Inhalt

•  
  Summary
•  
   Radical and Radical Ion Probes for Enzymatic Investigations
•  
   Translating Short-Lived Radical Cations into Long-Lived Ones in Solution
•  
   Design, Synthesis and Cyclic Voltammetric Investi
•  
   Design, Synthesis and Studies of Electroactive Surfactants for Modulation of Surface Wetting Properties
•  
  Introduction
•  
   Mechanistic Investigations on Coenzyme B12-Dependent Enzymes
•  
   Charged Radicals
•  
  Radical Enzymes
•  
  Present State of Knowledge
•  
  Ribonucleotide Reductase
•  
   Classification
•  
   Mode of Action
•  
   Biomimetic and Theoretical Modelling Studies
•  
   Diol Dehydratase
•  
   Active Site Description and Binding of the Adenosylcobalamin
•  
   Mechanism of Action
•  
   Biomimetic Modelling Studies
•  
  Scission of Ether Bonds by Enzymes
•  
   Introduction
•  
   Mechanism
•  
  Methods of Detection of Radicals and Radical Ions
•  
   Spectroscopic Methods
•  
   Chemical Methods and Radical Clocks
•  
   Cyclopropylmethyl Radical as Probe for Reaction Mechanisms in Enzyme Catalysed Reactions
•  
   Objective
•  
  Conceptual Basis of the Present Work
•  
   Concept to Investigate Radical Ionic Species Directly at the Active Site of the Enzyme
•  
   Concept to Investigate Radical Intermediates Directly at the Active Site of the Enzyme
•  
  Work Plan
•  
   Mechanistic Probes for Diol, Glycerol and Phenoxyethanol Dehydratase
•  
  Design and Retrosynthesis of Radical and Radical Ion for Enzymatic Investigations
•  
   Design and Retrosynthesis of Radical Cation Probes for Enzymatic Investigations
•  
   Design and Retrosynthesis of Radical Anion Probes for Enzymatic Investigations
•  
   Design and Retrosynthesis of Neutral Radical Probes for Enzymatic Investigations
•  
   Design and Retrosynthesis of Probes for Phenoxyethanol Dehydratase to Test the Hydrophobic and Electronic Tolerance of the Active Site
•  
  Results
•  
  Synthesis of Enzmye Probes
•  
  Synthesis of Radical and Radical Ion Probes for Enzymatic Investigations
•  
   Synthesis of 4-Ferrocenyl-butane-1,2-diol (25)
•  
   Synthesis of 5-Ferrocenylpent-4-yn-1,2,3-triol (27)
•  
   Synthesis of 5-Ferrocenylpentan-1,2,3-triol (28)
•  
   Synthesis of 1, 2-Diferrocenylethane-1,2-diol (29)
•  
   Attempted Synthesis of 1-Ferrocenylethane-1,2-diol (23) and 1-Ferrocenyl-propane-1,2,3-triol (26)
•  
   Synthesis of 3-(1,4-Benzoquinoyl)propane-1,2-diol (35)
•  
   Attempted Synthesis of Radical Anion Probes 36, 37 and 38 for Enzymatic Investigations
•  
   Attempted Synthesis of Neutral Radical Probes 52-54 Containing TEMPO as the Persistent Radical Source
•  
   Synthesis of radical probe 2-(2,2,6,6-tetramethylpiperidinoxy)-propane-1,2-diol (62) and 2-methyl-2-(2,2,6,6-tetramethylpiperidinoxy)propane-1,2-diol (63)
•  
   Synthesis of Phenoxyethanol Derivatives for Enzymatic Investigations
•  
   Synthesis of Mechanistic Probes for Solution Studies
•  
   Design and Synthesis of Substrates to Mimic Eliminase Reactions with Ketones as Radical Precursors
•  
   Design and Synthesis of Substrate Mimic 75 for Eliminase Reaction using Barton ester as Radical Initiator
•  
   Synthesis of Barton Ester 78
•  
   Synthesis of Substrates to Mimic Eliminase Reaction using Fluorenoneoxime Derivatives as Radical Precursors
•  
   Synthesis of Substrate to Mimic Eliminase Reaction Based on Cobalt-Carbon Bond Homolysis
•  
  Cyclic Voltammetry and UV-Vis Spectroscopic Investigation of Mechanistic Probes
•  
   Cyclic Voltammetric Investigations
•  
   Cyclic Voltammetric Investigation of 79
•  
   UV-Vis Spectroscopic Investigation of the Radical Cation of Ferrocene-based Enzyme Probes
•  
   UV-Vis Study to Check the Solubility of Phenoxyethanol Derivatives 57a-g in Buffer Solution at pH 8
•  
  Enzymatic Testing of Radical and Radical Ion Probes
•  
   Testing of Radical and Radical Ion Probes on Diol and Gylceroldehydratase from E. Coli.
