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Durham E-Theses Durham E-Theses S-nitrosothiols: novel decomposition pathways including reactions with sulfur and nitrogen nucleophiles Munro, Andrew P. How to cite: Munro, Andrew P. (1999) S-nitrosothiols: novel decomposition pathways including reactions with sulfur and nitrogen nucleophiles, Durham theses, Durham University. Available at Durham E-Theses Online: http://etheses.dur.ac.uk/4605/ Use policy The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that: • a full bibliographic reference is made to the original source • a link is made to the metadata record in Durham E-Theses • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders. Please consult the full Durham E-Theses policy for further details. Academic Support Oce, Durham University, University Oce, Old Elvet, Durham DH1 3HP e-mail: [email protected] Tel: +44 0191 334 6107 http://etheses.dur.ac.uk 2 S-NITROSOTHIOLS : NOVEL DECOMPOSITION PATHWAYS INCLUDING REACTIONS WITH SULFUR AND NITROGEN NUCLEOPHILES by Andrew P. Munro, B.Sc. (Hons.) (Graduate Society) The copyright of this thesis rests with the author. No quotation from it should be published without die written consent of die author and information derived from it should be acknowledged. A thesis submitted for the degree of Doctor of Philosophy in the Department of Chemistry, University of Durham September 1999 2 1 JAN 2000 S-NTTROSOTfflOLS : NOVEL DECOMPOSITION PATHWAYS INCLUDING REACTIONS WITH SULFUR AND NITROGEN NUCLEOPHILES by Andrew P. Munro A thesis submitted for the degree of Doctor of Philosophy in the Department of Chemistry, University of Durham, September 1999. ABSTRACT Spectrophotometric (including stopped-flow) techniques were used to examine the kinetics of NO-group transfer reactions (transnitrosation) between S-nitrosothiols (RSNO) and a wide range of sulfur/nitrogen nucleophiles in aqueous solution. A metal-ion chelator was added in all experiments to prevent RSNO decay and NO liberation catalysed by copper ions. In most cases reaction was envisaged as rate- determining attack of the nucleophile at the nitrogen atom of the -SNO moiety, and hence S-nitrosothiols essentially acted as electrophilic nitrosating agents. Sulfite, thiosulfate, thiourea, thiocyanate and thiomethoxide, were sufficiently nucleophilic to induce nitrosothiol decomposition at physiological pH. Reaction with sulfide (pH > 7.4) afforded the orange-yellow anion, SSNO, and embodies a potential quantitative test for RSNOs. S-Nitrosopenicillamine was reactive enough to allow a thorough investigation into its reaction at basic pH with primary, secondary (creating carcinogenic N-nitrosamines), and tertiary amines, as well as ambident (e.g. thiomorpholine) and alpha nucleophiles (e.g. azide ion). Parallels could be made with analogous studies using other nitroso compounds such as MNTS. The generality of the reaction of a S-nitrosothiol with a large excess of the corresponding or a different thiol was also assessed. Ammonia and not nitric oxide was confirmed as the primary nitrogenous product of this highly complicated process. Mechanistic details of the copper(I) catalysed decomposition of some novel S- nitroso derivatives (e.g. a synthesised S-nitroso-l-thiosugar) are reported. The two- stage degradation pathway involved an initial Cu+ promoted component that halted at incomplete conversion, and was accompanied by a large thermal reaction. An explanation of this unique pattern has been offered in terms of the generation of a disulfide-Cu2+ complex, in which copper is/is not accessible to reduction. ACKNOWLEDGEMENTS I am indebted to my supervisor, Professor D. Lyn H. Williams for his guidance and friendship throughout the course of my studies. The regular discussions about the turbulent state of Welsh sport will be greatly missed. Many thanks go to the exceptional computer magician (and story teller), Mr. Colin 'Ceeg' Greenhalgh, and I appreciate the time and effort spent by Dr. Andy Dicks in proof reading this thesis. It is impossible to name everyone who has made my time in Durham so memorable, but a few people deserve a particular mention. Firstly, I wish to express my gratitude to my lab colleagues and friends; Ian, Gibbo, Coupie, Lynsey, Kathryn, Tony, Darren, Seve, Dave Moss, Parkin, Geordie Dave, Jeanette, Anna and E. I must also thank the Jas Pal lads, Bedders, Pricey, Alex, Phil, Fraggle, and Stella, for making the social life as entertaining as the work life. Coffee breaks will never be the same without the 'girls', Hazel and Jean. Additional recognition goes to my grandparents, Chris, the Neath boys, Brian and Marian, and I am extremely grateful to my parents for their unremitting moral