Elements of molecular and biomolecular electrochemistry : an electrochemical approach to electron transfer chemistry /: an electrochemical approach to electron transfer chemistry. (2019)

• Record Type: Book
• Further Information: Note: Jean-Michel Savéant, Cyrille Costentin.
• Authors: Savéant, Jean Michel; Costentin, Cyrille, 1972-
• Contents: Preface; ; CHAPTER 1. Single electron transfer at an electrode ; ; 1.1. Introduction; ; 1.2. Cyclic voltammetry of fast electron transfers. Nernstian waves; ; 1.2.1. One-electron transfer to molecules attached to the electrode surface; ; 1.2.2. One-electron transfer to free moving molecules; ; 1.3. Technical aspects; ; 1.3.1. The cyclic voltammetry experiment. Faradaic and double layer charging currents. Ohmic drop; ; 1.3.2. Other techniques. Convolution; ; 1.4. Electron transfer kinetics; ; 1.4.1. Introduction; ; 1.4.2. Butler-Volmer law and Marcus-Hush-Levich (MHL) model; ; 1.4.3. Extraction of electron transfer kinetics from cyclic voltammetric signals. Comparison with other techniques; ; 1.4.4. Experimental testing of the electron transfer models; ; 1.5. Successive one-electron transfers vs. two-electron transfers; ; 1.5.1. Introduction; ; 1.5.2. Cyclic voltammetric responses. Convolution; ; 1.5.3. Response of molecules containing identical and independent reducible or oxidizable groups; ; 1.5.4. An example of the predominating role of solvation: the oxidoreduction of carotenoids; ; 1.5.5. An example of the predominating role of structural changes: the reduction of trans-2, 3-dinitro-2 butene; ; 1.6. References and Notes; ; CHAPTER 2. Coupling of electrode electron transfers with homogeneous chemical reactions. ; ; 2.1. Introduction; ; 2.2. Establishing the mechanism and measuring the rate constants for homogeneous reactions by means of cyclic voltammetry and potential step chronoamperometry; ; 2.2.1. The EC mechanism; ; 2.2.2. The CE mechanism; ; 2.2.3. The square scheme mechanism; ; 2.2.4. The ECE and DISP mechanisms; ; 2.2.5. Electrodimerization; ; 2.2.6. Homogeneous catalytic reaction schemes; ; 2.2.7. Electrodes as catalysts. Electron-transfer catalyzed reactions; ; 2.2.8. Numerical computations. Simulations. Diagnostic criteria. Working curves; ; 2.3. Product distribution in preparative electrolysis; ; 2.3.1. Introduction; ; 2.3.2.General features; ; 2.3.3. Product distribution resulting from competition between follow-up reactions; ; 2.3.4. The ECE-DISP competition; ; 2.3.5. Other reactions schemes; ; 2.4. Classification and examples of electron transfer coupled chemical reactions; ; 2.4.1. Coupling of single electron transfer with acid-base reactions; ; 2.4.2. Electrodimerizations; ; 2.4.3. Electropolymerization; ; 2.4.4. Reduction of carbon dioxide; ; 2.4.5. H-atom transfer vs. electron + proton transfer; ; 2.4.6. The SRN1 substitution. Electrodes and electrons as catalysts; ; 2.4.7. Conformational changes, isomerization and electron transfer; ; 2.5. Redox properties of transient radicals; ; 2.5.1. Introduction 2.5.2. The direct electrochemical approach; ; 2.5.3. Laser flash electron injection 2.5.4. Photomodulaltion voltammetry; ; 2.6. Electrochemistry as a trigger for radical chemistry or for ionic chemistry; ; 2.7. References and notes; ; CHAPTER 3. Coupling between electron transfer and heavy atom-bond breaking and formation ; ; 3.1. Introduction; ; 3.2. Dissociative electron transfer; ; 3.2.1. Thermodynamics. Microscopic reversibility; ; 3.2.2. The Morse curve model; ; 3.2.3. Values of the symmetry factor and variation with the driving force; ; 3.2.4. Entropy of activation; ; 3.3. Interactions between fragments in the product cluster; ; 3.3.1. Influence on the dynamics of dissociative electron transfers; ; 3.3.2. A typical example: dissociative electron transfer to carbon tetrachloride; ; 3.3.3. Stabilities of ion-radical adducts as a function of the solvent; ; 3.3.4. Dependency of in-cage ion-radical interactions upon the leaving group; ; 