•  
   Enzyme Assay
•  
  Testing of Radical, Radical Ion Probes and Phenoxyethanol Derivatives on Phenoxyethanol Dehydratase from Acetobacterium sp.
•  
   Materials
•  
   Kinetic Investigations to Determine the Nature of the Inhibition of Phenoxyethanol Dehydratase by Racemic4-Ferrocenylbutane-1,2-diol (25)
•  
   Generation and Intermolecular Trapping of Enol Radical Cations
•  
  Photochemical Studies on Barton Ester 75
•  
   Effect of TFA Concentration on Absorption at \(m
•  
   Photochemical Investigation of Barton Ester 75
•  
   Photolysis of 75 in Presence of Organic Acids
•  
   Photolysis of 75 in Presence of Formic Acid
•  
   Photolysis of 75 in Presence of TFA
•  
   Photochemical Investigations on Barton Ester 78
•  
   Product Distribution after Photolysis in 75 and 78
•  
   Characterisation of 104 by TR-ESR (In collaboration with Dr. G. Bucher)
•  
   Laser Flash Photolysis Investigations on 75 and 78
•  
   Generation and Intramolecular Trapping of Enol Radical Cation: A Pulse Radiolysis Investigation
•  
   Pulse Radiolysis Investigations on Ethylene Glycol
•  
   Pulse Radiolysis Investigation of 25 and 27
•  
  Discussion
•  
   Enzymatic Investigations on the Radical, Radical Ion Probes and Phenoxyethanol Derivatives
•  
   Enzymatic Investigations of Radical and Radical Ion Probes
•  
   Testing of Hydrophobic and Electronic Tolerance of Phenoxyethanol Dehydratase
•  
   Solution Studies Using Various Solution Probes
•  
   Conclusion
•  
   Future Perspectives
•  
  One Electron Oxidation Chemistry of Enols
•  
   Introduction
•  
   Movement of Ions in the Electrochemical Cell
•  
   Classification of Electrochemical Techniques
•  
   Cyclic Voltammetry
•  
   Electrode Kinetics
•  
   Reactivity Pattern of Enols
•  
   Objective
•  
  Results
•  
  Synthesis of Model Compounds Based on ß,ß-Dimesi
•  
   Synthesis of ß,ß-Dimesityl Enols E2-E4, with Six
•  
   Synthesis of ß,ß-Dimesityl Enol with 5-membered
•  
   Synthesis of ß,ß-Dimesityl Enols with Propargyl
•  
  Role of Hydrogen Bonding on Oxidation Potential of Enol Radical Cations
•  
   OH…N Hydrogen Bonding Interactions in E2-E4 \(So
•  
   UV-Visible Spectroscopic Investigation for Enols E2-E4:
•  
   Cyclic Voltammetric Investigations on Enols E2-E4
•  
   Cyclic Voltammetric Investigation of (,(-dimesitylethenol Containing 5-membered Heterocycles (E5) in the (-Position
•  
   UV-Vis Kinetic Investigation on Enol E5
•  
   Cyclic Voltammetric Investigation of Novel (,(-Dimesitylethenols Containing Propargyl Alcohol and Homologues in the (-Position
•  
   UV-Vis Investigation of Enols E9-E12
•  
   Generation and Investigation of Enolates and (-Carbonyl Radicals by Cyclic Voltammetry
•  
  Discussion
•  
   ß,ß-Dimesityl Enols with Six-membered Nitrogen H
•  
   Effect of ß,ß-Dimesitylenols with 5-Membered Het
•  
   ß,ß-Dimesityl Enols Containing Propargyl Alcohol
•  
   Comparison of Oxidation Potential of Enols and En
•  
   Comparison of Oxidation Potential of a-Carbonyl Radicals with Oxidation Potential of Carbon-Centred Radicals
