagnosis 407 3.10.4 Staging 409 3.10.5 Treatments 409 References 414 Index 417

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Book SynopsisHyaluronic acid is an essential part of connective, epithelial and neural tissues, and contributes to cell proliferation and migration. It is used as a stimulating agent for collagen synthesis and is a common ingredient in skin-care products, a multi-billion dollar industry, as it is believed to be a key factor in fighting the aging process. Hyaluronic Acid: Production, Properties, Application in Biology and Medicine consists of six chapters discussing the various issues of hyaluronic acid research. In Chapter 1, a historical analysis recounts the discovery and milestones of the research leading to the practical applications of hyaluronan. Chapter 2 is dedicated to biological role of the hyaluronic acid in nature, in particular in the human body. The chapter starts from the phylogenesis of hyaluronic acid, then describes hyaluronan functions in human ontogenesis and especially the role which hyaluronan plays in extracellular matrix of the different tissues. Chapter 3 dTable of ContentsForeword xi Introduction xiii 1 The History of Hyaluronic Acid Discovery, Foundational Research and Initial Use 1 1.1 Discovery 1 1.2 Foundational Research 2 1.3 Initial Medical Applications 3 1.4 Sources of Hyaluronan 4 1.5 Current Medical Study and Use 6 1.6 Impact and Future Directions 7 References 7 2 The Biological Role of Hyaluronic Acid 9 2.1 Hyaluronic Acid Phylogenesis 9 2.1.1 Polysaccharide Structure and the Problems of Phylogenesis 13 2.1.2 Physico-Chemical and Functional Differences of Polysaccharides 18 2.1.3 Biochemical Features of Hyaluronic Acid and Other Glycosaminoglycans 20 2.2 Functions of Hyaluronan in Human Ontogenesis 22 2.2.1 Role of Hyaluronic Acid in Fertilization 22 2.2.2 Hyaluronan and Other Glucosaminoglycans in Cell Division, Migration and Differentiation 25 2.2.3 Hyaluronic Acid and Sulfated Glycosaminoglycans in Maintaining a Differentiated Status of Cells 33 2.2.4 Hyaluronan and Induction of Cellular Cycles for Differentiated Cells 35 2.2.5 The Source of Hyaluronic Acid’s Functional Properties and the Dynamics of its Synthesis and Degradation 44 2.2.6 The Rules of Biopolymer Functional Cleavage 52 2.3 Hyaluronan Signalling Systems 53 2.4 Hyaluronan Functions in the Extracellular Matrix 59 2.4.1 Extracellular Space 60 2.4.2 Composition and Functioning of the Extracellular Matrix 60 2.4.3 The Role of Hyaluronan in Transportation of Substances through the Extracellular Matrix: Diffusion, Osmosis, Electro-Osmosis and Vesicular Transportation 63 2.4.4 Hyaluronan in the Extracellular Matrix of Different Connective Tissues 65 References 67 3 Methods of Hyaluronic Acid Production 77 3.1 Hyaluronan Sources and Extraction 77 3.1.1 Hyaluronan Production from Animal Sources: General Methods 77 3.1.2 Hyaluronan Purification 78 3.1.3 The Chemical Production of Hyaluronan from Chicken Combs 81 3.1.4 HA Production for Ophthalmology 82 3.2 Bacterial Methods of Hyaluronic Acid Production 84 3.3 Hyaluronan Destruction during Production, Storage and Sterilization 85 3.4 Enzymatic Destruction of Hyaluronan 86 3.4.1 Hyaluronidase Classification 86 3.4.2 Properties and Functions of Hyaluronidases 87 3.5 Non-Enzymatic Destruction of Hyaluronan 88 3.5.1 Acid-Base Hydrolysis of Hyaluronan 88 3.5.2 Oxidation-Reduction Depolymerization of Hyaluronan 88 3.6 Quality of Hyaluronan Commercial Products of Animal and Bacterial Origin 89 References 92 4 Molecular and Supramolecular Structure of Hyaluronic Acid 97 4.1 Primary Structure of Hyaluronic Acid 97 4.2 Structure of Hyaluronan in Solution 101 4.3 Rheological Properties of Hyaluronic Acid 104 References 116 5 Chemical Modifications, Solid Phase, Radio-Chemical and Enzymatic Transformations of Hyaluronic Acid 121 5.1 Main Characteristics of Cross-Linked Hydrogels 122 5.2 Methods of Hyaluronic Acid Cross-Linking 124 5.2.1 Cross-Linking with Carbodiimides 124 5.2.2 Cross-Linking with Aldehydes 126 5.2.3 Cross-Linking with Divinylsulfone 126 5.2.4 Cross-Linking by the Ions of Polyvalent Metals 127 5.2.5 Cross-Linking with Epoxides 127 5.2.6 Photo-Cross-Linking 128 5.2.7 Solid-State Cross-Linking under High Pressure and Shear Deformation (Solid-State Reactive Blending: SSRB) 130 5.3 Radiochemical Transformations (Radiolysis) of Hyaluronan Aqueous Solutions 134 References 137 6 Medical Applications of Hyaluronan 143 6.1 Hyaluronan and Aesthetic Medicine 143 6.1.1 Intradermal Hyaluronan-Based Microimplants 143 6.1.2 Cross-Linking of Hyaluronan into a Three-Dimensional Network 144 6.1.3 Hyaluronic Acid in Injection Cosmetology (Biorevitalization) 150 6.1.4 Molecular Weight of Hyaluronan in Biorevitalization Products 151 6.1.5 Antioxidant Efficiency of Hyaluronan and other Biologically Active Compounds as Potential Products for Aesthetic Medicine 154 6.1.6 Bio-Repairants as a New Class of Injectable Products Based on Hyaluronic Acid Modified with Low Molecular Weight Bio-Regulators 161 6.2 Hyaluronan in Arthrology 170 6.3 Hyaluronan in Ophthalmology 176 6.4 Hyaluronan in Oncology 176 6.5 The Role of Hyaluronan in Healing Wounds 183 6.6 Hyaluronan in Immunology 186 References 186 Conclusion 193 Index 195

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Book SynopsisMineral elements are found in foods and drink of all different types, from drinking water through to mothers milk. The search for mineral elements has shown that many trace and ultratrace-level elements presented in food are required for a healthy life.Table of ContentsList of Contributors Preface Chapter 1 The importance of minerals in the human diet Chapter 2 Dietary Intake of minerals Chapter 3 Bioavailability of minerals in foods Chapter 4 Human risk Chapter 5 The oligoelements Chapter 6 The toxic elements Chapter 7 Geographical variation of land mineral composition Chapter 8 Variation of food mineral content during industrial and culinary processing Chapter 9 Speciation Chapter 10 Atomic Absorption Spectrometry Chapter 11 Elemental composition analysis of food by FAES and ICP-OES Chapter 12 ICP-MS Chapter 13 Application of electrochemical techniques Chapter 14 X-ray Chapter 15 Vibrational spectroscopy Chapter 16 Ion chromatography Chapter 17 Neutron Activation Analysis Chapter 18 Speciation Chapter 19 Drinking water Chapter 20 Elemental composition in grapes and wine role Chapter 21 Vegetables and fruits Chapter 22 Cereals and pulses Chapter 23 Bread and bakery products Chapter 24 Edible fats and oils Chapter 25 Elemental Composition of Sugar and Honey Chapter 26 Meat Chapter 27 Fish and seafood Chapter 28 Milk and dairy products Chapter 29 Mineral content of eggs Chapter 30 Mineral content of seasonings, salt and vinegar Chapter 31 Other foods of plant origin Chapter 32 Baby foods Chapter 33 Human milk Index

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Book SynopsisCombining the important research topic of multiple bond-forming transformations with green chemistry, this book helps chemists identify recent sustainable stereoselective synthetic sequences. Combines the important research topic of multiple bond-forming transformations with green chemistry and sustainable development Offers a valuable resource for preparing compounds with multiple stereogenic centers, an important field for synthetic chemists Organizes chapters by molecular structure of final products, making for a handbook-style resource Discusses applications of the synthesis of natural products and of drug intermediates Brings together otherwise-scattered information about a number of key, efficient chemical reactionsTable of ContentsList of Contributors xiii Foreword xvii Preface xix 1 Definitions and Classifications of MBFTs 1Damien Bonne and Jean Rodriguez 1.1 Introduction 1 1.2 Definitions 4 1.3 Conclusion and Outlook 6 References 7 PART I STEREOSELECTIVE SYNTHESIS OF HETEROCYCLES 9 2 Five-Membered Heterocycles 11Hanmin Huang and Pan Xie 2.1 Introduction 11 2.2 Monocyclic Targets 12 2.2.1 1,3-Dipolar Cycloaddition 12 2.2.2 Michael Addition-Initiated Domino Process 20 2.2.3 Multicomponent Reactions 23 2.2.4 Carbohalogenation Reactions 26 2.2.5 Radical Processes 26 2.3 Fused Polycyclic Targets 28 2.3.1 Cycloaddition Reactions 28 2.3.2 Domino Cyclization Reactions 32 2.4 Bridged Polycyclic Targets 34 2.5 Conclusion and Outlook 36 References 37 3 Six-Membered Heterocycles 45Giammarco Tenti, M. Teresa Ramos, and J. Carlos Menéndez 3.1 Introduction 45 3.2 Monocyclic Targets 47 3.2.1 Nitrogen-Only Heterocycles 47 3.2.2 Oxygen-Containing Heterocycles 58 3.3 Fused Polycyclic Targets 62 3.3.1 Nitrogen-Only Fused Polycyclic Targets 62 3.3.2 Oxygen-Containing Fused Polycyclic Targets 70 3.3.3 Sulfur-Containing Fused Polycyclic Targets 74 3.4 Bridged Polycyclic Targets 74 3.4.1 General Procedure for the Preparation of 2,6-DABCO-Derived Compounds 138 76 3.5 Polycyclic Spiro Targets 77 3.6 Summary and Outlook 79 References 79 4 Other Heterocycles 87Qian Wang and Jieping Zhu 4.1 Introduction 87 4.2 Synthesis of Medium-Sized Monocyclic, Fused and Bridged Polycyclic Heterocycles 88 4.2.1 Ring Synthesis by Ring Transformation via Rearrangements/Ring Expansions 88 4.2.2 Ring Synthesis by Annulation 99 4.3 Summary and Outlook 109 References 109 PART II STEREOSELECTIVE SYNTHESIS OF CARBOCYCLES 115 5 Three- and Four-Membered Carbocycles 117Renata Marcia de Figueiredo, Gilles Niel, and Jean-Marc Campagne 5.1 Introduction 117 5.2 Cyclopropane Derivatives 118 5.2.1 Organocatalysis and Related Reactions [Michael-Initiated Ring-Closure (MIRC) Reactions] 118 5.2.2 Organometallics and Metal Catalysis 123 5.2.3 Lewis Acid-Promoted Sequences 133 5.2.4 Pericyclic Domino Strategies 134 5.2.5 Radical Domino Strategies 135 5.3 Cyclobutane Derivatives 136 5.3.1 Organocatalyzed Cyclobutanations 136 5.3.2 Organometallics and Metal Catalysis 137 5.3.3 Acid- or Base-Promoted Transformations 143 5.3.4 Multicomponent Reactions (MCRs) 145 5.4 Summary and Outlook 146 References 146 6 Five-Membered Carbocycles 157Vijay Nair and Rony Rajan Paul 6.1 Introduction 157 6.2 Monocyclic Targets 158 6.2.1 Metal-Catalyzed Reactions 158 6.2.2 Organocatalytic Reactions 158 6.2.3 Miscellaneous Reactions 167 6.3 Fused Polycyclic Targets 169 6.3.1 Metal-Catalyzed Reactions 169 6.3.2 Organocatalytic Reactions 170 6.3.3 Lewis Acid-Catalyzed Reactions 172 6.3.4 Miscellaneous Reactions 173 6.4 Bridged Polycyclic Targets 176 6.5 Conclusion and Outlook 178 References 179 7 Stereoselective Synthesis of Six-Membered Carbocycles 185Muriel Amatore, Corinne Aubert, Marion Barbazanges, Marine Desage-El Murr, and Cyril Ollivier 7.1 Introduction 185 7.2 Metal-Catalyzed Stereoselective Multiple Bond-Forming Transformations 186 7.2.1 Introduction 186 7.2.2 Cycloadditions 186 7.2.3 Metal-Catalyzed Cascades as Formal [2+2+2] Cycloadditions 191 7.2.4 Metal-Catalyzed Cycloisomerization Cascades 192 7.3 Enantioselective Organocatalyzed Synthesis of Six-Membered Rings 195 7.3.1 Organocatalyzed Miscellaneous Reactions 195 7.3.2 Organocatalyzed Cascade and Multicomponent Reactions 197 7.3.3 Polycyclization Cascade Reactions 201 7.4 Stereoselective Multiple Bond-Forming Radical Transformations 202 7.4.1 Intermolecular Cascade Reactions 202 7.4.2 Intramolecular Cascade Reactions 203 7.5 Conclusions 204 References 205 8 Seven- and Eight-Membered Carbocycles 211Gérard Buono, Hervé Clavier, Laurent Giordano, and Alphonse Tenaglia 8.1 Introduction 211 8.2 Cycloheptenes 212 8.3 Cycloheptadienes 219 8.4 Cycloheptatrienes 221 8.5 Cyclooctenes 222 8.6 Cyclooctadienes 225 8.7 Cyclooctatrienes 229 8.8 Cyclooctatetraenes 234 8.9 Concluding Remarks 235 References 235 PARTIII STEREOSELECTIVE SYNTHESIS OF SPIROCYCLIC COMPOUNDS 241 9 Metal-Assisted Methodologies 243Gaëlle Chouraqui, Laurent Commeiras, and Jean-Luc Parrain 9.1 Introduction 243 9.2 Quaternary Spirocenter 244 9.2.1 Copper-Assisted Methodologies 245 9.2.2 Gold-Assisted Methodologies 247 9.2.3 Palladium-Assisted Methodologies 247 9.2.4 Rhodium-Assisted Methodologies 251 9.2.5 Platinum-Assisted Methodologies 252 9.3 α-Heteroatom-Substituted Spirocenter 252 9.3.1 Zinc-, Magnesium-, and Copper-Assisted Methodologies 253 9.3.2 Titanium-Assisted Methodologies 254 9.3.3 Gold- and Platinum-Assisted Methodologies 255 9.3.4 Palladium-Assisted Methodologies 258 9.3.5 Rhodium-Assisted Methodologies 259 9.4 α,α′-Diheteroatom-Substituted Spirocenter 261 9.5 Conclusion and Outlook 264 References 265 10 Organocatalyzed Methodologies 271Ramon Rios 10.1 Introduction 271 10.2 Enantioselective Synthesis of All-Carbon Spirocenters 275 10.2.1 Organocatalytic Enantioselective Methodologies for the Synthesis of Spirooxindoles 275 10.2.2 Other Spirocycles 292 10.3 Enantioselective Synthesis Spirocenters with at Least One Heteroatom 299 10.3.1 Synthesis of Spirooxindoles 299 10.3.2 Synthesis of Other Spirocycles 301 10.4 Conclusion and Outlook 301 References 302 PARTIV STEREOSELECTIVE SYNTHESIS OF ACYCLIC COMPOUNDS 307 11 Metal-Catalyzed Methodologies 309Gabriela Guillena and Diego J. Ramón 11.1 Introduction 309 11.2 Anion Relay Approach 310 11.3 Mannich Reaction 312 11.3.1 Diastereoselective Approach 312 11.3.2 Enantioselective Approach 312 11.4 Reactions Involving Isonitriles 314 11.4.1 Diastereoselective Passerini Reaction 314 11.4.2 Enantioselective Passerini Reaction 315 11.4.3 Diastereoselective Ugi Reaction 316 11.5 1,2-Addition-Type Processes 317 11.5.1 Diastereoselective Approach 317 11.5.2 Enantioselective Approach 320 11.6 Michael-Type Processes 324 11.6.1 Diastereoselective Approach 324 11.6.2 Enantioselective Approach 327 11.7 Summary and Outlook 331 References 332 12 Organocatalyzed Methodologies 339 Vincent Coeffard, Christine Greck, Xavier Moreau, and Christine Thomassigny 12.1 Introduction 339 12.2 Aminocatalysis 340 12.2.1 Enamine–Enamine Activation 340 12.2.2 Iminium–Enamine Activation 343 12.3 N-Heterocyclic Carbene (NHC) Activation 353 12.4 H-Bonding Activation 357 12.5 Phase-Transfer Catalysis 358 12.6 Summary and Outlook 359 References 359 PART V MULTIPLE BOND-FORMING TRANSFORMATIONS: SYNTHETIC APPLICATIONS 363 13 MBFTs for the Total Synthesis of Natural Products 365Yanxing Jia 13.1 Introduction 365 13.2 Anionic-Initiated MBFTs 366 13.3 Cationic-Initiated MBFTs 371 13.4 Radical-Mediated MBFTs 375 13.5 Pericyclic MBFTs 379 13.6 Transition-Metal-Catalyzed MBFTs 385 13.7 Summary and Outlook 388 References 390 14 Synthesis of Biologically Relevant Molecules 393Matthijs J. van Lint, Eelco Ruijter, and Romano V.A. Orru 14.1 Introduction 393 14.2 Organocatalyzed MBFTs for BRMs 394 14.3 Multicomponent MBFTs for BRMs 404 14.4 Palladium-Catalyzed MBFTs for BRMs 413 14.5 Conclusion and Outlook 418 References 419 15 Industrial Applications of Multiple Bond-Forming Transformations (MBFTs) 423 Tryfon Zarganes-Tzitzikas, Ahmad Yazbak, Alexander Dömling 15.1 Introduction 423 15.2 Applications of MBFTs 424 15.2.1 Xylocaine 424 15.2.2 Almorexant 424 15.2.3 (−)-Oseltamivir (Tamiflu®) 427 15.2.4 Telaprevir (Incivek®) 429 15.2.5 Ezetimibe (Zetia®) 431 15.2.6 Crixivan (Indinavir®) 433 15.2.7 Oxytocine Antagonists: Retosiban and Epelsiban 436 15.2.8 Praziquantel (Biltricide®) 439 15.3 Summary and Outlook 442 References 442 Index 447

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Book SynopsisMembrane reactors combine membrane functions such as separation, reactant distribution, and catalyst support with chemical reactions in a single unit. The benefits of this approach include enhanced conversion, increased yield, and selectivity, as well as a more compact and cost-effect design of reactor system. Hence, membrane reactors are an effective route toward chemical process intensification. This book covers all types of porous membrane reactors, including ceramic, silica, carbon, zeolite, and dense metallic reactors such as Pd or Pd-alloy, oxygen ion-conducting, and proton-conducting ceramics. For each type of membrane reactor, the membrane transport principles, membrane fabrication, configuration and operation of membrane reactors, and their current and potential applications are described comprehensively. A summary of the critical issues and hurdles for each membrane reaction process is also provided, with the aim of encouraging successful commercial applications.Table of ContentsPreface xi 1 Fundamentals of Membrane Reactors 1 1.1 Introduction 1 1.2 Membrane and Membrane Separation 1 1.2.1 Membrane Structure 2 1.2.2 Membrane Separation 4 1.2.3 Membrane Performance 6 1.3 Inorganic Membranes 7 1.3.1 Types of Inorganic Membranes 7 1.3.2 Fabrication of Inorganic Membranes 11 1.3.3 Characterization of Inorganic Membranes 13 1.3.4 Applications of Inorganic Membranes 13 1.4 Inorganic Membrane Reactors 14 1.4.1 Basic Principles of Membrane Reactors 14 1.4.2 Incorporation of Catalyst in Membrane Reactors 17 1.4.3 Configuration of Membrane Reactors 20 1.4.4 Classification of Membrane Reactors 23 References 25 2 Porous Membrane Reactors 27 2.1 Introduction 27 2.2 Gas Permeation in Porous Membranes 28 2.2.1 Types of Porous Membranes 28 2.2.2 Transport Mechanisms 30 2.2.3 Gas Permeation Flux through Porous Membranes 33 2.3 Preparation of Porous Membranes 38 2.3.1 Dip-Coating Method 39 2.3.2 Sol-Gel Method 41 2.3.3 Chemical Vapor Deposition Method 42 2.3.4 Phase Inversion Method 44 2.3.5 O ther Preparation Methods 46 2.4 Porous Membranes for Chemical Reactions 47 2.4.1 Membrane Materials 47 2.4.2 Membrane Functions 49 2.5 Catalysis in Porous Membrane Reactors 50 2.5.1 Catalyst in Membrane Reactors 50 2.5.2 Catalyst Deposition in Porous Membranes 52 2.6 O peration of Porous Membrane Reactors 53 2.6.1 Packed Bed Membrane Reactors 53 2.6.2 Catalytic Membrane Reactors 55 2.6.3 Coupling of Membrane Functions 57 2.6.4 Non-uniform Distribution of Membrane Permeability 57 2.7 Applications of Porous Membrane Reactors 59 2.7.1 Dehydrogenation Reactions 59 2.7.2 Reforming Reactions for Hydrogen Production 60 2.7.3 Partial Oxidation Reactions 62 2.7.4 Gas–Liquid–Solid Multiphase Reactions 65 2.7.5 O ther Reactions 66 2.8 Prospects and Challenges 67 Notation 68 References 70 3 Zeolite Membrane Reactors 75 3.1 Introduction 75 3.2 Permeation in Zeolite Membranes 76 3.2.1 Types of Zeolite Membranes 76 3.2.2 Transport Mechanisms 76 3.2.3 Permeation Flux in Zeolite Membranes 78 3.3 Preparation of Zeolite Membranes 80 3.3.1 In-Situ Crystallization Method 80 3.3.2 Secondary Growth Method 82 3.3.3 Vapor-Phase Transport Method 84 3.3.4 Microwave Synthesis Method 85 3.4 Configuration of Zeolite Membrane Reactors 86 3.4.1 Packed Bed Membrane Reactor 87 3.4.2 Catalytic Membrane Reactor 87 3.4.3 Pervaporation Membrane Reactor 88 3.4.4 Membrane Microreactor 89 3.5 Applications of Zeolite Membrane Reactors 90 3.5.1 Dehydrogenation Reactions 90 3.5.2 Dehydration Reactions 90 3.5.3 Oxidative Reactions 93 3.5.4 Isomerization Reactions 94 3.6 Prospects and Challenges 94 Notation 96 References 97 4 Dense Metallic Membrane Reactors 101 4.1 Introduction 101 4.2 Gas Permeation in Dense Metallic Membranes 102 4.2.1 Types of Dense Metallic Membranes 102 4.2.2 Hydrogen Permeation Mechanism in Pd-Based Membranes 103 4.2.3 Effect of Substrate on H2 Permeation 108 4.3 Preparation of Dense Metallic Membranes 110 4.3.1 Cold-Rolling and Diffusion Welding Method 110 4.3.2 Electroless Plating Method 111 4.3.3 Electroplating Method 113 4.3.4 Chemical Vapor Deposition Method 114 4.3.5 High-Velocity Oxy-Fuel Spraying Method 115 4.3.6 Magnetron Sputtering Method 115 4.3.7 Summary 115 4.4 Configurations of Metallic Membrane Reactors 117 4.4.1 Packed Bed Membrane Reactor 117 4.4.2 Membrane Microreactor 122 4.5 Applications of Dense Metallic Membrane Reactors 123 4.5.1 Dehydrogenation Reactions 123 4.5.2 Reforming Reactions for H2 Production 126 4.5.3 Direct Hydroxylation of Aromatic Compounds 133 4.5.4 Direct Synthesis of Hydrogen Peroxide 134 4.6 Challenges and Prospects 135 Notation 136 References 137 5 Dense Ceramic Oxygen-Permeable Membrane Reactors 143 5.1 Introduction 143 5.2 Oxygen Permeation in Dense Ceramic Membranes 146 5.2.1 Membrane Materials 146 5.2.2 O xygen Permeation Flux in MIEC Membranes 148 5.3 Preparation of Dense Ceramic Membranes 154 5.3.1 Isostatic Pressing 154 5.3.2 Extrusion 154 5.3.3 Phase Inversion 155 5.3.4 Slurry Coating 156 5.3.5 Tape Casting 156 5.4 Dense Ceramic Membrane Reactors 157 5.4.1 Principles of Dense Ceramic Membrane Reactors 157 5.4.2 Configurations of Dense Ceramic Membrane Reactors 159 5.5 Applications of Dense Ceramic Oxygen Permeable Membrane Reactors 160 5.5.1 Partial Oxidation of Methane to Syngas 161 5.5.2 Oxidative Coupling of Methane 165 5.5.3 Oxidative Dehydrogenation of Alkanes (Ethane and Propane) 169 5.5.4 Decomposition of H2O, NO x, and CO2 170 5.6 Prospects and Challenges 176 Notation 178 References 179 6 Proton-Conducting Ceramic Membrane Reactors 187 6.1 Introduction 187 6.2 Proton/Hydrogen Permeation in Proton-Conducting Ceramic Membranes 187 6.2.1 Proton-Conducting Ceramics 187 6.2.2 Hydrogen/Proton Permeation in Mixed Conducting Membranes 189 6.3 Preparation of Proton-Conducting Ceramic Membranes 193 6.3.1 Suspension Coating 193 6.4 Configuration of Proton-Conducting Membrane Reactors 195 6.5 Applications of Proton-Conducting Ceramic Membrane Reactors 198 6.5.1 Dehydrogenation Coupling of Methane 199 6.5.2 Dehydrogenation of Alkanes into Alkenes 201 6.5.3 WGS Reaction and Water Electrolysis for Hydrogen Production 203 6.5.4 Decomposition of NOx 205 6.5.5 Synthesis of Ammonia 206 6.5.6 Challenges and Future Work 208 Notation 210 References 210 7 Fluidized Bed Membrane Reactors 215 7.1 Introduction 215 7.2 Configurations and Construction of FBMRs 216 7.3 Applications 222 7.3.1 Methane Steam Reforming and Dehydrogenation Reactions 222 7.3.2 Partial Oxidation Reactions 224 7.4 Prospects and Challenges 224 References 225 8 Membrane Microreactors 227 8.1 Introduction 227 8.2 Configurations and Fabrication of Membrane Microreactors 228 8.2.1 Plate-Type Membrane Microreactors 228 8.2.2 Tubular Membrane Microreactors 233 8.3 Applications of Membrane Microreactors 238 8.3.1 Pd-MMRs for Hydrogenation/Dehydrogenation Reactions 238 8.3.2 Zeolite-MMRs for Knoevenagel Condensation and Selective Oxidation Reactions 241 8.3.3 Catalytic MMRs for G–L–S Reactions 243 8.4 Fluid Flow in Membrane Microreactors 244 8.5 Prospects and Challenges 246 References 247 9 Design of Membrane Reactors 251 9.1 Introduction 251 9.2 Design Equations for Membrane Reactors 251 9.2.1 Packed Bed Membrane Reactors 252 9.3 Flow-Through Catalytic Membrane Reactors 259 9.3.1 Fluidized Bed Membrane Reactors 261 9.4 Modeling Applications 264 9.4.1 Oxidative Dehydrogenation of n-Butane in a Porous Membrane Reactor 264 9.4.2 Coupled Dehydrogenation and Hydrogenation Reactions in a Pd/Ag Membrane Reactor 265 9.4.3 POM in a Dense Ceramic Oxygen-Permeable Membrane Reactor 268 9.5 Concluding Remarks 274 Notation 275 References 277 Index 279

