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The Chemistry of Nitrosation

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The Chemistry of Nitrosation Durham E-Theses The role of L-ascorbic acid in S-nitrosothiol decomposition and aspects of the nitrosation of thiones Holmes, Anthony J. How to cite: Holmes, Anthony J. (2000) The role of L-ascorbic acid in S-nitrosothiol decomposition and aspects of the nitrosation of thiones, Durham theses, Durham University. Available at Durham E-Theses Online: http://etheses.dur.ac.uk/4228/ 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 The Role of L-Ascorbic Acid in 5-Nitfosothiol Decomposition and Aspects of the Nitrosation of Thiones Anthony J. Holmes BSc GRSC Thesis submitted for the degree of Doctor of Philosophy University of Durham September 2000 The copyright of this thesis rests with the author. No quotation from it should he published in any form, including Electronic and the Internet, without the author's prior written consent. All information derived from this thesis must he acknowledged a|)propriately. JUN 2001 Abstract Abstract Ascorbic acid has been found to promote nitrosothiol decomposition via two pathways. In the first, ascorbic acid acts as a reducing agent for added or adventitious copper (II), producing copper (I). This reacts with the nitrosothiol, giving nitric oxide and disulfide as the ultimate products. The reaction requires only small quantities of ascorbic acid, and is catalytic in copper. The second pathway requires higher concentrations of ascorbic acid, the stoichiometry being one mole of ascorbic acid to two moles of nitrosothiol. The products are nitric oxide and thiol, and the reaction has been interpreted in terms of rate limiting nucleophilic attack by ascorbate at the nitroso nitrogen, followed by decomposition of the 0-nitroso ascorbate formed to nitric oxide and dehydroascorbic acid. The rate equation is first order in both the nitrosothiol and ascorbic acid, and the entropy of activation is significantiy negative. pH - rate profiles reveal the ascorbate dianion is much more reactive than the monoanion, and that the neutral form has negligible reactivity. Nitrosation of thione-containing nitrogen heterocycles by nitrous acid leads to the equilibrium formation of ^SNO"^ species; large equilibrium constants are observed. The reactions exhibit many of the features generally observed in nitrosation, including catalysis by hahdes and thiocyanate, and some participation by dinitrogen trioxide as a nitrosating agent. The nitrosation rate constants are large, approaching values representing the encounter-controUed limit. The =SNO+ species are generally unstable, decomposing under acidic conditions to nitric oxide and a disulfide. Decomposition of J-nitrosated 4-thiopyridine showed hydrolysis occurs at pH 7.4, re-forming the thione. The nitroso species reacts rapidly with ascorbate, forming nitric oxide and thione. Declaration and Copyright Declaration The work in this thesis was carried out in the Chemistry Department at the University of Durham between 1" October 1997 and 30* September 2000. It has not been submitted for any other degree and is the author's own work, except where acknowledged by reference. Copyright The copyright of this thesis rests with the author. No quotation from it should be pubhshed without prior written consent and information derived from it should be acknowledged. No part of this thesis may be reproduced, stored in a retrieval system or transmitted in any form or by any means without the written consent of the author. m Acknmvkdgments Acknowledgements I would like to thank my supervisor, Professor Lyn WiUiams, for his help during my PhD studies. I acknowledge the financial support received from the EPSRC, and the University of Durham and ICI for graduate scholarships. I feel I should probably thank all my lab colleagues for giving me plenty to laugh at over the last three years, especially Darren, Paul, Dave, Andy, Seve, Lynsey and Linda. I wovild put in some siUy nicknames for them all, but Two Pint Wonder Darren would hit me. Ah, too late. Dave must be cursed for his persistence in leading me into pubhc houses (hope you're not superstitious Dave). Thank you also to Colin Greenhalgh, for keeping all the equipment running. A special thank you is due to my fiancee vKathrynV for all her support, including the unfortunate task of proof reading this vast white elephant. May chicken dippers be on the menu for the many years of married life to come! I would also like to thank