•  
   Biological Relevance of Oxidation Potentials of Enols, Enolate and a-Carbonyl Radicals
•  
   Conclusion
•  
  Design and Synthesis of Electroactive Surfactants to Modulate Surface Wetting Properties
•  
   Introduction to Wetting Phenomena
•  
   Electroactive Surfactants
•  
  Objective
•  
   Design of Electroactive Surfactants Based on 1,4-Dimethyl-2,3-dialkylpyrazinium Tetrafluoroborates
•  
   Design of Electroactive Surfactants Based on Ferrocene
•  
  Results
•  
  Synthesis of Electroactive Surfactants
•  
   Synthesis of 1,4-Dimethyl-2,3-dialkylpyrazinium Tetrafluoroborates (167a-d)
•  
   Synthesis of N-methyl-2,3-Dialkylpyrazinium Iodide
•  
   Synthesis of Ferrocene Based Electroactive Surfactants
•  
   UV-Vis Spectroscopic Investigation
•  
   Cyclic Voltammetry Investigations
•  
   Stability of N,N´-Dimethyl-2,3-dialkylpyrazinium
•  
   Spectroelectrochemical Investigation
•  
   LB-Experiments
•  
   Langmuir-Blodgett Film Balance Experiment for 167d
•  
   Langmuir-Blodgette Film Balance Experiment on Ferrocene Based Electroactive Surfactant
•  
   Discussion and Conclusion
•  
   Future perspective
•  
  Experimental Section
•  
   Instruments Used
•  
  Synthesis
•  
   4-Ferrocenyl-1,2-dihydroxybutane (ML01161)
•  
   3-Ferrocenylpropan-1,2,3-triol (ML02062.1)
•  
   5-Ferrocenylpent-4-yne-1,2,3-triol (ML02063)
•  
   5-Ferrocenylpentane-1,2,3-triol (ML02057)
•  
   1,2-Diferrocenylethane-1,2-diol (ML01135)
•  
   1-Benzyloxy-4-ferrocenyl-but-3-yne-2-ol (ML01115.12)
•  
   1-Ferrocenyl-4,5-isopropylidene-pent-1-yne-3-ol (ML02042.2)
•  
   5-Ferrocenyl-1,2-isopropylidene-pentan-3-ol (ML02047)
•  
   2-Benzyloxy-1-ferrocenylethan-1-ol (ML01119.2)
•  
   2,3-Isopropylidene-1-ferrocenylpropane-1-ol (ML01181)
•  
   32-(2,3-Dihydroxy-propyl)-[1,4]benzoquinone (ML02054)
•  
   3-3-(2-Hydroxy-phenyl)-propane-1,2-diol63 (ML02048)
•  
   Acetic acid 2-allyl-phenyl ester (ML02045)
•  
   4-(2,5-Dimethoxy-phenyl)-butane-1,2-diol (ML02022)
•  
   1-Benzyloxy-4-(2,5-dimethoxy-phenyl)-but-3yn-2-ol (ML02021)
•  
   2-Ethynyl-1,4-dimethoxy-benzene (ML02015)
•  
   2-(1-Chloro-vinyl)-1,4-dimethoxy-benzene (ML02010)
•  
   2,4,5,7-Tetranitrofluorene (ML02007)
•  
   2-(2-Hydroxy-ethoxy)-isoindole-1,3-dione (ML02095)
•  
   2,2,6,6-Tetramethyl-N-piperidinoxyl (ML02093)
•  
   2,2,6,6-Tetramethyl-1-hydroxy-piperidine74b (ML02064)
•  
   2-(2,2,6,6-Tetramethyl-piperidin-1-yloxy)-propane-1,3-diol (ML02134.22)
•  
   2-Methyl-2-(2,2,6,6-tetramethyl-piperidin-1-yloxy)-propane-1,3-diol (ML05076.12)
•  
   2-\(2,2,6,6-Tetramethyl-piperidin-1-yloxy\)-ma
•  
   2-Methyl-2-(2,2,6,6-tetramethyl-piperidin-1-yloxy)-malonic acid diethyl ester (ML05075.11)
•  
   General synthesis of substituted phenoxyethanols (57a-k)
•  
   2-(2,6-Dimethyl-phenoxy)-ethanol78 (ML04109H)
•  
   2-(2,4-Dimethyl-phenoxy)-ethanol78 (ML04109I)
•  
   2-(2,4,6-Trimethyl-phenoxy)-ethanol (ML04109G)
•  
   2-(2-Propyl-phenoxy)-ethanol (ML0109D)
