Note: Intro -- Advances in Physical Organic Chemistry -- Copyright -- Contents -- Contributors -- Preface -- Chapter One: Beyond transition state theory-Non-statistical dynamic effects for organic reactions -- 1. Introduction -- 1.1. Transition state theory (TST) -- 1.2. Assumptions that are not always valid -- 1.3. When should one suspect that TST is not sufficient? -- 1.4. Entropic intermediates -- 2. Characterizing non-TST effects -- 2.1. Ab initio molecular dynamics (AIMD) -- 2.2. Simulation results -- 2.3. The relationship between experiment and theory -- 3. Representative examples -- 3.1. Dynamic matching -- 3.2. Post-transition state bifurcations (PTSBs) -- 3.3. Recrossing -- 3.4. Roaming -- 4. Concluding remarks -- Acknowledgments -- Glossary -- References -- Chapter Two: Synthesis of π-extended non-alternant hydrocarbons based on azulene (5-7), pentalene (5-5) and heptalene (7- ... -- 1. Introduction -- 2. Construction of azulene- or pentalene framework through activation of sp-carbons with Lewis acid metals -- 2.1. Synthesis of PAH having an azulene subunit from enediyne frameworks -- 2.2. Catalytic cycloisomerization of conjugated bisbutatrienes into π-extended pentalenes with a,f-ring fusion mode -- 3. Synthesis and characterization of dibenzo[a,f]pentalene derivatives -- 4. Elucidation of interrelation between open-shell and antiaromatic characters in diareno[a,f]pentalenes -- 5. Synthesis and characterization of planar heptalene derivative with open-shell and antiaromatic characters -- 6. Conclusions and outlook remarks -- References -- Chapter Three: Phenanthrylene-alkynylene macrocycles, phenanthrene-fused dicyclopenta[b,g]naphthalene, as well as relevan ... -- 1. Introduction -- 2. Tetraalkoxyphenanthrene-fused octadehydro[12]annulenes -- 3. Tetraalkoxyphenanthrylene-alkynylene macrocycles -- 4. Benzo- and naphthopentalenes. , 5. Phenanthrene-fused dicyclopenta[b,g]naphthalene and related structures -- 6. Difluoreno[4,3-b:3,4-d]furan -- 7. Summary and perspective -- Acknowledgments -- References.

Note: Front Cover -- ADVISORY BOARD -- Advances in Physical Organic Chemistry -- Copyright -- CONTENTS -- CONTRIBUTORS -- PREFACE -- Chapter One - Is the Single-Transition-State Model Appropriate for the Fundamental Reactions of Organic Chemistry? Experime ... -- 1. INTRODUCTION -- 2. KINETIC METHODS TO DIFFERENTIATE BETWEEN SINGLE-STEP AND COMPLEX MECHANISMS -- 3. SN2 REACTIONS IN THE GAS PHASE AND IN SOLUTION -- 4. PROTON TRANSFER REACTIONS OF SIMPLE AND ARYL NITROALKANES IN SOLUTION AND IN THE GAS PHASE -- 5. HYDRIDE TRANSFER REACTIONS OF NADH/NAD+ MODEL AND RELATED SYSTEMS -- 6. COMPUTATION STUDIES OF ELECTROPHILIC AROMATIC SUBSTITUTION -- 7. CONCLUSIONS -- ACKNOWLEDGMENTS -- REFERENCES -- Chapter Two - The Influence of Structure on Reactivity in Alkene Metathesis -- 1. INTRODUCTION -- 2. INITIATION OF METATHESIS PRECATALYSTS -- 3. THE EFFECTS OF SUBSTRATE STRUCTURE ON REACTIVITY -- 4. TOOLS FOR STUDYING CATALYTIC METATHESIS -- 5. SUMMARY AND OUTLOOK -- ACKNOWLEDGMENTS -- REFERENCES -- Chapter Three - In This Molecule There Must Be a Conical Intersection -- 1. INTRODUCTION -- 2. INTRODUCTION TO QUALITATIVE VB THEORY -- 3. UNDERSTANDING CONICAL INTERSECTIONS USING VB THEORY: 4 ORBITALS WITH 4 ELECTRONS AND 3 ORBITALS WITH 3 ELECTRONS -- 4. UNDERSTANDING 6 ORBITALS WITH 6 ELECTRONS CONICAL INTERSECTIONS: BENZENE PHOTOCHEMISTRY4 -- 5. OTHER N ORBITAL WITH N ELECTRONS CONICAL INTERSECTIONS -- 6. QUALITATIVE VB ANALYSIS OF CONICAL INTERSECTIONS INVOLVING CHARGE TRANSFER, LONE PAIRS AND PROTON TRANSFER -- 7. CONCLUSIONS -- ACKNOWLEDGMENTS -- REFERENCES -- Chapter Four - Structure and Mechanism in Ketene Chemistry -- 1. INTRODUCTION -- 2. SUBSTITUENT EFFECTS ON KETENE STABILITY AND REACTIVITY -- 3. PREPARATION OF KETENES -- 4. KETENE REACTIONS -- 5. CONCLUSION -- REFERENCES -- SUBJECT INDEX -- AUTHOR INDEX -- CUMULATIVE INDEX OF TITLES. , CUMULATIVE INDEX OF AUTHORS -- Color Plates.