my family for all their support throughout my PhD studies and the rest of my education. Indeed, the whole of my life. I will contemplate joining the real world eventually. Thanks also to Kathryn's parents for their kindness and hospitality. I would also like to thank my friend Craig, who hasn't really seen much of me over the last three years, and when he has we've been too drunk to recognise each other. That bit was a joke, by the way... A special thank you is extended to one Anthony J. Holmes, who wrote this thing. I bet you all wished he hadn't! I hope I haven't offended anybody during the above, other than those people I intended to. There are many other people I would like to thank, but there isn't space. Actually, there is a httie bit of space. Just enough to praise the brilliance of the Goons, Fawlty Towers, Monty Python (but not the circus), Mr. Bean (I want to be him). Black Adder, Just a Minute, the News Quiz, the NOW! Show, and the other ones. In addition, I must say: Hooray! for glue, pens, paper, chairs, tables, food, and all of those other htde objects we all use and take for granted every day. There's still a bit of space left so I suppose I should really use it to thank the people I said I would thank if I had enough space to do so. Well, here goes. Thank you to iv Dedication To the view along the East Coast and Midland Mainlines, without which this would have been completed sooner Contents Chapters 1-2 Introduction 1 Introduction - The Chemistry of Nitrosation 1 1.1 Reagents for Use in Nitrosation 2 1.1.1 Acidified Nitrous Acid and the Nitrosonium Ion 2 1.1.2 Dinitrogen Trioxide 4 1.1.3 Dinitrogen Tetroxide, Nitrogen Dioxide, Nitric Oxide, and Peroxynitrite 6 1.1.4 Nitrosyl Hahdes and Nitrosyl Thiocyanate 7 1.1.5 Nitrosonium Salts 9 1.1.6 Nitrosation by Nitroso Compounds 9 1.2 Substrates for Nitrosation 9 1.2.1 N-Nitrosation 10 1.2.2 C-Nitrosation 13 1.2.2.1 Ahphatic and Ahcychc C-Nitrosation 13 1.2.2.2 Aromatic C-Nitrosation 14 1.2.3 0-Nitrosation 16 1.2.3.1 Nitrosation of Ascorbic Acid 18 1.2.4 J-Nitrosation 20 1.2.4.1 Nitrosation of Thiones 22 1.3 References 24 2 Introduction - The Chemistry and Physiology of Nitric Oxide and 5-Nitrosothiols 27 2.1 Nitric Oxide 28 2.1.1 Physical Properties of Nitric Oxide 28 2.1.2 The Chemistry of Nitric Oxide 29 2.1.2.1 Reactivity as a Free Radical 29 2.1.2.2 Co-ordination Chemistry of Nitric Oxide 31 2.1.2.3 The Atmospheric Chemistry of Nitric Oxide 32 2.1.3 Physiology of Nitric Oxide 33 2.1.3.1 Biosynthesis of Nitric Oxide 33 2.1.3.2 Vasodilation 35 2.1.3.3 Platelet Aggregation 36 2.1.3.4 Immune Defence 37 2.1.3.5 Apoptosis 37 2.1.3.6 Neurotransmission 38 VI Contents 2.1.3.7 Other Processes 39 2.1.3.8 Nitric Oxide in Medicine 39 2.2 Nitrosotiiiols 40 2.2.1 Physical Properties of J-Nitrosothiols 40 2.2.2 The Chemistry of J-Nitrosotiiiols 41 2.2.2.1 Thermal and Photochemical Decomposition 42 2.2.2.2 Hg2+ / Ag+ Promoted Decomposition 42 2.2.2.3 Cu+ Catalysed Decomposition of J'-Nitrosothiols 43 2.2.2.4 Decomposition by Seleno Compovmds 47 2.2.2.5 Reaction of Nitrosothiols witii Thiols 47 2.2.2.6 Nitrosothiol Decomposition by Other Sulfiir Nucleophiles 50 2.2.2.7 Reaction Between Nitrosothiols and Nitrogen Nucleophiles 50 2.2.2.8 Reaction of Nitrosothiols with Hydrogen Peroxide and Superoxide 51 2.2.2.9 Ascorbic Acid and Nitrosothiol Decomposition 52 2.2.3 J'-Nitrosothiol Physiology 53 2.3 References 55 Chapters 3-6 Ascorbic Acid in the Decomposition Reactions of 5-Nitrosothiols 3 Identification of Two Pathways for Ascorbic Acid Mediated 5-Nitrosothiol Decomposition 60 3.1 Introduction 61 3.1.1 Structure and Properties of Ascorbic Acid 61 3.1.2 Redox Chemistry of Ascorbic Acid 62 3.1.2.1 Autoxidation 63 3.1.2.2 Catalysis by Transition Metal Ions 63 3.1.2.3 Ascorbic Acid and Thiols: Redox Interactions 65 3.1.3 Physiology of Ascorbic Acid 66 3.1.4 Aims 68 3.2 Initial Studies 68 3.2.1 Effect of Metal Chelation 70 3.2.2 Estabhshing the Stoichiometry 73 3.2.3 Product Studies 75 3.2.3.1 Source of the Increasing Absorbance at 340 nm 75 3.2.3.2 Determination of Sulfur Containing Products 77 vu Contents 3.2.3.3 Determination of Nitrogen Containing Products 82 3.2.3.4 Summary of Products 83 3.3 Further Studies on the Copper Dependent Pathway 84 3.3.1 Varying the Copper Concentration 84 3.3.2 Varying the Ascorbic Acid Concentration 85 3.3.3 Reversal of GSSG Inhibition of GSNO Decomposition 86 3.4 Conclusion 90 3.5 References 92 4 Kinetics and Mechanism of the Copper Independent Reaction
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