A novel heme-thiolate peroxygenase AaeAPO and its implications for C-H activation chemistry. ([2016])

• Record Type: Book
• Further Information: Note: Xiaoshi Wang.
• Authors: Wang, Xiaoshi
• Contents: Parts of this thesis have been published in the following journal articles:; Supervisor's Foreword; Abstract; Acknowledgements; Contents; List of Figures; List of Tables; List of Schemes; 1 Hydrocarbon Oxygenation by Heme-Thiolate Enzymes; Abstract; 1.1 Introduction; 1.1.1 Cytochrome P450S (CYPs); 1.1.2 Chloroperoxidase (CPO); 1.1.3 P450SP alpha and P450BS beta ; 1.1.4 Aromatic Peroxygenase (AaeAPO); 1.2 Mechanistic Investigations of Intermediates in the Catalytic Cycle; 1.2.1 Compound 0; 1.2.2 Compound I; 1.2.3 Compound II; 1.2.4 Diagnostic Radical Clocks; 1.2.5 Kinetic Isotope Effects. 1.3 Application on the Design of New Biocatalysts with Protein Engineering1.4 Conclusions; References; 2 Efficient and Selective Alkane Hydroxylation Reactions Catalyzed by the Fungal Peroxygenase AaeAPO; Abstract; 2.1 Introduction; 2.2 Results and Discussion; 2.2.1 Hydroxylation of Alkanes with High Efficiency and Selectivity; 2.2.2 Hydroxylation at Benzyl Position with a High Degree of Stereoselectivity; 2.2.3 Hydroxylation of Neopentane and Ethane; 2.2.4 Drug Metabolites; 2.2.5 Flavin Cofactors and Glucose Oxidase Coenzymes; 2.2.5.1 Too Much H2O2 Can Kill the Activity of the Enzyme. 2.2.5.2 Glucose Oxidase Coenzymes Catalytic Cycle2.2.5.3 Flavin Cofactors Catalytic Cycle; 2.3 Conclusions; 2.4 Experimental; References; 3 Hydrocarbon Hydroxylations Catalyzed by AaeAPO: Evidence of Radical Intermediates and Kinetic Isotope Effects; Abstract; 3.1 Introduction; 3.2 Results and Discussion; 3.2.1 Radical Clocks; 3.2.1.1 Bicycloheptane; 3.2.1.2 Bicyclo[2.1.0]Pentane; 3.2.1.3 TMCP; 3.2.2 Kinetic Isotope Effect (KIE); 3.2.2.1 N-Hexane-1, 1, 1, 2, 2, 3, 3-D7; 3.2.2.2 Methyl Group Stepwise Deuterated Toluenes; 3.2.2.3 Single Methyl Group Deuterated Xylenes. 3.2.2.4 Stereo-Deuterated Ethylbenzene3.3 Conclusions; 3.4 Experimental; 3.4.1 Synthesis of Substrates and Authentic Samples; References; 4 Detection and Kinetic Characterization of a Highly Reactive Heme-Thiolate Peroxygenase AaeAPO Compound I; Abstract; 4.1 Results and Discussion; 4.1.1 Kinetic Characterization of AaeAPO Binding with Substrates; 4.1.2 Detection and Generation of AaeAPO-I; 4.1.3 Kinetic Characterization of AaeAPO-I Towards a Series of Alkanes; 4.2 Conclusions; 4.3 Experimental; References; 5 Driving Force for Oxygen Atom Transfer by Heme-Thiolate Enzymes ; Abstract. 5.1 Results and Discussion5.1.1 Kinetic Characterization of Compound I Generation by Hypohalous Acids; 5.1.2 Kinetic Characterization of Compound I Reaction with Halide Ions; 5.1.3 Determination the Redox Potential of Compound I and the Nernst Plots; 5.1.4 Implication of Compound I Redox Properties on C -- H Activation; 5.2 Conclusions; 5.3 Experimental; References; 6 Detection and Characterization of Heme-Thiolate Compound II from AaeAPO Peroxygenase; Abstract; 6.1 Introduction; 6.2 Results and Discussion; 6.2.1 Direct Reductive Generation of AaeAPO-II from AaeAPO-I with Nitroxyl Radicals. 6.2.2 Determination of the Ferryl -- OH pKa in AaeAPO-II.
• Publisher Details: Cham : Springer
• Publication Date: 2016
• Extent: 1 online resource (xxxii, 130 pages)
• Subjects: 612.1/111; Chemistry; Heme oxygenase; Hydroxylation; Alkanes; Chemistry, Organic; Enzymes; Catalysis; MEDICAL -- Physiology; SCIENCE -- Life Sciences -- Human Anatomy & Physiology; Alkanes; Heme oxygenase; Hydroxylation; Science -- Life Sciences -- Biochemistry; Science -- Chemistry -- Industrial & Technical; Enzymology; Catalysis; Science -- Chemistry -- Organic; Organic chemistry; Heme Oxygenase (Decyclizing) -- physiology; Electronic books
• Languages: English
• ISBNs: 9783319032368; 3319032364
• Related ISBNs: 9783319032351; 3319032356; 9783319032351
• Notes: Note: Includes bibliographical references.; Note: Vendor-supplied metadata.
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