Note: Front Cover -- Advances in Physical Organic Chemistry -- Copyright -- Contents -- Contributors -- Preface -- Chapter One: Time-Resolved Electron Paramagnetic Resonance Spectroscopy: History, Technique, and Application to Supramolec ... -- 1. Introduction -- 2. Definition of the TREPR Experiment -- 3. Experimental Considerations for TREPR -- 4. TREPR System Components -- 4.1. Lasers and Optics -- 4.2. Resonator, Sample, Cell, and Pump Requirements -- 4.3. Microwave Bridge Preamplifier -- 4.4. Boxcar (Digitizer), Computer, and EPR Scan Time -- 4.5. Timing and Monitoring (Delay Generator, Photodiode, and Oscilloscope) -- 4.6. Test Systems -- 5. Chemically Induced Electron Spin Polarization (CIDEP) Mechanisms -- 5.1. The Triplet Mechanism (TM) -- 5.2. The Radical-Triplet Pair Mechanism -- 5.3. The Radical Pair Mechanism (RPM) -- 5.4. Confinement and the Spin-Correlated Radical Pair Mechanism -- 5.5. Superpositions of CIDEP Mechanisms -- 6. Applications of TREPR -- 6.1. Applications in Supramolecular Chemistry -- 6.2. Applications in Macromolecular Chemistry -- 6.2.1. Characterization of Main-Chain Radicals from the Photodegradation of Acrylic Polymers -- 6.2.2. Model Systems for Acrylic Polymeric Radicals -- 6.2.3. Degradation of Block Copolymers -- 6.2.4. RTPM as a Tool for Studying Long-Range Chain Dynamics in Polymers -- 7. Summary and Outlook -- Acknowledgments -- References -- Chapter Two: Avoiding CO2 in Catalysis of Decarboxylation -- 1. Introduction -- 1.1. Decarboxylation and the Formation of CO2 -- 1.2. Alternatives to Direct Formation of CO2 -- 2. Enzyme Catalysis -- 2.1. Enzymes Can Catalyze Decarboxylation Beyond Our Expectations -- 2.2. Enzyme-Catalyzed Decarboxylation by Addition to Thiamin Diphosphate -- 2.3. The Predecarboxylation Intermediate -- 3. Mechanistic Issues -- 3.1. Tautomeric Intermediates -- 3.2. Insights on Reversibility. , 3.3. Reversion as a General Problem in Decarboxylation Reactions -- 3.4. Carbanion Reactivity and Nonperfect Synchronization -- 4. Lessons from Theory -- 4.1. Computational Modeling Applied to Decarboxylation -- 5. CO2 - Reactivity and Reverse Reactions -- 5.1. Internal Return -- 5.2. Consequences of Low Solubility of CO2 -- 6. Alternatives to CO2 - Carbonic Acid Derivatives -- 6.1. Back to Bicarbonate -- 6.2. Acid Catalysis and Alternative Mechanisms for Decarboxylation -- 6.3. Energy of Alternatives to CO2 -- 6.4. Evidence for Associative Pathways: Decarboxylation of Pyrrole-2-Carboxylic Acid -- 6.5. Protonated Carbonic Acid -- 7. Reactions Proceeding Through Hydrated Intermediates -- 7.1. Reexamination of Aromatic Decarboxylation Reactions -- 7.2. Aromatic Decarboxylation: Mesitoic Acid -- 7.3. Aromatic Decarboxylation -- 7.4. Generalized Aromatic Decarboxylation Pathways -- 7.5. Decarboxylation is not Always a Unimolecular Dissociative Process -- 7.6. Base-Catalyzed Decarboxylation of Thiamin-Derived Intermediates -- 7.7. Hydration of Esters and Acids -- 7.8. Hydration of Carboxylates -- 8. Rethinking the Decarboxylation of Trichloroacetic Acid -- 8.1. Historical Asides on Base-Catalyzed Decarboxylation -- 8.2. Base-Catalyzed Decarboxylation of Trichloroacetate as a Disproof of the Dualistic Theory of Bonding139 -- 8.3. Modern Interpretation of Reported Base-Catalyzed Decarboxylations -- 8.4. Potential Intermediates Along the Base-Catalyzed Route -- 9. A Basis for Mechanistic Diversity -- 9.1. Diverse Associative Catalytic Routes -- 10. The Role of Metal Ions -- 10.1. Do Lewis Acids Activate CO2 or Carbonic Acid Derivatives? -- 11. Conclusions and Prospects -- Acknowledgments -- References -- Chapter Three: Binding and Reactivity at Bilayer Membranes -- 1. Introduction -- 1.1. Biological and Synthetic Membranes. , 1.2. Organization and Motion Within Lipid Bilayers -- 1.3. Analytical Platforms for Studying Bilayers -- 1.3.1. Vesicles -- 1.3.2. Supported Bilayers -- 1.3.3. ``Black´´ Lipid Membranes -- 2. Binding to Membranes -- 2.1. The Effect of the Bilayer Environment on Molecular Recognition -- 2.2. Multivalent Recognition at Bilayers -- 2.2.1. Receptor Lipid Clustering Mediated by Multivalent Ligands -- 2.2.2. Understanding the Avidity of Multivalent Ligands -- 2.2.3. The Interdependence of Clustering and Multivalent Recognition of Bilayer-Embedded Lipids -- 2.2.4. Multivalent Intermembrane Recognition: Vesicle Aggregation and Fusion -- 3. Chemical Reactivity at Membranes -- 3.1. Reactions Between Soluble Reactants at the Membrane Interface -- 3.2. Reactions Between Membrane-Bound Reactants/Catalysts and Soluble Reactants -- 3.3. Reactions Between Reactants Both Embedded in Membranes -- 4. Conclusions -- Acknowledgments -- References -- Subject Index -- Author Index -- Cumulative Index of Titles -- Cumulative Index of Authors -- Color Plate.

Note: Front Cover -- Advances in Physical Organic Chemistry -- ADVISORY BOARD -- Advances in Physical Organic Chemistry -- Copyright -- Contents -- CONTRIBUTORS -- PREFACE -- One - Equilibrium Effective Molarity As a Key Concept in Ring-Chain Equilibria, Dynamic Combinatorial Chemistry, Co ... -- 1. INTRODUCTION -- 2. EFFECTIVE MOLARITY -- 3. EQUILIBRIUM MACROCYLIZATIONS -- 3.1 Ring-Chain Equilibria -- 3.2 Ring-Ring Equilibria -- 3.3 Self-Assembly Macrocyclizations -- 4. DYNAMIC COMBINATORIAL CHEMISTRY -- 4.1 One-Monomer Dynamic Libraries -- 4.1.1 Dynamic Libraries From Transesterification Reaction -- 4.1.2 Dynamic Libraries From Olefin Metathesis Reaction -- 4.1.3 Dynamic Libraries From Transacetalation (Formal Metathesis) Reaction -- 4.1.4 Dynamic Libraries From Imine Metathesis -- 4.1.5 Dynamic Libraries From Hydrogen Bonding Interactions (Supramolecular DLs) -- 4.2 Two-Monomer Dynamic Libraries -- 4.3 Templated Dynamic Libraries -- 5. COOPERATIVITY AND SELF-ASSEMBLY -- 5.1 Statistical Factors and Microscopic Constants -- 5.1.1 The Symmetry Number Method -- 5.1.2 The Direct Counting Method -- 5.2 Allosteric Cooperativity -- 5.3 Chelate Effect and Chelate Cooperativity -- 5.4 Interannular Cooperativity -- 5.5 Stability of an Assembly -- 6. CONCLUSION -- REFERENCES -- Two - Thermodynamic Effective Molarities for Supramolecular Complexes -- 1. INTRODUCTION -- 1.1 Multivalency and Cooperativity -- 1.2 Effective Molarity -- 2. EFFECTIVE MOLARITIES FOR SUPRAMOLECULAR COMPLEXES -- 2.1 Data Collection -- 2.2 Examples of Different Types of Supramolecular Complex -- 2.2.1 DMC -- 2.2.2 H-Bonding Interactions -- 2.2.3 Coordination -- 2.2.4 Hydrophobic Effects -- 2.2.5 Multiple Binding -- 2.2.6 Biomolecules -- 2.3 Distribution of Effective Molarity Values -- 2.3.1 Relationship Between Association Constants and Values of Effective Molarity. , 2.4 Supramolecular Complexes With Very Large Values of Effective Molarity -- 2.5 Supramolecular Complexes With Very Small Values of Effective Molarity -- 2.6 Solvent Effects on Effective Molarity -- 3. CONCLUSION -- APPENDIX: COLLECTION OF THERMODYNAMIC EFFECTIVE MOLARITY VALUES FOR SUPRAMOLECULAR COMPLEXES -- ACKNOWLEDGEMENTS -- REFERENCES -- Three - Reactivity of Nucleic Acid Radicals -- 1. INTRODUCTION -- 2. RADICAL FORMATION IN NUCLEIC ACIDS -- 3. THE NORRISH TYPE I PHOTOREACTION -- 4. C1′-RADICAL GENERATION, REACTIVITY AND RELATED MECHANISTIC IMPLICATIONS -- 4.1 C1′-Radical Formation -- 4.2 C1′-Radical Reactivity -- 4.3 Utility of C1′-Radical Generation as a Source of 2-Deoxyribonolactone in Mechanistic Studies -- 4.4 Probing DNA Repair Enzyme Activity Using Independently Generated 2′-Deoxyuridin-1′-yl Radical (3) -- 5. C2′-RADICAL GENERATION AND REACTIVITY IN DNA, RIBONUCLEOSIDES AND RNA -- 5.1 C2′-Radical Formation Following Irradiation of 5-Halopyrimidine Nucleotides in DNA -- 5.2 Generation and Reactivity of the 2′-Radical in RNA -- 5.3 C2′-Radical Formation and Reactivity Following Irradiation of 5-Bromouridine in RNA -- 6. C3′-RADICAL GENERATION AND REACTIVITY IN DNA -- 6.1 C3′-Radical Formation Following Irradiation of Transition Metal Coordination Complexes -- 6.2 Independent Generation and Reactivity of Thymidin-3′-yl Radical (35) -- 7. C4′-RADICAL GENERATION AND REACTIVITY IN DNA AND RNA -- 7.1 C4′-Radical Formation -- 7.2 C4′-Radical Reactivity in DNA -- 7.3 Independent Generation and Reactivity of C4′-Radicals in DNA -- 7.4 Double-Strand Cleavage via a Single C4′-Radical -- 7.5 The Role of Independent C4′-Radical Generation in Understanding Electron Transfer in DNA -- 7.6 C4′-Radical Reactivity in RNA -- 8. C5′-RADICAL GENERATION AND REACTIVITY IN DNA -- 8.1 C5′-Radical Formation -- 8.2 C5′-Radical Reactivity in DNA. , 8.3 Independent Generation and Reactivity of C5′-Radicals -- 9. NUCLEOBASE RADICAL GENERATION AND REACTIVITY IN DNA AND RNA -- 9.1 Nucleobase Radical Formation -- 9.2 Nucleobase Radical Reactivity -- 9.3 Independent Generation and Reactivity of DNA Nucleobase Radical Adducts -- 9.4 Independent Generation and Reactivity of RNA Nucleobase Radical Adducts -- 9.5 Independent Generation and Reactivity of DNA 5-(2′-Deoxyuridinyl)methyl and 5-(2′-Deoxycytidinyl)methyl Radicals -- 9.6 Independent Generation and Reactivity of Neutral Purine Radicals -- 10. SUMMARY AND FUTURE CONSIDERATIONS -- ACKNOWLEDGEMENT -- REFERENCES -- Four - Computational Studies of Environmental Effects and Their Interplay With Experiment -- 1. INTRODUCTION -- 2. COMPUTATIONAL MODELS -- 2.1 QM/Classical Models -- 2.1.1 Ground-State Theory -- 2.1.2 Extension to Molecular Excited States -- 3. THE INTERPLAY WITH EXPERIMENTS: THE SOLVATED MOLECULE AND ITS SPECTROSCOPIC RESPONSES -- 3.1 Ground-State Spectroscopies -- 3.2 Excited-State Spectroscopies -- 4. BEYOND THE SOLVATED MOLECULE -- 5. CONCLUSIONS -- REFERENCES -- SUBJECT INDEX -- A -- B -- C -- D -- E -- F -- G -- H -- I -- J -- K -- L -- M -- N -- O -- P -- Q -- R -- S -- T -- U -- Z -- AUTHOR INDEX -- A -- B -- C -- D -- E -- F -- G -- H -- I -- J -- K -- L -- M -- N -- O -- P -- Q -- R -- S -- T -- U -- V -- W -- X -- Y -- Z -- CUMULATIVE INDEX OF TITLES -- Back Cover.

Note: Front Cover -- Advances in Physical Organic Chemistry -- Copyright -- Contents -- Contributors -- Chapter One: Computational asymmetric catalysis: On the origin of stereoselectivity in catalytic reactions -- 1. Introduction -- 2. Asymmetric dearomative amination of β-naphthols -- 3. Pd-Catalyzed C-H Arylation -- 4. Desymmetrization of three-substituted oxetanes -- 5. Enantioselective heck matsuda arylation -- 6. Enantioselective synthesis of indoles -- 7. Asymmetric α-allylation of aldehydes -- 8. Summary and outlook -- References -- Chapter Two: The transition state and cognate concepts -- 1. Introduction -- 2. Conceptual power of the transition state -- 3. Glossary of terms -- 3.1. Potential-energy surface (PES) -- 3.2. Saddle point -- 3.3. Minimum energy reaction path -- 3.4. Reaction coordinate (part 1) -- 3.5. Activated complex -- 3.6. Transition structure -- 3.7. Intrinsic reaction coordinate -- 3.8. Transition vector -- 3.9. Transition-state structure -- 3.10. Transition state -- 4. Computation and experiment for simple systems -- 4.1. Application of statistical mechanics to a single transition structure -- 4.2. Inference of transition-state structure from empirical studies -- 4.3. Complications: Saddle points in series and in parallel-Virtual transition states -- 4.4. Potential energy vs free energy -- 5. Transition state for condensed systems: Concepts and simulations -- 5.1. Free-energy surfaces for condensed systems -- 5.2. Collective variables -- 5.3. Minimum free-energy paths -- 5.4. Variational transition state theory -- 5.5. Transmission coefficient -- 5.6. Reaction coordinate (part 2) -- 5.7. The equicommittor and the error in TST -- 6. Concluding remarks -- Acknowledgments -- References -- Chapter Three: Computational physical organic chemistry using the empirical valence bond approach -- 1. Introduction. , 2. Theoretical background -- 3. Dissecting catalysis using the empirical valence bond approach -- 4. Using the empirical valence bond approach to understand linear free energy relationships in enzymatic reactions -- 5. Using the empirical valence bond approach to understand the temperature dependence of activation free energies -- 6. Using the empirical valence bond approach to explore kinetic isotope effects in proton and hydride transfer reactions -- 7. Using the empirical valence bond approach to understand the evolution of enzyme function -- 8. Conclusion -- Acknowledgments -- References -- Back Cover.