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Book SynopsisThe f-elements and their compounds often possess an unusually complex electronic structure, governed by the high number of electronic states arising from open f-shells as well as large relativistic and electron correlation effects. A correct theoretical description of these elements poses the highest challenges to theory.Table of ContentsContributors xiii Preface xvii 1 Relativistic Configuration Interaction Calculations for Lanthanide and Actinide Anions 1 Donald R. Beck, Steven M. O’Malley and Lin Pan 1.1 Introduction 1 1.2 Bound Rare Earth Anion States 2 1.3 Lanthanide and Actinide Anion Survey 3 1.3.1 Prior Results and Motivation for the Survey 3 1.3.2 Techniques for Basis Set Construction and Analysis 6 1.3.3 Discussion of Results 9 1.4 Resonance and Photodetachment Cross Section of Anions 12 1.4.1 The Configuration Interaction in the Continuum Formalism 13 1.4.2 Calculation of the Final State Wavefunctions 15 2 Study of Actinides by Relativistic Coupled Cluster Methods 23 Ephraim Eliav and Uzi Kaldor 2.1 Introduction 23 2.2 Methodology 25 2.2.1 The Relativistic Hamiltonian 25 2.2.2 Fock-Space Coupled Cluster Approach 25 2.2.3 The Intermediate Hamiltonian CC method 27 2.3 Applications to Actinides 30 2.3.1 Actinium and Its Homologues: Interplay of Relativity and Correlation 31 2.3.2 Thorium and Eka-thorium: Different Level Structure 35 2.3.3 Rn-like actinide ions 39 2.3.4 Electronic Spectrum of Superheavy Elements Nobelium (Z=102) and Lawrencium (Z=103) 42 2.3.5 The Levels of U4+ and U5+: Dynamic Correlation and Breit Interaction 45 2.3.6 Relativistic Coupled Cluster Approach to Actinide Molecules 48 2.4 Summary and Conclusion 49 3 Relativistic All-Electron Approaches to the Study of f Element Chemistry 55 Trond Saue and Lucas Visscher 3.1 Introduction 55 3.2 Relativistic Hamiltonians 59 3.2.1 General Aspects 59 3.2.2 Four-Component Hamiltonians 61 3.2.3 Two-Component Hamiltonians 65 3.2.4 Numerical Example 69 3.3 Choice of Basis Sets 71 3.4 Electronic Structure Methods 73 3.4.1 Coupled Cluster Approaches 75 3.4.2 Multi-Reference Perturbation Theory 80 3.4.3 (Time-Dependent) Density Functional Theory 82 3.5 Conclusions and Outlook 83 4 Low-Lying Excited States of Lanthanide Diatomics Studied by Four-Component Relativistic Configuration Interaction Methods 89 Hiroshi Tatewaki, Shigeyoshi Yamamoto and Hiroko Moriyama 4.1 Introduction 89 4.2 Method of Calculation 90 4.2.1 Quaternion Symmetry 90 4.2.2 Basis Set and HFR/DC Method 91 4.2.3 GOSCI and RASCI Methods 91 4.3 Ground State 92 4.3.1 CeO Ground State 92 4.3.2 CeF Ground State 97 4.3.3 Discussion of Bonding in CeO and CeF 101 4.3.4 GdF Ground State 102 4.3.5 Summary of the Chemical Bonds, of CeO, CeF, GdF 104 4.4 Excited States 106 4.4.1 CeO Excited States 106 4.4.2 CeF Excited States 108 4.4.3 GdF Excited States 108 4.5 Conclusion 116 5 The Complete-Active-Space Self-Consistent-Field Approach and Its Application to Molecular Complexes of the f-Elements 121 Andrew Kerridge 5.1 Introduction 121 5.1.1 Treatment of Relativistic Effects 123 5.1.2 Basis Sets 123 5.2 Identifying and Incorporating Electron Correlation 124 5.2.1 The Hartree Product Wavefunction 124 5.2.2 Slater Determinants and Fermi Correlation 124 5.2.3 Coulomb Correlation 126 5.3 Configuration Interaction and the Multiconfigurational Wavefunction 127 5.3.1 The Configuration Interaction Approach 127 5.3.2 CI and the Dissociation of H2 128 5.3.3 Static Correlation and Crystal Field Splitting 130 5.3.4 Size Inconsistency and Coupled Cluster Theory 131 5.3.5 Computational Expense of CI and the Need for Truncation 132 5.4 CASSCF and Related Approaches 133 5.4.1 The Natural Orbitals 133 5.4.2 Optimisation of the CASSCF Wavefunction 133 5.4.3 Variants and Generalisations of CASSCF 137 5.5 Selection of Active Spaces 138 5.5.1 Chemical Intuition and Björn’s Rules 138 5.5.2 Natural Orbital Occupations 139 5.5.3 RAS Probing 139 5.6 Dynamical Correlation 139 5.6.1 Multireference Configuration Interaction 140 5.6.2 Multireference Second Order Perturbation Theory 140 5.7 Applications 141 5.7.1 Bonding in Actinide Dimers 141 5.7.2 Covalent Interactions in the U-O Bond of Uranyl 142 5.7.3 Covalency and Oxidation State in f-Element Metallocenes 143 5.8 Concluding Remarks 144 6 Relativistic Pseudopotentials and Their Applications 147 Xiaoyan Cao and Anna Weigand 6.1 Introduction 147 6.2 Valence-only Model Hamiltonian 149 6.2.1 Pseudopotentials 150 6.2.2 Approximations 151 6.2.3 Choice of the Core 153 6.3 Pseudopotential Adjustment 155 6.3.1 Energy-Consistent Pseudopotentials 155 6.3.2 Shape-Consistent Pseudopotentials 158 6.4 Valence Basis Sets for Pseudopotentials 161 6.5 Selected Applications 162 6.5.1 DFT Calculated M–X (M = Ln, An; X = O, S, I) Bond Lengths 163 6.5.2 Lanthanide(III) and Actinide(III) Hydration 166 6.5.3 Lanthanide(III) and Actinide(III) Separation 170 6.6 Conclusions and Outlook 172 7 Error-Balanced Segmented Contracted Gaussian Basis Sets: A Concept and Its Extension to the Lanthanides 181 Florian Weigend 7.1 Introduction 181 7.2 Core and Valence Shells: General and Segmented Contraction Scheme 182 7.3 Polarization Functions and Error Balancing 185 7.4 Considerations for Lanthanides 187 8 Gaussian Basis Sets for Lanthanide and Actinide Elements: Strategies for Their Development and Use 195 Kirk A. Peterson and Kenneth G. Dyall 8.1 Introduction 195 8.2 Basis Set Design 196 8.2.1 General Considerations 196 8.2.2 Basis Sets for the f Block 197 8.3 Overview of Existing Basis Sets for Lanthanides and Actinide Elements 204 8.3.1 All-Electron Treatments 204 8.3.2 Effective Core Potential Treatments 205 8.4 Systematically Convergent Basis Sets for the f Block 206 8.4.1 All-Electron 207 8.4.2 Pseudopotential-Based 208 8.5 Basis Set Convergence in Molecular Calculations 210 8.6 Conclusions 213 9 4f, 5d, 6s, and Impurity-Trapped Exciton States of Lanthanides in Solids 217 Zoila Barandiarán and Luis Seijo 9.1 Introduction 217 9.2 Methods 220 9.2.1 Embedded-Cluster Methods 221 9.2.2 Combined Use of Periodic Boundary Condition Methods and Embedded Cluster Methods 227 9.2.3 Absorption and Emission Spectra 227 9.3 Applications 228 9.3.1 Bond Lengths 228 9.3.2 Energy Gaps 231 9.3.3 Impurity-Trapped Excitons 232 9.3.4 Solid-State-Lighting Phosphors 234 10 Judd-Ofelt Theory — The Golden (and the Only One) Theoretical Tool of f-Electron Spectroscopy 241 Lidia Smentek 10.1 Introduction 241 10.2 Non-relativistic Approach 245 10.2.1 Standard Judd-Ofelt Theory and Its Original Formulation of 1962 248 10.2.2 Challenges of ab initio Calculations 251 10.2.3 Problems with the Interpretation of the f -Spectra 255 10.3 Third-Order Contributions 257 10.3.1 Third-Order Electron Correlation Effective Operators 259 10.4 Relativistic Approach 260 10.5 Parameterizations of the f -Spectra 262 11 Applied Computational Actinide Chemistry 269 André Severo Pereira Gomes, Florent Réal, Bernd Schimmelpfennig, Ulf Wahlgren and Valérie Vallet 11.1 Introduction 269 11.1.1 Relativistic Correlated Methods for Ground and Excited States 270 11.1.2 Spin-Orbit Effects on Heavy Elements 272 11.2 Valence Spectroscopy and Excited States 273 11.2.1 Accuracy of Electron Correlation Methods for Actinide Excited States: WFT and DFT Methods 273 11.2.2 Valence Spectra of Larger Molecular Systems 275 11.2.3 Effects of the Condensed-Phase Environment 276 11.2.4 Current Challenges for Electronic Structure Calculations of Heavy Elements 278 11.3 Core Spectroscopies 278 11.3.1 X-ray Photoelectron Spectroscopy (XPS) 279 11.3.2 X-ray Absorption Spectroscopies 280 11.4 Complex Formation and Ligand-Exchange Reactions 283 11.5 Calculations of Standard Reduction Potential and Studies of Redox Chemical Processes 286 11.6 General Conclusions 288 12 Computational Tools for Predictive Modeling of Properties in Complex Actinide Systems 299 Jochen Autschbach, Niranjan Govind, Raymond Atta-Fynn, Eric J. Bylaska, John W. Weare and Wibe A. de Jong 12.1 Introduction 299 12.2 ZORA Hamiltonian and Magnetic Property Calculations 300 12.2.1 ZORA Hamiltonian 300 12.2.2 Magnetic properties 303 12.3 X2C Hamiltonian and Molecular Properties from X2C Calculations 312 12.4 Role of Dynamics on Thermodynamic Properties 319 12.4.1 Sampling Free Energy Space with Metadynamics 319 12.4.2 Hydrolysis constants for U(IV), U(V), and U(VI) 320 12.4.3 Effects of Counter Ions on the Coordination of Cm(III) in Aqueous Solution 322 12.5 Modeling of XAS (EXAFS, XANES) Properties 325 12.5.1 EXAFS of U(IV) and U(V) Species 327 12.5.2 XANES Spectra of Actinide Complexes 330 13 Theoretical Treatment of the Redox Chemistry of Low Valent Lanthanide and Actinide Complexes 343 Christos E. Kefalidis, Ludovic Castro, Ahmed Yahia, Lionel Perrin and Laurent Maron 13.1 Introduction 343 13.2 Divalent Lanthanides 349 13.2.1 Computing the Nature of the Ground State 349 13.2.2 Single Electron Transfer Energy Determination in Divalent Lanthanide Chemistry 352 13.3 Low-Valent Actinides 356 13.3.1 Actinide(III) Reactivity 356 13.3.2 Other Oxidation State (Uranyl…) 361 13.4 Conclusions 365 14 Computational Studies of Bonding and Reactivity in Actinide Molecular Complexes 375 Enrique R. Batista, Richard L. Martin and Ping Yang 14.1 Introduction 375 14.2 Basic Considerations 376 14.2.1 Bond Energies 376 14.2.2 Effect of Scalar Relativistic Corrections 377 14.2.3 Spin-Orbit Corrections 378 14.2.4 Relativistic Effective Core Potentials (RECP) 379 14.2.5 Basis Sets 380 14.2.6 Density Functional Approximations for Use with f-Element Complexes 381 14.2.7 Example of application: Performance in Sample Situation (UF6→UF5 +F) [39, 40] 382 14.2.8 Molecular Systems with Unpaired Electrons 384 14.3 Nature of Bonding Interactions 385 14.4 Chemistry Application: Reactivity 387 14.4.1 First Example: Study of C–H Bond Activation Reaction 387 14.4.2 Study of Imido-Exchange Reaction Mechanism 395 14.5 Final Remarks 397 15 The 32-Electron Principle: A New Magic Number 401 Pekka Pyykkö, Carine Clavaguéra and Jean-Pierre Dognon 15.1 Introduction 401 15.1.1 Mononuclear, MLn systems 401 15.1.2 Metal Clusters as ‘Superatoms’ 402 15.1.3 The Present Review: An@Ln-Type Systems 404 15.2 Cases So Far Studied 404 15.2.1 The Early Years: Pb2−12 and Sn2−12 Clusters 404 15.2.2 The Validation: An@C28 (An = Th, Pa+, U2+, Pu4+) Series 410 15.2.3 The Confirmation: [U@Si20]6−-like Isoelectronic Series 413 15.3 Influence of Relativity 418 15.4 A Survey of the Current Literature on Lanthanideand Actinide-Centered Clusters 420 15.5 Concluding Remarks 421 16 Shell Structure, Relativistic and Electron Correlation Effects in f Elements and Their Importance for Cerium(III)-based Molecular Kondo Systems 425 Michael Dolg 16.1 Introduction 425 16.2 Shell Structure, Relativistic and Electron Correlation Effects 429 16.2.1 Shell Structure 430 16.2.2 Relativistic Effects 433 16.2.3 Electron Correlation Effects 437 16.3 Molecular Kondo-type Systems 439 16.3.1 Bis(η8-cyclooctatetraenyl)cerium 440 16.3.2 Bis(η8-pentalene)cerium 443 16.4 Conclusions 446 Index 451 Color plates appear between pages 342 and 343

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Book SynopsisMartin Fleischmann was truly one of the fathers' of modern electrochemistry having made major contributions to diverse topics within electrochemical science and technology. These include the theory and practice of voltammetry and in situ spectroscopic techniques, instrumentation, electrochemical phase formation, corrosion, electrochemical engineering, electrosynthesis and cold fusion. While intended to honour the memory of Martin Fleischmann, Developments in Electrochemistry is neither a biography nor a history of his contributions. Rather,the bookis a series of critical reviews of topics in electrochemical science associated with Martin Fleischmann but remaining important today.The authors are all scientists with outstanding international reputations who have made their own contribution to their topic; most have also worked with Martin Fleischmann and benefitted from his guidance. Each of the 19 chapters within this volume begin with an outline of MartinTrade Review“The high quality chapters presented in this volume contribute greatly to achieving the editors’ goal.” (Chromatographia, 1 May 2015)Table of ContentsList of Contributors xiii 1 Martin Fleischmann – The Scientist and the Person 1 2 A Critical Review of the Methods Available for Quantitative Evaluation of Electrode Kinetics at Stationary Macrodisk Electrodes 21 Alan M. Bond, Elena A. Mashkina and Alexandr N. Simonov 2.1 DC Cyclic Voltammetry 23 2.1.1 Principles 23 2.1.2 Processing DC Cyclic Voltammetric Data 26 2.1.3 Semiintegration 29 2.2 AC Voltammetry 32 2.2.1 Advanced Methods of Theory–Experiment Comparison 35 2.3 Experimental Studies 36 2.3.1 Reduction of [Ru(NH3)6]3+ in an Aqueous Medium 36 2.3.2 Oxidation of FeII(C5H5)2 in an Aprotic Solvent 40 2.3.3 Reduction of [Fe(CN)6]3− in an Aqueous Electrolyte 42 2.4 Conclusions and Outlook 43 References 45 3 Electrocrystallization: Modeling and Its Application 49 Morteza Y. Abyaneh 3.1 Modeling Electrocrystallization Processes 53 3.2 Applications of Models 56 3.2.1 The Deposition of Lead Dioxide 58 3.2.2 The Electrocrystallization of Cobalt 60 3.3 Summary and Conclusions 61 References 63 4 Nucleation and Growth of New Phases on Electrode Surfaces 65 Benjamin R. Scharifker and Jorge Mostany 4.1 An Overview of Martin Fleischmann’s Contributions to Electrochemical Nucleation Studies 66 4.2 Electrochemical Nucleation with Diffusion-Controlled Growth 67 4.3 Mathematical Modeling of Nucleation and Growth Processes 68 4.4 The Nature of Active Sites 69 4.5 Induction Times and the Onset of Electrochemical Phase Formation Processes 71 4.6 Conclusion 72 References 72 5 Organic Electrosynthesis 77 Derek Pletcher 5.1 Indirect Electrolysis 79 5.2 Intermediates for Families of Reactions 80 5.3 Selective Fluorination 84 5.4 Two-Phase Electrolysis 85 5.5 Electrode Materials 87 5.6 Towards Pharmaceutical Products 88 5.7 Future Prospects 90 References 91 6 Electrochemical Engineering and Cell Design 95 Frank C. Walsh and Derek Pletcher 6.1 Principles of Electrochemical Reactor Design 96 6.1.1 Cell Potential 96 6.1.2 The Rate of Chemical Change 97 6.2 Decisions During the Process of Cell Design 98 6.2.1 Strategic Decisions 98 6.2.2 Divided and Undivided Cells 98 6.2.3 Monopolar and Bipolar Electrical Connections to Electrodes 99 6.2.4 Scaling the Cell Current 100 6.2.5 Porous 3D Electrode Structures 100 6.2.6 Interelectrode Gap 101 6.3 The Influence of Electrochemical Engineering on the Chlor-Alkali Industry 102 6.4 Parallel Plate Cells 105 6.5 Redox Flow Batteries 106 6.6 Rotating Cylinder Electrode Cells 107 6.7 Conclusions 108 References 109 7 Electrochemical Surface-Enhanced Raman Spectroscopy (EC-SERS): Early History, Principles, Methods, and Experiments 113 Zhong-Qun Tian and Xue-Min Zhang 7.1 Early History of Electrochemical Surface-Enhanced Raman Spectroscopy 116 7.2 Principles and Methods of SERS 117 7.2.1 Electromagnetic Enhancement of SERS 118 7.2.2 Key Factors Influencing SERS 119 7.2.3 “Borrowing SERS Activity” Methods 121 7.2.4 Shell-Isolated Nanoparticle-Enhanced Raman Spectroscopy 123 7.3 Features of EC-SERS 124 7.3.1 Electrochemical Double Layer of EC-SERS Systems 124 7.3.2 Electrolyte Solutions and Solvent Dependency 125 7.4 EC-SERS Experiments 125 7.4.1 Measurement Procedures for EC-SERS 125 7.4.2 Experimental Set-Up for EC-SERS 127 7.4.3 Preparation of SERS Substrates 128 Acknowledgments 131 References 131 8 Applications of Electrochemical Surface-Enhanced Raman Spectroscopy (EC-SERS) 137 Marco Musiani, Jun-Yang Liu and Zhong-Qun Tian 8.1 Pyridine Adsorption on Different Metal Surfaces 138 8.2 Interfacial Water on Different Metals 141 8.3 Coadsorption of Thiourea with Inorganic Anions 143 8.4 Electroplating Additives 146 8.5 Inhibition of Copper Corrosion 147 8.6 Extension of SERS to the Corrosion of Fe and Its Alloys: Passivity 149 8.6.1 Fe-on-Ag 150 8.6.2 Ag-on-Fe 150 8.7 SERS of Corrosion Inhibitors on Bare Transition Metal Electrodes 150 8.8 Lithium Batteries 152 8.9 Intermediates of Electrocatalysis 154 Acknowledgments 156 References 156 9 In-Situ Scanning Probe Microscopies: Imaging and Beyond 163 Bing-Wei Mao 9.1 Principle of In-Situ STM and In-Situ AFM 164 9.1.1 Principle of In-Situ STM 164 9.1.2 Principle of In-Situ AFM 166 9.2 In-Situ STM Characterization of Surface Electrochemical Processes 167 9.2.1 In-Situ STM Study of Electrode–Aqueous Solution Interfaces 167 9.2.2 In-Situ STM Study of Electrode–Ionic Liquid Interface 167 9.3 In-Situ AFM Probing of Electric Double Layer 170 9.4 Electrochemical STM Break-Junction for Surface Nanostructuring and Nanoelectronics and Molecular Electronics 173 9.5 Outlook 176 References 177 10 In-Situ Infrared Spectroelectrochemical Studies of the Hydrogen Evolution Reaction 183 Richard J. Nichols 10.1 The H+/H2 Couple 183 10.2 Single-Crystal Surfaces 184 10.3 Subtractively Normalized Interfacial Fourier Transform Infrared Spectroscopy 186 10.4 Surface-Enhanced Raman Spectroscopy 189 10.5 Surface-Enhanced IR Absorption Spectroscopy 190 10.6 In-Situ Sum Frequency Generation Spectroscopy 193 10.7 Spectroscopy at Single-Crystal Surfaces 194 10.8 Overall Conclusions 197 References 198 11 Electrochemical Noise: A Powerful General Tool 201 Claude Gabrielli and David E. Williams 11.1 Instrumentation 202 11.2 Applications 204 11.2.1 Elementary Phenomena 204 11.2.2 Bioelectrochemistry 205 11.2.3 Electrocrystallization 207 11.2.4 Corrosion 209 11.2.5 Other Systems 215 11.3 Conclusions 217 References 217 12 From Microelectrodes to Scanning Electrochemical Microscopy 223 Salvatore Daniele and Guy Denuault 12.1 The Contribution of Microelectrodes to Electroanalytical Chemistry 224 12.1.1 Advantages of Microelectrodes in Electroanalysis 224 12.1.2 Microelectrodes and Electrode Materials 226 12.1.3 New Applications of Microelectrodes in Electroanalysis 227 12.2 Scanning Electrochemical Microscopy (SECM) 230 12.2.1 A Brief History of SECM 230 12.2.2 SECM with Other Techniques 231 12.2.3 Tip Geometries and the Need for Numerical Modeling 233 12.2.4 Applications of SECM 234 12.3 Conclusions 235 References 235 13 Cold Fusion After A Quarter-Century: The Pd/D System 245 Melvin H. Miles and Michael C.H. McKubre 13.1 The Reproducibility Issue 247 13.2 Palladium–Deuterium Loading 247 13.3 Electrochemical Calorimetry 249 13.4 Isoperibolic Calorimetric Equations and Modeling 250 13.5 Calorimetric Approximations 251 13.6 Numerical Integration of Calorimetric Data 252 13.7 Examples of Fleischmann’s Calorimetric Applications 254 13.8 Reported Reaction Products for the Pd/D System 256 13.8.1 Helium-4 256 13.8.2 Tritium 256 13.8.3 Neutrons, X-Rays, and Transmutations 257 13.9 Present Status of Cold Fusion 257 Acknowledgments 258 References 258 14 In-Situ X-Ray Diffraction of Electrode Surface Structure 261 Andrea E. Russell, Stephen W.T. Price and Stephen J. Thompson 14.1 Early Work 262 14.2 Synchrotron-Based In-Situ XRD 264 14.3 Studies Inspired by Martin Fleischmann’s Work 266 14.3.1 Structure of Water at the Interface 266 14.3.2 Adsorption of Ions 268 14.3.3 Oxide/Hydroxide Formation 268 14.3.4 Underpotential Deposition (upd) of Monolayers 270 14.3.5 Reconstructions of Single-Crystal Surfaces 275 14.3.6 High-Surface-Area Electrode Structures 275 14.4 Conclusions 277 References 277 15 Tribocorrosion 281 Robert J.K. Wood 15.1 Introduction and Definitions 281 15.1.1 Tribocorrosion 282 15.1.2 Erosion 282 15.2 Particle–Surface Interactions 283 15.3 Depassivation and Repassivation Kinetics 283 15.3.1 Depassivation 284 15.3.2 Repassivation Rate 286 15.4 Models and Mapping 287 15.5 Electrochemical Monitoring of Erosion–Corrosion 290 15.6 Tribocorrosion within the Body: Metal-on-Metal Hip Joints 291 15.7 Conclusions 293 Acknowledgments 293 References 293 16 Hard Science at Soft Interfaces 295 Hubert H. Girault 16.1 Charge Transfer Reactions at Soft Interfaces 295 16.1.1 Ion Transfer Reactions 296 16.1.2 Assisted Ion Transfer Reactions 298 16.1.3 Electron Transfer Reactions 299 16.2 Electrocatalysis at Soft Interfaces 300 16.2.1 Oxygen Reduction Reaction (ORR) 301 16.2.2 Hydrogen Evolution Reaction (HER) 302 16.3 Micro- and Nano-Soft Interfaces 304 16.4 Plasmonics at Soft Interfaces 305 16.5 Conclusions and Future Developments 305 References 307 17 Electrochemistry in Unusual Fluids 309 Philip N. Bartlett 17.1 Electrochemistry in Plasmas 310 17.2 Electrochemistry in Supercritical Fluids 314 17.2.1 Applications of SCF Electrochemistry 321 17.3 Conclusions 325 Acknowledgments 325 References 325 18 Aspects of Light-Driven Water Splitting 331 Laurence Peter 18.1 A Very Brief History of Semiconductor Electrochemistry 332 18.2 Thermodynamic and Kinetic Criteria for Light-Driven Water Splitting 334 18.3 Kinetics of Minority Carrier Reactions at Semiconductor Electrodes 336 18.4 The Importance of Electron–Hole Recombination 338 18.5 Fermi Level Splitting in the Semiconductor–Electrolyte Junction 339 18.6 A Simple Model for Light-Driven Water-Splitting Reaction 341 18.7 Evidence for Slow Electron Transfer During Light-Driven Water Splitting 343 18.8 Conclusions 345 Acknowledgments 345 References 346 19 Electrochemical Impedance Spectroscopy 349 Samin Sharifi-Asl and Digby D. Macdonald 19.1 Theory 350 19.2 The Point Defect Model 350 19.2.1 Calculation of Y0F 355 19.2.2 Calculation of ΔC0 i ΔU 355 19.2.3 Calculation of ΔCL v ΔU 356 19.3 The Passivation of Copper in Sulfide-Containing Brine 357 19.4 Summary and Conclusions 363 Acknowledgments 363 References 363 Index 367

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Book SynopsisEdited by the academic who first discovered this important phenomenon, Aggregation-Induced Emission is the first book to cover the applications of Aggregation-Induced Emission. This groundbreaking text explores the high-tech applications of AIE materials in optoelectronic devices, chemical sensors, and biological probes. A valuable resource for scientists, physicists, and biological chemists, topics covered include: AIE materials for LEDs and lasers; mechanochromic AIE materials; new chemo- and biosensors based on AIE fluorophores; AIE dye-encapsulated nanoparticles for optical bioimaging; and chiral recognition and enantiomeric excess determination based on AIE.Table of ContentsList of Contributors xi Preface xiii 1 AIE or AIEE Materials for Electroluminescence Applications 1 Chiao-Wen Lin and Chin-Ti Chen 1.1 Introduction 1 1.2 EL Background, EL Efficiency, Color Chromaticity, and Fabrication Issues of OLEDs 2 1.3 AIE or AIEE Silole Derivatives for OLEDs 7 1.4 AIE or AIEE Maleimide and Pyrrole Derivatives for OLEDs 10 1.5 AIE or AIEE Cyano-Substituted Stilbenoid and Distyrylbenzene Derivatives for OLEDs 14 1.6 AIE or AIEE Triarylamine Derivatives for OLEDs 17 1.7 AIE or AIEE Triphenylethene and Tetraphenylethene Derivatives for OLEDs 17 1.8 White OLEDs Containing AIE or AIEE Materials 31 1.9 Perspectives 36 References 37 2 Crystallization-Induced Phosphorescence for Purely Organic Phosphors at Room Temperature and Liquid Crystals with Aggregation-Induced Emission Characteristics 42 Wang Zhang Yuan, Yongming Zhang, and Ben Zhong Tang 2.1 Crystallization-Induced Phosphorescence for Purely Organic Phosphors at Room Temperature 42 2.1.1 Introduction 42 2.1.2 Molecular luminogens with crystallization-induced phosphorescence at room temperature 43 2.2 Liquid crystals with aggregation-induced emission characteristics 51 2.2.1 Luminescent liquid crystals 51 2.2.2 Aggregation-induced emission strategy towards high-efficiency luminescent liquid crystals 52 2.3 Conclusions and Perspectives 56 References 57 3 Mechanochromic Aggregation-Induced Emission Materials 60 Zhenguo Chi and Jiarui Xu 3.1 Introduction 60 3.2 Mechanochromic Non-AIE Compounds 61 3.3 Mechanochromic AIE Compounds 63 3.4 Conclusion 81 References 82 4 Chiral Recognition and Enantiomeric Excess Determination Based on Aggregation-Induced Emission 86 Yan-Song Zheng 4.1 Introduction to Chiral Recognition 86 4.2 Chiral Recognition and Enantiomeric Excess Determination of Chiral Amines 87 4.3 Chiral Recognition and Enantiomeric Excess Determination of Chiral Acids 90 4.3.1 Enantiomeric excess determination of chiral acids using chiral AIE amines 90 4.3.2 Enantiomeric excess determination of chiral acids using a chiral receptor in the presence of an AIE compound 97 4.4 Mechanism of chiral recognition based on AIE 100 4.4.1 Mechanism of chiral recognition by a chiral AIE monoamine 101 4.4.2 Mechanism of chiral recognition by a chiral AIE diamine 101 4.5 Prospects for chiral recognition based on AIE 103 References 104 5 AIE Materials Towards Efficient Circularly Polarized Luminescence, Organic Lasing, and Superamplified Detection of Explosives 106 Jianzhao Liu, Jacky W.Y. Lam, and Ben Zhong Tang 5.1 Introduction 106 5.2 AIE Materials with Efficient Circularly Polarized Luminescence and Large Dissymmetry Factor 106 5.2.1 Aggregation-induced circular dichroism 107 5.2.2 AIE, fluorescence decay dynamics and theoretical understanding 109 5.2.3 Aggregation-induced circularly polarized luminescence 112 5.2.4 Supramolecular assembly and structural modeling 114 5.3 AIE Materials for Organic Lasing 117 5.3.1 Fabrication of nano-structures 117 5.3.2 Lasing performances 118 5.4 AIE Materials for Superamplified Detection of Explosives 120 5.4.1 Hyperbranched polymer-based sensor 121 5.4.2 Mesoporous material-based sensor 126 5.5 Conclusion 126 References 127 6 Aggregation-Induced Emission and Applications of Aryl-Substituted Pyrrole Derivatives 129 Bin Tong and Yuping Dong 6.1 Introduction 129 6.2 Luminescence Properties of Triphenylpyrrole Derivatives in the Aggregated State 130 6.3 Applications 134 6.4 Aggregation-Induced Emission of Pentaphenylpyrrole 145 6.5 AIEE Mechanism of Pentaphenylpyrrole 148 6.6 Conclusion 150 References 150 7 Biogenic Amine Sensing with Aggregation-Induced Emission-Active Tetraphenylethenes 154 Takanobu Sanji and Masato Tanaka 7.1 Introduction 154 7.1.1 Biogenic amines 154 7.1.2 Sensing methods for biogenic amines 154 7.2 Fluorimetric Sensing of Biogenic Amines with AIE-Active TPEs 155 7.2.1 Design for fluorimetric sensing of biogenic amines 155 7.2.2 Sensing studies and statistical analysis 155 7.2.3 Determination of histamine concentration 159 7.2.4 Fluorimetric sensing of melamine with AIE-active TPEs 160 7.3 Summary and Outlook 160 References 161 8 New Chemo-/Biosensors with Silole and Tetraphenylethene Molecules Based on the Aggregation and Deaggregation Mechanism 162 Ming Wang, Guanxin Zhang, and Deqing Zhang 8.1 Introduction 162 8.2 Cation and Anion Sensors 163 8.3 Fluorimetric Biosensors for Biomacromolecules 166 8.4 Fluorimetric Assays for Enzymes 170 8.5 Fluorimetric Detection of Physiologically Important Small Molecules 177 8.6 Miscellaneous Sensors 180 8.7 Conclusion and Outlook 182 References 182 9 Carbohydrate-Functionalized AIE-Active Molecules as Luminescent Probes for Biosensing 186 Qi Chen and Bao-Hang Han 9.1 Introduction 186 9.2 Carbohydrate-Bearing AIE-Active Molecules 187 9.2.1 Carbohydrate-bearing siloles 188 9.2.2 Carbohydrate-bearing phosphole oxides 189 9.2.3 Carbohydrate-bearing tetraphenylethenes 190 9.3 Luminescent Probes for Lectins 192 9.4 Luminescent Probes for Enzymes 196 9.5 Luminescent Probes for Viruses and Toxins 200 9.6 Conclusion 202 Acknowledgments 202 References 202 10 Aggregation-Induced Emission Dyes for In Vivo Functional Bioimaging 205 Jun Qian, Dan Wang, and Sailing He 10.1 Introduction 205 10.2 AIE Dyes for Macro In Vivo Functional Bioimaging 206 10.2.1 AIE dye-encapsulated phospholipid–PEG nanomicelles 206 10.2.2 AIE dye-encapsulated nanomicelles for SLN mapping of mice 206 10.2.3 AIE dye-encapsulated nanomicelles for tumor targeting of mice 212 10.2.4 Other types of AIE-nanoparticles for in vivo functional bioimaging 217 10.3 Multiphoton-Induced Fluorescence from AIE Dyes and Applications in In Vivo Functional Microscopic Imaging 219 10.3.1 Two- and three-photon-induced fluorescence of AIE dyes 219 10.3.2 AIE dye-encapsulated nanomicelles for two-photon blood vessel imaging of live mice 223 10.3.3 AIE dye-encapsulated nanomicelles for two-photon brain imaging of live mice 226 10.4 Summary and Perspectives 228 Acknowledgments 230 References 230 11 Specific Light-Up Bioprobes with Aggregation-Induced Emission Characteristics for Protein Sensing 234 Jing Liang, Haibin Shi, Ben Zhong Tang, and Bin Liu 11.1 Introduction 234 11.2 In Vitro Detection of Integrin avb3 Using a TPS-Based Probe 235 11.2.1 Detection mechanisms 236 11.2.2 Synthesis and characterization of the TPS-2cRGD probe 236 11.2.3 Detection of integrin in solutions 238 11.2.4 In vitro sensing of integrin in cancer cells 239 11.3 Real-Time Monitoring of Cell Apoptosis and Drug Screening with a TPE-Based Probe 240 11.3.1 Design principles 240 11.3.2 Synthesis and characterization of Ac-DEVEK-TPE probe 241 11.3.3 Detection of caspase and kinetic study of caspase activities in solutions 242 11.3.4 Imaging of cell apoptosis and screening of apoptosis-inducing agents 243 11.4 In Vivo Monitoring of Cell Apoptosis and Drug Screening with PyTPE-Based Probe 246 11.4.1 Working principles 246 11.4.2 Synthesis and characterization of DEVD-PyTPE probe 247 11.4.3 Monitoring of caspase activities in solutions 248 11.4.4 In vitro and in vivo imaging of cell apoptosis 248 11.5 Conclusion 250 Acknowledgments 250 References 251 12 Applications of Aggregation-Induced Emission Materials in Biotechnology 254 Yuning Hong, Jacky W.Y. Lam, and Ben Zhong Tang 12.1 Introduction 254 12.2 AIE Materials for Nucleic Acid Studies 255 12.2.1 Quantitation and gel visualization of DNA and RNA 255 12.2.2 Specific probing of G-quadruplex DNA formation 257 12.3 AIE Materials for Protein Studies 258 12.3.1 Quantitation and PAGE staining of proteins 258 12.3.2 Fluorescence immunoassay by AIE materials 261 12.3.3 Monitoring of the unfolding/refolding process of human serum albumin 261 12.3.4 Monitoring and inhibition of amyloid fibrillation of insulin 262 12.4 AIE Materials for Live Cell Imaging 264 12.4.1 AIE bioprobes for long-term cell tracking 264 12.4.2 AIE nanoparticles for cell staining 264 12.5 Conclusion 266 References 267 Index 271

