Chemiluminescence in Organic Chemistry

30.03.1987

Englisch

9783540171553

Springer Berlin

Reactivity and Structure: Concepts in Organic Chemistry

Nein

Frank McCapra

218

Gebundene Ausgabe

23

organic chemistry, oxygen, polymer

PNN - Organische Chemie

I. Introduction.- A. Physiochemical Background.- II. General Concepts in Chemiluminescence.- II. 1 Chemiluminescence Efficiency.- II. 1.1 Energetics of the Reactions.- II. 1.2 Formation of the Excited State.- 11.1.2.1 The Reaction Co-ordinate.- 11.1.2.2 Molecular Geometry.- 11.1.2.3 Spin Restrictions.- II. 1.2.4 Symmetry Restrictions.- II. 1.2.5 Potential Energy Surfaces.- II.2 Electron Transfer Reactions.- II. 3 Singlet Oxygen as a Cause of Chemi- and Bioluminescence; the Role of Triplet Oxygen.- II. 4 References (for Preface, Chaps. I and II).- B. Chemiluminescent Reactions.- III. Autoxidation Reactions.- III. 1 Hydrocarbons.- III. 1.1 The Excitation Step.- III. 1.2 Polymers.- III. 1.3 Base-catalysed Autoxidation of Carbonyl Compounds.- III. 1.4 Grignard Compounds.- III. 1.5 Inhibitors.- III. 1.6 Miscellaneous Oxidation Reactions.- III. 1.6.1 Oxidative Chemiluminescence of Coals.- III.1.6.2 Cysteine and Glutathione.- III. 2 References.- IV. Chemiluminescent Peroxide Decompositions, I (except Dioxetans).- IV. 1 Peroxide Chemiluminescence by CIEEL.- IV. 2 Acyclic sec. -Peroxy-esters.- IV. 3 Dioxetanones.- IV.4 Diphenoyl Peroxide.- IV.5 Other Cyclic Diacyl Peroxides. Phthaloyl Peroxide.- IV. 6 Chemiluminescence of o-Dicarboxylic Acid Chlorides.- IV.7 Other Cyclic Peroxides.- IV. 8 Acene Endo-Peroxides.- IV.9 Polyhydroxy-phenol- and Purpurogallin Chemiluminescence.- IV. 10 References.- V. Peroxide Decompositions, II: Dioxetans.- V. l Simple Dioxetans.- V.2 Excitation Yields and Multiplicity.- V.3 Measurement of Singlet and Triplet Yields.- V.4 Thermochemistry and Kinetics.- V.5 Mechanism of Excited State Formation from Dioxetans.- V.5.1 The Diradical Mechanism.- V.5.2 The Concerted or Electron Transfer Mechanism.- V. 6 Quenching Reactions of Dioxetans.- V.7 Symmetry Forbidden Reactions in Chemiluminescence.- V. 8 References.- VI. Peroxy Oxalate Chemiluminescence.- VI. 1 Requirements for Oxalate Chemiluminescence.- VI.2 The Mechanism.- VI. 3 References.- VII. Luminol and Related Compounds.- VII. 1 Structure and Activity of Phthalic Acid Hydrazides.- VII. 1.1 Miscellaneous Cyclic Hydrazides.- VII. 1.1.1 Compounds with Multiple Hydrazide Groups.- VII.2 The Emitting Species.- VII.3 Energy Transfer in Luminol Type Chemiluminescence.- VII.4 Solvent Effects.- VII. 5 Effect of Micelle-forming Agents.- VII.6 Catalyst Activity.- VII.7 The Mechanism of Luminol Chemiluminescence.- VII.7.1 Ionic Species Derived from Luminol.- VII.7.2 Diazaquinone Chemiluminescence.- VII.7.3 Intermediate Peroxides.- VII.7.4 1,4-Dialkoxy Phthalazines as Potential Precursors of the Luminol-”endoperoxide”.- VII.7.5 Luminol Radical Anions as Intermediates (Pulse Radiolysis Experiments).- VII.7.6 Present State of Hypotheses on Luminol Chemiluminescence Mechanism.- VII.8 Monoacylhydrazides.- VII.8.1 Chemiluminescence Mechanism of Monoacylhydrazides.- VII. 9 References.- VIII. Acridine Derivatives.- VIII. 1 Lucigenin.- VIII. 1.1 The Reaction Mechanism.- VIII.1.2 Energy Transfer in Lucigenin Chemiluminescence.- VIII. 1.3 Influence of Micelle Forming Agents on the Lucigenin Reaction.- VIII.2 Acridinium Salts and Acridans.- VIII. 3 References.