Chemical and Biological Generation of Excited States

1st Edition - January 28, 1982
Editor: Waldermar Adam
Language: English
eBook ISBN:
9 7 8 - 0 - 3 2 3 - 1 5 2 3 0 - 3

Chemical and Biological Generation of Excited States discusses major aspects of chemical and biological generation of electronic excitation. This book is organized into 11 chapters… Read more

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Chemical and Biological Generation of Excited States discusses major aspects of chemical and biological generation of electronic excitation. This book is organized into 11 chapters that focus on both chemi- and bioenergized processes. This book first discusses some of the fundamental aspects of the description of excited state behavior in condensed media. It then examines the field of gas-phase dioxetane chemiluminescence both by itself and in relation to solution-phase studies. The presented analysis is based on statistical mechanics and supported by a very simple limiting case calculation. Chapter 4 describes the state-of-the-art of how excitation yields are determined experimentally in chemienergized processes. This is followed by a discussion on activation parameters and stability trends, focusing on solution-phase data. Chapters 6 and 7 examine solution-phase chemiluminescence resulting from high-energy electron-transfer reaction, often involving aromatic radical ions, and the mechanism of excitation step. The next chapters cover the generation of electronic excited states in bioluminescence and the evaluation of luminescent oxidation mechanisms using oxygen tracers. The chapters also explain the formation of electronically excited products in dark biological processes and the mechanism of chemiexcitation as it relates to redox metabolism. Specific examples of biological oxygenation reactions yielding luminescence are also presented. Furthermore, this book discusses the concept and applicability of chemiluminigenic probing for the quantification and differentiation of oxygenation activities in mammalian phagocytes. The concluding chapter is devoted to the possible formation of singlet oxygen in various systems and processes that mimic singlet oxygen reactions. The book intends to attract young scientists as well as established research workers to broaden the horizons of this rapidly growing and potentially very important field.

List of Contributors

Preface

1 Photophysical Concepts in Condensed Media

I. Introduction

II. Unimolecular Decay Processes

III. Bimolecular Interactions Involving an Electronically Excited State

References

2 Gas-Phase Dioxetane Chemiluminescence

I. Introduction

II. Basic Information

III. Gas-Phase Experiments in Dioxetane Chemiluminescence

IV. Discussion

References

3 Synthesis of 1,2-Dioxetanes

I. Introduction

II. Hazards and Safety Precautions

III. 1,2-Dioxetanes from Cyclization of Hydroperoxides

IV. 1,2-Dioxetanes from Oxidation of Alkenes with Singlet Oxygen

V. Other Methods of Preparing 1,2-Dioxetanes

VI. Characterization of 1,2-Dioxetanes

References

4 Determination of Chemiexcitation Yields in the Thermal Generation of Electronic Excitation from 1,2-Dioxetanes

I. Introduction

II. Photophysical Methods

III. Photochemical Methods

IV. Dioxetane Excitation Yields

V. Conclusions

References

5 Determination of Activation Parameters and the Thermal Stability of 1,2-Dioxetanes

I. Introduction

II. Determination of Activation Parameters

III. Structure and Stability Relationships

IV. Concluding Remarks

References

6 Electrochemiluminescence

I. Introduction

II. Basic Concepts

III. Experimental Techniques

IV. Theoretical Basis for Excited State Production

V. Diagnosis of Reaction Pathway

VI. More Complex Chemistry

VII. Special Effects at Semiconductors

References

7 Chemically Initiated Electron-Exchange Luminescence

I. Introduction

II. Mechanism of the Excitation Step

III. Efficient CIEEL Systems

IV. Conclusions

References

8 Mechanism of Bioluminescence

I. Introduction

II. Generation of Electronic Excited States in Bioluminescence

III. Mechanisms of Luminescent Oxidation Studied with Oxygen Tracers

References

9 Electronic Excitation in Dark Biological Processes

I. Introduction

II. Enzyme-Generated Excited Species

III. Energy Transfer

IV. Mechanisms of Energy Transfer

V. Possible Secondary Effects of the Generation of Excited Species

VI. Biological Implications and Remarks

VII. Concluding Remarks

References

10 Biochemiexcitation: Chemiluminescence and the Study of Biological Oxygenation Reactions

I. Introduction

II. Bioenergetics and Redox Metabolism

III. Biological Oxidations

IV. Polymorphonuclear Leukocyte: Redox Metabolism and Chemiluminescence

V. Streptococcus faecalis: O2 Redox Activity and Chemiluminescence

VI. Chemilumigenic Probes for the Study of Biological Oxygenation Activities

VII. Luminol

VIII. Lucigenin

IX. Differential Quantification of Oxygenation Activities by Chemilumigenic Probes

X. Considerations for the Future

References

11 Singlet Oxygen in Biological Processes

I. Introduction

II. Possible Formation of Singlet Oxygen in Various Systems

III. Processes That Mimic Singlet Oxygen Reactions

IV. Conclusions

References

Index