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Book SynopsisDetails energy and exergy efficiencies of all major aspects of bioenergy systems Covers all major bioenergy processes starting from photosynthesis and cultivation of biomass feedstocks and ending with final bioenergy products, like power, biofuels, and chemicals Each chapter includes historical developments, chemistry, major technologies, applications as well as energy, environmental and economic aspects in order to serve as an introduction to biomass and bioenergy A separate chapter introduces a beginner in easy accessible way to exergy analysis and the similarities and differences between energy and exergy efficiencies are underlined Includes case studies and illustrative examples of 1st, 2nd, and 3rd generation biofuels production, power and heat generation (thermal plants, fuel cells, boilers), and biorefineries Traditional fossil fuels-based technologies are also described in order to cTable of ContentsPreface xv Acknowledgments xix About the Author xxi PART I | Background and Outline Chapter 1 | Bioenergy Systems: An Overview 3 1.1 Energy and the Environment 3 1.2 Biomass as a Renewable Energy Source 13 1.3 Biomass Conversion Processes 22 1.4 Utilization of Biomass 27 1.5 Closing Remarks 34 References 34 Chapter 2 | Exergy Analysis 37 2.1 Sustainability and Efficiency 37 2.2 Thermodynamic Analysis of Processes 42 2.3 Exergy Concept 52 2.4 Exergetic Evaluation of Processes and Technologies 67 2.5 Renewability of Biofuels 81 2.6 Closing Remarks 86 References 86 PART II | Biomass Production and Conversion Chapter 3 | Photosynthesis 93 3.1 Photosynthesis: An Overview 93 3.2 Exergy of Thermal Radiation 99 3.3 Exergy Analysis of Photosynthesis 106 3.4 Global Photosynthesis 116 3.5 Closing Remarks 120 References 120 Chapter 4 | Biomass Production 123 4.1 Overview 123 4.2 Efficiency of Solar Energy Capture 133 4.3 Fossil Inputs for Biomass Cultivation and Harvesting 140 4.4 Fossil Inputs for Biomass Logistics 146 4.5 Closing Remarks 150 References 150 Chapter 5 | Thermochemical Conversion: Gasification 153 5.1 Gasification: An Overview 153 5.2 Gasification of Carbon 171 5.3 Gasification of Biomass 183 5.4 Gasification of Typical Fuels 191 5.5 Closing Remarks 198 References 198 Chapter 6 | Gasification: Parametric Studies and Gasification Systems 203 6.1 Effect of Fuel Chemical Composition on Gasification Performance 203 6.2 Effect of Biomass Moisture Content, Gasification Pressure, and Heat Addition on Gasification Performance 211 6.3 Improvement of Gasification Exergetic Efficiency 215 6.4 Gasification Efficiency Using Equilibrium versus Nonequilibrium Models 230 6.4.1 Quasi-Equilibrium Thermodynamic Models 231 6.4.2 Comparison of Gasification Efficiency 231 6.5 Performance of Typical Gasifiers 233 6.5.1 Comparison of FICFB and Viking Gasifiers 233 6.5.2 Fluidized-Bed Gasifiers for the Production of H2-Rich Syngas 238 6.5.3 Downdraft Fixed-Bed Gasifier 241 6.5.4 Updraft Fixed-Bed Gasifier 242 6.6 Plasma Gasification 244 6.6.1 Plasma Gasification Technology 244 6.6.2 Plasma Gasification of Sewage Sludge 244 6.7 Thermochemical Conversion in Sub- and Supercritical Water 246 6.7.1 Conversion of Wet Biomass in Hot Compressed Water 246 6.7.2 Supercritical Water Gasification (SCWG) 247 6.7.3 Hydrothermal Upgrading (HTU) under Subcritical Water Conditions 251 6.8 Closing Remarks 253 References 253 PART III | Biofuels First-Generation Biofuels Chapter 7 | Biodiesel 261 7.1 Biodiesel: An Overview 261 7.1.1 Introduction 261 7.1.2 Historical Development 262 7.1.3 Chemistry 263 7.1.4 Feedstocks 265 7.1.5 Production Process 266 7.1.6 Biodiesel as Transport Fuel 268 7.1.7 Energy, Environmental, and Economic Performance 269 7.2 Biodiesel from Plant Oils 272 7.2.1 Exergy Analysis of Transesterification 272 7.2.2 Exergy Analysis of Overall Production Chain 275 7.3 Biodiesel from Used Cooking Oil 278 7.3.1 Exergy Analysis of Biodiesel Production 278 7.3.2 Exergy Analysis of Overall Production Chain 281 7.4 Biodiesel from Microalgae 281 7.4.1 Introduction 281 7.4.2 Exergy Analysis of Transesterification of Algal Oil 282 7.4.3 Exergy Analysis of Overall Production Chain of Algal Biodiesel 284 7.5 Closing Remarks 286 References 286 Chapter 8 | Bioethanol 289 8.1 Bioethanol: An Overview 289 8.1.1 Introduction 289 8.1.2 Historical Development 290 8.1.3 Ethanol as Transport Fuel 291 8.1.4 Chemistry 293 8.1.5 Bioethanol Production Methods 295 8.1.6 Energy, Environmental and Economic Aspects 302 8.2 Exergy Analysis of Ethanol from Sugar Crops 305 8.2.1 Introduction 305 8.2.2 Ethanol from Sugarcane 306 8.2.3 Exergetic Performance of Sugarcane Ethanol Plants for Various Cogeneration Configurations 310 8.2.4 Ethanol from Sugar Beets 313 8.2.5 Renewability of Ethanol from Sugar Crops 315 8.3 Exergy Analysis of Ethanol from Starchy Crops 317 8.3.1 Introduction 317 8.3.2 Corn Ethanol: Exergy Analysis 317 8.3.3 Corn Ethanol: Cumulative Exergy Consumption (CExC) and Renewability 319 8.3.4 Wheat Ethanol 322 8.4 Exergy Analysis of Lignocellulosic Ethanol (Second Generation) 323 8.4.1 Introduction 323 8.4.2 Ethanol from Wood (NREL Process) 324 8.4.3 Impact of Biomass Pretreatment and Process Configuration 328 8.4.4 Comparison of Exergetic Efficiency 330 8.4.5 Renewability of Lignocellulosic Ethanol from Tropical Tree Plantations 331 8.5 Alternative Ethanol Processes 332 8.5.1 Fossil Ethanol from Mineral Oil 332 8.5.2 Ethanol via Water Electrolysis 333 8.6 Closing Remarks 334 References 334 Second-Generation Liquid Biofuels Chapter 9 | Fischer–Tropsch Fuels 341 9.1 Fischer–Tropsch Synthesis: An Overview 341 9.1.1 Introduction 341 9.1.2 Historical Development 342 9.1.3 Process Chemistry 343 9.1.4 Comparison of F-T Fuels to Conventional Transport Fuels 345 9.1.5 Process Design 346 9.1.6 Process Performance 348 9.2 Exergy Analysis of Coal-to-Liquid (CTL) Process 351 9.2.1 Description of CTL Process 351 9.2.2 Mass Balance and Energy Analysis 353 9.2.3 Exergy Analysis 354 9.3 Exergy Analysis of Gas-to-Liquid (GTL) Processes 355 9.3.1 GTL Process with Tail Gas Recycling: Internal and External 356 9.3.2 Impact of Reformer Temperature on GTL Efficiency: External Tail Gas Recycling 361 9.4 Exergy Analysis of Biomass-to-Liquid (BTL) Processes 365 9.4.1 Introduction 365 9.4.2 Once-Through F-T Process 366 9.4.3 Impact of Biomass Feedstock on Process Efficiency 373 9.4.4 Reforming and Recycling of F-T Reactor Tail Gas 377 9.4.5 Recycling of F-T Reactor Tail Gas to Biomass Gasifier 382 9.5 Closing Remarks 383 References 383 Chapter 10 | Methanol 387 10.1 Methanol: An Overview 387 10.1.1 Introduction 387 10.1.2 Historical Development 388 10.1.3 Chemistry 389 10.1.4 Methanol as Transport Fuel 390 10.1.5 Process Design 392 10.1.6 Process Performance 393 10.2 Methanol from Fossil Fuels 396 10.2.1 Methanol from Natural Gas 396 10.2.2 Methanol from Coal 400 10.3 Methanol from Biomass 405 10.3.1 Methanol from Waste Biomass (Sewage Sludge) 405 10.3.2 Other Biomass-Based Methanol Processes 413 10.4 Closing Remarks 414 References 415 Chapter 11 | Thermochemical Ethanol 419 11.1 Thermochemical Ethanol: An Overview 419 11.1.1 Introduction 419 11.1.2 Process Chemistry 420 11.1.3 Catalysts for Ethanol Synthesis 422 11.1.4 Process Design 423 11.1.5 Energy, Environmental and Economic Aspects 426 11.2 Exergy Analysis 427 11.2.1 Process Description 428 11.2.2 Mass and Energy Balances (Rh-Based Catalyst) 431 11.2.3 Exergy Analysis (Rh-Based Catalyst) 433 11.2.4 Impact of Ethanol Synthesis Catalyst (MoS2-Based Target Catalyst) 435 11.2.5 Impact of Gasification Temperature 438 11.3 Closing Remarks 439 References 440 Chapter 12 | Dimethyl Ether (DME) 445 12.1 Dimethyl Ether: An Overview 445 12.1.1 Introduction 445 12.1.2 Historical Development 446 12.1.3 Process Chemistry 447 12.1.4 DME as Energy Carrier 448 12.1.5 Production Technology 449 12.1.6 Energy, Environmental, and Economic Aspects 451 12.2 Dimethyl Ether from Fossil Fuels 452 12.2.1 DME from Natural Gas 452 12.2.2 DME from Coal 458 12.2.3 DME from Co-Feed of Natural Gas and Coal 462 12.3 Dimethyl Ether from Biomass 462 12.3.1 DME via Indirect Steam Gasification 462 12.3.2 Influence of Syngas Preparation Method on Process Efficiency 468 12.4 Closing Remarks 472 References 472 Chapter 13 | Hydrogen 475 13.1 Hydrogen: An Overview 475 13.1.1 Introduction 475 13.1.2 History: from Discovery to Hydrogen Economy 476 13.1.3 Chemistry of Hydrogen Production 477 13.1.4 Hydrogen Use 479 13.1.5 Hydrogen Storage 480 13.1.6 Production Methods 481 13.1.7 Energy, Environmental, and Economic Performance 482 13.2 Exergy Analysis of Hydrogen from Fossil Fuels 485 13.2.1 Hydrogen from Natural Gas 485 13.2.2 Comparison of Efficiency for Hydrogen-from-Natural Gas Processes 489 13.2.3 Hydrogen-from-Coal Gasification 490 13.2.4 Comparison of Efficiency for Hydrogen-from-Coal Processes 493 13.3 Exergy Analysis of Hydrogen from Water Electrolysis 494 13.3.1 Process Description 494 13.3.2 Mass and Energy Balances 495 13.3.3 Exergy Analysis 495 13.4 Exergy Analysis of Future Hydrogen Production Processes 496 13.4.1 Thermochemical Cycles 497 13.4.2 Geothermal Energy 499 13.4.3 Solar Energy 500 13.5 Exergy Analysis of Hydrogen Production from Biomass Gasification 501 13.5.1 Exergy Analysis of Hydrogen from Wood 501 13.5.2 Influence of Biomass Feedstocks on Exergetic Efficiency 506 13.5.3 Influence of Gasification System Configurations on Exergetic Efficiency 507 13.5.4 Comparison of Efficiency for Hydrogen-from-Biomass Gasification 511 13.6 Exergy Analysis of Biological Hydrogen Production 512 13.6.1 Process Description 512 13.6.2 Mass and Energy Balances 514 13.6.3 Exergy Analysis 515 13.7 Closing Remarks 517 References 517 Chapter 14 | Substitute Natural Gas (SNG) 523 14.1 Substitute Natural Gas: An Overview 523 14.1.1 Introduction 523 14.1.2 Historical Development 524 14.1.3 Chemistry of Methanation 526 14.1.4 Natural Gas as Energy Carrier 527 14.1.5 SNG Production Technology 529 14.1.6 Energy, Environmental and Economic Aspects 530 14.2 SNG from Coal 533 14.2.1 Description of Coal-to-SNG Process 533 14.2.2 Process Modeling 537 14.2.3 Mass and Energy Balances 537 14.2.4 Exergy Analysis 538 14.2.5 Overview of Coal-to-SNG Processes 540 14.3 SNG from Biomass Gasification 540 14.3.1 SNG via Wood Gasification 540 14.3.2 Comparison of SNG Production from Various Biomass Feedstocks 550 14.3.3 Overview of Biomass-to-SNG Processes 555 14.4 Closing Remarks 555 References 556 PART IV | Bioenergy Systems Chapter 15 | Thermal Power Plants, Heat Engines, and Heat Production 561 15.1 Biomass-Based Power and Heat Generation: An Overview 561 15.1.1 Introduction 561 15.1.2 Historical Development 563 15.1.3 Technologies for Power Generation from Biomass 564 15.1.4 Biofuels in Internal Combustion Engines and Gas Turbines 567 15.1.5 Biomass Heating Systems 568 15.1.6 Performance and Cost of Power Generation Systems 569 15.1.7 Environmental Aspects 571 15.2 Biomass Combustion Power Systems 571 15.2.1 Introduction 571 15.2.2 Biomass Steam Cogeneration Plant 572 15.2.3 Externally Fired Gas Turbine–Combined Cycle 575 15.2.4 Biomass-Fired Organic Rankine Cycle (ORC) 580 15.3 Biomass Gasification Power Systems 584 15.3.1 Introduction 584 15.3.2 Biomass Integrated Gasification Gas Turbine–Combined Cycle (BIG/GT-CC) 585 15.3.3 Improving Efficiency BIG/GT-CC Plants 588 15.3.4 Biomass Integrated Gasification Internal Combustion Engine–Combined Cycle (BIG/ICE-CC) 589 15.4 Comparison of Various Biomass-Fueled Power Plants 591 15.4.1 Internally and Externally Fired Gas Turbine Simple Cogeneration Cycles 592 15.4.2 Internally and Externally Fired Gas Turbine: Simple and Combined Cycles 597 15.4.3 Comparison of Biomass Combustion and Gasification CHP Plants 602 15.5 Biomass-Fueled Internal Combustion Engines and Gas Turbines 608 15.5.1 Ethanol-Fueled Spark-Ignition Engines 609 15.5.2 Biodiesel-Fueled Compression-Ignition Engines 610 15.5.3 Biofuel-Fired Gas Turbines 612 15.6 Polygeneration of Electricity, Heat, and Chemicals 615 15.6.1 Introduction 615 15.6.2 Methanol Synthesis 615 15.6.3 Ethanol Production 621 15.7 Biomass Boilers and Heating Systems 624 15.7.1 Introduction 624 15.7.2 Biomass Boilers 625 15.7.3 Energy Utilization in Buildings 627 15.8 Closing Remarks 628 References 628 Chapter 16 | Biomass-Based Fuel Cell Systems 633 16.1 Biomass-Based Fuel Cell Systems: An Overview 633 16.1.1 Introduction 633 16.1.2 Historical Development 634 16.1.3 Fuel Cell Fundamentals 635 16.1.4 Fuel Cell Types 636 16.1.5 Fuel Cell Thermodynamics 638 16.1.6 Overview of Biomass-Based Fuel Cell Configurations 640 16.1.7 Energy Efficiency, Cost, and Environmental Impact 642 16.2 Biomass Integrated Gasification–Solid Oxide Fuel Cell (BIG/SOFC) Systems 642 16.2.1 Central Power Production Using BIG/SOFC/GT Systems 643 16.2.2 Other Central Power Production Studies Using BIG/SOFC Systems 647 16.2.3 Distributed Power Production Using BIG/SOFC Systems 648 16.2.4 Integration of Supercritical Water Gasification (SCWG) with SOFC/GT Hybrid System 650 16.3 Biomass Integrated Gasification–Proton Exchange Membrane Fuel Cell (BIG/PEMFC) Systems 652 16.3.1 Distributed Combined Heat and Power Generation Based on Central Hydrogen Production 652 16.3.2 Effect of Hydrogen Quality on Efficiency of Distributed CHP Systems 659 16.4 Fuel Cell Systems Fed with Liquid Biofuels 660 16.4.1 Introduction 660 16.4.2 Maximum Electricity Obtainable from Various Fuels 661 16.4.3 Integrated Fuel Processor–Fuel Cell (FP-FC) System 663 16.4.4 Direct Liquid Fuel Cell Systems 668 16.5 Closing Remarks 669 References 669 Chapter 17 | Biorefineries 673 17.1 Biorefineries: An Overview 673 17.1.1 Introduction 673 17.1.2 Historical Development 674 17.1.3 Chemical Value of Biomass 675 17.1.4 Biorefinery Systems 677 17.1.5 Biorefinery Technology 679 17.2 Comparison of Various Biomass Utilization Routes 681 17.2.1 Biomass Utilization Routes 681 17.2.2 Power Generation 682 17.2.3 Biofuels Production 683 17.2.4 Chemical Biorefinery 683 17.3 Exergy Inputs to Basic Biorefinery Steps 684 17.3.1 Biorefinery Model 684 17.3.2 Processing Simple Carbohydrates into Fermentable Sugars 686 17.3.3 Processing Complex Carbohydrates into Fermentable Sugars 686 17.3.4 Processing Fermentable Sugars into Ethanol 688 17.3.5 Processing Ethanol into Ethylene 689 17.3.6 Fatty Acids Processing 690 17.3.7 Amino Acids Processing 692 17.3.8 Lignin Processing 695 17.3.9 Ash and Residuals Processing 695 17.4 Optimal Biomass Crops as Biorefinery Feedstock 696 17.4.1 Biomass versus Petrochemical Route for the Production of Bulk Chemicals 696 17.4.2 Cumulative Fossil Fuel Consumption in the Biomass Route 697 17.4.3 Cumulative Fossil Fuel Consumption in the Petrochemical Route 698 17.4.4 Fossil Fuel Savings 699 17.4.5 Optimal Crops for Biorefineries 699 17.5 Closing Remarks 702 References 702 Postface 707 Appendixes Appendix A – Conversion Factors 709 Appendix B – Constants 711 Appendix C – SI Prefixes 713 Glossary of Selected Terms 715 Notation 721 Acknowledgments for Permission to Reproduce Copyrighted Material 729 Author Index 733 Subject Index 745

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Book SynopsisThe first seven metals in the periodic table are lithium, beryllium, sodium, magnesium, aluminium, potassium and calcium, known collectively as the lightest metals. The growing uses of these seven elements are enmeshing them ever more firmly into critical areas of 21st century technology, including energy storage, catalysis, and various applications of nanoscience. This volume provides comprehensive coverage of the fundamentals and recent advances in the science and technology of the lightest metals. Opening chapters of the book describe major physical and chemical properties of the metals, their occurrence and issues of long-term availability. The book goes on todisucss a broad range of chemical features, including low oxidation state chemistry, organometallics, metal-centered NMR spectroscopy, and cation-p interactions. Current and emerging applications of the metals are presented, including lithium-ion battery technology, hydrogen storage chemistry, superconductor materiTable of ContentsContributors XI Series Preface XV Volume Preface XVII PART 1: BACKGROUND 1 Interrelationships between the Lightest Metals 3Nicholas C. Boyde and Timothy P. Hanusa Occurrence and Production of Beryllium 23Stephen Freeman Occurrence of Magnesia Minerals and Production of Magnesium Chemicals and Metal 35Mark A. Shand Occurrence and Production of Aluminum 47Halvor Kvande Status as Strategic Metals 57Deborah A. Kramer Resource Sustainability 67David A. Atwood PART 2: FUNDAMENTALS 71 Low Oxidation State Chemistry 73Michael S. Hill Solution NMR of the Light Main Group Metals 91Timothy P. Hanusa Solid-State NMR of the Light Main Group Metals 117Robert W. Schurko and Michael J. Jaroszewicz Cation–π Interactions 173Yi An and Steven E. Wheeler Ion Channels and Ionophores 185Peter J. Cragg Beryllium Metal Toxicology: A Current Perspective 205Terence M. Civic PART 3: APPLICATIONS 211 Reimagining the Grignard Reaction 213Sven Krieck and Matthias Westerhausen Aryllithiums and Hetaryllithiums: Generation and Reactivity 231D. W. Slocum Magnesium and Calcium Complexes in Homogeneous Catalysis 255Merle Arrowsmith Aluminum-Based Catalysis 281Mark R. Mason Lithium-Ion Batteries: Fundamentals and Safety 303Isidor Buchmann Li-Ion Batteries and Beyond: Future Design Challenges 315Yoon Hwa and Elton J. Cairns High-Pressure Synthesis of Hydrogen Storage Materials 335Hiroyuki Saitoh, Shigeyuki Takagi, Katsutoshi Aoki and Shin-ichi Orimo Processing and Applications of Transparent Ceramics 343Ling Bing Kong, Yizhong Huang, Zhili Dong, Tianshu Zhang, Wenxiu Que, Jian Zhang, Dingyuan Tang and Sean Li Light-Element Superconductors 371Andreas Hermann One-dimensional Nanostructure-enhanced Catalysis 387Sibo Wang, Zheng Ren, Yanbing Guo and Pu-Xian Gao Lithium Pharmacology 417Philip G. Janicak and Bradley R. Cutler Solar Energy and Photovoltaics 427Arnulf Jäger-Waldau Abbreviations and Acronyms 437 Index 441

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Book SynopsisChemistry: The Study of Matter and Its Changes, 7e will provide the necessary practice, support and individualized instruction that ensures success in the General Chemistry course. This text provides the forum for problem solving and concept mastery of chemical phenomena that leads to proficiency and success in the General Chemistry course.

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Book SynopsisThe Study Guide to accompany Chemistry: The Molecular Nature of Matter, 7th Edition.

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Book SynopsisBioactive compounds play a central role in high-value product development in the chemical industry. Bioactive compounds have been identified from diverse sources and their therapeutic benefits, nutritional value and protective effects in human and animal healthcare have underpinned their application as pharmaceuticals and functional food ingredients. The orderly study of biologically active products and the exploration of potential biological activities of these secondary metabolites, including their clinical applications, standardization, quality control, mode of action and potential biomolecular interactions, has emerged as one of the most exciting developments in modern natural medicine. Biotechnology of Bioactive Compounds describes the current stage of knowledge on the production of bioactive compounds from microbial, algal and vegetable sources. In addition, the molecular approach for screening bioactive compounds is also discussed, as well as examples of applicaTable of ContentsList of contributors ix Foreword xvii Preface xix Section I: Bioactive compounds from diverse plant microbial and marine sources 1 Bioactive compounds from vegetable and fruit by-products 3 B. De Ancos C. Colina-Coca D. González-Pena and C. Sánchez-Moreno 2 Bioactive compounds in fresh-cut fruits: Occurrence and impact of processing and cold storage 37 María Elida Pirovani Andrea Marcela Piagentini and Franco Van de Velde 3 Pressurized hot water extraction of polyphenols from plant material 63 José Rodrigo Vergara-Salinas José Cuevas-Valenzuela and José R. Pérez-Correa 4 Bioactive compounds in cereals: Technological and nutritional properties 103 Bart³omiej Makowski Justyna Rosicka-Kaczmarek and Ewa Nebesny 5 Antimicrobials from medicinal plants: Research initiatives challenges and the future prospects 123 Anita Pandey and Vasudha Agnihotri 6 Coccoloba uvifera as a source of components with antioxidant activity 151 Maira Segura Campos Jorge Ruiz Ruiz Luis Chel Guerrero and David Betancur Ancona 7 Bioactive compounds and medical significance of some endangered medicinal plants from the Western Ghats region of India 163 Manoharan Melvin Joe Abitha Benson Muniappan Ayyanar and Tongmin Sa 8 Fungal bioactive compounds: An overview 195 Gerardo Díaz-Godínez 9 Arbuscular mycorrhizal fungi: Association and production of bioactive compounds in plants 225 Marcela C. Pagano and Partha P. Dhar 10 Extremophiles as source of novel bioactive compounds with industrial potential 245 Mohamed Neifar Sameh Maktouf Raoudha Ellouze Ghorbel Atef Jaouani and Ameur Cherif 11 New trends in microbial production of natural complex bioactive isoprenoids 269 Rama Raju Baadhe Ravichandra Potumarthi Naveen Kumar Mekala and Vijai K. Gupta 12 Production of c-phycocyanin and its potential applications 283 Mohammed Kuddus Poonam Singh George Thomas and Athar Ali Section II: Chemistry biotechnology and industrial relevance 13 Glycosides: From biosynthesis to biological activity toward therapeutic application 303 Maria Henriques L. Ribeiro 14 Trehalose mimics as bioactive compounds 345 Davide Bini Antonella Sgambato Luca Gabrielli Laura Russo and Laura Cipolla 15 Virtual screening and prediction of the molecular mechanism of bioactive compounds in silico 371 Bashir A. Akhoon Krishna P. Singh Madhumita Karmakar Suchi Smita Rakesh Pandey and Shailendra K. Gupta 16 Steroids in natural matrices: Chemical features and bioactive properties 395 Joao C.M. Barreira and Isabel C.F.R. Ferreira 17 Bioactive compounds obtained through biotechnology 433 Gustavo Molina Franciele M. Pelissari Marina G. Pessoa and Gláucia M. Pastore 18 Metabolic engineering of bioactive compounds in berries 463 Ivayla Dincheva Ilian Badjakov and Violeta Kondakova 19 Food-derived multifunctional bioactive proteins and peptides: Sources and production 483 Dominic Agyei Ravichandra Potumarthi and Michael K. Danquah 20 Food-derived multifunctional bioactive proteins and peptides: Applications and recent advances 507 Dominic Agyei Ravichandra Potumarthi and Michael K. Danquah Section III: Biochemistry and nutraceutical or health-related applications 21 An overview of the molecular and cellular interactions of some bioactive compounds 527 Amro Abd Al Fattah Amara 22 Bioactive compounds as growth factors and 3D matrix materials in stem cell research 555 Naveen Kumar Mekala Rama Raju Baadhe and Ravichandra Potumarthi 23 Phytosterols: Biological effects and mechanisms of hypocholesterolemic action 565 Rafaela da Silva Marineli Cibele Priscila Busch Furlan Anne y Castro Marques Juliano Bicas Gláucia Maria Pastore and Mário Roberto Maróstica Jr. 24 Overview of the role of food bioactive compounds as complementary therapy for celiac disease 583 Antonio Cilla Laia Alemany Juan Antonio Giménez and José Moisés Laparra 25 Bioactive lipid components from ruminant milk and meat: The new face of human health 599 Malgorzata Szumacher-Strabel Mohamed El-Sherbiny Adam Cieslak Joanna Szczechowiak and Hanna Winiarska 26 The milk fat globule membrane: A potential source of health-promoting glycans 631 Sarah A. Ross Jonathan A. Lane Michelle Kilcoyne Lokesh Joshi and Rita M. Hickey 27 Seaweed and milk derived bioactive peptides and small molecules in functional foods and cosmeceuticals 669 Maria Hayes Melani García-García Ciarán Fitzgerald and Tomas Lafarga Index 693