and financial support. Finally, but most importantly, I would like to say a special thank you to Madeleine for her patience, humour, and care, over the past few months. Acknowledgement is made to the EPSRC for funding this research. DECLARATION The material in this thesis is the result of research carried out in the Department of Chemistry, University of Durham, between October 1996 and September 1999. It has not been submitted for any other degree and is the authors own work, except where acknowledged by reference. STATEMENT OF COPYRIGHT The copyright of this thesis lies with the author. No quotation from it should be published without his prior written consent and information derived from it should be acknowledged. 1 To my parents CONTENTS Chapter 1 : Introduction 1 1.1 Nitric Oxide 2 1.1.1 Introduction 2 1.1.2 Physical Properties 3 1.1.3 The Early Reputation of NO 3 1.1.4 The Physiological Functions of Nitric Oxide 5 1.1.4.1 Vasodilation 5 1.1.4.2 Biosynthesis of NO 7 1.1.4.3 Macrophage Cytotoxicity 8 1.1.4.4 Neurotransmission 9 1.1.4.5 Platelet Aggregation 9 1.1.5 Nitric Oxide Donor Compounds 10 1.1.5.1 Nitrovasodilators 10 1.1.5.2 Organic Nitrates and Nitrites 10 1.1.5.3 Metal Nitrosyls 12 1.1.5.4 S-Nitrosothiols 13 1.1.5.5 Furoxans 13 1.1.5.6 C-Nitroso Compounds 14 1.1.5.7 Sydnonimines 14 1.1.5.8 Oxatriazole-5-imine Derivatives 15 1.1.5.9 NONOates 15 1.1.5.10 N-Hydroxyguanidine Compounds 16 1.1.5.11 N-Nitropyrazoles 16 1.2 S-Nitrosothiols 17 1.2.1 Introduction 17 1.2.2 Physical Properties 17 1.2.3 History of S-Nitrosothiols 18 1.2.4 S-Nitrosothiol Formation 23 1.2.4.1 S-Nitrosation and Nitrosating Agents 23 1.2.4.2 Kinetics of S-Nitrosation 28 1,3 Reactions of S-Nitrosothiols 30 1.3.1 Introduction 30 1.3.2 Thermal/Photochemical Decomposition 30 1.3.3 Metal Ion Induced Decay 31 1.3.3.1 Copper Ion Catalysed Decomposition 31 1.3.3.2 Decomposition Induced by Mercury 35 and Silver Salts 1.3.3.3 Iron Ion Catalysed Decomposition 36 1.3.3.4 Decomposition Induced by Other Metal Ions 37 1.3.4 Acid Catalysed Hydrolysis 38 1.3.5 S-Nitrosothiols as a Source of NO+ 39 1.3.5.1 Reactions with Nucleophiles 39 1.3.5.2 Reactions with Thiols (Transnitrosation) 39 1.3.5.3 Reactions with Amines 42 1.3.5.4 Reactions with Ascorbate (Vitamin C) 44 1.3.5.5 Reactions with Iodide/Iodine 45 1.3.5.6 Reactions with Hydrogen Peroxide 45 1.3.5.7 Reactions with Diethyl Dithiocarbamate 46 1.3.5.8 Reactions with Phenolic Nucleophiles 47 1.3.6 Decomposition Induced by Other Species 48 1.3 .6.1 Reactions with Inorganic Complexes 48 1.3.6.2 Reactions with Seleno Compounds and 49 Glucose Peroxidase 1.3.6.3 Reactions with Superoxide 50 1.3.6.4 Enzymatic and Cell-Mediated Reactions 51 1.3 .7 Analytical Reactions 51 References 52 Chapter 2 : The Reaction of S-Nitrosothiols with Thiols 59 at High Thiol Concentration 2.1 Introduction 60 2.2 Thiol Induced S-Nitrosothiol Decomposition 61 2.2.1 Kinetic Studies 61 2.2.2 Reactions of S-Nitrosothiols with the Parent Thiol 63 2.2.3 Reactions of S-Nitrosothiols with Thiols other than 69 the Parent Thiol 2.2.4 Reactions of S-Nitrosothiols with Mixed Thiols 71 2.3 Determination of Reactive Species 73 2.4 Product Analysis 77 2.4.1 Detection of Ammonia 77 2.4.2 Detection of Nitrite 78 2.4.3 Detection of Nitrous Oxide 79 2.4.4 Detection of Disulfide 79 2.4.5 Composition of Reaction Products 80 2.5 Anaerobic Reaction 82 2.6 Proposed Decay Mechanism 84 2.7 Conclusion 86 References 87 Chapter 3 : Reactivity of Nitrogen Nucleophiles 89 Towards S-Nitrosopenicillamine 3.1 Introduction 90 3.2 Reactions of Secondary Amines 92 3.2.1 Effect of Amine Concentration on S-Nitrosopenicillamine 92 Decomposition 3 .2.2 Active Form of the Amine 96 3.2.3 Second Order Rate Constants 100 3.2.4 Reactivity 103 3.2.5 Reaction under Anaerobic Conditions 104 3 .2 .6 Identification of Decomposition Products 105 3.2.6.1 Nitrogen-Derived Species 105 3.2.6.2 Sulfur-Derived Species 107 3.2.7 Activation Parameters of Reaction 109 3.2.8 Deduced Reaction Mechanism 113 3.2.9 Alkaline Hydrolysis 114 3.3 Reactions of Primary Amines 121 3.3.1 Interactions at Low Amine Concentration 121 3.3.1.1 Effect of pH and Amine Basicity upon Reactivity 121 3.3.1.2 End Products 125 3.3.1.3 Proposed Mechanism of Deamination 126 3.3.2 Interactions at High Amine Concentration 127 3.3.2.1 Kinetic Characteristics 127 3.3.2.2 Nitrosothiol-Amine Complex Formation 129 3.4 Reactions of Tertiary Amines 133 3.5 Reactions of Other Nitrogen Nucleophiles 13 5 3.6 Reactions of Ambident Nucleophiles 139 3.7 Correlation and Discussion of Kinetic Results 143 3.8 Conclusion 147 References 148 Chapter 4 : Reactivity of Sulfur Nucleophiles 151 Towards S-Nitrosothiols
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