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TABLE of CONTENT
PREFACE TO RUSSIAN EDITION
PREFACE TO ENGLISH EDITION
VI
IX
CHAPTER 1. HISTORICAL ASPECT OF THE CONCEPT OF CHEMICAL CONJUGATION
1.1. THE ORIGINATION OF THE CHEMICAL CONJUGATION CONCEPT
1
1.2. DEVELOPMENT OF THE CONJUGATED REACTION THEORY IN
LATER WORKS
7
1.3. ANALYSIS OF THE “ACTIVE OXYGEN” CONCEPT FROM MODERN POSITIONS OF
OXIDATION PROCESSES
8
1.4. INDUCED DISSOCIATION OF PEROXIDE COMPOUNDS 11
1.5. HIGH-TEMPERATURE OXIDATION MECHANISM AND ACTIVE OXYGEN CONCEPT
REFERENCES 24
1
18
CHAPTER 2. THE THEORY OF INTERACTION BETWEEN SYNCHRONOUS REACTIONS:
CHEMICAL INTERFERENCE LOGICS 26
INTRODUCTION
26
2.1. INTER-REACTION INTERACTIONS TYPES
30
2.2. THREE-COMPONENT CONJUGATED PROCESSES
35
2.3. THE DETERMINANT EQUATION AND COHERENCE CONDITION OF CHEMICAL
INTERFERENCE
38
2.4. INTERFERENCE OF HYDROGEN PEROXIDE DISSOCIATION AND SUBSTRATE
OXIDATION REACTIONS
50
2.5. THE DIFFERENCE BETWEEN INITIATION AND INDUCTION PHENOMENA
57
2.6. CONCLUSION
59
REFERENCES 60
CHAPTER 3. CONJUGATED CHEMICAL REACTION MORPHOLOGY AND MEMBRANE
CATALYSIS IN MITOCHONDRIAL PROTON TRANSFER
62
3.1. THE MECHANISM AND KINETICS OF CONJUGATED REACTIONS
62
3.2. ENERGY TRANSFER IN CONJUGATED REACTIONS
80
3.3. IDEALIZED MODEL OF CONJUGATED CATALYTIC REACTIONS: THE MEMBRANE
CATALYSIS IN MITOCHONDRIAL PROTON TRANSFER
87
REFERENCES 121
CHAPTER 4. CONJUGATED REACTIONS OF OXIDATION WITH HYDROGEN PEROXIDE IN
THE GAS PHASE
124
4.1. HYDROGEN PEROXIDE DISSOCIATION KINETICS AND THE MECHANISM
125
4.2. INITIATION AND INDUCTION PROCESSES INVOLVING HYDROGEN PEROXIDE 129
4.3. THERMODYNAMIC ASPECTS OF CHEMICAL CONJUGATION
132
4.4. CONJUGATED DEHYDROGENATION WITH HYDROGEN PEROXIDE
137
4.4.1. Specific features of dehydrogenation mechanism 137
4.4.2. Alkane and alkene dehydrogenation
143
4.4.3. Naphthene hydrocarbon dehydrogenation 146
4.4.4. Alkyl benzene dehydrogenation 152
4.4.5. Dehydrogenation and oxidation of heterocyclic compounds 155
4.4.6. Dehydrogenation of alcohols
159
4.5. CONJUGATED OXIDATION WITH HYDROGEN PEROXIDE
161
4.5.1. Methane and methanol oxidation to formaldehyde 161
4.5.2. Direct pressurized oxidation of methane to methanol with hydrogen peroxide
170
4.5.3. High-temperature oxidation of natural methane with hydrogen peroxide
176
4.5.4. Lower olefin oxidation
180
4.6. CONJUGATED HYDROGENOLYSIS OF TOLUENE TO BENZENE WITH HYDROGEN
PEROXIDE
185
4.7. NITROGEN FIXATION AT CONJUGATED OXIDATION
187
REFERENCES 194
CHAPTER 5. KINETICS AND THE MECHANISM OF SYNCHRONOUS (INTERFERING)
REACTIONS OF HYDROGEN PEROXIDE DISSOCIATION AND OXIDATION OF SUBSTRATES
IN THE GAS PHASE 204
5.1. DEHYDROGENATION MECHANISM AND GAS-PHASE HO•2 -DEPENDENT ELEMENTARY
REACTIONS 204
5.2. CONJUGATED DEHYDROGENATION AND OXIDATION WITH HYDROGEN PEROXIDE
214
5.2.1. Dehydrogenation alkylbenzenes 215
5.2.2. Cyclohexane and cyclopentane dehydrogenation 219
5.2.3. Methane oxidation to formaldehyde
222
5.2.5. Methane oxidation to H2, CO and CO2
237
5.2.6. Oxidative fixation of molecular nitrogen
246
REFERENCES 254
CHAPTER 6. THE PHENOMENA OF INTERFERENCE IN CHEMICAL AND BIOCHEMICAL
REDOX REACTIONS WITH HYDROGEN PEROXIDE 257
6.1. HYDROGEN PEROXIDE DISSOCIATION IN THE LIQUID PHASE 257
6.2. OXIDATION WITH HYDROGEN PEROXIDE
263
6.3. THE MECHANISMS OF CATALASE, PEROXIDASE AND MONOOXYGENASE REACTIONS
273
6.4. CO-FACTORS AND THEIR ROLE IN THE INTERACTION AND SYNCHRONIZATION OF
BIOCHEMICAL REACTIONS 301
REFERENCES 311
CHAPTER 7. NEW APPROACHES TO SIMULATION OF ENZYMATIC REACTIONS: MIMETIC
CATALYSIS
319
7.1. CRITERIA OF MIMETIC CATALYSIS BASED ON CONFORMITIES AND DIVERSITIES
BETWEEN ENZYMATIC AND CHEMICAL CATALYSES 320
7.2. BIOMIMETIC CATALYSTS (BIOMIMICS) FOR CATALASE, PEROXIDASE AND
MONOOXYGENASE REACTIONS
327
REFERENCES 396
CHAPTER 8. ENZYMATIC BIOSENSORS AND THEIR BIOMIMETIC ANALOGUES – ADVANCED
ANALYTICAL APPLIANCES
403
8.1. CATALASE-BIOMIMETIC SENSORS
408
8.2. PEROXIDASE-MIMETIC SENSOR FOR DETECTION OF ETHANOL IN LOW
CONCENTRATIONS IN AQUEOUS SOLUTIONS
420
REFERENCES 428
CHAPTER 9. GENERAL ISSUES OF SELECTIVITY AND FLEXIBILITY OF CHEMICAL SYSTEMS
429
REFERENCES 439