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Book Synopsis

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Book SynopsisExamines in a pedagogical way all pertinent molecular and macroscopic processes that govern the distribution and fate of organic chemicals in the environment and provides simple modeling tools to quantitatively describe these processes and their interplay in a given environmental system Treats fundamental aspects of chemistry, physics, and mathematical modeling as applied to environmentally relevant problems, and gives a state of the art account of the field Teaches the reader how to relate the structure of a given chemical to its physical chemical properties and intrinsic reactivities Provides a holistic and teachable treatment of phase partitioning and transformation processes, as well as a more focused and tailor-made presentation of physical, mathematical, and modeling aspects that apply to environmental situations of concern Includes a large number of questions and problems allowing teachers to explore the depth of understanding of tTable of ContentsPreface xiii About the Companion Website xvii 1 General Topic and Overview 1 1.1 Introduction 2 1.2 Assessing Organic Chemicals in the Environment 4 1.3 What is This Book All About? 7 1.4 Bibliography 14 Part I Background Knowledge 17 2 Background Knowledge on Organic Chemicals 19 2.1 The Makeup of Organic Compounds 20 2.2 Intermolecular Forces Between Uncharged Molecules 37 2.3 Questions and Problems 40 2.4 Bibliography 43 3 The Amazing World of Anthropogenic Organic Chemicals 45 3.1 Introduction 47 3.2 A Lasting Global Problem: Persistent Organic Pollutants (POPs) 47 3.3 Natural but Nevertheless Problematic: Petroleum Hydrocarbons 48 3.4 Notorious Air and Groundwater Pollutants: Organic Solvents 53 3.5 Safety First: Flame Retardants All Around Us 56 3.6 How to Make Materials “Repellent”: Polyfluorinated Chemicals (PFCs) 58 3.7 From Washing Machines to Surface Waters: Complexing Agents, Surfactants, Whitening Agents, and Corrosion Inhibitors 60 3.8 Health, Well-Being, and Water Pollution: Pharmaceuticals and Personal Care Products 63 3.9 Fighting Pests: Herbicides, Insecticides, and Fungicides 65 3.10 Our Companion Compounds: Representative Model Chemicals 69 3.11 Questions 72 3.12 Bibliography 73 4 Background Thermodynamics, Equilibrium Partitioning and Acidity Constants 81 4.1 Important Thermodynamic Functions 83 4.2 Using Thermodynamic Functions to Quantify Equilibrium Partitioning 89 4.3 Organic Acids and Bases I: Acidity Constant and Speciation in Natural Waters 98 4.4 Organic Acids and Bases II: Chemical Structure and Acidity Constant 107 4.5 Questions and Problems 116 4.6 Bibliography 119 5 Earth Systems and ComPartments 121 5.1 Introduction 123 5.2 The Atmosphere 125 5.3 Surface Waters and Sediments 131 5.4 Soil and Groundwater 148 5.5 Biota 154 5.6 Questions 155 5.7 Bibliography 158 6 Environmental Systems: Physical Processes and Mathematical Modeling 165 6.1 Systems and Models 167 6.2 Box Models: A Concept for a Simple World 174 6.3 When Space Matters: Transport Processes 191 6.4 Models in Space and Time 196 6.5 Questions and Problems 203 6.6 Bibliography 211 Part II Equilibrium Partitioning in Well-Defined Systems 213 7 Partitioning Between Bulk Phases: General Aspects and Modeling Approaches 215 7.1 Introduction 216 7.2 Molecular Interactions Governing Bulk Phase Partitioning of Organic Chemicals 217 7.3 Quantitative Approaches to Estimate Bulk Phase Partition Constants/Coefficients: Linear Free Energy Relationships (LFERs) 225 7.4 Questions 232 7.5 Bibliography 234 8 Vapor Pressure (pi∗) 237 8.1 Introduction and Theoretical Background 238 8.2 Molecular Interactions Governing Vapor Pressure and Vapor Pressure Estimation Methods 246 8.3 Questions and Problems 253 8.4 Bibliography 257 9 Solubility (Csatiw ) and Activity Coefficient (𝜸satiw ) in Water; Air–Water Partition Constant (Kiaw) 259 9.1 Introduction and Thermodynamic Considerations 261 9.2 Molecular Interactions Governing the Aqueous Activity Coefficient and the Air–Water Partition Constant 267 9.3 LFERs for Estimating Air–Water Partition Constants and Aqueous Activity Coefficients/Aqueous Solubilities 270 9.4 Effect of Temperature, Dissolved Salts, and pH on the Aqueous Activity Coefficient/Aqueous Solubility and on the Air–Water Partition Constant 272 9.5 Questions and Problems 282 9.6 Bibliography 285 10 Organic Liquid–Air and Organic Liquid–Water Partitioning 289 10.1 Introduction 291 10.2 Thermodynamic Considerations and Comparisons of Different Organic Solvents 291 10.3 The Octanol–Water System: The Atom/Fragment Contribution Method for Estimation of the Octanol–Water Partition Constant 298 10.4 Partitioning Involving Organic Solvent–Water Mixtures 301 10.5 Evaporation and Dissolution of Organic Compounds from Organic Liquid Mixtures–Equilibrium Considerations 307 10.6 Questions and Problems 311 10.7 Bibliography 317 11 Partitioning of Nonionic Organic Compounds Between Well-Defined Surfaces and Air or Water 321 11.1 Introduction 322 11.2 Adsorption from Air to Well-Defined Surfaces 322 11.3 Adsorption from Water to Inorganic Surfaces 335 11.4 Questions and Problems 342 11.5 Bibliography 345 Part III Equilibrium Partitioning in Environmental Systems 349 12 General Introduction to Sorption Processes 351 12.1 Introduction 352 12.2 Sorption Isotherms and the Solid–Water Equilibrium Distribution Coefficient (Kid) 354 12.3 Speciation (Sorbed versus Dissolved or Gaseous), Retardation, and Sedimentation 360 12.4 Questions and Problems 366 12.5 Bibliography 368 13 Sorption from Water to Natural Organic Matter (NOM) 369 13.1 The Structural Diversity of Natural Organic Matter Present in Aquatic and Terrestrial Environments 371 13.2 Quantifying Natural Organic Matter–Water Partitioning of Neutral Organic Compounds 376 13.3 Sorption of Organic Acids and Bases to Natural Organic Matter 388 13.4 Questions and Problems 392 13.5 Bibliography 397 14 Sorption of Ionic Organic Compounds to Charged Surfaces 405 14.1 Introduction 407 14.2 Cation and Anion Exchange Capacities of Solids in Water 408 14.3 Ion Exchange: Nonspecific Adsorption of Ionized Organic Chemicals from Aqueous Solutions to Charged Surfaces 414 14.4 Surface Complexation: Specific Bonding of Organic Compounds with Solid Phases in Water 426 14.5 Questions and Problems 432 14.6 Bibliography 436 15 Aerosol–Air Partitioning: Dry andWet Deposition of Organic Pollutants 441 15.1 Origins and Properties of Atmospheric Aerosols 442 15.2 Assessing Aerosol–Air Partition Coefficients (KiPMa) 445 15.3 Dry and Wet Deposition 453 15.4 Questions and Problems 459 15.5 Bibliography 464 16 Equilibrium Partitioning From Water and Air to Biota 469 16.1 Introduction 471 16.2 Predicting Biota–Water and Biota–Air Equilibrium Partitioning 471 16.3 Bioaccumulation and Biomagnification in Aquatic Systems 485 16.4 Bioaccumulation and Biomagnification in Terrestrial Systems 498 16.5 Baseline Toxicity (Narcosis) 503 16.6 Questions and Problems 507 16.7 Bibliography 514 Part IV Mass Transfer Processes in Environmental Systems 523 17 Random Motion, Molecular and Turbulent Diffusivity 525 17.1 Random Motion 526 17.2 Molecular Diffusion 534 17.3 Other Random Transport Processes in the Environment 545 17.4 Questions and Problems 550 17.5 Bibliography 557 18 Transport at Boundaries 559 18.1 The Role of Boundaries in the Environment 560 18.2 Bottleneck Boundaries 562 18.3 Wall Boundaries 567 18.4 Hybrid Boundaries 572 18.5 Questions and Problems 577 18.6 Bibliography 580 19 Air–Water Exchange 581 19.1 The Air–Water Interface 583 19.2 Air–Water Exchange Models 585 19.3 Measurement of Air–Water Exchange Velocities 592 19.4 Air–Water Exchange in Flowing Waters 599 19.5 Questions and Problems 604 19.6 Bibliography 613 20 Interfaces Involving Solids 617 20.1 The Sediment–Water Interface 618 20.2 Transport in Unsaturated Soil 626 20.3 Questions and Problems 630 20.4 Bibliography 634 Part V Transformation Processes 635 21 Background Knowledge on Transformation Reactions of Organic Pollutants 637 21.1 Identifying Reactive Sites Within Organic Molecules 638 21.2 Thermodynamics of Transformation Reactions 643 21.3 Kinetics of Transformation Reactions 650 21.4 Questions and Problems 657 21.5 Bibliography 661 22 Hydrolysis And ReactionsWith Other Nucleophiles 663 22.1 Nucleophilic Substitution and Elimination Reactions Involving Primarily Saturated Carbon Atoms 665 22.2 Hydrolytic Reactions of Carboxylic and Carbonic Acid Derivatives 680 22.3 Enzyme-Catalyzed Hydrolysis Reactions: Hydrolases 695 22.4 Questions and Problems 701 22.5 Bibliography 710 23 Redox Reactions 715 23.1 Introduction 716 23.2 Evaluating the Thermodynamics of Redox Reactions 719 23.3 Examples of Chemical Redox Reactions in Natural Systems 730 23.4 Examples of Enzyme-Catalyzed Redox Reactions 747 23.5 Questions and Problems 756 23.6 Bibliography 765 24 Direct Photolysis in Aquatic Systems 773 24.1 Introduction 775 24.2 Some Basic Principles of Photochemistry 776 24.3 Light Absorption by Organic Compounds in Natural Waters 788 24.4 Quantum Yield and Rate of Direct Photolysis 800 24.5 Effects of Solid Sorbents (Particles, Soil Surfaces, Ice) on Direct Photolysis 803 24.6 Questions and Problems 804 24.7 Bibliography 811 25 Indirect Photolysis: Reactions with Photooxidants in Natural Waters and in the Atmosphere 815 25.1 Introduction 816 25.2 Indirect Photolysis in Surface Waters 817 25.3 Indirect Photolysis in the Atmosphere (Troposphere): Reaction with Hydroxyl Radical (HO∙) 829 25.4 Questions and Problems 833 25.5 Bibliography 838 26 Biotransformations 845 26.1 Introduction 847 26.2 Some Important Concepts about Microorganisms Relevant to Biotransformations 848 26.3 Initial Biotransformation Strategies 858 26.4 Rates of Biotransformations 864 26.5 Questions and Problems 882 26.6 Bibliography 889 27 Assessing Transformation Processes Using Compound-Specific Isotope Analysis (CSIA) 897 27.1 Introduction, Methodology, and Theoretical Background 898 27.2 Using CSIA for Assessing Organic Compound Transformations in Laboratory and Field Systems 914 27.3 Questions and Problems 930 27.4 Bibliography 936 Part VI Putting Everything Together 945 28 Exposure Assessment of Organic Pollutants Using Simple Modeling Approaches 947 28.1 One-Box Model: The Universal Tool for Process Integration 948 28.2 Assessing Equilibrium Partitioning in Simple Multimedia Systems 952 28.3 Simple Dynamic Systems 956 28.4 Systems Driven by Advection 960 28.5 Bibliography 974 Appendix 977 Index 995

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Book SynopsisProvides a modern, practical approach to the understanding and measurement procedures relevant to the fracture of brittle materials This book examines the testing and analysis of the fracture of brittle materials. Expanding on the measurement and analysis methodology contained in the first edition, it covers the relevant measurements (toughness and strength), material types, fracture mechanics, measurement techniques, reliability and lifetime predictions, microstructural considerations, and material/test selection processes appropriate for the analysis of the fracture behavior of brittle materials. The Fracture of Brittle Materials: Testing and Analysis, Second Edition summarizes the concepts behind the selection of a test procedure for fracture toughness and strength, and goes into detail on how the statistics of fracture can be used to assure reliability. It explains the importance of the role of microstructure in these determinations and emphasizes theTable of ContentsPreface ix Acknowledgements xi 1. Introduction 1 2. Fracture Mechanics Background 7 3. Environmentally Enhanced Crack Growth 23 4. Fracture Mechanics Tests 37 5. Strength Testing 79 6. Thermally Induced Fracture 129 7. Modeling of Brittle Fracture 145 8. Quantitative Fractography 167 9. Microstructural Effects 207 10. Reliability and Time-dependent Fracture 223 11. Concluding Remarks 235 Subject Index 239

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Book SynopsisThis book will focus on lignocellulosic fibres as a raw material for several applications. It will start with wood chemistry and morphology. Then, some fibre isolation processes will be given, before moving to composites, panel and paper manufacturing, characterization and aging.Table of ContentsPreface xxi Part 1: Wood and Fibres: Raw Materials 1 Introduction and State-of-the-Art 3 Mohamed Naceur Belgacem and Antonio Pizzi 2 Wood and Wood Fiber Characteristics: Moisture, Biological, Thermal and Weathering 7 Roger M. Rowel 2.1 Introduction 7 2.2 Moisture 8 2.3 Biological 20 2.4 Thermal 30 2.5 Fire Retardants 36 2.6 Weathering 41 References 45 3 Chemical Composition and Properties of Wood 49 Tatjana Stevanovic 3.1 Introduction 49 3.2 Cellulose 50 3.3 Hemicelluloses of Wood 68 3.4 Lignin(s) 80 3.5 Wood Extractives 96 References 103 4 Recycled Fibers 107 Nathalie Marlin and Bruno Carre 4.1 The Context and the Key Data 107 4.2 Recovered Paper and Board Grades 110 4.3 Unit Operations for Paper Recycling Processes 113 4.4 Recycling and Deinking Lines 119 4.5 Deinked Pulp Quality and Controls 122 4.6 The Limits of Paper Recycling 129 Acknowledgement 129 References 130 5 Recovered Papers Deinking by Froth Flotation 133 Davide Beneventi, Jeremy Allix, Patrice Nortier and Elisa Zeno 5.1 Introduction 133 5.2 Mass Transfer Mechanisms 135 5.3 Control of Process Performance by Chemical Additives 143 5.4 Flotation Deinking Process Modeling 149 References 152 6 High-Yield Pulps: An Interesting Concept for Producing Lignocellulosic Fibers 157 Michel Petit-Conil, Michael Lecourt and Valrie Meyer 6.1 Introduction 157 6.2 History of Mechanical Pulping 158 6.3 Principles of Mechanical Pulping Processes and Quality of Pulps 161 6.4 Quality of Mechanical Pulping Processes 171 6.5 Industrial Production of Mechanical Pulps 176 6.6 Bleaching of Mechanical Pulps 181 6.7 New Technologies under Development 185 6.8 Conclusion 201 References 201 7 Kraft Pulping 207 Dominique Lachenal 7.1 Introduction 207 7.2 Chemical Reagents 208 7.3 Mechanism of Delignification 209 7.4 Degradation of Carbohydrates during Kraft Pulping 213 7.5 Composition of Kraft Pulps 216 7.6 Improvement of the Kraft Process 217 7.7 Recovery of Cooking Reagents 220 7.8 Conclusion 222 References 222 8 Sulphite Pulping 225 Dmitry V. Evtuguin 8.1 Introduction 225 8.2 Brief History of Pulping Processes 227 8.3 Sulphite Pulping Chemicals 228 8.4 General Aspects of Sulphite Pulping 230 8.5 Reactions of Sulphite Pulping 234 References 243 Part 2: Wood and Fibres: Composites and Panels 9 Synthetic Adhesives for Wood Fibers and Composites: Chemistry and Technology 247 A. Pizzi 9.1 Introduction 247 9.2 Urea-Formaldehyde (UF) Adhesives 248 9.3 Melamine-Formaldehyde (MF) and Melamine-Urea-Formaldehyde (MUF) Adhesives 252 9.4 Phenolic Resins 255 9.5 Resorcinol Adhesives 259 9.6 Thermosetting Adhesives Based on Natural Resources 262 9.7 Isocyanate and Polyurethane Wood Adhesives 263 9.8 Chemistry of Isocyanate Wood Adhesives 263 9.9 Technology of Isocyanate Adhesives 264 9.10 Conditions of Application of Isocyanate Adhesives for Wood 269 9.11 Emulsion Polymer Isocyanates (EPI) 270 9.12 Polyvinyl Acetate (PVAc), EVAs and Acrylics 271 9.13 Hot Melts 272 References 273 10 Natural Adhesives, Binders and Matrices for Wood and Fiber Composites: Chemistry and Technology 277 A. Pizzi 10.1 Introduction 277 10.2 Tannin Adhesives 278 10.3 Lignin Adhesives 282 10.4 Mixed Tannin-Lignin Adhesives and Resins 285 10.5 Protein Adhesives 286 10.6 Carbohydrate Adhesives 287 10.7 Unsaturated Oil Adhesives 287 10.8 Wood Welding without Adhesives 289 10.9 Alternative Systems to Weld Wood 299 References 301 11 Chemically-Based Modern Wood Composites 305 Gerd Wegener and Elisabeth Windeisen 11.1 Introduction 305 11.2 Conventional Concepts and Products 305 11.3 New Concepts and Products 306 11.4 Outlook 310 References 310 12 Chemical Modification of Solid Wood 313 Philippe Gerardin 12.1 Introduction 313 12.2 Chemical Modifications Involving the Use of Chemicals 314 12.3 Chemical Modifications Using Heat Treatments 317 12.4 Conclusions 320 References 321 13 Modification of Natural Fibers Using Physical Technologies and Their Applications for Composites 323 Stephane Molina 13.1 Introduction 323 13.2 Wave and Radiation Technologies for Cellulosic Fiber Surface Modification 325 13.3 Physicochemical Technologies for Surface Modification of Cellulosic Fibers 334 13.4 Mechanical and Thermomechanical Technologies for Surface Modification of Cellulosic Fibers 335 13.5 Conclusions 340 References 340 14 Wood and Fiber-Based Composites: Surface Properties and Adhesion 345 Douglas Gardner, Gloria Oporto, and William Tze 14.1 Introduction: Practical Significance of Surface Properties and Adhesion 345 14.2 Adhesion Theories and Mechanisms 346 14.3 Interfacial Phenomena in Wood and Fiber Adhesion 347 14.4 Adhesion Interactions as a Function of Length Scale 349 14.5 Wood Bonding Considerations 350 14.6 Wood and Fiber Surface Properties 352 14.7 Wood Surface Modification 354 14.8 Analytical Techniques to Measure Wood and Fiber Surface Properties 359 References 378 15 Wood and Fiber Panels Technology 385 A.Pizzi 15.1 Introduction 385 15.2 Wood as a Substrate 385 15.3 Wood Plasticization 386 15.4 Types of Wood Panels 387 15.5 Influence of the Adhesive in Wood Panel Bonding 388 15.6 Influence of Wood in Wood Panel Production 389 15.7 Production Condition Parameters in Wood Panel Gluing 391 15.8 Correlation between Pressing Parameters and Physical Properties 398 References 402 Part 3: Wood and Fibres: Paper 16 Rheology: From Simple Fluids to Complex Suspensions 407 Raj P. Chhabra 16.1 Introduction 407 16.2 Classification of Fluid Behavior 409 16.3 Time-independent Fluid Behavior 412 16.4 Time-dependent Behavior 419 16.5 Viscoelastic Behavior 421 16.6 Small Amplitude Oscillatory Shear Motion 423 16.7 Elongational Flow 424 16.8 Rheology of Suspensions 427 16.9 Origins of Non-Newtonian Behavior 432 16.10 Implications in Engineering Applications 435 16.11 Concluding Summary 436 Acknowledgement 436 Nomenclature 436 References 437 17 Papermaking and Wet-End Chemistry 439 Eder Siqueira, Evelyne Mauret, Raphael Passas and Mohamed Naceur Belgacem 17.1 Introduction 439 17.2 Wet-end Chemicals, Fillers and Pigments: General Considerations 440 17.3 Functional Additives 444 17.4 Processing Aids 455 References 460 18 Paper Winding 463 David R. Roisutn 18.1 Introduction 463 18.2 Winder Types Found in a Paper Mill 464 18.3 Winder Classes and Types 464 18.4 Effect of Winder Classes and Types on Wound Roll Tightness 466 18.5 Roll Structure Theory and Control Curves 466 18.6 Tightness and Roll Quality Measurement 467 18.7 Winding Theory Stresses inside the Roll 469 18.8 Winding Defects 470 18.9 The Reel 471 18.10 Two-Drum Winders 472 18.11 Duplex Winders 473 18.12 Other Operations near the Rewinder 474 18.13 Automation and Productivity 474 18.14 Profile and Moisture 477 18.15 Paper Mills'Customers 478 18.16 Learning More about Winding 479 Abbreviations used in this section 479 References 479 19 Surface Treatments of Paper 481 Mohamed Naceur Belgacem and Julien Bras 19.1 Surface Sizing of Paper 481 19.2 Paper Coating 481 19.3 Specialty Papers by Coating 486 19.4 Coating Machines 489 References 491 20 Calendering of Papers and Boards: Processes and Basic Mechanisms 493 Didier Chaussy and David Guerin 20.1 Introduction 493 20.2 Calendering Processes 494 20.3 Applying Pressure in a Nip 505 20.4 Heat Transfer in the Nip 511 20.4.1 Heat Transfer Balance 511 20.5 Effect of Calendering on Paper Structure and Surface Properties 518 20.6 Conclusions and Trends in Calendering 525 References 526 21 Color and Color Reversion of Cellulosic and Lignocellulosic Fibers 531 Alain Castellan and Stephane Grelier 21.1 Introduction 531 21.2 Lignin-Free Cellulosic Fibers (Chemical Pulps) 532 21.3 Lignin-rich Cellulosic Fibers (High-yield Pulps) 539 21.4 Conclusion 549 References 549 Part 4 Wood and Fibres: Properties 22 Fire Behavior of Timber and Lignocellulose 555 Pedro Reszka and Jose L. Torero 22.1 Introduction 555 22.2 Wood in Structures 557 22.3 Basic Definition of Fire Growth 560 22.4 Degradation 561 22.5 Experimental Studies on Wood Behavior in Fire 567 22.6 Modeling Wood Behavior in Fire 570 22.7 Flammability Assessment Methods 571 22.8 The Role of Fire Retardants 22.9 Summary 577 References 578 23 Testing and Evaluation of Fire-retardant-treated Wood Products 583 Robert H. White 23.1 Introduction 583 23.2 Conditioning of Specimens 584 23.4 Regulatory Test Methods 587 23.5 Product Specific Regulatory Test Methods 588 23.6 Other Fire Test Methods 589 23.7 Tests for Smoke Obscuration 589 23.8 Other Properties of Fire-retardant-treated Wood 589 23.9 Specifications for Fire-retardant-treated Wood Products 590 23.10 Tests for Commonly Used Fire-retardant Chemicals 590 23.11 Concluding Remarks 591 References 591 24 Modern Timber Houses 595 Andreas Miiller, Hans-Peter Kolb and Maurice Brunner 24.1 Introduction 595 24.2 Tradition and Development of the Swiss Timber House 595 24.3 Timber House Systems 597 24.4 Heat Insulation and Protection against Moisture 600 24.5 Sound Protection 602 24.6 Fire Protection 604 24.7 Multistory Timber Buildings 606 24.8 Conclusions 609 References 610 25 Paper Characterization and Testing 611 Jean-Francis Block 25.1 Introduction and General Considerations 611 25.2 Composition and Structure 612 25.3 Mechanical Properties 616 25.4 Optical Properties 622 Suggested Literature 627 References 627 26 Dimensional Stabilization of Wood and Wood Composites 629 Michael Boonstra 26.1 Introduction 629 26.2 Thermal Modification 633 26.3 Chemical Modification 640 26.4 Wood Polymer Composites (WPC) 648 26.5 Other Applications 651 References 652 Index 657

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Book SynopsisThere is much industry guidance on implementing engineering projects and a similar amount of guidance on Process Safety Management (PSM). However, there is a gap in transferring the key deliverables from the engineering group to the operations group, where PSM is implemented. This book provides the engineering and process safety deliverables for each project phase along with the impacts to the project budget, timeline and the safety and operability of the delivered equipment.Table of ContentsList of Figure xvii List of Tables xviii Acronyms and Abbreviations xx Glossary xxviii Acknowledgments xxxii Files on the Web xxxiv Preface xxxvi 1 INTRODUCTION 1 1.1 Background and Scope 2 1.2 Why Integrating Process Safety is Important 3 1.3 What Type of Projects Are Included? 5 1.4 Project Life Cycle 7 1.5 Relationship to Other Programs 10 1.6 Structure of this Document 13 2 PROJECT MANAGEMENT CONCEPTS AND PRINCIPLES 16 2.1 Common Principles and Structure 16 2.1.1 Statement of Requirements 16 2.1.2 Project Scope 17 2.1.3 Basis of Design 17 2.1.4 Project Budget 18 2.1.5 Project Plan 18 2.1.6 Project Life Cycle 19 2.2 Project Management 20 2.3 Project Governance 21 2.4 Types of Project 22 2.4.1 Greenfield Projects 22 2.4.2 Brownfield Projects 22 2.4.3 Retrofit / Expansion Projects 23 2.4.4 Control System Upgrade Projects 24 2.4.5 Demolition Projects 24 2.4.6 Management of Change Projects 24 2.4.7 Mothballing Projects 25 2.4.8 Re-Commissioning Projects 25 2.4.9 Restarting a Project 25 2.4.10 Post-Incident Projects 26 2.5 Project Organization 26 2.5.1 Pre-Project Team 26 2.5.2 Typical Project Team 27 2.5.3 Unit Based Team 28 2.5.4 Equipment Based Team 28 2.5.5 Site Based Team 28 2.5.6 Small Projects 28 2.5.7 Roles and Responsibilities 29 2.6 Strategies for Implementation 32 2.6.1 Contractor Selection 35 2.6.2 Engineering Only 36 2.6.3 Engineering and Procurement 36 2.6.4 Engineering, Procurement and Construction 36 2.6.5 Operation 37 2.6.6 Contractor Oversight 37 2.7 Risk Management 38 2.8 Project Controls 40 2.8.1 Planning and Progress 40 2.8.2 Estimates, Budgets and Cost Control 41 2.8.3 Reporting 41 2.8.4 Metrics 41 2.8.5 Action Tracking 42 2.8.6 Change Management 42 2.9 Other Considerations 43 2.9.1 Materials Management 43 2.9.2 Quality Management 43 2.9.3 Lessons Learned 43 2.9.4 Post-Project Close-Out 44 2.10 Stage Gate Reviews 44 3 FRONT END LOADING 1 46 3.1 Preliminary Hazard Identification 48 3.2 Preliminary Inherently Safer Design Review 49 3.3 Concept Risk Analysis 51 3.4 Other Activities 52 3.4.1 Process Safety and EHS Plan 52 3.4.2 Risk Register 52 3.4.3 Action Tracking 52 3.5 Stage Gate Review 53 3.6 Summary 54 4 FRONT END LOADING 2 56 4.1 Evaluation of Development Options 58 4.1.1 Hazard Identification 59 4.1.2 Preliminary Inherently Safer Design Review 59 4.1.3 Concept Risk Analysis 60 4.1.4 Selection of the Development Option 60 4.2 Further Definition of the Selected Option 63 4.2.1 Design Hazard Management Process 63 4.2.2 Preliminary Inherently Safer Design (ISD) 68 4.2.3 Hazard Identification and Risk Analysis (HIRA) 68 4.2.4 Engineering Design Regulations, Codes, and Standards 69 4.2.5 Design Philosophies/Strategies 70 4.2.6 Preliminary Facility Siting Study 71 4.2.7 Preliminary Fire and Explosion Analysis 72 4.2.8 Transportation Studies 72 4.2.9 Preliminary Blowdown and Depressurization Study 74 4.2.10 Preliminary Fire & Gas Detection Study 74 4.2.11 Preliminary Fire Hazard Analysis 74 4.2.12 Preliminary Firewater Analysis 75 4.2.13 Preliminary Security Vulnerability Analysis 75 4.2.14 Other Engineering Design Considerations 75 4.3 Other Activities 76 4.3.1 EHS and Process Safety Plan 76 4.3.2 Risk Register 76 4.3.3 Action Tracking 76 4.3.4 HIRA Strategy 76 4.3.5 Docum entation 77 4.3.6 Stage Gate Review 77 4.4 Summary 79 5 FRONT END LOADING 3 80 5.1 Evaluation of Development Options 82 5.2 Further Definition of the Selected Option 82 5.2.1 Design Hazard Management Process 84 5.2.2 Inherently Safer Design Optimization 85 5.2.3 Facility Siting and Layout 86 5.2.4 Refine Design Safety Measures 93 5.2.5 Set Performance Standards 94 5.2.6 Hazard Identification and Risk Analysis (HIRA) 95 5.2.7 Safety Assessments 102 5.2.8 Re-Evaluate Major Accident Risk 113 5.2.9 Finalize Important Safety Decisions 113 5.2.10 Finalize Basis of Design 113 5.3 Other Engineering Considerations 114 5.3.1 Asset Integrity Management 114 5.3.2 Quality Management 115 5.3.3 Contractor Selection 115 5.3.4 Brownfield Developments 116 5.4 Other Activities 116 5.4.1 EHS and Process Safety Plans 116 5.4.2 Risk Register 116 5.4.3 Action Tracking 116 5.4.4 Change Management 116 5.4.5 Documentation 117 5.4.6 Preparation for Project Execution 117 5.5 Case for Safety 119 5.6 Stage Gate Review 119 5.7 Summary 120 6 DETAILED DESIGN STAGE 121 6.1 Detailed Design 124 6.1.1 Design Hazard Management Process 124 6.1.2 Inherently Safer Design Optimization 125 6.1.3 Site Layout 126 6.1.4 Design Safety Measures 126 6.1.5 Set Performance Standards 127 6.1.6 Hazard Identification and Risk Analysis (HIRA) 127 6.1.7 Safety Assessments 128 6.1.8 Re-Evaluate Major Accident Risk 129 6.1.9 Other Design Reviews 129 6.2 Procurement 130 6.3 Asset Integrity Management 131 6.4 Other Process Safety Activities 132 6.4.1 Case For Safety 132 6.5 Other Project Activities 133 6.5.1 EHS and Process Safety Plans 133 6.5.2 Risk Register 134 6.5.3 Action Tracking 134 6.5.4 Change Management 134 6.5.5 Documentation 135 6.5.6 Constructability 136 6.5.7 Contractor Selection 137 6.6 Preparation for Construction 138 6.7 Preparation for Pre-Commissioning, Commissioning, and Startup 139 6.8 Stage Gate Review 140 6.9 Summary 141 7 CONSTRUCTION 143 7.1 Planning 146 7.2 Pre-Mobilization 147 7.3 Mobilization 149 7.4 Execution 150 7.4.1 Procurement 151 7.4.2 Fabrication 151 7.4.3 Safety Culture 151 7.4.4 Workforce Involvement 152 7.4.5 Stakeholder Outreach 152 7.4.6 Contractor Management 152 7.4.7 Transportation 153 7.4.8 Equipment and Materials Handling 153 7.4.9 Hazard Evaluation 154 7.4.10 Engineering Design 156 7.4.11 Safe Work Practices 157 7.4.12 Operating, EHS and Process Safety Procedures 159 7.4.13 Training and Competence Assurance 159 7.4.14 Asset Integrity Management 160 7.4.15 Change Management 161 7.4.16 Emergency Response 162 7.4.17 Incident Investigation 163 7.4.18 Auditing 164 7.4.19 Performance Measurement 164 7.4.20 Operations Case for Safety 165 7.4.21 Pre-Commissioning 166 7.4.22 Mechanical Completion 170 7.4.23 Documentation 171 7.5 Other Project Activities 172 7.5.1 EHS and Process Safety Plans 172 7.5.2 Risk Register 172 7.5.3 Action Tracking 172 7.5.4 General Construction Management 172 7.6 De-Mobilization 173 7.7 Preparation for Commissioning and Startup 174 7.8 Final Evaluation and Close-out 175 7.9 Stage Gate Review 175 7.10 Summary 177 8 QUALITY MANAGEMENT 178 8.1 Design/Engineering 183 8.2 Procurement 186 8.3 Fabrication 187 8.4 Receipt 189 8.5 Storage and Retrieval 190 8.6 Construction and Installation 191 8.7 Operation 193 8.8 Documentation 194 8.9 Summary 194 9 COMMISSIONING AND STARTUP 196 9.1 Preparation 199 9.1.1 Planning 199 9.1.2 Safety 201 9.2 Operational Readiness 202 9.2.1 Pre-Startup Stage Gate Review 203 9.2.2 Operational Readiness Review 204 9.2.3 Start-Up Efficiency Review 207 9.3 Commissioning 208 9.3.1 Equipment Testing 209 9.3.2 Commissioning Procedures 211 9.4 Startup 213 9.4.1 Preparation for Startup 213 9.4.2 Calibration of Instruments and Analyzers 213 9.4.3 Startup with Process Chemicals/Fluids 214 9.5 Common Process Safety Elements 215 9.5.1 Hazard Evaluation 215 9.5.2 Safe Work Practices 216 9.5.3 Procedures 217 9.5.4 Training and Competence Assurance 217 9.5.5 Management of Change 218 9.5.6 Incident Investigation 219 9.5.7 Emergency Response 220 9.5.8 Auditing 221 9.5.9 Documentation 221 9.5.10 Performance Measurement 222 9.6 Other Project Activities 222 9.6.1 EHS and Process Safety Plans 222 9.6.2 Risk Register 223 9.6.3 Action Tracking 223 9.7 Performance Test Runs 223 9.8 Handover 224 9.9 Preparation for Ongoing Operation 225 9.10 Project Close-Out 226 9.10.1 Close Out Report 226 9.10.2 Post-Project Evaluation 226 9.11 Summary 227 10 OPERATION 228 10.1 Process Safety Management System 231 10.1.1 Process Safety Culture 233 10.1.2 Compliance with Standards 233 10.1.3 Process Safety Competency 233 10.1.4 Workforce Involvement 234 10.1.5 Stakeholder Outreach 234 10.1.6 Process Knowledge Management 234 10.1.7 Hazard Identification and Risk Analysis 234 10.1.8 Operating Procedures 235 10.1.9 Safe Work Practices 235 10.1.10 Asset Integrity and Reliability 236 10.1.11 Contractor Management 238 10.1.12 Training and Performance Assurance 239 10.1.13 Management of Change 239 10.1.14 Operational Readiness 239 10.1.15 Conduct of Operations 240 10.1.16 Emergency Management 240 10.1.17 Incident Investigation 240 10.1.18 Measurement and Metrics 241 10.1.19 Auditing 242 10.1.20 Management Review and Continuous Improvement 242 10.1.21 EHS and Process Safety Procedures 243 10.2 Other Project Activities 243 10.2.1 EHS and Process Safety Plans 243 10.2.2 Risk Register 243 10.2.3 Action Tracking 243 10.3 Technical Support 243 10.4 Performance Test Runs 244 10.5 Operation Stage Gate Rview 244 10.6 Post-Operational Review 245 10.7 Project Close-Out 246 10.8 Summary 246 11 END OF LIFE 247 11.1 Design for Decommissioning 249 11.2 Planning for Decommissioning 250 11.2.1 Engineering Survey 251 11.2.2 Hazard Evaluation 254 11.2.3 Hazardous Materials 254 11.2.4 Process Safety Plan 255 11.2.5 Utilities 255 11.2.6 Re-Engineering 256 11.3 Decommissioning Procedures 256 11.3.1 Late-Life Operations 257 11.3.2 Cessation of Production 258 11.3.3 Cleaning and Decontamination 258 11.3.4 Mothballed Facilities And Equipment 258 11.4 Deconstruction and Demolition 259 11.4.1 Deconstruction 259 11.4.2 Demolition 260 11.5 Process Safety for Decommissioning 261 11.5.1 Contractor Management 261 11.5.2 Safety Culture 262 11.5.3 Workforce Involvement 263 11.5.4 Stakeholder Outreach 263 11.5.5 Hazard Evaluation 263 11.5.6 Safe Work Practices 264 11.5.7 EHS and Process Safety Procedures 265 11.5.8 Training and Competence Assurance 266 11.5.9 Asset Integrity Management 267 11.5.10 Change Management 267 11.5.11 Operational Readiness Review 267 11.5.12 Emergency Management 268 11.5.13 Incident Investigation 269 11.5.14 Auditing 269 11.5.15 Disposal 270 11.5.16 Remediation 270 11.6 Other Project Activities 271 11.6.1 EHS and Process Safety Plans 271 11.6.2 Risk Register 271 11.6.3 Action Tracking 271 11.6.4 General Decommissioning Management 272 11.6.5 Stage Gate Reviews 272 11.7 Summary 274 12 DOCUMENTATION 275 12.1 Document Management 275 12.2 Process Knowledge Management 278 12.2.1 Front End Loading 1 Stage 278 12.2.2 Front End Loading 2 Stage 279 12.2.3 Front End Loading 3 Stage 280 12.2.4 Detailed Design Stage 281 12.2.5 Construction Stage 283 12.2.6 Commissioning and Startup Stage 286 12.2.7 Handover 287 12.2.8 Operation Stage 288 12.2.9 End of Life Stage 291 12.3 Summary 292 APPENDIX A. TYPICAL PROCESS SAFETY STUDIES OVER PROJECT LIFE CYCLE 293 APPENDIX B. PROJECT PROCESS SAFETY PLAN 295 APPENDIX C. TYPICAL HAZARD & RISK REGISTER 298 APPENDIX D. SAFETY CHECKLIST FOR PROCESS PLANTS 301 APPENDIX E. EXAMPLE OF SITE-SPECIFIC DECOMMISSIONING CHECKLIST / QUESTIONNAIRE 315 APPENDIX F. TYPICAL PROJECT DOCUMENTATION 322 APPENDIX G. STAGE GATE REVIEW PROTOCOL FOR PROCESS SAFETY 337 REFERENCES 365 INDEX 379