•  
   2-(2-Isopropyl-phenoxy)-ethanol (ML04109F)
•  
   2-(2-sec-Butyl-phenoxy)-ethanol (ML04109E)
•  
   2-(2-tert-Butyl-phenoxy)-ethanol80 (ML04109C)
•  
   2-(4-Methoxy-phenoxy)-ethanol83 (ML05033)
•  
  2-(4-Bromo-phenoxy)-ethanol
•  
   2-(4-Nitro-phenoxy)-ethanol
•  
  General synthesis of substituted phenoxyesters (58a-k)
•  
   Ethyl-(2-nitro-phenoxy) acetate81 (ML04107a)
•  
   Ethyl-(2,6-dimethyl-phenoxy) acetate77 (ML04107H)
•  
   Ethyl-(2,4-dimethyl-phenoxy) acetate77 (ML04107I)
•  
   Ethyl-(2, 4, 6-trimethyl-phenoxy) acetate79 (ML04107G):
•  
   Ethyl-(2-propyl-phenoxy) acetate (ML04107d)
•  
   Ethyl-(2-isopropyl-phenoxy) acetate (ML04107E)
•  
   Ethyl-(2-sec-butyl-phenoxy) acetate (ML04107F)
•  
   Ethyl-(2-tert-butyl-phenoxy) acetate (ML04107C)
•  
   Ethyl-(4-methoxy-phenoxy) acetate (ML05029)
•  
   2,2-Dimethyl-[1,3]dioxolane-4-carboxylic acid 2-thio-2H-pyridin-1yl-ester (ML02020)
•  
   2,2-Dimethyl-propanoic acid 2-thioxo-2H-pyridin-1-yl-ester90 (ML02105/ML050-88.1)
•  
   [D]-2,3-Isopropylideneglyceryl chloride (ML02050)
•  
   Potassium-[D]-2,3-isopropylideneglycerate89 (ML02016)
•  
   [D]-2,3-Isopropylideneglyceraldehyde89 (ML02042.1)
•  
   [D]-1,2,5,6-Diisopropylidenemannitol (ML01173)
•  
   2-(2,2-Dimethyl-[1,3]dioxolan-4-ylsulfanyl)-pyridine (ML05115.12)
•  
   2-tert-Butylsulphanyl-pyridine90 (ML05114.11)
•  
   1-Bromo-3,3-dimethyl-2-butanone (ML01073)
•  
   (2,2-Dimethyl-1-methylene-propoxy)-trimethylsilane86 (ML01022)
•  
   3,3-Dimethyl-1-trimethylsilanyloxy-butane-2-one86 (ML01045.3)
•  
   1-Benzyloxy-3,3-dimethyl-2-butanone (ML01052.2)
•  
   2-Benzyloxy-1-ferrocenyl-1-hydroxy-4,4-dimethyl-3-pentanone (ML01059)
•  
   (1-Benzyloxymethylene-2,2-dimethyl-propoxy)-trimethylsilane
•  
   4,4-Dimethyl-1-ferrocenylpent-1-ene-3-one (ML01032.2)
•  
   1-Ferrocenyl-1-hydroxy-4,4-dimethyl-3-pentanone (ML01034.1)
•  
   Fluorene-9-one O-(2-methoxyacetyl)-oxime (ML05034.1)
•  
   Fluorene-9-one O-\(2-methoxy-3-hydroxy-3-ferroc
•  
   Dibromo-(dimethylglyoximato)-cobalt (III)95 (ML05019)
•  
   Bromo-(4-tert-butyl-pyridine)-cobaloxime95 (ML05020)
•  
   4-Ferrocenyl-2-hydroxy-1-(2-iodobenzyloxy)-3-ethyne (ML01158.12)
•  
   (2-Iodo-benzyloxy)-acetaldehyde (ML01164.12)
•  
   1-(2,2-Diethoxy-ethoxymethyl)-2-iodo-benzene (ML01152.22)
•  
   2-Bromo-1,1-diethoxy-ethane (ML01151)
•  
   (E/Z)-2-Chloro-1-ferrocenylethene (ML02032.1)
•  
   1-Ferrocenylethyne196 (ML02038)
•  
   2,2-Dimesityl-1-(2-pyridyl)-ethenol (ML03064.1)
•  
   2,2-Dimesityl-1-(3-pyridyl)-ethenol (ML03067.1)
•  
   2,2-Dimesityl-1-(8-quinolinyl)-ethenol (ML03081.1)
•  
   2,2-Dimesityl-1-\(3´-thiophenyl\)-ethene-1-ol
•  
   Trisiopropyl-prop-2-ynyloxy-silane (ML03099.1)
•  
   5-Triisopropylsilanyloxy-1,1-bis-(2,4,6-trimethyl-phenyl)-pent-1-en-3-yn-2-ol (ML03115.1)
•  
   5,5-Bis-(2,4,6-trimethyl-phenyl)-pent-4-en-2-yne-1,4-diol (ML04050.1)
•  
   1-But-3-ynyloxy-triisopropyl-silane (ML03120.1)
•  
   6-Triisopropylsilanyloxy-1,1-bis-(2,4,6-trimethyl-phenyl)-hex-1-en-3-yn-2-ol (ML03124.1)