Note: Front Cover -- ADVISORY BOARD -- Advances in Physical Organic Chemistry -- Copyright -- CONTENTS -- CONTRIBUTORS -- PREFACE -- One - Metal Ion-Promoted Leaving Group Assistance in the Light Alcohols -- 1. INTRODUCTION -- 1.1 Problems with Water as a Solvent for Metal Ion-Promoted Solvolyses are Ameliorated in Alcohols -- 2. METAL ION-PROMOTED LGA -- 2.1 Brief Description of LGA and Modes of Involvement of the Metal Ion -- 2.2 Early Examples with Acetyl Imidazole and Its (NH3)5CoIII-Complex where the Metal Ions Act as Lewis Activators and Provide L ... -- 2.3 Early Examples with Esters Having Complex Mechanisms for Methanolysis Promoted by Lanthanides and a Triazacyclododecane:ZnI ... -- 2.4 DFT Computational Study of the Methanolysis of Carboxylate Esters Promoted by ZnII-Complexed Methoxide (18) -- 3. METAL ION-PROMOTED ALCOHOLYSIS OF PHOSPHATES -- 3.1 Proof of Concept: LGA Provided by a CuII:Phenanthroline in the Solvolysis of Closely Positioned tri-, di-, and Monophosphates -- 3.2 Bimolecular Catalytic Phosphate Cleavage Reactions where Metal Ion-Promoted LGA is Apparent -- 3.3 DFT Computational Study of the 23-Promoted Methanolytic Cleavage of 24f -- 3.4 Additional Systems where Metal Ion-Promoted LGA Occurs -- 3.4.1 Yb3+-Catalyzed Cleavage of Methyl Aryl Phosphate Diesters Having ortho-C(=O)OCH3 Groups40 -- 3.4.2 (La3+(−OCH3))2 Catalysis of the Methanolysis of Phosphate Triesters Having ortho-C(=O)OCH3 Group.46 -- 4. LGA PROVIDED BY METAL IONS IN THE ACYL TRANSFER FROM AMIDES, UREAS, AND CARBAMATES TO SOLVENT ROH -- 4.1 LGA in the Solvolysis of Amides: MII-Promoted Solvolysis of N,N-bis(2-picolyl) Benzamides -- 4.2 Metal Ion-Promoted LGA in Bis(2-picolyl)amine-Derived Ureas and Carbamates -- 4.2.1 Ureas -- 4.2.2 Carbamates -- 5. CONCLUSIONS AND SPECULATIONS -- ACKNOWLEDGMENTS -- REFERENCES. , Two - Medium Effects in Biologically Related Catalysis -- 1. INTRODUCTION -- 2. PHOSPHORYL TRANSFER REACTIONS -- 2.1 Overview of Phosphoryl Transfer in Aqueous Solution -- 2.2 Solvent Effects in Phosphoryl Transfer Reactions -- 2.3 Surfactants Effects on Phosphoryl Transfer Reactions -- 3. SOLVENT EFFECTS IN SULFURYL TRANSFER REACTIONS -- 4. SOLVENT EFFECTS IN SN2 REACTIONS OF S-ADENOSYLMETHIONINE -- 5. DECARBOXYLATION REACTIONS -- 5.1 Decarboxylation of Orotic Acid Derivatives -- 5.2 Decarboxylation of 3-Carboxybenzisoxazoles (Kemp Decarboxylation) -- 6. KEMP ELIMINATION -- 7. CONCLUSIONS AND IMPLICATIONS FOR BIOINSPIRED CATALYSIS -- ACKNOWLEDGMENTS -- REFERENCES -- Three - Combustion Pathways of Biofuel Model Compounds: A Review of Recent Research and Current Challenges Pertaini ... -- 1. INTRODUCTION -- 1.1 Kinetic Mechanisms -- 1.2 Experimental Techniques -- 1.3 Computational Techniques -- 1.4 Simplifying Detailed Mechanisms -- 1.5 High- and Low-Temperature Oxidation Pathways -- 1.6 Atmospheric Chemistry -- 2. OVERVIEW OF FIRST-GENERATION BIOFUELS AND THEIR MODEL COMPOUNDS -- 2.1 Combustion Pathways of Ethanol -- 2.1.1 Unimolecular Decomposition of Ethanol -- 2.1.2 Bimolecular Radical-Induced Decomposition of Ethanol -- 2.1.3 Reactions of Radical Intermediates Derived from Ethanol -- 2.1.3.1 Unimolecular Processes -- 2.1.3.2 Bimolecular Processes -- 2.2 Combustion Pathways of Biodiesel -- 2.2.1 Biodiesel Model Compounds -- 2.2.1.1 Methyl Butanoate and Related Small Esters -- 2.2.1.2 Large Methyl Esters -- 2.2.1.3 Unsaturated Methyl Esters -- 2.2.2 Elementary Reaction Kinetics for Biodiesel Fuels -- 2.3 General Challenges in Modeling First-Generation Biofuels -- 3. OVERVIEW OF SECOND-GENERATION BIOFUELS AND THEIR MODEL COMPOUNDS -- 3.1 Cellulose Model Compounds -- 3.1.1 Combustion Pathways of Furan and Methylfurans. , 3.1.2 Combustion Pathways of Saturated Ethers (Tetrahydrofuran, Tetrahydropyran, and Derivatives) -- 3.1.3 Mechanistic Studies of Other Functionalized Monocycles -- 3.1.3.1 Morpholine -- 3.1.3.2 Glucose and Fructose -- 3.1.3.3 Other Cyclic Oxygenates -- 3.2 Lignin Model Compounds -- 3.2.1 Phenethyl Phenyl Ether -- 3.2.2 Other Lignin Models -- 3.3 General Challenges in Modeling Lignocellulosic Biofuels -- 4. OVERVIEW OF THIRD- AND FOURTH-GENERATION BIOFUELS -- 5. CHALLENGES IN BIOFUEL COMBUSTION ENGINEERING -- 6. CONCLUSION -- REFERENCES -- Four - Mechanistic Perspectives on Stereocontrol in Lewis Acid-Mediated Radical Polymerization: Lessons from Small- ... -- 1. INTRODUCTION -- 2. IMPORTANT FEATURES OF RADICAL REACTIVITY -- 3. RADICAL POLYMERIZATION -- 4. LEWIS ACIDS IN RADICAL-BASED POLYMER SYNTHESIS -- 5. SYNTHETIC RADICAL TRANSFORMATIONS -- 6. LEWIS ACIDS IN RADICAL-BASED SYNTHETIC TRANSFORMATIONS -- 7. SOME LESSONS FROM SYNTHESIS -- 7.1 Is the Lewis Acid-Base Interaction Too Weak? -- 7.2 Is the Chelate Unstable? -- 7.3 Does the Chelate Favor Meso Propagation? -- 7.4 Does the Lewis Acid Bind in the Correct Position during Propagation? -- 7.5 Is the Lewis Acid Kinetically Labile? -- 7.6 Summary and Outlook -- 8. CONCLUSION -- ACKNOWLEDGMENTS -- REFERENCES -- SUBJECT INDEX -- A -- B -- C -- D -- E -- F -- G -- H -- I -- J -- K -- L -- M -- N -- O -- P -- R -- S -- T -- U -- V -- Y -- Z -- AUTHOR INDEX -- A -- B -- C -- D -- E -- F -- G -- H -- I -- J -- K -- L -- M -- N -- O -- P -- Q -- R -- S -- T -- U -- V -- W -- X -- Y -- Z -- CUMULATIVE INDEX OF TITLES -- A -- B -- C -- D -- E -- F -- G -- H -- I -- K -- L -- M -- N -- O -- P -- R -- S -- T -- U -- V -- W -- Y -- CUMULATIVE INDEX OF AUTHORS -- A -- B -- C -- D -- E -- G -- H -- I -- J -- K -- L -- M -- N -- O -- P -- Q -- R -- S -- T -- U -- W -- Y -- Z -- Color plate -- Back Cover.