- IX. Other Nitrogen-Containing Compounds-Imine Peroxides.- IX. 1 Tetrakis-dialkylaminoethylenes.- IX.2 Bis-Isoquinolinium Salts.- IX.3 Lophine and Related Compounds.- IX.4 Indole Derivatives.- IX.5 Chemiluminescent Schiff Bases.- IX. 6 References.- X. Miscellaneous Compounds.- X. l Chlorinated Cyclic Carbonates, Glycolides and Ethers.- X.2 Sulfuranes.- X.3 Thioesters.- X.4 Vinyl Halides.- X.5 Strained Hydrocarbon Isomerisation.- X.6 Metal Phosphides.- X. 7 References.- XI Electron Transfer Chemiluminescence.- XI. 1 Electrogenerated Chemiluminescence (ECL).- XI.1.1 Energy-sufficient and Energy-deficient ECL.- XI. 1.1.1 Energy-deficient ECL.- XI. 1.2 Chemiluminescent Reactions of Electrogenerated Radical Anions with Organic Halides.- XI. 1.3 Efficiency of ECL Reactions.- XI. 1.4 Ruthenium Chelate Complexes.- XI.2 Chemiluminescent Reactions of Radical Anions with Various Electron Acceptors.- XI.2.1 Wurster’s Blue-Type Compounds, subst. Triphenylamines.- XI.2.2 Electron Transfer Reactions in Metal Complexes.- XI. 3 Distinctions between Radical Mechanisms for the Generation of Excited States.- XI. 4 References.- C. Biohiminescence.- XII. Bioluminescence as a Special Case of Chemiluminescence.- XII. 1 Bioluminescent Organisms.- XII. 1.1 The Firefly.- XII. 1.2 Models for Firefly Luciferin.- XII. 1.3 Cypridina and Coelenterate Bioluminescence.- XII.1.4 Bacterial Bioluminescence.- XII.2 General Models for Bioluminescent Reactions.- XII.2.1 Electron-rich Dioxetans.- XII.2.2 Acridans as Model Compounds.- XII.2.3 Models for the Excitation Step.- XII.3 Other Bioluminescent Organisms.- XII. 4 References.- D. Applications.- XIII. Analytical and Other Applications of Chemi- and Bioluminescence..- XIII. A Analytical Applications.- XIII. A. 1 General and Inorganic Chemistry.- XIII. A. 1.1 Acid-Base-Titrations.- XIII. A. 1.2 Redox Titrations.- XIII.A.1.2.1 Oxidants.- XIII. A.1.2.1.1 Molecular Oxygen; Ozone.- XIII. A.1.3 Metal Ions.- XIII. A.1.4 Negative (inhibitory) Metal Catalysis…..- XIII. A.1.5 Bioluminescent Metal Assays.- XIII. A.2 Organic Compounds.- XIII. A.2.1 Amino Acids.- XIII.A.2.2 Oximes.- XIII.A.2.3 Organophosphorus Compounds.- XIII.A.2.4 Phenols, Naphthols.- XIII.A.2.5 Autoxidations.- XIII.A.2.5.1 Oxidative Degradation of Molecules Containing Long-Chain Aliphatic Residues.- XIII. A.2.5.2 Efficiency of Radical Chain Inhibitors and Initiators.- XIII.A.2.5.3 Determination of Low Concentrations of Molecular Oxygen;the”Oxygen Drop”.- XIII.A.2.5.4 Other Methods of Oxygen Determination.- XIII.A.2.6 Glucose.- XIII. A.2.7 Alcohols and Aldehydes.- XIII. A.3 Biological Systems.- XIII. A.3.1 ATP Assay with Firefly Bioluminescence.- XIII. A.3.1.1 Scope of the ATP Assay.- XIII.A.3.1.2 Creatine Kinase and Pyruvate Kinase.- XIII.A.3.2 Analytical Applications of Bacterial Bioluminescence.- XIII.A.3.2.1 Activity of Lipases.- XIII. A.3.2.2 Mutagenic Activity.- XIII.A.3.2.3 NAD (P)H-Assay.- XIII.A.4 Phagocytosis.- XIII.A.5 Chemiluminescent Immunoassays.- XIII.A.5.1 DrugAssay.- XIII.B Other Applications.- XIII.B.l Emergency Lighting.- XIII.B.2 Signalling and Marking.- XIII.B.3 Special Display Devices.- XIII.B.4 As Indicator Systems in Processes Involving Oxidants.- XIII. C References.- XIV. Instrumentation.- XIV. 1 References.- XV. Chemiluminescent Demonstrations.- XV. 1 References and Sources of Materials.- XVI. Chemiluminescence in the Future.- Appendix: Table of Luminol Type Hydrazides.

0 mm