3.4. Stepwise vs. concerted mechanisms; ; 3.4.1. Introduction; ; 3.4.2. Diagnostic criteria; ; 3.4.3. How molecular structure controls the mechanism?; ; 3.4.4. Passage from one mechanism to the other upon changing the driving force; ; 3.4.5. Photoinduced vs. thermal processes; ; 3.4.6. Does concerted mechanism means that the intermediate 'does not exist'?; ; 3.4.7. π and σ ion radicals. Competition between reaction pathways; ; 3.5. Cleavage of ion radicals. Reaction of radicals with nucleophiles; ; 3.5.1. Introduction3; ; 3.5.2. Heterolytic cleavages. Reaction of radicals with nucleophiles; ; 3.5.3.Homolytic cleavages; ; 3.6. Role of solvent in ion radical cleavage and in stepwise vs. concerted competitions; ; 3.6.1. Introduction; ; 3.6.2. Experimental clues; ; 3.6.3. A simplified model system; ; 3.7. Dichotomy and connections between SN2 reactions and dissociative electron transfers; ; 3.7.1. Introduction; ; 3.7.2. Experimental approaches; ; 3.7.3. Theoretical aspects; ; 3.8. References and Notes; ; CHAPTER 4. Proton-coupled electron transfers. ; ; 4.1. Introduction; ; 4.2. Fundamentals; ; 4.2.1. Concerted and stepwise pathways in proton-coupled electron transfer reactions; ; 4.2.2. Thermal (electrochemical and homogeneous) and photoinduced reactions; ; 4.2.3. Modeling concerted proton electron transfers; ; 4.3. Examples; ; 4.3.1. PCET in hydrogen bounded systems. H-bond relays; ; 4.3.2. PCET in water; ; 4.4. Breaking bonds with protons and electrons; ; 4.5. References and notes; ; CHAPTER 5. Molecular catalysis of electrochemical reactions. ; ; 5.1. Introduction; ; 5.2. Homogenous molecular catalysis; ; 5.2.1. Contrasting redox and chemical catalysis; ; 5.2.2. Applications of homogeneous redox catalysis to the characterization of short lived intermediates; ; 5.2.3. Overpotential, turnover frequency, catalysts’ benchmarking, catalytic Tafel plots, maximal turnover number; ; 5.2.4. Inhibition by intermediates and other secondary phenomena. Remedies; ; 5.2.5. Multi-electron multistep mechanisms; ; 5.2.6. Competition between heterolytic and homolytic catalytic mechanisms; ; 5.2.7. Intelligent design of molecular catalysts; ; 5.3. Supported molecular catalysis (immobilized catalysts); ; 5.3.1. Redox and chemical catalysis at monolayer and multilayer coated electrodes; ; 5.3.2. Catalysis at monolayer coated electrodes; ; 5.3.3. Permeation through electrode coatings. Inhibition; ; 5.3.4. Electron hopping conduction in assemblies of redox centers; ; 5.3.5. Ohmic conduction in mesoporous electrodes; ; 5.3.6. Catalysis at multilayer coated electrodes; ; 5.3.7. Combining an electron-shuttling mediator with a chemical catalyst in a multilayer electrode coating; ; 5.4. References and Notes; ; CHAPTER 6. Enzymatic catalysis of electrochemical reactions. ; ; 6.1. Introduction; ; 6.2. Homogenous enzymatic catalysis; ; 6.2.1. Introduction; ; 6.2.2. The ‘ping-pong mechanism’. Kinetic control by substrate and/or cosubstrate; ; 6.2.3. A model example: glucose oxidase with excess glucose; ; 6.2.5. Molecular recognition of an enzyme by artificial one-electron cosubstrates; ; 6.2.5. Deciphering a complex electro-enzymatic response: horseradish peroxidase; ; 6.3. Immobilized enzymes in monomolecular layers; ; 6.3.1. Introduction; ; 6.3.2. The ‘ping-pong mechanism’ with an immobilized enzyme and the cosubstrate in solution; ; 6.3.3. Antigen-antibody immobilization of glucose oxidase. Kinetic analysis; ; 6.3.4. Application to the kinetic characterization of biomolecular recognition; ; 6.3.5. Immobilized horseradish peroxidase; <
• Edition: Second edition
• Publisher Details: Hoboken, New Jersey : John Wiley & Sons, Inc
• Publication Date: 2019
• Extent: 1 online resource
• Subjects: 541.37; Electrochemistry; Charge exchange; Chemical kinetics
• Languages: English
• ISBNs: 9781119292357; 9781119292340
• Notes: Note: Description based on CIP data; resource not viewed.
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