Note: Front Cover -- Advances in Physical Organic Chemistry -- Copyright -- Contents -- Contributors -- Preface -- References -- Chapter One: The Factors Determining Reactivity in Nucleophilic Substitution -- 1. Introduction -- 2. The Nucleophile in Methyl Transfer Reactions -- 2.1. Reactions in Solution: Swain and Scott's Nucleophilicity Scale -- 2.2. Nucleophilicity in Gas Phase Reactions -- 2.3. Relationship Between Methyl Cation Affinity and Proton Affinity -- 2.4. Identity SN2 Reactions -- 2.5. The Double-Well Potential Model -- 2.6. Marcus Theory: Relating the Intrinsic Barrier and Reaction Enthalpy to Actual Reaction Barriers -- 2.7. Towards Accurate Models for Methyl Transfer Reactions -- 2.8. The Alpha Effect -- 3. The Leaving Group -- 4. The Substrate -- 4.1. Alkyl-Substituted Carbon Centres -- 4.2. Cyclic Substrates -- 4.3. Benzylic and Allylic Substrates -- 4.4. Aromatic and Vinylic Nucleophilic Substitution -- 4.5. SN2 at Centres of Group 14-18 Elements -- 5. Cationic Reactions and Shift to SN1 -- 6. Kinetic Isotope Effects -- 7. Understanding SN2 Reactivity -- 7.1. Correlations Between Barrier Heights and Physical Observables -- 7.2. VB Theory -- 7.3. HSAB Theory and Related Approaches -- 7.4. Energy Decomposition Analysis -- 8. Reaction Dynamics -- 9. Role of the Solvent -- 10. Summary and Outlook -- References -- Chapter Two: Negative Ion Photoelectron Spectroscopy and Its Use in Investigating the Transition States for Some Organic ... -- 1. Introduction -- 1.1. Transition States -- 1.2. Negative Ion Photoelectron Spectroscopy12,13 -- 1.2.1. Vibrational Bands in NIPE Spectra -- 1.2.2. Franck-Condon Factors for Vibrational Progressions in NIPE Spectra -- 1.2.3. The NIPE Spectrum of CO4∙- and Its Simulation -- 2. Transition State Spectroscopy -- 2.1. TS Spectroscopy of X∙+H-X Hydrogen Abstraction Reactions. , 2.1.1. The NIPE Spectrum of I-H-I- -- 2.1.2. The PES for the Reaction XA∙+H-XBXA-H+XB∙ -- 2.1.3. Antisymmetric Stretching Vibrations on the X-H-X PES -- 2.1.4. Symmetric Stretching Vibrations on the X-H-X PES -- 2.2. TS Spectroscopy of Singlet COT -- 2.2.1. Predicted Violations of Hund's Rule in [4n]Annulenes -- 2.2.2. PESs for Ring Inversion and Bond Shifting in Singlet and Triplet COT and in COT∙- -- 2.2.3. NIPE Spectroscopy of COT∙- -- 2.3. TS Spectroscopy of Singlet OXA -- 2.3.1. The NIPE Spectrum of OXA∙- -- 2.4. TS Spectroscopy of Singlet and Triplet (CO)3 -- 2.4.1. The MOs of (CO)3 -- 2.4.2. The PES for Singlet (CO)3 -- 2.4.3. The PES for Triplet (CO)3 -- 2.4.4. Calculated Franck-Condon Factors -- 2.4.5. The NIPE Spectrum of CO3∙- and Its Simulation -- 3. Summary -- Acknowledgment -- References -- Chapter Three: Probing Transition State Analogy in Glycoside Hydrolase Catalysis -- 1. Scope and Purpose for This Review -- 2. General Introduction -- 2.1. Transition State Analogy -- 2.2. Glycoside Hydrolases -- 2.3. Glycoside Hydrolases: Transition State Analogy -- 3. Intrinsic Reactivity -- 3.1. Furanoside Solvolyses -- 3.2. Pyranoside Solvolyses -- 4. Catalytic Efficiency and Proficiency -- 4.1. Measurement of Uncatalysed Rate Constants at High Temperatures -- 4.2. Extrapolation of Uncatalysed Reaction Rate Constants Using Activated Substrates -- 5. Evaluation of Transition State Analogy by LFERs -- 5.1. Experiments Using Site-Directed Mutagenesis -- 5.2. Experiments Using a Panel of Substrate and Inhibitor Dyads -- 5.3. Experiments Involving Mechanism-Based Covalent Inhibitors -- 6. Recent Examples -- 6.1. Transition State Analogy in GH84 O-GlcNAc Hydrolase -- 6.2. Covalent Inhibitors of Yeast α-Glucosidase -- References -- Chapter Four: Phosphate Ester Hydrolysis: The Path From Mechanistic Investigation to the Realization of Artificial Enzymes. , 1. Introduction -- 2. Phosphate Ester Hydrolysis -- 2.1. The Rate of Phosphate Ester Hydrolysis -- 2.2. The Mechanisms of Phosphate Ester Hydrolysis -- 2.3. Computational Investigations -- 2.4. What Controls the Hydrolytic Reactivity of Phosphate Esters -- 3. Metal Ion Catalysis of Hydrolytic Phosphate Ester Cleavage -- 3.1. The Mechanism of the Metal-Catalysed Reaction -- 3.2. Catalytic Roles of the Metal Ions -- 3.3. Dissection of the Metal Ion Activation Factors -- 3.4. Strategies to Improve the Lewis Acid Activation Effect -- 3.5. Strategies to Improve the Nucleophile Activation -- 4. Comparison Between Enzymes and Artificial Agents Catalysis -- 5. Conclusions -- References -- Chapter Five: Physicochemical Aspects of Aqueous and Nonaqueous Approaches to the Preparation of Nucleosides, Nucleotides ... -- 1. Introduction -- 2. Physicochemical Properties of Nucleosides, Nucleotides and Polyphosphates -- 2.1. Acid-Base Properties -- 2.2. Intermolecular Interactions Between Nucleosides -- 3. Synthetic Methods -- 3.1. An Overview of Widely Used Methods for Phosphoanhydride Bond Formation -- 3.2. New Nonaqueous Solvent-Based Transformations -- 3.2.1. New Methods for Phosphoanhydride Bond Formation -- 3.2.1.1. The Development of New P(III) Strategies -- 3.2.1.2. The Development of New P(V) Strategies -- 3.2.2. Phosphate Nucleophiles -- 3.2.3. Sulphurization -- 3.3. Aqueous Transformations -- 3.4. Ionic Liquid-Based and Solvent-Free Transformations -- 3.4.1. Ionic Liquids -- 3.4.2. Mechanochemical Methods -- 3.4.2.1. Nucleoside Synthesis -- 3.4.2.2. Preparation of Phosphorylated Species -- 4. Conclusions -- Acknowledgments -- References -- Back Cover.