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Book SynopsisThis Guideline presents the framework of process safety knowledge and expertise versus the desired competency level in a super-matrix format, vertically and diagonally.Table of ContentsDedication xiList of Tables xviiFiles on the Web Accompanying This Book xixAcronyms and Abbreviations xxiGlossary xxiiiAcknowledgements xxvPreface xxviiExecutive Summary xxixORGANIZATION OF THIS BOOK xxixINTRODUCTION 11.1 Why process safety competency? 11.2 Purpose 21.3 Audience 31.4 How to Use This Process 41.5 Risk Based Process Safety Elements 51.6 CCPS Vision 20/20 101.7 References 112. IDENTIFY PROCESS SAFETY ROLES & COMPETENCY NEEDS 13 2.1 List of generic job roles 132.2 List of proficiency levels 182.3 List of process safety knowledge/skills 213. PROCESS SAFETY COMPETENCY MATRIX 233.1 What is the matrix? 233.2 How to customize the matrix 253.3 Uses of the Matrix 313.4 References 384. INDIVIDUAL AND ORGANIZATIONAL PROCESS SAFETY COMPETENCIES 394.1 Develop organization specific competencies 394.2 Assure compliance with regulations 414.3 Example Templates and Checklists 444.4 References 465. ASSESS COMPETENCIES VS. NEEDS 495.1 Assessing existing competencies 495.2 Training for assessors 505.3 Identify Gaps between current status and needs 516. DEVELOP GAP CLOSURE PLAN 536.1 Methods for closing the gaps 546.2 Supporting materials 556.3 Pre-requisites before progressing to the next level 576.4 EXAMPLE of MANAGing GAP CLOSURE 577. SUSTAINING COMPETENCIES 597.1 Strategies for Sustaining Competencies 597.2 Review and Update Competency Needs 617.3 Organizational Process Safety Culture 627.4 References 62APPENDIX 1: EXAMPLE COMPETENCIES FOR AUDITING 63APPENDIX 2: PHM COORDINATOR & HA FACILITATOR QUALIFICATIONS 65A2.1 Purpose 65A2.2 Assumptions 65A2.3 Full Time Equivalent (FTE) Resource Alignment 68A2.4 Expertise and Experience 69A2.5 EHS and PHM Alignment 69A2.6 Overview of Duties and Responsibilities 72A2.7 Competency-Based Knowledge (Training) Road Map for Qualification 73APPENDIX 3: HAZOP FACILITATOR 75APPENDIX 4: SHOWING GAP CLOSURE PROGRESSIndex 81

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Book SynopsisDrug therapy via inhalation route is at the cutting edge of modern drug delivery research. There has been significant progress on the understanding of drug therapy via inhalation products.Table of ContentsList of Contributors xiii Series Preface xvii Preface xix 1. Lung Anatomy and Physiology and Their Implications for Pulmonary Drug Delivery 1Rahul K. Verma, Mariam Ibrahim, and Lucila Garcia-Contreras 1.1 Introduction 2 1.2 Anatomy and Physiology of Lungs 2 1.2.1 Macro- and Microstructure of the Airways and Alveoli as It Pertains to Drug Delivery 2 1.2.2 Lung Surfactant 4 1.2.3 Pulmonary Blood Circulation 5 1.3 Mechanisms of Aerosol Deposition 5 1.3.1 Impaction 6 1.3.2 Sedimentation 6 1.3.3 Interception 6 1.3.4 Diffusion 7 1.4 Drug Absorption 7 1.4.1 Mechanisms of Drug Absorption from the Lungs 7 1.5 Physiological Factors Affecting the Therapeutic Effectiveness of Drugs Delivered by the Pulmonary Route 8 1.5.1 Airway Geometry 8 1.5.2 Inhalation Mode 8 1.5.3 Airflow Rate 9 1.5.4 Mechanism of Particle Clearance 9 1.5.5 Lung Receptors 10 1.5.6 Disease States 11 1.5.7 Effect of Age and Gender Difference 11 1.6 Computer Simulations to Describe Aerosol Deposition in Health and Disease 11 1.6.1 Semiempirical Models 12 1.6.2 Deterministic Models 12 1.6.3 Trumpet Models (One-Dimensional) 12 1.6.4 Stochastic, Asymmetric Generation Models 13 1.6.5 Computation Fluid Dynamics (CFD)-Based Model 13 1.7 Conclusions 13 References 14 2. The Role of Functional Lung Imaging in the Improvement of Pulmonary Drug Delivery 19Andreas Fouras and Stephen Dubsky 2.1 Introduction 19 2.1.1 Particle Deposition 20 2.1.2 Regional Action of Delivered Drug 22 2.1.3 The Role of Functional Lung Imaging in Pulmonary Drug Delivery 22 2.2 Established Functional Lung Imaging Technologies 23 2.2.1 Computed Tomography 23 2.2.2 Ventilation Measurement using 4DCT Registration-based Methods 24 2.2.3 Hyperpolarized Magnetic Resonance Imaging 24 2.2.4 Electrical Impedance Tomography 25 2.2.5 Nuclear Medical Imaging (PET/SPECT) 25 2.3 Emerging Technologies 26 2.3.1 Phase-contrast Imaging 26 2.3.2 Grating Interferometry 27 2.3.3 Propagation-based Phase-contrast Imaging 28 2.3.4 Functional Lung Imaging using Phase Contrast 28 2.3.5 Laboratory Propagation-based Phase-contrast Imaging 29 2.4 Conclusion 30 References 31 3. Dry Powder Inhalation for Pulmonary Delivery: Recent Advances and Continuing Challenges 35Simone R. Carvalho, Alan B. Watts, Jay I. Peters, and Robert O. Williams III 3.1 Introduction 36 3.2 Dry Powder Inhaler Devices 37 3.2.1 Overview 37 3.2.2 Recent Innovations in Dry Powder Inhaler Technology 39 3.3 New Developments in DPI Formulations and Delivery 43 3.3.1 Particle Surface Modification 43 3.3.2 Particle Engineering Technology for Pulmonary Delivery 44 3.4 Characterization Methods of Dry Powder Inhaler Formulations 50 3.5 Conclusion 52 References 53 4. Pulmonary Drug Delivery to the Pediatric Population – A State-of-the-Art Review 63Marie-Pierre Flament 4.1 Introduction 63 4.2 Patient Consideration 64 4.2.1 Anatomy and Physiology of Children’s Lungs 64 4.2.2 Nasal Versus Oral Inhalation 65 4.2.3 Patient-related Factors Influencing Aerosol Deposition 66 4.2.4 Age and Dosage Forms of Choice 67 4.3 Delivery Systems for the Pediatric Population 69 4.3.1 Nebulizers 69 4.3.2 Pressurized Metered Dose Inhalers 72 4.3.3 Dry Powder Inhalers 73 4.3.4 Interfaces 74 4.4 Recommendations 80 4.5 Conclusion 82 References 82 5. Formulation Strategies for Pulmonary Delivery of Poorly Soluble Drugs 87Nathalie Wauthoz and Karim Amighi 5.1 Introduction 88 5.1.1 In vivo Fate of Inhaled Poorly Water-soluble Drugs 89 5.1.2 The Pharmacokinetics of Inhaled Poorly Water-soluble Drugs Administered for Local and Systemic Action 92 5.1.3 Formulation Strategies for Pulmonary Delivery of Poorly Water-soluble Drugs 93 5.2 Co-solvents 93 5.3 Cyclodextrins 97 5.4 PEGylation 99 5.5 Reduction of Size to Micro-/Nanoparticles 100 5.5.1 Nanocrystal Suspension 101 5.5.2 Nanocrystals in a Hydrophilic Matrix System 102 5.5.3 Nanoclusters 103 5.6 Solid Dispersion/Amorphization 103 5.7 Micelles 106 5.8 Liposomes 108 5.9 Solid Lipid Nanoparticles and Nanostructured Lipid Carriers 110 5.10 Conclusion 111 References 114 6. Lipidic Micro- and Nano-Carriers for Pulmonary Drug Delivery – A State-of-the-Art Review 123Yahya Rahimpour, Hamed Hamishehkar, and Ali Nokhodchi 6.1 Introduction 124 6.2 Pulmonary Drug Delivery 125 6.3 Liposomal Pulmonary Delivery 126 6.4 Nebulization of Liposomes 126 6.5 Liposomal Dry-powder Inhalers 128 6.6 Solid Lipid Microparticles in Pulmonary Drug Delivery 129 6.7 Solid Lipid Nanoparticles in Pulmonary Drug Delivery 131 6.8 Nanostructured Lipid Carrier (NLC) in Pulmonary Drug Delivery 133 6.9 Nanoemulsions in Pulmonary Drug Delivery 134 6.10 Conclusion and Perspectives 135 References 136 7. Chemical and Compositional Characterisation of Lactose as a Carrier in Dry Powder Inhalers 143Rim Jawad, Gary P. Martin and Paul G. Royall 7.1 Introduction 144 7.2 Production of Lactose 145 7.3 Lactose: Chemical Forms, Solid-State Composition, Physicochemical Properties 147 7.4 Epimerisation of Lactose 150 7.5 Analysis of Lactose 151 7.5.1 Powder X-ray Diffraction 152 7.5.2 Nuclear Magnetic Resonance 153 7.5.3 Infrared Spectroscopy 156 7.5.4 Differential Scanning Calorimetry 157 7.5.5 Polarimetry 158 7.6 The Influence of the Chemical and Solid-State Composition of Lactose Carriers on the Aerosolisation of DPI Formulations 159 7.7 Conclusions 163 References 163 8. Particle Engineering for Improved Pulmonary Drug Delivery Through Dry Powder Inhalers 171Waseem Kaialy and Ali Nokhodchi 8.1 Introduction 172 8.2 Dry Powder Inhalers 172 8.3 Particle Engineering to Improve the Performance of DPIs 172 8.3.1 Crystallization 173 8.3.2 Spray-drying 174 8.3.3 Spray-freeze-drying 177 8.3.4 Supercritical Fluid Technology 177 8.3.5 Pressure Swing Granulation (PSG) Technique 178 8.4 Engineered Carrier Particles for Improved Pulmonary Drug Delivery from Dry Powder Inhalers 178 8.5 Relationships between Physical Properties of Engineered Particles and Dry Powder Inhaler Performance 182 8.5.1 Particle Size 182 8.5.2 Flow Properties 184 8.5.3 Particle Shape 185 8.5.4 Particle Surface Texture 187 8.5.5 Fine Particle Additives 188 8.5.6 Surface Area 188 8.6 Conclusions 189 References 189 9. Particle Surface Roughness – Its Characterisation and Impact on Dry Powder Inhaler Performance 199Bernice Mei Jin Tan, Celine Valeria Liew, Lai Wah Chan, and Paul Wan Sia Heng 9.1 Introduction 200 9.2 What is Surface Roughness? 200 9.3 Measurement of Particle Surface Roughness 202 9.3.1 General Factors to Consider During a Measurement 202 9.3.2 Direct Methods to Profile or Visualise Surface Roughness 204 9.3.3 Indirect Measurement of Surface Roughness 206 9.4 Impact of Surface Roughness on Carrier Performance – Theoretical Considerations 206 9.4.1 Mixing and Blend Stability 206 9.4.2 Drug-carrying Capacity 207 9.4.3 Drug Adhesion 207 9.4.4 Drug Detachment 208 9.4.5 Particle Arrangement in Ordered Mixtures After the Addition of Fine Excipient 209 9.5 Particle Surface Modification 210 9.5.1 Spray Drying 210 9.5.2 Solution Phase Processing 211 9.5.3 Crystallisation 213 9.5.4 Sieving 213 9.5.5 Fluid-bed Coating 213 9.5.6 Dry Powder Coating 213 9.6 Conclusion 215 References 215 10. Dissolution: A Critical Performance Characteristic of Inhaled Products? 223Ben Forbes, Nathalie Hauet Richer, and Francesca Buttini 10.1 Introduction 223 10.2 Dissolution of Inhaled Products 224 10.2.1 Dissolution Rate 224 10.2.2 Dissolution in the Lungs 224 10.2.3 Case for Dissolution Testing 225 10.2.4 Design of Dissolution Test Systems 226 10.3 Particle Testing and Dissolution Media 226 10.3.1 Particle Collection 226 10.3.2 Dissolution Media 229 10.4 Dissolution Test Apparatus 230 10.4.1 USP Apparatus 1 (Basket) 231 10.4.2 USP Apparatus 2 (Paddle) and USP Apparatus 5 (Paddle Over Disc) 232 10.4.3 USP Apparatus 4 (Flow-Through Cell) 232 10.4.4 Diffusion-Controlled Cell Systems (Franz Cell, Transwell, Dialysis) 233 10.4.5 Methodological Considerations 234 10.5 Data Analysis and Interpretation 235 10.5.1 Modelling 236 10.5.2 Comparing Dissolution Profiles (Model-independent Method for Comparison) 237 10.6 Conclusions 237 References 238 11. Drug Delivery Strategies for Pulmonary Administration of Antibiotics 241Anna Giulia Balducci, Ruggero Bettini, Paolo Colombo, and Francesca Buttini 11.1 Introduction 242 11.2 Antibiotics Used for the Treatment of Pneumoniae 243 11.3 Antibiotic Products for Inhalation Approved on the Market 244 11.4 Nebulisation 246 11.5 Antibiotic Dry Powders for Inhalation 250 11.5.1 Tobramycin 251 11.5.2 Capreomycin 252 11.5.3 Gentamicin 253 11.5.4 Ciprofloxacin 254 11.5.5 Levofloxacin 255 11.5.6 Colistimethate Sodium 256 11.6 Device and Payload of Dose 256 11.7 Conclusions 258 References 258 12. Molecular Targeted Therapy of Lung Cancer: Challenges and Promises 263Jaleh Barar, Yadollah Omidi, and Mark Gumbleton 12.1 Introduction 265 12.2 An Overview on Lung Cancer 266 12.3 Molecular Features of Lung Cancer 268 12.3.1 Tumor Microenvironment (TME) 269 12.3.2 Tumor Angiogenesis 269 12.3.3 Tumor Stromal Components 270 12.3.4 Pharmacogenetic Markers: Cytochrome P450 270 12.4 Targeted Therapy of Solid Tumors: How and What to Target? 271 12.4.1 EPR Effect: A Rational Approach for Passive Targeting 272 12.4.2 Toward Long Circulating Anticancer Nanomedicines 273 12.4.3 Active/Direct Targeting 273 12.4.4 Overcoming Multidrug Resistance (MDR) 273 12.4.5 Antibody-Mediated Targeting 274 12.4.6 Aptamer-Mediated Targeted Therapy 276 12.4.7 Folate Receptor-Mediated Targeted Therapy 276 12.4.8 Transferrin-Mediated Targeted Therapy 276 12.4.9 Targeted Photodynamic Therapy 277 12.4.10 Multimodal Theranostics and Nanomedicines 278 12.5 Final Remarks 278 References 279 13. Defining and Controlling Blend Evolution in Inhalation Powder Formulations using a Novel Colourimetric Method 285David Barling, David Morton, and Karen Hapgood 13.1 Introduction 286 13.1.1 Introduction to Blend Pigmentation 287 13.1.2 Previous Work in the Use of Coloured Tracers to Assess Powder Blending 288 13.1.3 Colour Tracer Properties and Approach to Blend Analysis 288 13.2 Uses and Validation 290 13.2.1 Assessment of Mixer Characteristics and Mixer Behaviour 290 13.2.2 Quantification of Content Uniformity and Energy Input 293 13.2.3 Detection and Quantification of Unintentional Milling during Mixing 295 13.2.4 Robustness of Method with Tracer Concentration 295 13.3 Comments on the Applied Suitability and Robustness in of the Tracer Method 296 13.4 Conclusions 297 Acknowledgements 297 References 297 14. Polymer-based Delivery Systems for the Pulmonary Delivery of Biopharmaceuticals 301Nitesh K. Kunda, Iman M. Alfagih, Imran Y. Saleem, and Gillian A. Hutcheon 14.1 Introduction 302 14.2 Pulmonary Delivery of Macromolecules 302 14.3 Polymeric Delivery Systems 303 14.3.1 Micelles 304 14.3.2 Dendrimers 305 14.3.3 Particles 305 14.4 Preparation of Polymeric Nano/microparticles 305 14.4.1 Emulsification Solvent Evaporation 306 14.4.2 Emulsification Solvent Diffusion 307 14.4.3 Salting Out 307 14.5 Formulation of Nanoparticles as Dry Powders 308 14.5.1 Freeze-drying 308 14.5.2 Spray-drying 309 14.5.3 Spray-freeze-drying 309 14.5.4 Supercritical Fluid Drying 310 14.6 Carrier Properties 310 14.6.1 Size 310 14.6.2 Morphology 311 14.6.3 Surface Properties 311 14.7 Toxicity of Polymeric Delivery Systems 311 14.8 Pulmonary Delivery of Polymeric Particles 312 14.9 Conclusions 313 References 313 15. Quality by Design: Concept for Product Development of Dry-powder Inhalers 321Al Sayyed Sallam, Sami Nazzal, Hatim S. AlKhatib, and Nabil Darwazeh 15.1 Introduction 322 15.2 Quality Target Product Profile (QTPP) 324 15.3 Critical Quality Attributes (CQA) 324 15.4 Quality Risk Management 325 15.5 Design of Experiments 326 15.6 Design Space 328 15.7 Control Strategies 328 15.8 Continual Improvement 329 15.9 Process Analytical Technology/Application in DPI 329 15.10 Particle Size 329 15.11 Crystallinity and Polymorphism 330 15.12 Scale-up and Blend Homogeneity 331 15.13 Applying of QbD Principles to Analytical Methods 331 15.14 Conclusion 332 References 332 16. Future Patient Requirements on Inhalation Devices: The Balance between Patient, Commercial, Regulatory and Technical Requirements 339Orest Lastow 16.1 Introduction 340 16.1.1 Inhaled Drug Delivery 340 16.1.2 Patients 340 16.2 Requirements 341 16.2.1 Patient Requirements 341 16.2.2 Technical Requirements 343 16.2.3 Performance Requirements 345 16.3 Requirement Specifications 346 16.3.1 Requirement Hierarchy 346 16.3.2 Developing the Requirements 347 16.4 Product Development 350 16.5 Conclusions 351 References 352 Index 353

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Book SynopsisTable of ContentsList of Figures ix List of Tables xxvii Foreword xxxi Acknowledgments xxxiii 1 Book Organization 1 By T. Stack 2 The Basics of Ergonomics 5 By T. Stack 3 Anthropometry 21 By L. Ostrom 4 Office Ergonomics 77 By C. Wilhelmsen 5 Administrative Controls and Stretch and Flex Program 111 By C. Wilhelmsen 6 Elements of Ergonomics Programs 121 By L. Ostrom 7 Biomechanics 163 By T. Stack 8 Psychophysics 181 By L. Ostrom 9 Hand Tools 207 By L. Ostrom 10 Vibration 233 By L. Ostrom 11 Industrial Workstation Design 247 By L. Ostrom 12 Manual Materials Handling 271 By T. Stack 13 Work-Related Musculoskeletal Disorders 283 By T. Stack 14 How to Conduct an Ergonomic Assessment and Ergonomic Assessment Tools 327 By T. Stack 15 Ergonomics in the Healthcare Industry 363 By L. Ostrom 16 Case Studies 413 By L. Ostrom Appendix A Exercises 443 By T. Stack Appendix B Guides 455 By T. Stack Appendix C Tools 471 By T. Stack Glossary 505 Acronyms 509 Index 511

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Book SynopsisPhosphorus Pollution Control Policies and Strategies Deterioration and decline of water resources due to pollution caused by humans and their activities has become a universal health, environmental, social and economic problem. Excess discharges of nutrients, in particular, phosphorus, has been recognized as the most prevalent water pollution problem globally. Moreover, its perpetual occurrence and expansion creates imminent threats to water and food security. Despite extensive research during the past ?ve decades, many key questions in eutrophication science remain unanswered. This book summarizes the most recent policies and strategies for phosphorus removal and recovery from municipal, residential and agricultural wastewater effluents and runoff into a concise and up-to-date volume. The book will be of interest to environmental and water resources scientists and engineers, consultants, policy makers, and practitioners working in the field.Table of ContentsAuthor Biography ix Acknowledgements x List of Abbreviations xii 1 The Looming Threat of Eutrophication 1 1.1 Introduction 1 1.2 Trophic Classes of Water Bodies 3 1.3 The Role of Phosphorus in Eutrophication 4 1.4 Impacts of Eutrophication 7 1.5 The Extent of Eutrophication 8 1.6 Global Climate Change and Eutrophication 10 Further Reading/Resources 10 2 Water Quality Legislation and Policy for Phosphorus Pollution Control 11 2.1 Introduction 11 2.2 Water Policies to Protect Water Quality from Phosphorus Pollution 13 2.3 Governance of Innovative Technologies for Phosphorus Removal 30 2.4 ETV for Innovative Phosphorus Removal Technologies and Practices 36 3 Phosphorus Removal Methods and Technologies 41 3.1 Introduction 41 3.2 P Removal from Municipal Wastewater Treatment Effluents (MWWTE) 43 3.3 Phosphorus Removal from Residential Wastewater Effluents (Onsite Residential Wastewater and Disposal Treatment Systems) 50 3.4 North American Onsite Wastewater Treatment Market 64 3.5 Agricultural Phosphorus Pollution and Mitigation Measures and Strategies 70 3.6 Phosphorus Removal from Urban Stormwater Runoff 94 3.7 In‐Lake Treatment of P 98 4 Phosphorus Recovery Technologies 100 4.1 Introduction 100 4.2 P Recovery from Municipal Wastewater Treatment Effluents 102 4.3 P Recovery from Manure 108 4.4 P Recovery from Alternative Sources – Water and Soil Management Systems 112 4.5 Phosphorus Recovery Regulations 113 4.6 Conclusions 115 References 117 Index 153