•  
   6,6-Bis-(2,4,6-trimethyl-phenyl)-hex-5-ene-3-yne-1,5-diol (ML04051.1-3)
•  
   Triisopropyl-pent-4-ynyloxy-silane (ML04057.1)
•  
   7-Triisopropylsilanyloxy-1,1-bis-(2,4,6-trimethyl-phenyl)-hept-1-en-3-yn-2-ol (ML04059.1)
•  
   7,7-Bis-(2,4,6-trimethyl-phenyl)-hept-6-en-4-yne-1,6-diol (ML04096.1-b)
•  
   6,7-Bis-trimethylsilanyloxy-dodec-6-ene (ML03071a)
•  
   7-Hydroxy-dodecan-6-one (ML03071b)
•  
   Dodecane-6,7-dione (ML03074.11)
•  
   2,3-Dipentyl-pyrazine (ML03076.11)
•  
   1,4-Dimethyl-2,3-dipentyl-pyrazinium tetrafluoroborate (ML03078)
•  
   8,9-Bis-trimethylsilanyloxy-hexadec-8-ene (ML03072a)
•  
   9-Hydroxy-hexadecan-8-one (ML03072b)
•  
   Hexadecan-8,9-dione (ML03075.1)
•  
   2,3-Diheptyl-pyrazine (ML03077.1)
•  
   1,4-Dimethyl-2,3-diheptyl-pyrazinium tetrafluoroborate
•  
   12,13- Bis-trimethylsilanyloxy-tetracos-12-ene (ML03016.11)
•  
   13-Hydroxy-tetracosan-12-one199 (ML03016.12)
•  
   Tetracosane-12,13-dione (ML03028.1)
•  
   5,6-Diundecyl-2,3-dihydro-pyrazine (ML03030.12)
•  
   2,3-Diundecyl-pyrazine (ML03062)
•  
   1,4-Dimethyl-2,3-diundecyl-pyrazinium tetrafluoroborate (ML030-80)
•  
   18,19-Bis-trimethylsilanyloxy-hexatriacont-18-ene (ML03086a)
•  
   19-Hydroxy-hexatriacontan-18-one (ML03086.12)
•  
   Hexatriacontane-18,19-dione (ML03103.1)
•  
   2,3-Diheptadecyl-pyrazine (ML03126.12)
•  
   2,3-Diheptadecyl-1-methyl-pyrazinium iodide (ML05038.1)
•  
   2,3-Dihetadecyl-1,4-dimethyl-pyrazinium tetrafluoroborate (ML0401-4.1)
•  
   Butyl-(4-ferrocenyl-2-hydroxy)-hexadecanoate (ML04068.12)
•  
   Bis-( [4-ferrocenyl]-butyl) hexadecanoate (ML04068.11)
•  
   Bis-( [4-ferrocenyl]-butyl) hexadecanoate (ML04070.1)
•  
   HPLC-DATA for photolysis of 75 and 78
•  
   ESI-MS Spectrum of 79
•  
   Kinetics of X5+ decay as observed by UV-Vis spectroscopy
•  
   Cyclic-Voltammograms of Enolates
•  
   ESI-MS Characterisation of 2,3-dialkylpyrazinium Tetrafluoroborates 167a-d
•  
   ESI-MS Characterisation of 172 a Ferrocene-based Electroactive Surfactant
•  
  Crystal Structures
•  
   Crystal Structure Analysis of Racemic 4-Ferrocenylbutan-1,2-diol (25)
•  
   Crystal Structure of 2,2,6,6-Tetramethylpiperidin-1-oxyl (21)
•  
   Crystal Structure Analysis of 2-(2,2,6,6-Tetramethylpiperidin-1-yloxy) propane diol (62)
•  
   Crystal Structure Analysis of Diethyl-2-(2,2,6,6-tetramethylpiperidin-1-yloxy)malonate (65)
•  
   Crystal Structure Analysis of 2,2-Dimesityl-ethanols with Various Six Membered Nitrogen Heterocycles (E2, E3, E4)
•  
   Crystal Structure Determination of E6
•  
   Crystal Structure Analysis of 1,1-Dimesityl-5-hydroxypentane-1-ene-2-ol (E11)
•  
  Appendix I
•  
   Methods of Determining Enzyme Inhibition
•  
   Appendix II
•  
  Appendix III
•  
   Crystal Structure Data of 25
•  
   Crystal Structure Data of 21
•  
   Crystal Structure Data of 62
•  
   Crystal Structure Data of 65
•  
   Crystal Data of E2-E4
•  
   Crystal Structure Data of E6
•  
   Crystal Structure Data of E11
•  
   Reference