Note: Front Cover -- Advances in Physical Organic Chemistry -- Copyright -- Contents -- Contributors -- Preface -- Chapter One: The Conundrum of the (C4H7)+ Cation: Bicyclobutonium and Related Carbocations -- 1. Introduction -- 1.1. Early Studies -- 1.2. Terminology -- 1.3. Kinetic Isotope Effects -- 1.4. Gas-Phase Studies -- 1.5. Vibrational Spectroscopy -- 1.6. Structures and Equilibrium of Bicyclobutonium and Cyclopropylmethyl Cations -- 1.7. NMR Spectroscopic Investigations -- 1.8. EIEs on NMR Spectra of Fast-Rearranging (C4H7)+ Cations -- 1.9. Quantum-Chemical Calculations of EIEs in (C4H7)+ Cations -- 1.9.1. The Size and the Direction of the EIEs -- 1.9.2. Population of the Equilibrating Sites -- 1.9.3. The Size of the EIE -- 1.9.4. The EIE-Induced Direction of the NMR Chemical Shifts of the Averaged Methylene Signals -- 1.9.5. Quantum-Chemical Calculations for the (C4H7)+ Cation System -- 2. Substituted (C4H7)+ Carbocations -- 2.1. Fast-Equilibrating Substituted Bicyclobutonium Ions -- 2.1.1. Solvolysis Results of Substituted Cyclobutyl Derivatives -- 2.2. NMR Spectroscopic and Computational Investigations of Substituted (C4H7)+ Cations -- 2.2.1. 1-Methyl-Bicyclobutonium Cation -- 2.2.2. The 1-(Trimethylsilyl)Bicyclobutonium Ion -- 2.3. EIEs in Substituted Cyclopropylmethyl and Substituted Cyclobutyl Cations -- 2.4. Static Substituted Bicyclobutonium Ions -- 2.5. Spin-Spin Coupling Constants -- 2.6. 1,3-Disubstituted Static Bicyclobutonium Ions -- 3. Conclusion -- References -- Chapter Two: Organic Reaction Outcomes in Ionic Liquids -- 1. Introduction -- 1.1. Scope of This Review -- 1.2. Ionic Liquids: Common Structures and Nomenclature -- 2. Understanding Reaction Outcomes in Ionic Liquids: Key Milestones -- 2.1. Not All Ionic Liquids Are Created Equal -- 2.2. The Importance of the Proportion of the Ionic Liquid in the Reaction Mixture. , 2.3. Understanding the Microscopic Origins of Ionic Liquid Effects -- 2.4. Correlating Reaction Outcomes With Solvent Parameters -- 3. Opportunities Delivered by the Understanding Gained -- 3.1. Extending the Knowledge to Other Systems -- 3.2. Rational Design of an Ionic Liquid Solvent -- 3.3. Biasing Product Selectivity -- 4. Summary and Outlook -- Acknowledgments -- References -- Chapter Three: Polymer Mechanochemistry: A New Frontier for Physical Organic Chemistry -- 1. Introduction -- 2. A Quantitative Model of Mechanochemical Kinetics -- 2.1. Approximate Solutions of the Master Equation of Mechanochemical Kinetics -- 2.1.1. Zeroth-Order Approximation: The EB Model -- 2.1.2. First-Order Approximation: Tilted Potential Energy Surface (TPES) and Cusp Models -- 2.1.3. Second-Order and Complete Harmonic Approximations -- 2.2. Accuracy of the Conventional Approximations and Systematic Strategies of Improving Them -- 2.3. Complicating Factors: Ensemble Effects, the Minimum Length of the Macromolecular Segment, Multibarrier Reactions, an ... -- 3. Experimental Techniques of Polymer Mechanochemistry -- 3.1. SMFS -- 3.2. Flow Fields -- 3.2.1. Quasi-Steady-State Elongational Flows -- 3.2.2. Sonication -- 3.3. Mechanochemical Reactivity Without Macroscopic Motion -- 4. Brief Analysis of Empirical Research in Mechanochemistry -- 4.1. Much Ado About Dissociation of the Disulfide Bond -- 4.2. Emerging Trends in Contemporary Empirical Studies -- 5. Summary -- References -- Back Cover.

Note: Intro -- Advances in Physical Organic Chemistry -- Copyright -- Contents -- Contributors -- Chapter One: A brief insight into the physicochemical properties of room-temperature acidic ionic liquids and their catal ... -- 1. Introduction -- 2. Classification of acidic ionic liquids -- 2.1. Brønsted acidic ILs -- 2.2. Lewis acidic ILs -- 2.3. Brønsted-Lewis acidic ILs -- 3. Physicochemical properties of RTAILs -- 3.1. Conductivity of RTAILs -- 3.1.1. Effect of constituent ions -- 3.1.2. Effect of solvent -- 3.1.3. Effect of temperature -- 3.2. Density -- 3.3. Thermal stability of RTAILs -- 3.4. Acidity of the RTAILs -- 3.5. Electrochemical stability of RTAILs -- 3.6. Viscosity of RTAILs -- 3.7. Surface tension of RTAILs -- 3.8. Surfactant-like properties of RTAILs -- 3.9. Solvatochromic parameters of RTAILs -- 4. Catalytic uses in CC bond formation reactions -- 4.1. One-pot multicomponent reaction (MCR) -- 4.1.1. Mannich reaction -- 4.1.2. Biginelli reaction -- 4.1.3. Preparation of N-heterocycles and O-heterocycles -- 4.2. Condensation reactions -- 4.3. Electrophilic aromatic substitution -- 4.4. Michael addition -- 4.5. Rearrangements -- 5. Conclusion and future scope -- Acknowledgements -- References -- Chapter Two: Differential features of short-lived intermediates: Structure, properties and reactivity -- 1. Introduction -- 2. General aspects -- 2.1. Radical species -- 2.2. Excited states -- 3. Case studies for some short-lived intermediates -- 3.1. sym-Triazines -- 3.2. Enol ether radical cations -- 3.3. Aminium/aminyl radicals -- 4. Conclusion -- Acknowledgements -- References -- Chapter Three: Steric attraction: A force to be reckoned with -- 1. Introduction -- 1.1. Steric attraction vs steric repulsion -- 1.2. London dispersion forces and their hidden significance -- 2. Quantifying London dispersion forces. , 2.1. Computing London dispersion forces -- 2.2. Experimentally quantifying London dispersion -- 3. Interactions dominated by London dispersion forces -- 3.1. Hydrophobic interactions -- 3.2. π-π Stacking -- 3.3. Aurophilicity -- 3.4. Halogen/chalcogen bonding -- 4. London dispersion as a design tool -- 4.1. Stabilization by steric attraction -- 4.2. Dispersion enhanced catalysis -- 4.3. Fullerenes -- 5. Concluding remarks -- References -- Chapter Four: Quantum mechanics/molecular mechanics multiscale modeling of biomolecules -- 1. Introduction -- 2. Overview of QM/MM methodological aspects -- 2.1. How to partition the system -- 2.1.1. Link atom method -- 2.1.2. Localized orbitals methods -- 2.1.3. Adaptive partitioning -- 2.2. How to calculate the energy of a QM/MM system -- 2.2.1. Subtractive scheme -- 2.2.2. Additive scheme -- 2.2.3. Mechanical embedding -- 2.2.4. Electrostatic embedding -- 2.2.5. Polarizable embedding -- 2.3. Dealing with a very large number of particles in QM-based multiscale approaches -- 2.4. Some codes used for QM/MM calculations -- 3. QM/MM applications to study the binding of ligands to biomolecules -- 3.1. QM/MM optimizations for the study of the binding of supramolecular ligands to proteins and peptides: Molecular tweez ... -- 3.2. QM/MM MD simulations allow investigating the binding of a small molecule to an HTT exon-1 protein with pathogenic tr ... -- 3.3. QM/MM geometry optimization of the binding of the substrate at the active site: Predicted incorporation of non-nativ ... -- 3.4. A combination of QM/MM and MD simulations delivers valuable insights into substrate-enzyme interactions: Antibiotic ... -- 3.5. A detailed QM/MM study addressing cooperative binding: QM/MM study of the active species of the human cytochrome P45. , 3.6. QM/MM MD simulations for understanding the mode of action of HIV protease inhibitors: Synthesis and structural studi ... -- 3.7. QM/MM modeling to investigate the effect of the orientation of an inhibitor in its biding to the enzyme: Identificat ... -- 4. Concluding remarks -- Acknowledgments -- References.