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Book SynopsisMolecular processes in nature affect human health, the availability of resources and the Earth s climate. Molecular modelling is a powerful and versatile toolbox that complements experimental data and provides insights where direct observation is not currently possible.Table of ContentsList of Contributors xi Preface xiii 1 Introduction to the Theory and Methods of Computational Chemistry 1 David M. Sherman 1.1 Introduction 1 1.2 Essentials of Quantum Mechanics 2 1.2.1 The Schrödinger Equation 4 1.2.2 Fundamental Examples 4 1.3 Multielectronic Atoms 7 1.3.1 The Hartree and Hartree–Fock Approximations 7 1.3.2 Density Functional Theory 13 1.4 Bonding in Molecules and Solids 17 1.4.1 The Born–Oppenheimer Approximation 17 1.4.2 Basis Sets and the Linear Combination of Atomic Orbital Approximation 18 1.4.3 Periodic Boundary Conditions 20 1.4.4 Nuclear Motions and Vibrational Modes 21 1.5 From Quantum Chemistry to Thermodynamics 22 1.5.1 Molecular Dynamics 24 1.6 Available Quantum Chemistry Codes and Their Applications 27 References 28 2 Force Field Application and Development 33 Marco Molinari, Andrey V. Brukhno, Stephen C. Parker, and Dino Spagnoli 2.1 Introduction 33 2.2 Potential Forms 35 2.2.1 The Non-bonded Interactions 35 2.2.2 The Bonded Interactions 37 2.2.3 Polarisation Effects 37 2.2.4 Reactivity 39 2.2.5 Fundamentals of Coarse Graining 40 2.3 Fitting Procedure 42 2.3.1 Combining Rules Between Unlike Species 42 2.3.2 Optimisation Procedures for All-Atom Force Fields 43 2.3.3 Deriving CG Force Fields 45 2.3.4 Accuracy and Limitations of the Fitting 47 2.3.5 Transferability 48 2.4 Force Field Libraries 48 2.4.1 General Force Fields 48 2.4.2 Force Field Libraries for Organics: Biomolecules with Minerals 49 2.4.3 Potentials for the Aqueous Environment 50 2.4.4 Current CGFF Potentials 51 2.4.5 Multi-scale Methodologies 53 2.5 Evolution of Force Fields for Selected Classes of Minerals 54 2.5.1 Calcium Carbonate 54 2.5.2 Clay Minerals 56 2.5.3 Hydroxides and Hydrates 60 2.5.4 Silica and Silicates 60 2.5.5 Iron-Based Minerals 61 2.6 Concluding Remarks 63 References 64 3 Quantum-Mechanical Modeling of Minerals 77 Alessandro Erba and Roberto Dovesi 3.1 Introduction 77 3.2 Theoretical Framework 79 3.2.1 Translation Invariance and Periodic Boundary Conditions 79 3.2.2 HF and KS Methods 80 3.2.3 Bloch Functions and Local BS 81 3.3 Structural Properties 82 3.3.1 P–V Relation Through Analytical Stress Tensor 83 3.3.2 P–V Relation Through Equation of State 85 3.4 Elastic Properties 86 3.4.1 Evaluation of the Elastic Tensor 86 3.4.2 Elastic Tensor-Related Properties 89 3.4.3 Directional Seismic Wave Velocities and Elastic Anisotropy 89 3.5 Vibrational and Thermodynamic Properties 91 3.5.1 Solid-State Thermodynamics 93 3.6 Modeling Solid Solutions 95 3.7 Future Challenges 98 References 99 4 First Principles Estimation of Geochemically Important Transition Metal Oxide Properties: Structure and Dynamics of the Bulk, Surface, and Mineral/Aqueous Fluid Interface 107 Ying Chen, Eric Bylaska, and John Weare 4.1 Introduction 107 4.2 Overview of the Theoretical Methods and Approximations Needed to Perform AIMD Calculations 109 4.3 Accuracy of Calculations for Observable Bulk Properties 113 4.3.1 Bulk Structural Properties 113 4.3.2 Bulk Electronic Structure Properties 118 4.4 Calculation of Surface Properties 123 4.4.1 Surface Structural Properties 123 4.4.2 Electronic Structure in the Surface Region 127 4.4.3 Water Adsorption on Surface 129 4.5 Simulations of the Mineral–Water Interface 130 4.5.1 CPMD Simulations of the Vibrational Structure of the Hematite (012)–Water Interface 130 4.5.2 CPMD Simulations of Fe2+ Species at the Mineral–Water Interface 132 4.6 Future Perspectives 134 Acknowledgments 134 Appendix 134 A.1 Short Introduction to Pseudopotentials 135 A.1.1 The Spin Penalty Pseudopotential 137 A.1.2 Projected Density of States from Pseudo-Atomic Orbitals 138 A.2 Hubbard-Like Coulomb and Exchange (DFT+U) 138 A.3 Overview of the PAW Method 139 References 143 5 Computational Isotope Geochemistry 151 James R. Rustad 5.1 A Brief Statement of Electronic Structure Theory and the Electronic Problem 152 5.2 The Vibrational Eigenvalue Problem 154 5.3 Isotope Exchange Equilibria 156 5.4 Qualitative Insights 159 5.5 Quantitative Estimates 160 5.6 Relationship to Empirical Estimates 169 5.7 Beyond the Harmonic Approximation 171 5.8 Kinetic Isotope Effects 172 5.9 Summary and Prognosis 172 Acknowledgments 173 References 173 6 Organic and Contaminant Geochemistry 177 Daniel Tunega, Martin H. Gerzabek, Georg Haberhauer, Hans Lischka, and Adelia J. A. Aquino 6.1 Introduction 177 6.1.1 Review Examples of Molecular Modeling Applications in Organic and Contaminant Geochemistry 179 6.2 Molecular Modeling Methods 184 6.2.1 Molecular Mechanics: Brief Summary 184 6.2.2 Quantum Mechanics: Overview 187 6.2.3 Molecular Modeling Techniques: Summary 192 6.2.4 Models: Clusters, Periodic Systems, and Environmental Effects 195 6.3 Applications 196 6.3.1 Modeling of Surface Complexes of Polar Phenoxyacetic Acid-Based Herbicides with Iron Oxyhydroxides and Clay Minerals 197 6.3.2 Modeling of Adsorption Processes of Polycyclic Aromatic Hydrocarbons on Iron Oxyhydroxides 217 6.3.3 Modeling of Interactions of Polar and Nonpolar Contaminants in Organic Geochemical Environment 220 6.4 Perspectives and Future Challenges 227 Glossary 229 References 231 7 Petroleum Geochemistry 245 Qisheng Ma and Yongchun Tang 7.1 Introduction: Petroleum Geochemistry and Basin Modeling 245 7.2 Technology Development of the Petroleum Geochemistry 246 7.2.1 Thermal Maturity and Vitrinite Reflectance 246 7.2.2 Rock-Eval Pyrolysis 247 7.2.3 Kerogen Pyrolysis and Gas Chromatography Analysis 248 7.2.4 Kinetic Modeling of Kerogen Pyrolysis 249 7.2.5 Natural Gases and C/H Isotopes 253 7.3 Computational Simulations in Petroleum Geochemistry 253 7.3.1 Ab Initio Calculations of the Unimolecular C–C Bond Rapture 253 7.3.2 Quantum Mechanical Calculations on Natural Gas 13C Isotopic Fractionation 256 7.3.3 Deuterium Isotope Fractionations of Natural Gas 258 7.3.4 Molecular Modeling of the 13C and D Doubly Substituted Methane Isotope 260 7.4 Summary 262 References 262 8 Mineral–Water Interaction 271 Marie-Pierre Gaigeot and Marialore Sulpizi 8.1 Introduction 271 8.2 Brief Review of AIMD Simulation Method 275 8.2.1 Ab Initio Molecular Dynamics and Density Functional Theory 275 8.3 Calculation of the Surface Acidity from Reversible Proton Insertion/Deletion 280 8.4 Theoretical Methodology for Vibrational Spectroscopy and Mode Assignments 282 8.5 Property Calculations from AIMD: Dipoles and Polarisabilities 284 8.6 Illustrations from Our Recent Works 286 8.6.1 Organisation of Water at Silica–Water Interfaces: (0001) α-Quartz Versus Amorphous Silica 286 8.6.2 Organisation of Water at Alumina–Water Interface: (0001) α-Alumina Versus (101) Boehmite 291 8.6.3 How Surface Acidities Dictate the Interfacial Water Structural Arrangement 293 8.6.4 Vibrational Spectroscopy at Oxide–Liquid Water Interfaces 295 8.6.5 Clay–Water Interface: Pyrophyllite and Calcium Silicate 299 8.7 Some Perspectives for Future Works 302 References 304 9 Biogeochemistry 311 Weilong Zhao, Zhijun Xu, and Nita Sahai 9.1 Introduction 311 9.1.1 Mineral–Water Interactions 313 9.1.2 Mineral–Organic Interactions 313 9.2 Challenges and Approaches to Computational Modeling of Biomineralization 314 9.2.1 Biominerals: Structure, Nucleation, and Growth 314 9.2.2 Conformational Sampling in Modeling Biomineralization 317 9.2.3 Force Field Benchmarking 324 9.2.4 Ab Initio MD and Hybrid QM/MM Approaches 325 9.3 Case Studies 326 9.3.1 Apatite 327 9.3.2 Calcite 331 9.4 Concluding Remarks and Future Perspectives 334 Acknowledgments 335 References 335 10 Vibrational Spectroscopy of Minerals Through Ab Initio Methods 341 Marco De La Pierre, Raffaella Demichelis, and Roberto Dovesi 10.1 Introduction 341 10.2 Theoretical Background and Methods 342 10.2.1 Calculation of Vibrational Frequencies 344 10.2.2 Splitting of the Longitudinal Optical (LO) and Transverse Optical (TO) Modes 346 10.2.3 Calculation of Infrared (IR) and Raman Peak Intensities and of the IR Dielectric Function 347 10.2.4 Estimation of the Anharmonic Constant for X–H Stretching Modes 349 10.2.5 Accuracy of Basis Set and Hamiltonian 350 10.3 Examples and Applications 352 10.3.1 Vibrational Properties of Calcium and Magnesium Carbonates 353 10.3.2 A Complex Mineral: The IR Spectra of Ortho-enstatite 359 10.3.3 Treatment of the O─H Stretching Modes: The Vibrational Spectra of Brucite and Diaspore 360 10.4 Simulation of Vibrational Properties for Crystal Structure Determination 363 10.4.1 Proton Disorder in γ-AlOOH Boehmite 364 10.5 Future Challenges 368 Acknowledgements 368 References 368 11 Geochemical Kinetics via Computational Chemistry 375 James D. Kubicki and Kevin M. Rosso 11.1 Introduction 375 11.2 Methods 379 11.2.1 Potential Energy Surfaces 379 11.2.2 Choice of Solvation Methods 384 11.2.3 Activation Energies and Volumes 386 11.2.4 Transition States and Imaginary Frequencies 390 11.2.5 Rate Constants 391 11.2.6 Types of Reaction Mechanisms 393 11.3 Applications 394 11.3.1 Diffusion 394 11.3.2 Ligand Exchange Aqueous Complexes 395 11.3.3 Adsorption 396 11.3.4 Dissolution 396 11.3.5 Nucleation 398 11.4 Future Challenges 399 11.4.1 Femtosecond Spectroscopy 399 11.4.2 H-Bonding 400 11.4.3 Roaming 400 11.4.4 Large-Scale Quantum Molecular Dynamics 401 11.4.5 Reactive Force Fields 401 References 403 Index 415

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Book SynopsisIntroduces the reader to the field of ion chromatography, species analysis and hyphenated methods IC-MS and IC-ICP-MS including the theory and theirs applications Covers the importance of species analysis and hyphenated methods in ion chromatography Includes practical applications of IC-MS and IC-ICP-MS in environmental analysis Details sample preparation methods for ion chromatography Discusses hyphenated methods IC-MS and IC-ICP-MS used in determining both the total element contents and its elements Details speciation analysis used in studying biochemical cycles of selected chemical compounds; determining toxicity and ecotoxicity of elements; food and pharmaceuticals quality control; and in technological process control and clinical analytics Table of ContentsList of Contributors ix Preface xi 1 Principles and Applications of Ion Chromatography 1 Rajmund Michalski 1.1 Principles of Ion Chromatography, 1 1.1.1 Introduction, 1 1.1.2 Stationary Phases, 6 1.1.3 Eluents, 13 1.1.4 Suppressors, 16 1.1.5 Detection Methods, 18 1.2 Ion Chromatography Applications, 23 1.2.1 Speciation Analysis with the Hyphenated Methods of IC-ICP-MS and IC-MS, 29 1.3 Sample Preparation for Ion Chromatography, 32 1.4 Selected Methodological Aspects of Ion Determination with Ion Chromatography, 34 1.5 Ion Chromatography Development Perspectives, 37 1.6 References, 37 2 Mass Spectrometric Detectors for Environmental Studies 47 Maria Balcerzak 2.1 Introduction, 47 2.2 Mass Spectrometric Detectors, 49 2.2.1 Ionization Methods, 50 2.2.2 Mass Analyzers, 58 Acknowledgments, 62 2.3 References, 62 3 High-Performance Liquid Chromatography Coupled to Inductively Coupled Plasma MS/Electrospray Ionization MS 79 Jürgen Mattusch 3.1 Separation Principles, 79 3.1.1 Ion Chromatography (Anion/Cation Exchange, Mixed Mode), 80 3.1.2 High-Performance Liquid Chromatography (Reversed-Phase Mode, HILIC), 81 3.1.3 Size Exclusion Chromatography (SEC) (Gel Filtration Chromatography, GFC), 82 3.2 Detection Principles, 83 3.2.1 Common Detection in IC: Conductivity, UV–Vis, Electrochemical Detection, 83 3.2.2 Element Specific Detection, 83 3.3 Hyphenated Techniques, 87 3.3.1 HPLC(IC)–ICP-MS, 87 3.4 HPLC(IC)–ICP-MS/ESI-MS, 90 3.4.1 Fundamentals, 90 3.4.2 Methodology of Data Evaluation, 90 3.4.3 Technical Requirements, 91 3.5 Applications and Conclusion, 91 3.6 References, 102 4 Application of IC-MS in Organic Environmental Geochemistry 109 Klaus Fischer 4.1 Introduction, 109 4.2 Carboxylic Acids, 114 4.2.1 Molecular Structure, Molecular Interaction Potential, and Chromatographic Retention, 114 4.2.2 Environmental Analysis of Carboxylic Acids by Ion Exclusion Chromatography–Mass Spectrometry (HPICE-MS), 116 4.2.3 Environmental Analysis of Carboxylic Acids by Ion-Exchange Chromatography–Mass Spectrometry (HPI-EC-MS), 124 4.3 Carbohydrates, 135 4.3.1 Structural Diversity and Ion Chromatographic Behavior, 135 4.3.2 Environmental Analysis of Carbohydrates by Various IC-MS Methods, 136 4.4 Amines and Amino Acids, 143 4.5 Trends and Perspectives, 144 4.6 References, 145 5 Analysis of Oxyhalides and Haloacetic Acids in Drinking Water Using IC-MS and IC-ICP-MS 152 Koji Kosaka 5.1 Introduction, 152 5.2 Source of Oxyhalides and HAAs, 154 5.3 Analysis of Oxyhalides and HAAs, 158 5.3.1 Suppressed IC-MS, 158 5.3.2 Nonsuppressed IC-MS and LC-MS, 162 5.3.3 IC-ICP-MS, 165 5.4 Application for Monitoring of Oxyhalides and HAAs in Drinking Water, 166 5.4.1 Oxyhalides, 166 5.4.2 HAAs, 171 Summary, 171 5.5 References, 172 6 Analysis of Various Anionic Metabolites in Plant and Animal Material by IC-MS 178 Adam Konrad Jagielski and Michal Usarek 6.1 Introduction, 178 6.2 Optimization of HPIC and Ms Settings, 179 6.2.1 HPIC Settings, 179 6.2.2 MS Settings, 183 6.2.3 HPIC-MS Settings, 185 6.2.4 Extraction of Metabolites from Cells and Tissues, 189 6.3 Application of the Method in Analysis of Metabolites in Plant and Animal Material, 191 6.3.1 Analysis of Metabolites from Cell Cultures (Primary Cultures as well as Established Cell Lines), 192 6.3.2 Analysis of Metabolites from Solid Tissues, 192 6.3.3 Extraction of Metabolites from Plants, 194 6.4 Conclusions, 196 6.5 References, 197 7 Analysis of Perchlorate Ion in Various Matrices Using Ion Chromatography Hyphenated with Mass Spectrometry 199 Jay Gandhi 7.1 Introduction, 199 7.2 Precautions Unique to Ion Chromatography–Mass Spectrometry, 200 7.2.1 Instrumental and Operating Parameters, 201 7.3 Results and Discussion, 204 Acknowledgment, 209 7.4 References, 209 8 Sample Preparation Techniques for Ion Chromatography 210 Wolfgang Frenzel and Rajmund Michalski 8.1 Introduction, 210 8.2 When and Why is Sample Preparation Required in Ion Chromatography? 213 8.3 Automation of Sample Preparation (IN-LINE Techniques), 215 8.4 Sample Preparation Methods, 217 8.4.1 Filtration and Ultrafiltration, 219 8.4.2 Solid-Phase Extraction (SPE), 220 8.4.3 Liquid–Liquid Extraction, 225 8.4.4 Gas-Phase Separations, 226 8.4.5 Precipitation, 226 8.4.6 Membrane-Based Separations and Sample Treatment, 227 8.5 Trace Analysis and Preconcentration for Ion Chromatographic Analysis, 238 8.5.1 Preconcentration Using SPE, 239 8.5.2 Membrane-Based In-Line Preconcentration, 241 8.6 In-Line Preseparations Using Two-Dimensional Ion Chromatography (2D-IC), 243 8.7 Sample Preparation of Solid Samples, 244 8.7.1 Dissolution and Aqueous or Acid Extraction, 246 8.7.2 Wet-Chemical Acid Digestions, 247 8.7.3 UV Photolytic Digestion, 248 8.7.4 Fusion Methods, 249 8.7.5 Dry Ashing and Combustion Methods, 249 8.8 Air Analysis Using Ion Chromatography – Application to Gases and Particulate Matter, 251 8.9 Postcolumn Eluent Treatment Prior to Ms Detection, 255 8.10 Concluding Remarks, 257 8.11 References, 258 Index 267

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Book SynopsisBiorenewable polymers based nanomaterials are rapidly emerging as one of the most fascinating materials for multifunctional applications. Among biorenewable polymers, cellulose based nanomaterials are of great importance due to their inherent advantages such as environmental friendliness, biodegradability, biocompatibility, easy processing and cost effectiveness, to name a few. They may be produced from biological systems such as plants or be chemically synthesised from biological materials. This book summarizes the recent remarkable achievements witnessed in green technology of cellulose based nanomaterials in different ?elds ranging from biomedical to automotive. This book also discusses the extensive research developments for next generation nanocellulose-based polymer nanocomposites. The book contains seventeen chapters and each chapter addresses some specific issues related to nanocellulose and also demonstrates the real potentialities of these nanomaterials in differentTable of ContentsPreface xvii Part 1: Synthesis and Characterization of Nanocellulose based Polymer Nanocomposites 1 1 Nanocellulose-Based Polymer Nanocomposites: An Introduction 3 Manju Kumari Thakur, Vijay Kumar Thakur and Raghavan Prasanth 1.1 Introduction 3 1.2 Nanocellulose: Source, Structure, Synthesis and Applications 5 1.3 Conclusions 12 References 13 2 Bacterial Cellulose-Based Nanocomposites: Roadmap for Innovative Materials 17 Ana R. P. Figueiredo, Carla Vilela, Carlos Pascoal Neto, Armando J. D. Silvestre and Carmen S. R. Freire 2.1 Introduction 17 2.2 Bacterial Cellulose Production, Properties and Applications 18 2.3 Bacterial Cellulose-Based Polymer Nanocomposites 28 2.4 Bacterial Cellulose-Based Hybrid Nanocomposite Materials 41 2.5 Acknowledgements References 55 3 Polyurethanes Reinforced with Cellulose 65 María L. Auad, Mirna A. Mosiewicki and Norma E. Marcovich 3.1 Introduction 65 3.2 Conventional Polyurethanes Reinforced with Nanocellulose Fibers 67 3.3 Waterborne Polyurethanes Reinforced with Nanocellulose Fibers 76 3.4 Biobased Polyurethanes Reinforced with Nanocellulose Fibers 78 Conclusions and Final Remarks 84 References 85 4 Bacterial Cellulose and Its Use in Renewable Composites 89 Dianne R. Ruka, George P. Simon and Katherine M. Dean 4.1 Introduction 89 4.2 Cellulose Properties and Production 91 4.3 Tailor-Designing Bacterial Cellulose 105 4.4 Bacterial Cellulose Composites 114 4.5 Biodegradability 121 4.6 Conclusions 123 References 123 5 Nanocellulose-Reinforced Polymer Matrix Composites Fabricated by In-Situ Polymerization Technique 131 Dipa Ray and Sunanda Sain 5.1 Introduction 131 5.2 Cellulose as Filler in Polymer Matrix Composites 132 5.3 Cellulose Nanocomposites 138 5.4 In-Situ Polymerized Cellulose Nanocomposites 138 5.5 Novel Materials with Wide Application Potential 140 5.6 Effect of In-Situ Polymerization on Biodegradation Behavior of Cellulose Nanocomposites 154 5.7 Future of Cellulose Nanocomposites 157 References 159 6 Multifunctional Ternary Polymeric Nanocomposites Based on Cellulosic Nanore- inforcements 163 D. Puglia, E. Fortunati, C. Santulli and J. M. Kenny 6.1 Introduction 163 6.2 Cellulosic Reinforcements (CR) 166 6.3 Interaction of CNR with Different Nanoreinforcements 171 6.4 Ternary Polymeric Systems Based on CNR 179 6.5 Conclusions 190 Acknowledgments 191 References 191 7 Effect of Fiber Length on Thermal and Mechanical Properties of Polypropylene Nanobiocomposites Reinforced with Kenaf Fiber and Nanoclay 199 Na Sim and Seong Ok Han 7.1 Introduction 199 7.2 Experimental 200 7.3 Results and Discussion 202 7.4 Conclusions 211 References 211 8 Cellulose-Based Liquid Crystalline Composite Systems 215 J. P. Borges, J. P. Canejo, S. N. Fernandes and M. H. Godinho 8.1 Introduction 215 8.2 Liquid Crystalline Phases of Cellulose and Its Derivatives 216 8.3 Conclusion 232 Acknowledgements 232 References 232 9 Recent Advances in Nanocomposites Based on Biodegradable Polymers and Nanocellulose 237 J. I. Morán, L. N. Ludueña and V. A. Alvarez 9.1 Introduction 237 9.2 Cellulose Bionanocomposites Incorporation of Cellulose Nanofibers into Biodegradable Polymers: General Effect on the Properties 243 9.3 Future Perspectives and Concluding Remarks 249 References 250 Part 2: Processing and Applications Nanocellulose based Polymer Nanocomposites 255 10 Cellulose Nano/Microfibers-Reinforced Polymer Composites: Processing Aspects 257 K. Priya Dasan and A. Sonia 10.1 Introduction 257 10.2 The Role of Isolation Methods on Composite Properties 260 10.3 Pretreatment of Fibers and Its Role in Composite Performance 262 10.4 Different Processing Methodologies in Cellulose Nanocomposites and Their Effect on Final Properties 264 10.5 Conclusion 268 References 268 11 Nanocellulose-Based Polymer Nanocomposite: Isolation, Characterization and Applications 273 H. P. S. Abdul Khalil, Y. Davoudpour, N. A. Sri Aprilia, Asniza Mustapha, Md. Nazrul Islam and Rudi Dungani 11.1 Introduction 274 11.2 Cellulose and Nanocellulose 274 11.3 Isolation of Nanocellulose 276 11.4 Characterization of Nanocellulose 283 11.5 Drying of Nanocellulose 289 11.6 Modifications of Nanocellulose 290 11.7 Nanocellulose-Based Polymer Nanocomposites 295 11.8 Conclusion 302 Acknowledgement 303 References 303 12 Electrospinning of Cellulose: Process and Applications 311 Raghavan Prasanth, Shubha Nageswaran, Vijay Kumar Takur and Jou-Hyeon Ahn 12.1 Cellulosic Fibers 311 12.2 Crystalline Structure of Electrospun Cellulose 312 12.3 Applications of Cellulose 313 12.4 Electrospinning 313 12.5 Electrospinning of Cellulose 317 12.6 Solvents for Electrospinning of Cellulose 318 12.7 Cellulose Composite Fibers 333 12.8 Conclusions 336 Abbreviations 336 Symbols 336 References 337 13 Effect of Kenaf Cellulose Whiskers on Cellulose Acetate Butyrate Nanocomposites Properties 341 Lukmanul Hakim Zaini, M. T. Paridah, M. Jawaid, AlothmanY. Othman and A. H. Juliana 13.1 Introduction 341 13.2 Experimental 342 13.3 Characterization 344 13.4 Result and Discussion 345 13.5 Conclusions 352 Acknowledgements 353 References 353 14 Processes in Cellulose Derivative Structures 355 Mihaela Dorina Onofrei, Adina Maria Dobos and Silvia Ioan 14.1 Introduction 355 14.2 Liquid Crystalline Polymers 357 14.3 Liquid Crystal Dispersed in a Polymer Matrix 359 14.4 Techniques for Obtaining Liquid Crystals Dispersed into a Polymeric Matrix 360 14.5 Some Methods to Characterize the Liquid Crystal State 360 14.6 Liquid Crystal State of Cellulose and Cellulose Derivatives in Solution 364 14.7 Cellulose Derivatives/Polymers Systems 373 Conclusions 383 References 384 15 Cellulose Nanocrystals: Nanostrength for Industrial and Biomedical Applications 393 Anuj Kumar, Samit Kumar, Yuvraj Singh Negi and Veena Choudhary 15.1 Introduction 393 15.2 Cellulose and Its Sources 394 15.3 Nanocellulose 396 15.4 Cellulose Nanocrystals 398 15.5 Aqueous Suspension and Drying of CNCs 408 15.6 Functionalization of CNCs 410 15.7 Processing of CNCs for Biocomposites 15.8 Applications of CNCs-Reinforced Biocomposites 416 15.9 Biomedical Applications 421 15.10 Conclusion 427 Acknowledgements 428 References 428 16 Medical Applications of Cellulose and Its Derivatives: Present and Future 437 Karthika Ammini Sindhu, Raghavan Prasanth and Vijay Kumar Thakur 16.1 Historical Overview 438 16.2 Use of Cellulose for Treatment of Renal Failure 439 16.3 Types of Membranes 444 16.4 Use of Cellulose for Wound Dressing 447 16.5 Cotton as Wound Dressing Material 448 16.6 Biosynthesis, Structure and Properties of MC 450 16.7 MC as a Wound Healing System 451 16.8 Microbial Cellulose/Ag Nanocomposite 456 16.9 Nanocomposites of Microbial Cellulose and Chitosan 458 16.10 Commercialization of Microbial Cellulose 461 16.11 Use of Cellulose as Implant Material 462 16.12 Dental Applications 470 Conclusions 471 Abbreviations 472 Symbols 472 References 473 17 Bacterial Cellulose and Its Multifunctional Composites: Synthesis and Properties 479 V. Thiruvengadam and Satish Vitta 17.1 Introduction 479 17.2 Magnetic Composites 485 17.3 Composites with Catalytic Activity 489 17.4 Electrically Conducting Composites 492 17.5 Composites as Fuel Cell Components, Electrodes and Membrane 496 17.6 Optically Transparent and Mechanically Flexible Composites 499 17.7 Summary and Outlook 502 References 502

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Book SynopsisA comprehensive introduction to the fundamental aspects of surface chirality, covering both chemical and physical consequences Written by a leading expert in the field, Chirality at Solid Surfaces offers an introduction to the concept of chirality at surfaces, starting from the foundation of chirality in isolated molecules and bulk systems. Fundamental properties such as surface energy and surface stress are then linked to a universal systematization of surface structure and symmetry. The author includes key examples of surface chemistry and physics, such as the interplay between adsorbate and substrate chirality, amplification of chirality, chiral catalysis, and the influence of surface chirality upon optical and magnetic phenomena. The book also explores the chirality apparent in the electronic structure of graphene, topological insulators and half-metallic materials. This important reference: Provides an introduction to the fundamental concept of chiralityContains discussions of Table of ContentsPreface xiii Acknowledgements xxiii 1 Fundamentals of Chirality 1 1.1 Point and Space Groups 2 1.2 Proper and Improper Symmetry 4 1.3 Chirality in Finitude and Infinity 5 1.3.1 Molecular Chirality 5 1.3.2 Crystalline Chirality 8 1.4 Routes to Surface Chirality 9 1.4.1 Surfaces of Intrinsically Chiral Crystals 9 1.4.2 Intrinsically Chiral Surfaces of Achiral Crystals 10 1.4.3 Chiral Modification of Achiral Surfaces 11 1.5 Diastereoisomerism Defined 14 1.6 Quantifying Chirality? 15 1.7 Enantiomeric Excess 17 1.8 Synthesis, Separation and Sensing 19 References 20 2 Surface Symmetry and Structure 21 2.1 Spherical Representation of Symmetry 21 2.2 Spherical Representation of Structure 24 2.3 Stereographic Projections: Flattening the Globe 27 2.4 Surfaces of the Face-Centred Cubic Structure 29 2.4.1 Reconciliation of Symmetry and Primary Structure 29 2.4.2 Secondary and Tertiary Structure 32 2.4.3 Commentary 34 2.5 Surfaces of the Body-Centred Cubic Structure 36 2.5.1 Reconciliation of Symmetry and Primary Structure 37 2.5.2 Secondary and Tertiary Structure 39 2.5.3 Commentary 40 2.6 Surfaces of the Hexagonal Close-Packed Structure 42 2.6.1 Symmetry 43 2.6.2 Primary Structure 48 2.6.3 Reconciliation of Symmetry and Primary Structure 52 2.6.4 Commentary 55 2.7 Surfaces of the Diamond Structure 56 2.7.1 Symmetry 56 2.7.2 Primary Structure 58 2.7.3 Reconciliation of Symmetry and Primary Structure 59 2.7.4 Commentary 62 References 63 3 Surface Energy and Surface Stress 65 3.1 Thermodynamic Definition of Surface Energy 65 3.2 The Tensor Nature of Surface Stress 70 3.3 Visualisations of Surface Stress: Iconic Conics 71 3.3.1 The Normal Stress Conic 72 3.3.2 The Shear Stress Quartic 73 3.3.3 The Stress Ellipse 74 3.4 Symmetry of the Surface Stress: Eccentricity and Orientation 75 3.4.1 Stereography and Surface Stress 77 3.4.2 Racemic Surface Stress 79 3.4.3 Adsorbate-Induced Asymmetry in Surface Stress 80 3.5 Measurement of Differential Surface Stress 81 3.5.1 Island Shape Measurement 81 3.5.2 Contact Angle Measurement 82 3.5.3 Cantilever Deformation 85 3.6 Facet Formation and theWulff Construction 86 3.6.1 Ridge-and-Furrow Facets 86 3.6.2 Pyramid-and-Pit Facets 88 3.6.3 Geometrical Construction 89 References 91 4 Asymmetric Adsorption on Achiral Substrates 93 4.1 Achiral Adsorbates: GlidingThrough Broken Mirrors 93 4.2 Prochiral Adsorbates: Chirality in Context 97 4.2.1 Guanine on Au{111} 98 4.2.2 Stilbene Derivatives on Cu{100} and Cu{110} 101 4.2.3 Glycine on Cu{110} and Cu{311} 102 4.2.4 Succinic and Fumaric Acids on Cu{110} 107 4.2.5 Meso-Tartaric Acid on Cu{110} 111 4.3 Chiral Adsorbates: Act Locally,Think Globally 112 4.3.1 Alanine on Cu{110} and Cu{311} 112 4.3.2 Proline on Cu{110} and Cu{311} 120 4.3.3 Serine and Lysine on Cu{110} 125 4.3.4 Cysteine on Cu{110} and Au{110} 128 4.3.5 Tartaric Acid on Cu{110} 135 4.3.6 Glutamic Acid on Ag{110} and Ag{100} 140 4.3.7 2-Butanol on Au{111} 145 4.3.8 Tartaric Acid on Ni{111} 146 4.3.9 Alanine on Pd{111} 147 4.4 Chiral Facetting: Remodelling the Surface 149 4.4.1 Glycine, Alanine and Lysine on Cu{100} 150 4.5 Chiral Metallorganic Frameworks: Into the Second Dimension 151 4.5.1 Glutamic Acid on Ni/Au{111} 152 4.5.2 Lysine on Ni/Au{111} 153 4.5.3 Proline on Ni/Au{111} 154 4.6 Executive Summary 156 References 159 5 Asymmetric Adsorption on Chiral Substrates 165 5.1 Achiral Adsorbates on Intrinsically Chiral Substrates: Fault-Lines and Facets 165 5.1.1 Oxygen on Cu{531} 165 5.1.2 Cyclohexanone on Cu{643} 167 5.1.3 NaCl on Cu{532} 168 5.2 Prochiral Adsorbates on Intrinsically Chiral Substrates: Familiar and Strange 168 5.2.1 Glycine on Cu{531} 169 5.3 Chiral Adsorbates on Intrinsically Chiral Substrates: Diastereomeric Effects I 171 5.3.1 Alanine on Cu{531} 171 5.3.2 Serine on Cu{531} 173 5.3.3 Cysteine on Cu{531} and Au{17 11 9} 174 5.3.4 Tartaric Acid on Cu{531} 176 5.3.5 Propylene Oxide and 3-Methylcyclohexanone on Cu{643} 176 5.3.6 3-Methylcyclohexanone on Cu{531}, Cu{651} and Cu{13 9 1} 180 5.3.7 Alanine, Serine, Lysine, Phenylalanine and Aspartic Acid on Cu{3 1 17} 182 5.4 Chiral Adsorbates on Chirally Modified Substrates: Diastereomeric Effects II 184 5.4.1 Propylene Oxide on 2-Butanol-Modified Pd{111} and Pt{111} 185 5.4.2 Propylene Oxide on 2-Methylbutanoic Acid-Modified Pd{111} and Pt{111} 188 5.4.3 Propylene Oxide on Amino Acid-Modified Pd{111} 189 5.4.4 Glycidol on Tartaric Acid-Modified Pd{111} 190 5.4.5 Propylene Oxide on Lysine-Modified Cu{100} 191 5.5 Executive Summary 191 References 193 6 Chiral Amplification 197 6.1 Kinetic Amplification: Surface Explosions 197 6.1.1 Tartaric and Malic Acids on Cu{110} 200 6.1.2 Tartaric Acid on Cu{643}, Cu{17 5 1}, Cu{531} and Cu{651} 202 6.2 Thermodynamic Amplification: Sergeants, Soldiers and Majority Rule 206 6.2.1 Tartaric, Succinic and Malic Acids on Cu{110} 206 6.2.2 Heptahelicene on Cu{111}, Ag{111} and Au{111} 210 6.2.3 Aspartic Acid on Cu{111} 215 6.2.4 Supramolecular Assemblies on Highly Ordered Pyrolytic Graphite 217 References 222 7 Asymmetric Heterogeneous Catalysis 225 7.1 Electro-Oxidation of Glucose on Pt{643} and Pt{321} 227 7.2 Electron-Stimulated Oxidation of Methyl Lactate on Cu{643} 235 7.3 Hydrogenation of ;;-Ketoesters over Platinum: The Orito Reaction 236 7.3.1 Adsorption Geometry of Methyl and Ethyl Pyruvate 237 7.3.2 Adsorption Geometry of Cinchonidine and its Cousins 240 7.3.3 Binding and Reaction in the Chiral Complex 244 7.4 Hydrogenation of ;;-Ketoesters over Nickel: The Izumi Reaction 247 7.4.1 Adsorption Geometry of Methyl Acetoacetate 247 7.4.2 Two-Dimensional Cocrystallisation: Tartaric/Glutamic Acid Modification 248 7.4.3 Defect-Localised Oligomerisation:Modification by Aspartic Acid 250 References 253 8 Optical Consequences of Surface Chirality 257 8.1 The Nature of Light 258 8.2 Planar and Twisted Light 258 8.2.1 Linear and Circular Polarisation 259 8.2.2 Polarisation on a Helix 261 8.3 Dichroic Photoemission 262 8.4 Non-linear Optics in Chiral Systems 267 8.4.1 Symmetry Constraints on Non-linear Optical Phenomena 267 8.4.2 Implications for Chiral Surfaces 272 8.4.3 Chiral SHG on Cu{111} and Au{110} 273 8.5 Near-Field Phenomena 276 References 277 9 Magnetic Consequences of Surface Chirality 279 9.1 Spin and Orbital Magnetism 279 9.1.1 Fermions and the Dirac Equation 280 9.1.2 Spin–Orbit Coupling 283 9.2 Bulk Magnetocrystalline Anisotropy 285 9.2.1 Laue Class Oh (Cubic Crystal System: Oh, Td and O) 287 9.2.2 Laue Class Th (Cubic Crystal system: Th and T) 287 9.2.3 Laue Class D6h (Hexagonal Crystal System: D6h, D3h, C6;; and D6) 287 9.2.4 Laue Class C6h (Hexagonal Crystal System: C6h, C3h and C6) 288 9.2.5 Laue Class D3d (Trigonal Crystal System: D3d, C3;; and D3) 288 9.2.6 Laue Class S6 (Trigonal Crystal System: S6 and C3) 289 9.2.7 Laue Class D4h (Tetragonal Crystal System: D4h, D2d, C4;; and D4) 289 9.2.8 Laue Class C4h (Tetragonal Crystal System: C4h, S4, & C4) 290 9.2.9 Laue Class D2h (Orthorhombic Crystal System: D2h, C2;;, and D2) 290 9.2.10 Laue Class C2h (Monoclinic Crystal System: C2h, C1h, and C2) 292 9.2.11 Laue Class S2 (Triclinic Crystal System: S2 and C1) 293 9.2.12 General Comments 294 9.3 Surface Magnetocrystalline Anisotropy 295 9.3.1 Surface MCA of Face-Centred and Body-Centred Cubic Ferromagnets 296 9.3.2 Role of Adsorbates and Reconstruction 298 9.4 An Aside: Vectors and Pseudovectors 299 9.5 SpinWaves in Centrosymmetric Media 301 9.5.1 Spin Helices 301 9.5.2 Spin Spirals 303 9.6 SpinWaves at a Featureless Surface 304 9.6.1 Spin Helices 304 9.6.2 Spin Spirals 305 9.7 SpinWaves at Structured Surfaces 306 9.7.1 Spin Helices at Achiral Surfaces 306 9.7.2 Spin Helices at Chiral Surfaces 307 9.7.3 Spin Spirals at Achiral Surfaces 307 9.7.4 Spin Spirals at Chiral Surfaces 307 9.8 Surface Spin Spirals Observed 308 9.9 Skyrmions, or How to Brush a Hedgehog 309 References 313 10 Chiral Electronic States in Two Dimensions 315 10.1 Dirac Cones in Graphene 316 10.2 Dirac Cones at Half-Metal Surfaces 321 10.3 Dirac Cones at the Surfaces of Topological Insulators 323 10.4 Prospects for Electronic Chirality in the Chemical Context 328 References 329 11 Postscript 331 A List of Abbreviations 335 B Rules for Overlayer Periodicity Assignment 337 B.1 Substrate Lattice 337 B.2 Overlayer Lattice 338 B.3 Illustrative Examples 339 References 343 C Further Reading 345 Index 347