Note: Cover -- Half Title -- Title Page -- Copyright Page -- Table of Contents -- Preface -- Authors -- 1: Overview of air pollution -- 1.1 What is air pollution? -- 1.2 Historical perspectives -- 1.3 Classification of air pollutants -- 1.3.1 Types of air pollutants -- 1.3.2 Sources of air pollutants -- 1.3.3 Source emission data -- 1.3.3.1 Emission units -- 1.3.4 What is smog? -- 1.4 Why does air pollution need attention? -- 1.5 The basic atmosphere -- 1.5.1 The origins of our atmosphere -- 1.5.2 Natural constituents of air -- 1.5.3 Water in the atmosphere -- 1.5.4 The vertical structure of the atmosphere -- 1.5.4.1 Pressure -- 1.5.4.2 Temperature -- 1.5.5 Photochemical reactions in the atmosphere -- 1.5.5.1 Light absorption and emission processes -- 1.5.5.2 Examples of photochemical reactions -- 1.6 Methods of describing pollutant concentration -- 1.7 Units for expressing atmospheric concentrations -- 1.7.1 Concentration units -- 1.7.1.1 Conversion between gravimetric and volumetric units -- 1.7.1.2 Correction for non-standard temperature and pressure -- 1.7.2 Averaging time -- 1.8 Unconventional air pollutants -- 1.8.1 Incineration as a source of air pollutants -- 1.9 Case study - Historical perspective: The Great London Smog -- 1.9.1 Chronology -- 1.9.2 Health effects -- 1.9.3 Environmental effects -- 1.9.4 Socio-economic impacts -- References and further reading resources -- 2: Gaseous air pollutants -- 2.1 Primary gaseous emissions -- 2.2 Anthropogenic emissions -- 2.2.1 Energy-related emissions -- 2.2.2 Sulphur oxide emissions -- 2.2.2.1 Sulphur dioxide -- 2.2.2.2 Sulphur trioxide -- 2.2.3 Nitrogen oxide emissions -- 2.2.3.1 Nitric oxide -- 2.2.3.2 Nitrogen dioxide formation -- 2.2.4 Ammonia -- 2.2.5 Non-methane volatile organic compounds -- 2.2.6 Carbon monoxide -- 2.2.7 Hydrogen chloride -- 2.2.8 Persistent organic pollutants. , 2.2.8.1 Dioxins and furans -- 2.2.8.2 Polychlorinated biphenyls -- 2.2.8.3 Polybrominated diphenyl ethers -- 2.2.8.4 Polycyclic aromatic hydrocarbons -- 2.3 Secondary gaseous pollutants -- 2.3.1 Tropospheric ozone -- 2.3.2 Wintertime NO2 episodes -- 2.4 Measurement of gases -- 2.4.1 Sampling requirements -- 2.4.2 Gas sampling -- 2.4.2.1 Pumped systems -- 2.4.2.2 Preconcentration -- 2.4.2.3 Absorption -- 2.4.2.4 Adsorption -- 2.4.2.5 Condensation trapping -- 2.4.2.6 Grab sampling -- 2.4.3 Gas concentration measurement -- 2.4.3.1 Wet chemical methods -- 2.4.3.2 Real-time pumped systems -- 2.4.3.3 Real-time remote systems -- 2.4.3.4 Gas chromatography -- 2.4.3.5 Liquid chromatography -- 2.4.3.6 Chromatography with mass spectroscopy -- 2.4.3.7 Inductively coupled plasma spectroscopy -- 2.4.3.8 Optical spectroscopy -- 2.4.4 Quality control -- 2.4.4.1 Blanks -- 2.4.4.2 Calibration -- 2.4.4.3 Permeation tubes -- 2.4.4.4 Gas bottles -- 2.4.4.5 UV O3 generator -- 2.4.4.6 Zero air -- 2.5 Case study - Bhopal gas leak -- References and further reading resources -- 3: Particulate matter -- 3.1 Why particulates are a special case? -- 3.2 Particulate terminology -- 3.3 Particle size distributions -- 3.3.1 Relative sizes of particles and gas molecules -- 3.3.2 Specification of size -- 3.3.3 Presentation of size distributions -- 3.3.4 General features of real size distributions -- 3.4 Aerosol mechanics -- 3.4.1 Drag force -- 3.4.2 Sedimentation -- 3.4.3 Brownian diffusion -- 3.4.4 Coagulation -- 3.4.5 The influence of shape and density -- 3.4.5.1 Shape -- 3.4.5.2 Aerodynamic diameter -- 3.4.6 Relaxation time -- 3.4.6.1 Note on units and dimensions -- 3.4.7 Stopping distance -- 3.4.8 Impaction and interception -- 3.4.9 Stokes number and impactors -- 3.4.10 Thermophoresis -- 3.4.11 Erosion and resuspension -- 3.5 Particle sources -- 3.5.1 Primary particles. , 3.5.1.1 Wind erosion -- 3.5.1.2 Sea salt -- 3.5.1.3 Other natural sources -- 3.5.1.4 Anthropogenic sources -- 3.5.2 Secondary particles -- 3.6 Trends in particle emissions -- 3.7 Measurement of particles -- 3.7.1 Particle sampling -- 3.7.1.1 Isokinetic sampling -- 3.7.1.2 Calibration -- 3.7.2 Particle measurement methods -- 3.7.2.1 Filtration -- 3.7.2.2 British Standard smoke method -- 3.7.2.3 High-volume sampler -- 3.7.2.4 Optical methods -- 3.7.2.5 Beta-attenuation -- 3.7.2.6 Resonating microbalance -- 3.7.2.7 Size fractionation -- 3.7.2.8 Optical sizers -- 3.7.2.9 Aerosol spectrometer -- 3.7.2.10 Inertial impactors -- 3.7.2.11 Electrical mobility analysers -- 3.7.2.12 Diffusion batteries -- 3.7.2.13 Condensation particle counter -- 3.7.3 Chemical composition of aerosols -- 3.7.3.1 Particle microstructure -- 3.7.3.2 Real-time chemical analysis -- 3.7.4 Measurement of coarse particle deposition -- 3.8 Case study - Asbestos -- References and