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Book SynopsisThe past decade has seen a significant increase of research aimed at discovering new drugs for treating cancer, and the increasing number of new antineoplastic drugs approved by regulatory agencies reflects this. Until now, details on the synthesis of these newer agents have been scattered in various journals and in US and European patents. This timely volume deals with the organic chemistry involved in the synthesis of the agents found within antineoplastic drugs, including descriptions of the synthetic schemes for the preparation of over 200 compounds that have been granted non-proprietary names. Compounds are collected in chapters based on the mechanism of action rather than on their chemical structures. Each individual chapter is preceded by a brief description of that mechanism and includes detailed flow charts of the preparation of those compounds accompanied by discussions of the organic chemistry involved in each step. The first half of this volume is dedicated to the synthesesTable of ContentsPreface ix Introduction xi 1 Alkylating Agents 1 1.1 bis-Chloroethyl Amines 1 1.2 Several Other Chloroethyl Agents 5 1.3 Platinum-Based Antineoplastic Agents 6 1.4 Miscellaneous Alkylating Agents 8 2 Antimetabolites 13 2.1 Introduction 13 2.2 Folate Antagonists 14 2.3 Pyrimidines and Purines 21 3 Hormone Blocking Anticancer Drugs 31 3.1 Introduction 31 3.2 Estrogen Antagonists 32 3.3 Androgen Antagonists 44 4 Topoisomerase Inhibitors 55 4.1 Introduction 55 4.2 Anthracyclines 56 4.3 Anthraquinones and Anthrapyrazoles 59 4.4 Camptothecins 65 4.5 Miscellaneous Topoisomerase Inhibitors 74 5 Mitotic Inhibitors 81 5.1 Introduction 81 5.2 Taxanes 82 5.3 Wholly Synthetic Compounds 86 6 Matrix Metalloproteinase Inhibitors 97 6.1 Introduction 97 6.2 Hydroxamates 98 7 Histone Deacetylase Inhibitors 109 7.1 Introduction 109 7.2 Hydroxamates 110 7.3 Phenylenediamines 113 8 Enzyme Inhibitor, Part I, Tyrosine Kinases 117 8.1 Introduction 117 8.2 Epidermal Growth Factor Inhibitors 118 8.3 VEGF 124 8.4 SRC Nonreceptor Tyrosine Kinase 134 8.5 PDGF 138 8.6 EGF 141 8.7 Other TKI 143 8.8 Janus Kinase Inhibitors 154 9 Enzyme Inhibitors: Part II Additional Targets 161 9.1 Serine–Threonine Kinase Inhibitors 161 9.2 Additional Enzyme Inhibitors 166 10 Miscellaneous Antineoplastic Agents 187 10.1 Acyclic 187 10.2 Monocyclic 188 10.3 Two Linked Rings 190 10.4 Rings on a Chain 191 10.5 Fused Rings 195 Appendix A 203 Combinatorial Chemistry 203 Index of Heterocyclic Sytheses 205 Subject Index 207

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Book SynopsisDetailing formulation approaches by stage of discovery to early development, this book gives a playbook of practical and efficient strategies to formulate drug candidates with the least chance of failing in clinical development. Comes from contributing authors with experience developing formulations on the frontlines of the pharmaceutical industry Focuses on pre (or non-) clinical and early stage development, the phases where most compounds are used in drug research Features case studies to illustrate practical challenges and solutions in formulation selection Covers regulatory filing, drug metabolism and physical and chemical properties, toxicology formulation, biopharmaceutics classification system (BCS), screening approaches, early stage clinical formulation development, and outsourcingTable of ContentsList of Contributors vii Preface ix 1 Introduction 1Elizabeth Kwong 2 Lead Identification/Optimization 9Mei Wong and Mark McAllister 3 Oral Drug Formulation Development in Pharmaceutical Lead Selection Stage 39Shayne Cox Gad 4 Bridging End of Discovery to Regulatory Filing: Formulations for IND-and Registration-Enabling Nonclinical Studies 89Evan A. Thackaberry 5 Planning the First Clinical Trials with Clinical Manufacturing Organization (CMO) 115Elizabeth Kwong and Caroline McGregor 6 Formulation Strategies for High Dose Toxicology Studies: Case Studies 139Dennis H. Leung, Pierre Daublain, Mengwei Hu and Kung]I Feng 7 Formulation, Analytical, and Regulatory Strategies for First-in-Human Clinical Trials 165Lorenzo Capretto, Gerard Byrne, Sarah Trenfield, Lee Dowden and Steven Booth Index 243

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Book SynopsisIntroduces the reader to Circulating Tumor Cells (CTCs), their isolation method and analysis, and commercially available platforms Presents the historical perspective and the overview of the field of circulating tumor cells (CTCs) Discusses the state-of-art methods for CTC isolation, ranging from the macro- to micro-scale, from positive concentration to negative depletion, and from biological-property-enabled to physical-property-based approaches Details commercially available CTC platforms Describes post-isolation analysis and clinical translation Provides a glossary of scientific terms related to CTCs Table of ContentsList of Contributors xv Foreword xxi Preface xxv PART I INTRODUCTION 1 1 Circulating Tumor Cells and Historic Perspectives 3 Jonathan W. Uhr 1.1 Early Studies on Cancer Dormancy Led to the Development of a Sensitive Assay for CTCs (1970–1998) 3 1.2 Modern Era for Counting CTCs: 1998–2007 6 1.3 Proof of Malignancy of CTCs 7 1.4 New Experiments Involving CTCs 7 1.5 Clinical Cancer Dormancy 8 1.6 Human Epidermal Growth Factor Receptor 2 (HER2) Gene Amplification can be Acquired as Breast Cancer Progresses 10 1.7 uPAR and HER2 Co-amplification 11 1.8 Epithelial–Mesenchymal Transition (EMT) 12 1.9 New Instruments to Capture CTCs 14 1.10 Genotypic Analyses 15 1.11 Conclusions 18 References 20 2 Introduction to Microfluidics 33 Kangfu Chen and Z. Hugh Fan 2.1 Introduction 33 2.2 Scaling Law 36 2.3 Device Fabrication 39 2.4 Functional Components in Microfluidic Devices 43 2.5 Concluding Remarks 46 References 47 PART II ISOLATION METHODS 51 3 Ensemble-decision Aliquot Ranking (eDAR) for CTC Isolation and Analysis 53 Mengxia Zhao, Perry G. Schiro, and Daniel T. Chiu 3.1 Overview of eDAR 53 3.2 Individual Components and Analytical Performance of eDAR 55 3.3 Application and Downstream Analyses of eDAR 69 3.4 Conclusion and Perspective 80 References 81 4 Sinusoidal Microchannels with High Aspect Ratios for CTC Selection and Analysis 85 Joshua M. Jackson, Małgorzata A. Witek, and Steven A. Soper 4.1 Introduction 85 4.2 Parallel Arrays of High-Aspect-Ratio, Sinusoidal Microchannels for CTC Selection 90 4.3 Clinical Applications of Sinusoidal CTC Microchip 114 4.4 Conclusion 118 Acknowledgments 119 References 119 5 Cell Separation using Inertial Microfluidics 127 Nivedita Nivedita and Ian Papautsky 5.1 Introduction 127 5.2 Device Fabrication and System Setup 128 5.3 Inertial Focusing in Microfluidics 129 5.4 Cancer Cell Separation in Straight Microchannels 132 5.5 Cancer Cell Separation in Spiral Microchannels 136 5.6 Conclusions 142 References 142 6 Morphological Characteristics of CTCs and the Potential for Deformability-Based Separation 147 Simon P. Duffy and Hongshen Ma 6.1 Introduction 147 6.2 Limitations of Antibody-based CTC Separation Methods 148 6.3 Morphological and Biophysical Differences Between CTCs and Hematological Cells 149 6.4 Historical and Recent Methods in CTC Separation Based on Biophysical Properties 153 6.5 Microfluidic Ratchet for Deformability-Based Separation of CTCs 155 6.6 Resettable Cell Trap for Deformability-based Separation of CTCs 160 6.7 Summary 165 References 166 7 Microfabricated Filter Membranes for Capture and Characterization of Circulating Tumor Cells (CTCs) 173 Zheng Ao, Richard J. Cote, Ram H. Datar, and Anthony Williams 7.1 Introduction 173 7.2 Size-based Enrichment of Circulating Tumor Cells 174 7.3 Comparison Between Size-based CTC Isolation and Affinity-based Isolation 177 7.4 Characterization of CTCs Captured by Microfilters 178 7.5 Conclusion 180 References 181 8 Miniaturized Nuclear Magnetic Resonance Platform for Rare Cell Detection and Profiling 183 Sangmoo Jeong, Changwook Min, Huilin Shao, Cesar M. Castro, Ralph Weissleder, and Hakho Lee 8.1 Introduction 183 8.2 μNMR Technology 184 8.3 Clinical Application of μNMR for CTC Detection and Profiling 191 8.4 Conclusion 196 References 196 9 Nanovelcro Cell-Affinity Assay for Detecting and Characterizing Circulating Tumor Cells 201 Millicent Lin, Anna Fong, Sharon Chen, Yang Zhang, Jie-fu Chen, Paulina Do, Morgan Fong, Shang-Fu Chen, Pauline Yang, An-Jou Liang, Qingyu Li, Min Song, Shuang Hou, and Hsian-Rong Tseng 9.1 Introduction 202 9.2 Proof-of-Concept Demonstration of NanoVelcro Cell-Affinity Substrates 207 9.3 First-Generation NanoVelcro Chips for CTC Enumeration 209 9.4 Second-Generation NanoVelcro-LMD Technology for Single CTC Isolation 214 9.5 Third-Generation Thermoresponsive NanoVelcro Chips 219 9.6 Conclusions and Future Perspectives 220 Acknowledgment 221 References 221 10 Acoustophoresis in Tumor Cell Enrichment 227 Per Augustsson, Cecilia Magnusson, Hans Lilja, and Thomas Laurell 10.1 Introduction 227 10.2 Factors Determining Acoustophoresis Cell Separation 230 10.3 Acoustophoresis System for Separating Cells 234 10.4 Acoustophoresis Platform for Clinical Sample Processing 239 10.5 Unperturbed Cell Survival and Phenotype after Microchip Acoustophoresis 244 10.6 Summary 246 References 246 11 Photoacoustic Flow Cytometry for Detection and Capture of Circulating Melanoma Cells 249 John A. Viator, Benjamin S. Goldschmidt, Kiran Bhattacharyya, and Kyle Rood 11.1 Introduction 249 11.2 Current Methods for Detection and Capture of CMCs 254 11.3 Discussion 259 11.4 Future Work 261 References 262 12 Selectin-Mediated Targeting of Circulating Tumor Cells for Isolation and Treatment 267 Jocelyn R. Marshall and Michael R. King 12.1 Introduction 267 12.2 CTC Capture by E-selectin 271 12.3 Applications for E-selectin in Cancer Diagnosis and Treatment 273 12.4 Conclusions 278 References 279 13 Aptamer-Enabled Tumor Cell Isolation 287 Jinling Zhang and Z. Hugh Fan 13.1 Introduction 287 13.2 Aptamers and their Biomedical Applications 288 13.3 Aptamer-based Tumor Cell Isolation 290 13.4 Conclusion and Outlook 297 References 297 14 Depletion of Normal Cells for CTC Enrichment 301 Jeffrey J. Chalmers, Maryam B. Lustberg, Clayton Deighan, Kyoung-Joo Jenny Park, Yongqi Wu, and Peter Amaya 14.1 Introduction 301 14.2 Estimates of Number and Type of Cells in Blood 302 14.3 Summary of Examples of Negative Depletion 303 14.4 Types of Cells Observed After Depletion of Normal Cells 305 14.5 Incomplete Depletion of Normal Cells 305 14.6 Conclusion 310 References 311 PART III POST-ISOLATION ANALYSIS AND CLINICAL TRANSLATION 313 15 Tumor Heterogeneity and Single-cell Analysis of CTCs 315 Evelyn K. Sigal and Stefanie S. Jeffrey 15.1 Introduction 315 15.2 Tumor Heterogeneity 316 15.3 Single-Cell Analysis of CTCs and CTC Heterogeneity 318 15.4 Gene Expression Analysis 319 15.5 Mutational Analysis 321 15.6 Conclusion: Clinical Implications and Future Perspectives 323 References 324 16 Single-Cell Molecular Profiles and Biophysical Assessment of Circulating Tumor Cells 329 Devalingam Mahalingam, Pawel Osmulski, Chiou-Miin Wang, Aaron M. Horning, Anna D. Louie, Chun-Lin Lin, Maria E. Gaczynska, and Chun-Liang Chen 16.1 Introduction 329 16.2 Methods 331 16.3 CTC Applications 336 16.4 Conclusions 342 References 343 17 Directing Circulating Tumor Cell Technologies Into Clinical Practice 351 Benjamin P. Casavant, David Kosoff, and Joshua M. Lang 17.1 Introduction 351 17.2 Defining Biomarkers 352 17.3 The Technology 356 17.4 Translating Technology 357 17.5 Conclusions 360 References 361 PART IV COMMERCIALIZATION 365 18 DEPArray™ Technology for Single CTC Analysis 367 Farideh Z. Bischoff, Gianni Medoro, and Nicolo Manaresi 18.1 Challenges in Molecular Profiling of CTCs 367 18.2 DEPArray™ Technology Solution 368 18.3 DEPArray™ for Single Tumor Cell Analysis 369 18.4 Clinical Significance in Single CTC Profiling 373 18.5 Conclusion 374 References 374 19 CELLSEARCH® Instrument, Features, and Usage 377 Denis A. Smirnov, Brad W. Foulk, Mark C. Connelly, and Robert T. McCormack 19.1 Introduction 377 19.2 Principles of CELLSEARCH® 379 19.3 EpCAM Density and CTC Capture 380 19.4 Clinical Applications of CELLSEARCH® CTCs 383 19.5 Beyond EpCAM Capture 390 19.6 Discussion 391 References 394 PART V GLOSSARY 401 Circulating Tumor Cell Glossary 403 Jose I. Varillas and Z. Hugh Fan Index 423

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Book SynopsisVoet, Voet and Prattâs Fundamentals of Biochemistry, 5th Edition addresses the enormous advances in biochemistry, particularly in the areas of structural biology and Bioinformatics, by providing a solid biochemical foundation that is rooted in chemistry to prepare students for the scientific challenges of the future.

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Book Synopsis

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Book SynopsisProvides a holistic approach that looks at changing process conditions, possible process design changes, and process technology upgrades Includes process integration techniques for improving process designs and for applying optimization techniques for improving operations focusing on hydroprocessing units. Discusses in details all important aspects of hydroprocessing including catalytic materials, reaction mechanism, as well as process design, operation and control, troubleshooting and optimization Methods and tools are introduced that have a successful application track record at UOP and many industrial plants in recent years Includes relevant calculations/software/technologies hosted online for purchasers of the book Table of ContentsPREFACE xiii PART 1 FUNDAMENTALS 1 1 Overview of This Book 3 1.1 Energy Sustainability, 3 1.2 ULSD – Important Part of the Energy Mix, 4 1.3 Technical Challenges for Making ULSD, 7 1.4 What is the Book Written for, 8 References, 8 2 Refinery Feeds, Products, and Processes 9 2.1 Introduction, 9 2.2 ASTM Standard for Crude Characterization, 10 2.3 Important Terminologies in Crude Characterization, 12 2.4 Refining Processes, 13 2.5 Products and Properties, 15 2.6 Biofuel, 20 3 Diesel Hydrotreating Process 23 3.1 Why Diesel Hydrotreating?, 23 3.2 Basic Process Flowsheeting, 25 3.3 Feeds, 28 3.4 Products, 30 3.5 Reaction Mechanisms, 36 3.6 Hydrotreating Catalysts, 40 3.7 Key Process Conditions, 44 3.8 Different Types of Process Designs, 47 References, 48 4 Description of Hydrocracking Process 51 4.1 Why Hydrocracking, 51 4.2 Basic Processing Blocks, 53 4.3 Feeds, 58 4.4 Products, 59 4.5 Reaction Mechanism and Catalysts, 61 4.6 Catalysts, 67 4.7 Key Process Conditions, 70 4.8 Typical Process Designs, 75 References, 78 PART 2 HYDROPROCESSING DESIGN 79 5 Process Design Considerations 81 5.1 Introduction, 81 5.2 Reactor Design, 81 5.3 Recycle Gas Purity, 98 5.4 Wash Water, 102 5.5 Separator Design, 107 5.6 Makeup Gas Compression, 115 References, 121 6 Distillate Hydrotreating Unit Design 123 6.1 Introduction, 123 6.2 Number of Separators, 123 6.3 Stripper Design, 127 6.4 Debutanizer Design, 135 6.5 Integrated Design, 136 References, 147 7 Hydrocracking Unit Design 149 7.1 Introduction, 149 7.2 Single-stage Hydrocracking Reactor Section, 150 7.3 Two-stage Hydrocracking Reactor Section, 155 7.4 Use of a Hot Separator in Hydrocracking Unit Design, 158 7.5 Use of Flash Drums, 160 7.6 Hydrocracking Unit Fractionation Section Design, 161 7.7 Fractionator First Flow Scheme, 161 7.8 Debutanizer First Flow Scheme, 163 7.9 Stripper First Fractionation Flow Scheme, 166 7.10 Dual Zone Stripper Fractionation Flow Scheme, 168 7.11 Dual Zone Stripper – Dual Fractionator Flow Scheme, 170 7.12 Hot Separator Operating Temperature, 171 7.13 Hydrogen Recovery, 174 7.14 LPG Recovery, 175 7.15 HPNA Rejection, 177 7.16 Hydrocracking Unit Integrated Design, 181 References, 187 PART 3 ENERGY AND PROCESS INTEGRATION 189 8 Heat Integration for Better Energy Efficiency 191 8.1 Introduction, 191 8.2 Energy Targeting, 191 8.3 Grassroots Heat Exchanger Network (Hen) Design, 202 8.4 Network Pinch for Energy Retrofit, 206 Nomenclature, 213 References, 213 9 Process Integration for Low-Cost Design 215 9.1 Introduction, 215 9.2 Definition of Process Integration, 216 9.3 Grand Composite Curves (GCC), 218 9.4 Appropriate Placement Principle for Process Changes, 219 9.5 Dividing Wall Distillation Column, 225 9.6 Systematic Approach for Process Integration, 228 9.7 Applications of the Process Integration Methodology, 230 9.8 Summary of Potential Energy Efficiency Improvements, 246 References, 247 10 Distillation Column Operating Window 249 10.1 Introduction, 249 10.2 What is Distillation?, 249 10.3 Why Distillation is the Most Widely Used?, 251 10.4 Distillation Efficiency, 253 10.5 Definition of Feasible Operating Window, 255 10.6 Understanding Operating Window, 256 10.7 Typical Capacity Limits, 275 10.8 Effects of Design Parameters, 275 10.9 Design Checklist, 278 10.10 Example Calculations for Developing Operating Window, 281 10.11 Concluding Remarks, 296 Nomenclature, 297 References, 299 PART 4 PROCESS EQUIPMENT ASSESSMENT 301 11 Fired Heater Assessment 303 11.1 Introduction, 303 11.2 Fired Heater Design for High Reliability, 304 11.3 Fired Heater Operation for High Reliability, 310 11.4 Efficient Fired Heater Operation, 315 11.5 Fired Heater Revamp, 321 Nomenclature, 322 References, 322 12 Pump Assessment 323 12.1 Introduction, 323 12.2 Understanding Pump Head, 324 12.3 Define Pump Head – Bernoulli Equation, 325 12.4 Calculate Pump Head, 329 12.5 Total Head Calculation Examples, 330 12.6 Pump System Characteristics – System Curve, 332 12.7 Pump Characteristics – Pump Curve, 333 12.8 Best Efficiency Point (Bep), 338 12.9 Pump Curves for Different Pump Arrangement, 338 12.10 NPSH, 340 12.11 Spillback, 345 12.12 Reliability Operating Envelope (ROE), 346 12.13 Pump Control, 347 12.14 Pump Selection and Sizing, 347 Nomenclature, 351 References, 351 13 Compressor Assessment 353 13.1 Introduction, 353 13.2 Types of Compressors, 354 13.3 Impeller Configurations, 357 13.4 Type of Blades, 358 13.5 How a Compressor Works, 358 13.6 Fundamentals of Centrifugal Compressors, 360 13.7 Performance Curves, 362 13.8 Partial Load Control, 364 13.9 Inlet Throttle Valve, 366 13.10 Process Context for a Centrifugal Compressor, 367 13.11 Compressor Selection, 368 Nomenclature, 369 References, 369 14 Heat Exchanger Assessment 371 14.1 Introduction, 371 14.2 Basic Concepts and Calculations, 371 14.3 Understand Performance Criterion – U Values, 374 14.4 Understand Fouling, 380 14.5 Understand Pressure Drop, 382 14.6 Effects of Velocity on Heat Transfer, Pressure Drop, and Fouling, 384 14.7 Heat Exchanger Rating Assessment, 385 14.8 Improving Heat Exchanger Performance, 396 Nomenclature, 399 References, 400 15 Distillation Column Assessment 401 15.1 Introduction, 401 15.2 Define a Base Case, 401 15.3 Calculations for Missing and Incomplete Data, 403 15.4 Building Process Simulation, 406 15.5 Heat and Material Balance Assessment, 408 15.6 Tower Efficiency Assessment, 411 15.7 Operating Profile Assessment, 414 15.8 Tower Rating Assessment, 417 15.9 Guidelines, 419 Nomenclature, 420 References, 420 PART 5 PROCESS SYSTEM EVALUATION 423 16 Energy Benchmarking 425 16.1 Introduction, 425 16.2 Definition of Energy Intensity for a Process, 426 16.3 The Concept of Fuel Equivalent for Steam and Power (FE), 427 16.4 Data Extraction, 429 16.5 Convert All Energy Usage to Fuel Equivalent, 432 16.6 Energy Balance, 432 16.7 Fuel Equivalent for Steam and Power, 435 16.8 Energy Performance Index (EPI) Method for Energy Benchmarking, 441 16.9 Concluding Remarks, 444 16.10 Nomenclature, 445 References, 446 17 Key Indicators and Targets 447 17.1 Introduction, 447 17.2 Key Indicators Represent Operation Opportunities, 448 17.3 Define Key Indicators, 451 17.4 Set Up Targets for Key Indicators, 456 17.5 Economic Evaluation for Key Indicators, 460 17.6 Application 1: Implementing Key Indicators into an “Energy Dashboard”, 463 17.7 Application 2: Implementing Key Indicators to Controllers, 465 17.8 It is Worth the Effort, 466 Nomenclature, 467 References, 467 18 Distillation System Optimization 469 18.1 Introduction, 469 18.2 Tower Optimization Basics, 470 18.3 Energy Optimization for Distillation System, 475 18.4 Overall Process Optimization, 481 18.5 Concluding Remarks, 489 References, 490 PART 6 OPERATIONAL GUIDELINES AND TROUBLESHOOTING 491 19 Common Operating Issues 493 19.1 Introduction, 493 19.2 Catalyst Activation Problems, 494 19.3 Feedstock Variations and Contaminants, 495 19.4 Operation Upsets, 496 19.5 Treating/Cracking Catalyst Deactivation Imbalance, 497 19.6 Flow Maldistribution, 500 19.7 Temperature Excursion, 501 19.8 Reactor Pressure Drop, 504 19.9 Corrosion, 506 19.10 HPNA, 509 19.11 Conclusion, 511 20 Troubleshooting Case Analysis 513 20.1 Introduction, 513 20.2 Case Study I – Product Selectivity Changes, 514 20.3 Case Study II – Feedstock Changes, 516 20.4 Case Study III – Catalyst Deactivation Balance, 523 20.5 Case Study IV – Catalyst Migration, 526 20.6 Conclusion, 536 INDEX 537

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Book SynopsisOver the past decade, renewables-based technology and sustainability assessment methods have grown tremendously. Renewable energy and products have a significant role in the market today, and the same time sustainability assessment methods have advanced, with a growing standardization of environmental sustainability metrics and consideration of social issues as part of the assessment. Sustainability Assessment of Renewables-Based Products: Methods and Case Studies is an extensive update and sequel to the 2006 title Renewables-Based Technology: Sustainability Assessment. It discusses the impressive evolution and role renewables have taken in our modern society, highlighting the importance of sustainability principles in the design phase of renewable-based technologies, and presenting a wide range of sustainability assessment methods suitable for renewables-based technologies, together with case studies to demonstrate their applications. This book is a valuTable of ContentsList of Contributors xvii Series Editor’s Preface xxiii Preface xxvii 1 The Growing Role of Biomass for Future Resource Supply—Prospects and Pitfalls 1Helmut Haberl 1.1 Introduction 1 1.2 Global Ecological and Socioeconomic Biomass Flows 3 1.3 Global Biomass Potentials in 2050 5 1.4 Critical Socio-Ecological Feedbacks and Sustainability Issues 9 1.5 Conclusions 12 Acknowledgements 12 References 13 2 The Growing Role of Photovoltaic Solar, Wind and Geothermal Energy as Renewables for Electricity Generation 19W.G.J.H.M. van Sark, J.G. Schepers, and J.D.A.M. van Wees 2.1 General Introduction 19 2.2 Photovoltaic Solar Energy 21 2.3 Wind Energy 24 2.4 Geothermal Energy 28 2.5 Conclusion 33 References 34 3 Assessment of Sustainability within Holistic Process Design 37Alexei Lapkin, Philipp]Maximilian Jacob, Polina Yaseneva, Charles Gordon, and Amy Peace 3.1 Introduction: Holistic Process Design from Unit Operations to Systems Science Methods 37 3.2 Use of Life Cycle Assessment in Holistic Process Design 403.3 A Decision-Tree Methodology for Complex Process Design 41 3.4 Generation of New Synthesis Routes in Bio-Based Supply Chains 45 3.5 Conclusions 47 Acknowledgements 48 References 48 4 A Mass Balance Approach to Link Sustainable Renewable Resources in Chemical Synthesis with Market Demand 51Claudius Kormann and Andreas Kicherer 4.1 Introduction 51 4.2 Renewable Feedstock: Market Drivers, Political Frame 52 4.3 Traceability of Biomass as Feedstock in the Chemical Industry 53 4.4 Standard of Mass Balance in Chemical Synthesis 57 4.5 Sustainability Aspects of Renewable Resources 60 4.6 Discussion 61 4.7 Vision and Summary 62 References 63 5 Early R&D Stage Sustainability Assessment: The 5 Pillar Method 65Akshay D. Patel, John A. Posada, Li Shen, and Martin K. Patel 5.1 Introduction 65 5.2 Methodology 67 5.3 Case Study 73 5.4 Validation Case Study 75 5.5 Critical Review and Outlook 76 5.6 Conclusion 79 References 79 6 Assessing the Sustainability of Land Use: A Systems Approach 81Miguel Brandão 6.1 Introduction 81 6.2 Methodological Issue 1: Consequential Analysis of Land Use Decisions 82 6.3 Methodological Issue 2: Land Use Impacts on Ecosystems 87 6.4 Methodological Issue 3: Land Use Impacts on Climate 89 6.5 Methodological Issue 4: Economic and Social Impact Assessment 90 6.6 Methodological Issue 5: Integrating Environmental and Economic Assessments 92 6.7 Discussion 93 6.8 Conclusions 94 References 94 7 Water Use Analysis 97Francesca Verones, Stephan Pfister, and Markus Berger 7.1 Introduction 97 7.2 Methods and Tools for Assessing the Sustainable Use of Water 98 7.3 Case Study: Water Consumption Analysis of Biofuels and Fossil Fuels 102 7.4 Discussion and Conclusion 105 References 106 8 Material Intensity of Food Production and Consumption 109Lucia Mancini and Michael Lettenmeier 8.1 Introduction 109 8.2 Material Flow Based Approaches for Assessing Sustainable Production and Consumption Systems 110 8.3 MIPS Concept and Methodology 111 8.4 Material Intensity of Food Systems 113 8.5 Results of MIPS for Agricultural Products and Foodstuffs 118 8.6 Conclusions 121 References 122 9 Material and Energy Flow Analysis 125Goto Naohiro, Nova Ulhasanah, Hirotsugu Kamahara, Udin Hasanudin, Ryuichi Tachibana, and Koichi Fujie 9.1 Background 125 9.2 Methodology 128 9.3 Case Study 131 9.4 Conclusion 139 Acknowledgements 139 References 139 10 Exergy and Cumulative Exergy Use Analysis 141Sofie Huysman, Thomas Schaubroeck, and Jo Dewulf 10.1 What Is Exergy 141 10.2 Calculation of Exergy 142 10.3 Applications of Exergy 144 10.4 Cumulative Exergy Use Analysis 146 10.5 Conclusions 151 References 152 11 Carbon and Environmental Footprint Methods for Renewables based Products and Transition Pathways to 2050 155Geoffrey P. Hammond 11.1 Introduction 155 11.2 Carbon and Environmental (or Eco) Footprinting 159 11.3 The Relationship between Environmental Footprint Analysis (EFA) and Environmental Life]Cycle Assessment (LCA) 166 11.4 Carbon and Environmental Footprints Associated with Global Biofuel Production 167 11.5 Carbon and Environmental Footprints of Low Carbon Transition Pathways 171 11.6 Concluding Remarks 174 Acknowledgements 175 References 176 12 Tracking Supply and Demand of Biocapacity through Ecological Footprint Accounting 179David Lin, Alessandro Galli, Michael Borucke, Elias Lazarus, Nicole Grunewald, Jon Martindill, David Zimmerman, Serena Mancini, Katsunori Iha, and Mathis Wackernagel 12.1 Summary and Rationale 179 12.2 Methodology 182 12.3 Usage Recommendations 193 12.4 Future Developments 195 References 195 13 Life Cycle Assessment and Sustainability Supporting Decision Making by Business and Policy 201Sala Serenella, Fabrice Mathieux, and Rana Pant 13.1 Life Cycle Assessment: A Systemic Approach to Evaluate Impacts 201 13.2 LCA: Supporting Sustainability Assessment 205 13.3 Role of LCA in Supporting Decisions in Business and Policy Context 206 13.4 Tools and Support to Put LCA into Practice 210 13.5 Conclusion and the Way Forward 211 Acknowledgements 211 References 212 14 Life Cycle Costing 215Andreas Ciroth, Jutta Hildenbrand, and Bengt Steen 14.1 Life Cycle Costing – Definition and Principles 215 14.2 Environmental LCC 216 14.3 Societal LCC 220 14.4 LCC and Renewables 221 14.5 Example Case 222 References 228 15 Social Life Cycle Assessment: Methodologies and Practice 229Alessandra Zamagni, Pauline Feschet, Anna Irene De Luca, Nathalie Iofrida, and Patrizia Buttol 15.1 Introduction 229 15.2 Social Life Cycle Assessment: Scientific Background 230 15.3 Social Life Cycle Assessment in Practice 232 15.4 SLCA and Life Cycle Sustainability Assessment: Methodological Challenges 234 15.5 Conclusions and Outlook 236 References 237 16 Life Cycle Assessment of Solar Technologies 241F. Ardente, M. Cellura, S. Longo, and M. Mistretta 16.1 Introduction 241 16.2 Solar Technologies 242 16.3 Life Cycle Assessment (LCA) and Solar Technologies 245 16.3.1 Solar Thermal Plants 246 16.3.2 Photovoltaic Plants 246 16.3.3 Concentrating Solar Power (CSP) Plants and Solar Heating/Cooling Plants 249 16.4 Assessment of Solar Technologies 249 16.5 Conclusions 256 References 256 17 Assessing the Sustainability of Geothermal Utilization 259Ruth Shortall, Gudni Axelsson, and Brynhildur Davidsdottir 17.1 Introduction 259 17.2 Sustainable Geothermal Utilization 260 17.3 Broader Sustainability Assessment of Energy Developments 266 17.4 Sustainability Assessment Framework for Geothermal Power 266 17.5 Conclusion 271 References 271 18 Biofuels from Terrestrial Biomass: Sustainability Assessment of Sugarcane Biorefineries in Brazil 275Otavio Cavalett, Marcos D.B. Watanabe, Alexandre Souza, Mateus F. Chagas, Tassia L. Junqueira, and Antonio Bonomi 18.1 Introduction 275 18.2 The Virtual Sugarcane Biorefinery (VSB) 276 18.3 Methods Used in the VSB 277 18.4 Biorefinery Scenarios Case Study 279 18.5 Final Remarks 286 Acknowledgements 286 References 287 19 Algae as Promising Biofeedstock; Searching for Sustainable Production Processes and Market Applications 289Sue Ellen Taelman, Steven De Meester, and Jo Dewulf 19.1 Introduction 289 19.2 Algae Background 290 19.3 Algal Cultivation and Processing Methods 292 19.4 Algae: Production and Potential Applications 294 19.5 Environmental Sustainability of Algae Production 298 19.6 Conclusions 302 References 303 20 Life Cycle Assessment of Biobased and Fossil Based Succinic Acid 307Marieke Smidt, Jeroen den Hollander, Henk Bosch, Yang Xiang, Maarten van der Graaf, Anne Lambin, and Jean]Pierre Duda 20.1 Production of Succinic Acid 307 20.2 Life Cycle Assessment: Biobased Succinic Acid and Fossil]Based Equivalent 310 20.3 Sensitivity Analysis 316 20.4 Conclusions 319 References 320 21 Biobased Poly Vinylchloride (PVC) 323Rodrigo A.F. Alvarenga, Zdenek Hruska, Alain Wathelet, and Jo Dewulf 21.1 Introduction 323 21.2 Life Cycle Assessment of Biobased PVC 324 21.3 Carbon Footprint of Biobased Product 329 21.4 Environmental Sustainability of Bioethanol Use 330 21.5 Conclusions 331 References 332 22 Evaluation of Wood Cascading 335Karin Höglmeier, Gabriele Weber-Blaschke, and Klaus Richter 22.1 Introduction 335 22.2 Environmental Assessment of Wood Cascading by LCA 338 22.3 Discussion and Conclusion 343 Acknowledgements 345 References 345 23 Time]Dependent Life Cycle Assessment of Bio-Based Packaging Materials 347Maartje N. Sevenster 23.1 Introduction 347 23.2 Methodology 351 23.3 Results 353 23.4 Discussion 357 23.5 Conclusions 358 References 358 24 Conclusions 361Jo Dewulf 24.1 The Importance of Renewables]Based Products and Services 361 24.2 The Need for Sustainability Assessment for Renewables: Even More Than in the Past 362 24.3 The Growing Sustainability Assessment Toolbox 363 24.4 Outlook: Pending Challenges 364 Index

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Book SynopsisOrganic Reaction Mechanisms 2014, the 50th annual volume in this highly successful and unique series, surveys research on organic reaction mechanisms described in the available literature dated 2014.Table of Contents1. Reactions of Aldehydes and Ketones and their Derivativesby B. A. Murray 1 2. Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and their Derivativesby C. T. Bedford 87 3. Oxidation and Reductionby K. K. Banerji 123 4. Carbenes and Nitrenesby E. Gras and S. Chassaing 227 5. Aromatic Substitutionby M. R. Crampton 267 6. Carbocationsby D. A. Klumpp 339 7. Nucleophilic Aliphatic Substitutionby A. C. Knipe 367 8. Carbanions and Electrophilic Aliphatic Substitutionby M. L. Birsa 399 9. Elimination Reactionsby M. L. Birsa 423 10. Addition Reactions: Polar Additionby P. Ko¡covsk´y 435 11. Addition Reactions: Cycloadditionby N. Dennis 583 12. Molecular Rearrangementsby J. M. Coxon 621 Author Index 713 Cumulative Subject Index, 2010–2014 763

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Book SynopsisProvides a review of novel pharmaceutical approaches for Tuberculosis drugs Presents a novel perspective on tuberculosis prevention and treatment Considers the nature of disease, immunological responses, vaccine and drug delivery, disposition and response Multidisciplinary appeal, with contributions from microbiology, immunology, molecular biology, pharmaceutics, pharmacokinetics, chemical and mechanical engineering Table of ContentsList of Contributors xvi Foreword xviii Series Preface xxi Preface xxiii 1 Introduction: A Guide to Treatment and Prevention of Tuberculosis Based on Principles of Dosage Form Design and Delivery 1A.J. Hickey 1.1 Background 1 1.2 Dosage Form Classification 3 1.3 Controlled and Targeted Delivery 5 1.4 Physiological and Disease Considerations 6 1.5 Therapeutic Considerations 7 1.6 Conclusion 8 References 8 Section 1 Pathogen and Host 11 2 Host Pathogen Biology for Airborne Mycobacterium tuberculosis: Cellular and Molecular Events in the Lung 13Eusondia Arnett, Nitya Krishnan, Brian D. Robertson and Larry S. Schlesinger 2.1 Introduction 13 2.2 Lung 14 2.3 General Aspects of Mucus and Surfactant 17 2.4 General M. tuberculosis 18 2.5 M. tuberculosis Interaction with the Lung Macrophage 19 2.6 M. tuberculosis Interaction with other Respiratory Immune Cells 23 2.7 TB Granuloma 29 2.8 Conclusion 30 References 30 3 Animal Models of Tuberculosis 48David N. McMurray 3.1 Introduction 48 3.2 What is an Animal Model of TB? 49 3.3 How are Animal Models of TB Used? 50 3.4 TB Animal Models Currently Used for TB Drug and Vaccine Evaluation 51 3.5 Summary 58 References 59 Section 2 Immunological Intervention 67 4 Vaccine Preparation: Past, Present, and Future 69Dominique N. Price, Nitesh K. Kunda, Amber A. McBride and Pavan Muttil 4.1 Introduction 69 4.2 Early Efforts in TB Vaccine Development 71 4.3 Current BCG Vaccine Formulation 73 4.4 Novel TB Vaccination Strategies 76 4.5 Future Perspective 84 4.6 Conclusions 85 References 85 5 TB Vaccine Assessment 91Andre G. Loxton, Mary K. Hondalus and Samantha L. Sampson 5.1 Introduction 91 5.2 Preclinical Vaccine Assessment 92 5.3 Clinical Assessment of Vaccines 97 5.4 Laboratory Immunological Analysis and Assessment of Vaccine Trials 102 5.5 How well do the Available Preclinical Models Predict Vaccine Success in Humans? 103 References 105 Section 3 Drug Treatment 111 6 Testing Inhaled Drug Therapies for Treating Tuberculosis 113Ellen F. Young, Anthony J. Hickey and Miriam Braunstein 6.1 Introduction 113 6.2 The Need for New Drug Treatments for Tuberculosis 114 6.3 Inhaled Drug Therapy for Tuberculosis 114 6.4 Published Studies of Inhalation Therapy for TB 115 6.5 The Guinea Pig Model for Testing Inhaled Therapies for TB 116 6.6 Guinea Pig Study Design 117 6.7 Purchase and Grouping Animals 118 6.8 Infecting Guinea Pigs with Virulent Mycobacterium tuberculosis 118 6.9 Dosing Groups of Guinea Pigs with TB Drugs 119 6.10 Collecting Data 121 6.11 Aerosol Dosing Chambers and Practice 122 6.12 Nebulizer Aerosol Delivery Systems for Liquids 123 6.13 Dry-Powder Aerosol Delivery Systems for Solids 125 6.14 Summary 127 Acknowledgements 127 References 127 7 Preclinical Pharmacokinetics of Antitubercular Drugs 131Mariam Ibrahim and Lucila Garcia-Contreras 7.1 Introduction 131 7.2 Factors Influencing the Pharmacokinetic Behavior of Drugs 132 7.3 Pulmonary Delivery of Anti-TB Drugs 138 7.4 Pharmacokinetic Study Design 140 7.5 Implications of PK Parameters on Efficacy 144 7.6 Case Studies (Drugs Administered by Conventional and Pulmonary Routes) 146 References 152 8 Drug Particle Manufacture – Supercritical Fluid, High-Pressure Homogenization 156Kimiko Makino and Hiroshi Terada 8.1 Introduction 156 8.2 Preparation of Nano- and Micro-particles 157 References 159 9 Spray Drying Strategies to Stop Tuberculosis 161Jennifer Wong, Maurizio Ricci and Hak-Kim Chan 9.1 Introduction 161 9.2 Overview of Spray Drying 162 9.3 Advances in Spray Drying Technology 174 9.4 Anti-Tuberculosis Therapeutics Produced by Spray Drying 179 9.5 Conclusion 187 9.6 Acknowledgements 187 References 187 10 Formulation Strategies for Antitubercular Drugs by Inhalation 197Francesca Buttini and Gaia Colombo 10.1 Introduction 197 10.2 Lung Delivery of TB Drugs 198 10.3 Powders for Inhalation and Liquids for Nebulization 200 10.4 Antibacterial Powders for Inhalation: Manufacturing of Respirable Microparticles 202 10.5 Antibacterial Powders for Inhalation: Devices and Delivery Strategies 208 10.6 Conclusions and Perspectives 211 References 211 11 Inhaled Drug Combinations 213Sanketkumar Pandya, Anuradha Gupta, Rajeev Ranjan, Madhur Sachan, Atul Kumar Agrawal and Amit Misra 11.1 Introduction 213 11.2 Standard Combinations in Oral and Parenteral Regimens 214 11.3 The Rationale for Inhaled Therapies of TB 216 11.4 Combinations of Anti-TB Drugs with Other Agents 222 11.5 Formulation of Inhaled Drug Combinations 224 11.6 Conclusions 230 References 230 12 Ion Pairing for Controlling Drug Delivery 239Stefano Giovagnoli, Aurélie Schoubben and Carlo Rossi 12.1 Introduction 239 12.2 Ion Pairing Definitions and Concepts 240 12.3 Ion Pairs, Complexes and Drug Delivery 245 12.4 Remarks 252 References 254 13 Understanding the Respiratory Delivery of High Dose Anti-Tubercular Drugs 258Shyamal C. Das and Peter J. Stewart 13.1 Introduction 258 13.2 Tuberculosis 259 13.3 Drugs Used to Treat Tuberculosis, Doses, Challenges and Requirements for Therapy in Lungs 260 13.4 Approaches for Respiratory Delivery of Drugs 262 13.5 Current DPI Formulations and Their Mechanisms of Aerosolization 262 13.6 DPI Formulations for Tuberculosis and Requirements 264 13.7 Issues to Consider in Respiratory Delivery of Powders for Tuberculosis 264 13.8 Relationship between De-agglomeration and Tensile Strength 266 13.9 Strategies to Improve De-agglomeration 268 13.10 DPI Formulations having High Aerosolization 269 13.11 Devices for High Dose Delivery 270 13.12 Future Considerations 271 References 272 Section 4 Alternative Approaches 275 14 Respirable Bacteriophage Aerosols for the Prevention and Treatment of Tuberculosis 277Graham F. Hatfull and Reinhard Vehring 14.1 Introduction 277 14.2 Treatment or Prevention of Tuberculosis Using Phage-based Agents 282 14.3 Selection of Mycobacteriophages 284 14.4 Respiratory Drug Delivery of Phages 285 14.5 Summary and Outlook 288 Acknowledgements 288 References 288 15 RNA Nanoparticles as Potential Vaccines 293Robert DeLong 15.1 Introduction 293 15.2 Nanoparticles 293 15.3 RNA Nanoparticle Vaccines 294 15.4 Progression of Nanomedicines into the Clinic 295 15.5 The Stability Problem 295 15.6 The Delivery Problem 298 15.7 RNA as Targeting Agent or Adjuvant? 298 15.8 Challenges for RNA Nanoparticle Vaccine Characterization 300 15.9 On the Horizon 301 References 301 16 Local Pulmonary Host-Directed Therapies for Tuberculosis via Aerosol Delivery 307Mercedes Gonzalez-Juarrero 16.1 Introduction 307 16.2 Lung Immunity to Pulmonary M. tuberculosis Infection 309 16.3 Host-Directed Therapies 313 16.4 Limitations of Preclinical Studies to Develop Inhalational Host-Directed Therapies for Tuberculosis 317 16.5 Preclinical Testing of Inhaled Small Interference RNA as Host-Directed Therapies for Tuberculosis 318 Acknowledgements 319 References 319 Section 5 Future Opportunities 325 17 Treatments for Mycobacterial Persistence and Biofilm Growth 327David L. Hava and Jean C. Sung 17.1 Introduction 327 17.2 Mycobacterial Persistence and Drug Tolerance 328 17.3 Mycobacterial Multicellular Growth 329 17.4 Mycobacterial Lipids Involved in Biofilm Formation 330 17.5 Therapies to Treat Mycobacterial Biofilms and Persistence 332 17.6 Conclusion 339 References 339 18 Directed Intervention and Immunomodulation against Pulmonary Tuberculosis 346Dominique N. Price and Pavan Muttil 18.1 Introduction 346 18.2 TB Immunology 347 18.3 Animal Models of Immunotherapies and Vaccines for TB 351 18.4 The Current TB Vaccine – Bacille Calmette Guérin 353 18.5 Other Vaccines Platforms 357 18.6 Pulmonary Immunization 361 18.7 Immunotherapeutic Agents against TB 364 18.8 Conclusion 367 References 367 Section 6 Clinical Perspective 379 19 Clinical and Public Health Perspectives 381Ruvandhi R. Nathavitharana and Edward A. Nardell 19.1 Introduction 381 19.2 Background 382 19.3 Clinical Considerations 382 19.4 Public Health Considerations 385 19.5 Inhaled Drugs and Other Alternative Delivery Systems 387 19.6 Clinical Trials of Inhaled Injectable Drugs 388 19.7 Other Novel Delivery Strategies 393 19.8 Pediatric Delivery Systems 393 19.9 Conclusion 394 References 394 20 Concluding Remarks: Prospects and Challenges for Advancing New Drug and Vaccine Delivery Systems into Clinical Application 400P. Bernard Fourie and Richard Hafner 20.1 Introduction 400 20.2 Progress in the Formulation and Manufacturing of Drugs and Vaccines for Tuberculosis 401 20.3 Considerations in the Development of TB Drug and Vaccine Delivery Options 404 20.4 Concluding Remarks 410 References 411 Index 415

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Book SynopsisProvides solutions for two- and three-dimensional linear models of controlled-release systems Real-world applications are taken from used to help illustrate the methods in Cartesian, cylindrical and spherical coordinate systems Covers the modeling of drug-delivery systems and provides mathematical tools to evaluate and build controlled-release devices Includes classical and analytical techniques to solve boundary-value problems involving two- and three-dimensional partial differential equations Provides detailed examples, case studies and step-by-step analytical solutions to relevant problems using popular computational software Table of ContentsPreface ix Acknowledgements xi 1 Steady-State Analysis of a Two-Dimensional Model for Percutaneous Drug Transport 1 1.1 Separation of Variables in 2-D Cartesian Coordinates1 1.2 Model for Drug Transport across the Skin 3 1.3 Analytical Solution of the Diffusion Model in 2-D Cartesian Systems 4 1.4 Summary 6 1.5 Appendix: Maple, Mathematica, and Maxima Code Listings 6 Problems 10 References 12 2 Constant Drug Release from a Hollow Cylinder of Finite Length in Two Dimensions 13 2.1 Separation of Variables in 2-D Cylindrical Coordinates 13 2.2 Model for Drug Release from a Hollow Cylinder 15 2.3 Analytical Solution of the Transport Model in 2-D Cylindrical Coordinates 15 2.4 Summary 19 2.5 Appendix: Maple Code Listings 19 Problems 20 References 20 3 Analysis of Steady-State Growth Factor Transport Through Double-Layered Scaffolds 23 3.1 Governing Steady-State Transport Equations 23 3.2 Solution Procedure for Transport Through a Two-Layered Scaffold 25 3.3 Concentration Profile of Vascular Endothelial Growth Factor in Two Layers 31 3.4 Summary 32 3.5 Appendix: Maple Code Listings 33 Problems 37 References 38 4 Steady-State Two-Dimensional Diffusion in a Hollow Sphere 39 4.1 Separation of Variables and Legendre Polynomials in 2-D Spherical Coordinates 39 4.2 Model For 2-D Diffusion in a Sphere 43 4.3 Analytical Solution of 2-D Diffusion in Spherical Coordinates 46 4.4 Summary 49 4.5 Appendix: Maple, Mathematica, and Maxima Code Listings 49 Problems 56 References 57 5 Steady-State Three-Dimensional Drug Diffusion through Membranes from Distributed Sources 59 5.1 Separation of Variables in 3-D Cartesian Coordinates 59 5.2 Transport across the Membrane 61 5.3 Analytical Solution of the Diffusion Model in 3-D Cartesian Systems 63 5.4 Summary 68 5.5 Appendix: Maple Code Listings 69 Problems 73 References 73 6 Constant Drug Release from a Hollow Cylinder of Finite Length in Three Dimensions 75 6.1 Separation of Variables in 3-D Cylindrical Coordinates 75 6.2 Model For 3-D Drug Release from a Hollow Cylinder 77 6.3 Analytical Solution of the Transport Model in 3-D Cylindrical Coordinates 78 6.4 Summary 84 6.5 Appendix: Maple Code Listings 85 Problems 87 References 87 7 Sustained Drug Release from a Hollow Sphere in Three Dimensions 89 7.1 Method of Green’s Function in 3-D Spherical Coordinates 89 7.2 Model for Molecular Transport across the Wall of a Hollow Sphere 95 7.3 Analytical Solution of the Transport Model in 3-D Spherical Coordinates 96 7.4 Summary 97 7.5 Appendix: Maple, Mathematica and Maxima Code Listings 98 Problems 105 References 105 8 Analysis of Transient Growth Factor Transport Through Double-Layered Scaffolds 107 8.1 Laplace and Fourier-Bessel-based Methods in 2-D Cylindrical Coordinates 107 8.2 Governing Equations for Transport through Double-Layered Scaffolds 112 8.3 Concentration Profile of Vascular Endothelial Growth Factor in Two Layers 114 8.4 Summary 119 8.5 Appendix: Maple Code Listings 120 Problems 126 References 126 9 Molecular Diffusion through the Stomach Lining and into the Bloodstream 129 9.1 Laplace Transforms, Legendre Functions and Spherical Harmonics129 9.2 Spherical Diffusion in Three Dimensions 132 9.3 Analytical Solution of the Transient Transport Model in 3-D Spherical Coordinates 133 9.4 Summary 138 9.5 Appendix: Maple Code Listings 138 Problems 141 References 143 10 Diffusion-Controlled Ligand Binding to Receptors on Cell Surfaces 145 10.1 Weber’s Integral 145 10.2 Steady-State Diffusion-Limited Ligand Binding 148 10.3 Transient Diffusion-Controlled Ligand Binding in 2-D Cylindrical Coordinates 151 10.4 Summary 156 10.5 Appendix: Maple, Mathematica and Maxima Code Listings 156 Problems 167 References 168 11 Two-Dimensional Analysis of a Cylindrical Matrix Device with a Small Hole For Drug Release 169 11.1 Mathematical Modeling of Drug Transport through the Device 169 11.2 Drug Concentration Profile inside the Matrix 171 11.3 Normalized Cumulative Percentage of Drug Released 177 11.4 Summary 178 11.5 Appendix: Maple Code Listings 178 Problems 182 References 183 12 Three-Dimensional Drug Diffusion through Membranes from Distributed Sources 185 12.1 Governing Equations of the Transport Model 185 12.2 Analytical Solution of the Diffusion Model in 3-D Cartesian Systems 187 12.3 Average Dimensionless Concentration and Flux 194 12.4 Summary 194 12.5 Appendix: Maple and Mathematica Code Listings 195 Problems 207 References 207 13 Effective Time Constant for Two- and Three-Dimensional Controlled-Released Drug-Delivery Models 209 13.1 Effective Time Constant in Controlled-Release Drug-Delivery Systems 209 13.2 Intravitreal Drug Delivery using a 2-D Cylindrical Model 210 13.3 Analysis of a Rectangular Parallelepiped-Shaped Matrix with a Release Area 218 13.4 Summary 225 13.5 Appendix: Maple and Mathematica Code Listings 225 Problems 232 References 232 14 Data Fitting For Two- and Three-Dimensional Controlled- Release Drug-Delivery Models 233 14.1 Data Fitting in Controlled-Release Drug-Delivery Systems 233 14.2 Estimation of Diffusion Coefficient in a Solid Cylinder of Finite Length 234 14.3 Estimation of Diffusion Coefficient in a Rectangular Parallelepiped-Shaped Matrix 240 14.4 Summary 243 14.5 Appendix: Maple and Mathematica Code Listings 244 Problems 256 References 258 15 Optimization of Two- and Three-Dimensional Controlled-Released Drug-Delivery Models 259 15.1 Optimum Design of Controlled-Released Drug-Delivery Systems 259 15.2 Design of a 2-D Cylindrical Dosage Form with a Finite Mass Transfer Coefficient 260 15.3 Design of a Rectangular Parallelepiped-Shaped Matrix with a Finite Mass Transfer Coefficient 265 15.4 Summary 268 15.5 Appendix: Maple and Mathematica Code Listings 268 Problems 282 References 283 Index 285

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Book SynopsisThis book highlights the triumph of MALDI-TOF mass spectrometry over the past decade and provides insight into new and expanding technologies through a comprehensive range of short chapters that enable the reader to gauge their current status and how they may progress over the next decade. This book serves as a platform to consolidate current strengths of the technology and highlight new frontiers in tandem MS/MS that are likely to eventually supersede MALDI-TOF MS. Chapters discuss:Challenges of IdentifyingMycobacterium to the Species level Identification of Bacteroides and Other ClinicallyRelevant AnaerobesIdentification of Species inMixed Microbial PopulationsDetection of ResistanceMechanismsProteomics as a biomarkerdiscovery and validation platformDetermination of AntimicrobialResistance using Tandem Mass SpectrometryTable of ContentsList of Contributors xxi Preface xxix Part I MALDI-TOF Mass Spectrometry 1 1 A Paradigm Shift from Research to Front]Line Microbial Diagnostics in MALDI]TOF and LC]MS/MS: A Laboratory’s Vision and Relentless Resolve to Help Develop and Implement This New Technology amidst Formidable Obstacles 3Haroun N. Shah and Saheer E. Gharbia 2 Criteria for Development of MALDI]TOF Mass Spectral Database 39Markus Kostrzewa and Thomas Maier 3 Applications of MALDI]TOF Mass Spectrometry in Clinical Diagnostic Microbiology 55Onya Opota, Guy Prod’hom and Gilbert Greub 4 The Challenges of Identifying Mycobacterium to the Species Level using MALDI]TOF MS 93 5 Transformation of Anaerobic Microbiology since the Arrival of MALDI]TOF Mass Spectrometry 123Elisabeth Nagy, Mariann Abrok, Edith Urban, A.C.M. Veloo, Arie Jan van Winkelhoff, Itaru Dekio, Saheer E. Gharbia and Haroun N. Shah 6 Differentiation of Closely Related Organisms using MALDI]TOF MS 147Mark A. Fisher 7 Identification of Species in Mixed Microbial Populations using MALDI]TOF MS 167Pierre Mahe, Maud Arsac, Nadine Perrot, Marie]Helene Charles, Patrick Broyer, Jay Hyman, John Walsh, Sonia Chatellier, Victoria Girard, Alex van Belkum, and Jean]Baptiste Veyrieras 8 Microbial DNA Analysis by MALDI]TOF Mass Spectrometry 187 9 Impact of MALDI]TOF MS in Clinical Mycology; Progress and Barriers in Diagnostics 211Cledir R. Santos, Elaine Francisco, Mariana Mazza, Ana Carolina B. Padovan, Arnaldo Colombo and Nelson Lima 10 Development and Application of MALDI]TOF for Detection of Resistance Mechanisms 231Stefan Zimmermann and Irene Burckhardt 11 Discrimination of Burkholderia Species, Brucella Biovars, Francisella tularensis and Other Taxa at the Subspecies Level by MALDI]TOF Mass Spectrometry 249Axel Karger 12 MALDI]TOF]MS Based on Ribosomal Protein Coding in S10]spc]alpha Operons for Proteotyping 269Hiroto Tamura Part II Tandem MS/MS-Based Approaches to Microbial Characterization 311 13 Tandem Mass Spectrometry Analysis as an Approach to Delineate Genetically Related Taxa 313Raju V. Misra, Tom Gaulton, Nadia Ahmod, Min Fang, Martin Hornshaw, Jenny Ho, Saheer E. Gharbia and Haroun N. Shah 14 Mapping of the Proteogenome of Clostridium difficile Isolates of Varying Virulence 379Caroline H. Chilton, Saheer E. Gharbia, Raju V. Misra, Min Fang, Ian R. Poxton, Peter S. Borriello and Haroun N. Shah 15 Determination of Antimicrobial Resistance using Tandem MassSpectrometry 399Ajit J. Shah, Vlad Serafim, Zhen Xu, Hermine Mkrtchyan and Haroun N. Shah 16 Proteotyping: Tandem Mass Spectrometry Shotgun Proteomic Characterization and Typing of Pathogenic Microorganisms 419Roger Karlsson, Lucia Gonzales]Siles, Fredrik Boulund, Asa Lindgren, Liselott Svensson]Stadler, Anders Karlsson, Erik Kristiansson and Edward R.B. Moore 17 Proteogenomics of Pseudomonas aeruginosa in Cystic Fibrosis Infections 451Liang Yang and Song Lin Chua 18 Top]Down Proteomics in the Study of Microbial Pathogenicity 493Joseph Gault, Egor Vorontsov, Mathieu Dupre, Valeria Calvaresi, Magalie Duchateau, Diogo B. Lima, Christian Malosse and Julia Chamot]Rooke 19 Tandem Mass Spectrometry in Resolving Complex Gut Microbiota Functions 505Carolin Kolmeder, Kaarina Lahteenmaki, Pirjo Wacklin, Annika Kotovuori, Ilja Ritamo, Jaana Matto, Willem M. de Vos, and Leena Valmu 20 Proteogenomics of Non]model Microorganisms 529Jean Armengaud 21A Analysis of MALDI]TOF MS Spectra using the BioNumerics Software 539Katleen Vranckx, Katrien De Bruyne and Bruno Pot 21B Subtyping of Staphylococcus spp. Based upon MALDI]TOF MS Data Analysis 563Zhen Xu, Ali Olkun, Katleen Vranckx, Hermine V. Mkrtchyan, Ajit J. Shah, Bruno Pot, Ronald R. Cutler and Haroun N. Shah 21C Elucidating the Intra]Species Proteotypes of Pseudomonas aeruginosa from Cystic Fibrosis 579Ali Olkun, Ajit J. Shah and Haroun N. Shah References 588 Index 593

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