further reading resources -- 4: Area sources -- 4.1 Biogenic area sources -- 4.1.1 Wildfires -- 4.1.1.1 Forest management practices -- 4.1.2 Volcanic emissions -- 4.1.3 Soil emissions -- 4.2 Anthropogenic area sources -- 4.2.1 Landfills -- 4.2.1.1 Landfill directive -- 4.2.1.2 Emerging trends in landfill of waste electrical components -- 4.2.2 Farm emissions -- 4.2.3 Fugitive emissions from industrial processes -- 4.3 Measurement of area sources -- 4.3.1 Confined emissions -- 4.3.1.1 Measurement of volume flow rate -- 4.3.1.2 Measurement of gas concentrations -- 4.3.1.3 Measurement of particle concentrations -- 4.3.2 Unconfined emissions -- 4.3.3 Pervasive sensors -- 4.4 Measurement uncertainties -- 4.5 Modelling of area sources -- 4.6 Case study: The eruption of Eyjafjallajökull, Iceland -- 4.6.1 Volcanoes on Iceland -- 4.6.2 Chronology -- 4.6.3 Impacts of the eruption -- 4.6.4 Volcanic eruptions in the future. , References and further reading resources -- 5: Mobile sources -- 5.1 Road traffic emissions -- 5.1.1 Traffic congestion -- 5.1.2 Combustion of fuel -- 5.1.2.1 Petrol engines -- 5.1.2.2 Diesel engines -- 5.1.2.3 Traffic biofuel in developing countries -- 5.1.3 Combustion emissions -- 5.1.3.1 Emission concentrations -- 5.1.4 Specific pollutants -- 5.1.4.1 NOx -- 5.1.4.2 CO -- 5.1.4.3 Combustion HC -- 5.1.4.4 Benzene -- 5.1.4.5 Evaporation HC -- 5.1.4.6 The importance of air-fuel ratio -- 5.1.4.7 Exhaust particulate matter -- 5.1.4.8 Non-exhaust particulate emissions -- 5.1.4.9 Lead -- 5.1.4.10 Polycyclic aromatic hydrocarbons -- 5.1.5 Reduction of motor vehicle emissions -- 5.1.5.1 Burn less fuel! -- 5.1.5.2 Combustion optimisation -- 5.1.5.3 Emissions recycle -- 5.1.5.4 Vent controls -- 5.1.5.5 Exhaust gas recirculation -- 5.1.5.6 Three-way catalytic converters -- 5.1.6 Diesel exhausts -- 5.1.6.1 Diesel particulate filters -- 5.1.6.2 DeNOx -- 5.1.6.3 Diesel oxidation catalyst -- 5.1.7 Vehicle maintenance -- 5.1.8 Vehicle emission calculations -- 5.1.8.1 Diurnal variations -- 5.1.8.2 Emissions measurement from laboratory and real road tests -- 5.1.8.3 Effect of engine temperature -- 5.1.8.4 Effect of operating mode -- 5.1.8.5 Catalyst degradation -- 5.1.8.6 National vehicle fleets -- 5.1.9 Fuel composition -- 5.1.9.1 Basic specification -- 5.1.9.2 Fuel sulphur content -- 5.1.9.3 Fuel reformulation -- 5.1.10 Diesel versus petrol -- 5.1.10.1 Gaseous emissions -- 5.1.10.2 Particulate emissions -- 5.1.11 Impact of control measures -- 5.1.12 Cleaner vehicle technologies -- 5.1.12.1 Electric -- 5.1.12.2 Hybrid -- 5.1.12.3 Hydrogen -- 5.1.12.4 Fuel cell -- 5.1.13 Alternative fuels -- 5.2 Non-road mobile machinery emissions -- 5.3 Rail emissions -- 5.4 Shipping emissions -- 5.5 Aircraft emissions -- 5.5.1 Emission calculations -- 5.5.2 Aerosol precursors. , 5.5.3 Contrails -- 5.5.4 Dispersion of aircraft emissions -- 5.5.5 Future jet fuels -- 5.5.6 Airport emission standards -- 5.5.7 Carbon dioxide emissions from civil aviation -- 5.6 Generating emissions inventory for mobile sources -- 5.6.1 The Bentley approach -- 5.6.2 The UK National Atmospheric Emissions Inventory -- 5.7 Case study - Traffic restriction schemes -- 5.7.1 London congestion charging -- 5.7.2 Odd-even driving patterns during the Beijing Olympics -- 5.7.3 Odd-even car driving in New Delhi -- References and further reading resources -- 6: Ambient air quality -- 6.1 Gaseous pollutants -- 6.1.1 Nitrogen oxides -- 6.1.2 Sulphur dioxide -- 6.1.3 Carbon monoxide -- 6.1.4 Ozone -- 6.1.4.1 The general picture -- 6.1.5 Volatile organic compounds -- 6.2 Particulate matter -- 6.3 Patterns of occurrence -- 6.3.1 Automatic air quality monitoring networks -- 6.3.1.1 The UK national survey -- 6.3.1.2 Secondary networks -- 6.3.1.3 Data processing -- 6.3.1.4 Other surveys -- 6.3.2 Other measurement networks -- 6.4 Dry deposition of gases -- 6.4.1 Deposition velocity -- 6.4.2 Resistance -- 6.5 Wet deposition -- 6.5.1 Rainfall -- 6.5.2 Rainout -- 6.5.2.1 Washout -- 6.5.3 Dry reactions -- 6.5.4 Wet reactions -- 6.5.5 Cloudwater deposition -- 6.6 Total deposition and budgets -- 6.7 Analysis of an air quality data set -- 6.7.1 The raw data set -- 6.7.2 Time-series plot -- 6.7.3 Roses -- 6.7.4 Diurnal variations -- 6.7.5 Frequency distributions -- 6.7.6 Further statistical analyses -- 6.8 Effect of fireworks on ambient air quality -- 6.8.1 The art and science of fireworks -- 6.8.2 The physics of fireworks -- 6.8.3 The chemistry of fireworks -- 6.8.4 Pollutants associated with fireworks and bonfires -- 6.8.5 Effects on health -- 6.8.6 Effects on the local air quality -- 6.9 Case study: Buncefield Oil Storage Depot disaster. , 6.9.1 Impact of the event on the local air quality.