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Peroxynitrite Oxidation of Aromatic Thiols: Characterization of the Products Formed Through Oxidation of Thionitrobenzoic Acid and Thionitropyridine by Peroxynitrite

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Peroxynitrite Oxidation of Aromatic Thiols: Characterization of the Products Formed Through Oxidation of Thionitrobenzoic Acid and Thionitropyridine by Peroxynitrite W&M ScholarWorks Dissertations, Theses, and Masters Projects Theses, Dissertations, & Master Projects 2006 Peroxynitrite Oxidation of Aromatic Thiols: Characterization of the Products Formed through Oxidation of Thionitrobenzoic Acid and Thionitropyridine by Peroxynitrite Catherine Balchunas Mall College of William & Mary - Arts & Sciences Follow this and additional works at: https://scholarworks.wm.edu/etd Part of the Organic Chemistry Commons Recommended Citation Mall, Catherine Balchunas, "Peroxynitrite Oxidation of Aromatic Thiols: Characterization of the Products Formed through Oxidation of Thionitrobenzoic Acid and Thionitropyridine by Peroxynitrite" (2006). Dissertations, Theses, and Masters Projects. Paper 1539626852. https://dx.doi.org/doi:10.21220/s2-td8x-bb97 This Thesis is brought to you for free and open access by the Theses, Dissertations, & Master Projects at W&M ScholarWorks. It has been accepted for inclusion in Dissertations, Theses, and Masters Projects by an authorized administrator of W&M ScholarWorks. For more information, please contact [email protected]. PEROXYNITRITE OXIDATION OF AROMATIC THIOLS Characterization of the Products Formed Through Oxidation of Thionitrobenzoic Acid and Thionitropyridine by Peroxynitrite A Thesis Presented to The Faculty of the Department of Chemistry The College of William and Mary in Virginia In Partial Fulfillment Of the Requirements for the Degree of Master of Science by Catherine Balchunas Mall 2006 APPROVAL SHEET This thesis is submitted in partial fulfillment of the requirements for the degree of Master of Science t * fVkxXA Catherine Balchunas Mall Approved by the Committee, April 2006 Dr. Lisa M. Landino, Advisor and Chair Dr. Dr. Gaw W. Rice 11 DEDICATION This thesis is dedicated to my husband, Matthew Mall, for being the guy I always dreamed I would someday marry. Your love, support, and constant encouragement have made me a better person in so many ways. Thank you for everything you do. TABLE OF CONTENTS Page Acknowledgements..............................................................................................................v List of Tables ......................................................................................................................vi List of Figures....................................................................................................................vii List of Abbreviations ......................................................................................................... ix List of Structures and Observed Maximum Absorbances ...............................................x Abstract .............................................................................................................................xiii Introduction.......................................................................................................................... 2 Experimental Procedures and Methods ........................................................................... 13 Results and Discussion..................................................................................................... 26 I. Characterization of Peaks ................................................................................... 26 II. NBD-C1 Trapping of Sulfenic Acid .................................................................41 III. Dimedone Trapping of Sulfenic Acid .................................. 51 IV. Thiosulfinate Reactivity................................................................................... 60 Conclusions and Future W ork..........................................................................................67 References.......................................................................................................................... 69 Vita......................................................................................................................................72 iv ACKNOWLEDGEMENTS The writer would like to thank Dr. Landino, under whose guidance this project was conducted, for her wealth of knowledge and suggestions. Without her help and encouragement, this project could never have been completed. The author is also grateful to Dr. Abelt and Dr. Rice for serving on the committee to read and critique this manuscript, as well as their willingness to provide assistance with those areas of chemistry not well understood by the author. v LIST OF TABLES Table Page 1. Regular Method ............................................................................................................15 2. Extended Method ......................................................................................... ......15 LIST OF FIGURES Figure Page 1. Reactive Oxygen Species..........................................................................................2 2. Oxidation States of Sulfur.........................................................................................4 3. Reaction of Sulfenic Acid with Dimedone and NBD-C1 ........................................9 4. Peroxynitrite Oxidation of TNB........................................................................... 27 5. Performic Acid Oxidation of DTNB ......................................................................28 6. Structure of 3-Nitrobenzenesulfonic Acid, sodium salt ........................................ 30 7. Performic acid oxidation of DTNP................ .......................................................31 8. Peroxynitrite oxidation of TNB - Concentration Dependence...........................36 9. TNB thiosulfinate treated with base .....................................................................38 10. Effect of pH on TNB thiosulfinate formation .......................................................40 11. Peroxynitrite Oxidation of DTNB.........................................................................42 12. NBD-C1 trapping of TNP sulfenic acid ............................................................... 44 13. NBD-C1 trapping of TNB sulfenic acid ............................................................... 45 14. NBD-C1 trapping of TNB sulfenic acid - extended runtime ............................. 46 15. NBD-C1 trapping of TNP sulfenic acid over tim e .............................................. 48 16. NBD-C1 trapping of TNP sulfenic acid - peroxynitrite concentration dependence....................................................................................49 17. 14 minute Peak .........................................................................................................50 18. Dimedone trapping of TNB sulfenic acid - UV-Vis ........................................... 53 vii LIST OF FIGURES CONTINUED Figure Page 19. Dimedone trapping of TNB sulfenic acid - HPLC..............................................54 20. Dimedone purification............................................................................................ 55 21. Dimedone trapping of TNB sulfenic acid - temperature dependence .......................... 57 22. Dimedone trapping of TNB sulfenic acid - peroxynitrite concentration dependence.............................................................58 23. Dimedone trapping of TNB sulfenic acid - pH dependence ...................................................................................................... 59 24. Thiosulfinate reactivity with NBD-C1 .................................................................. 62 25. Lipoic A cid ..............................................................................................................65 LIST OF ABBREVIATIONS DTT - dithiothreitol DTNB - 5,5’-Dithio-bis(2-nitrobenzoic acid) DTNP - 2,2’-Dithiobis(5-nitropyridine) TNB - 5-thio-2-nitrobenzoic acid TNP - 2-thio-5-nitropyridine NBD-C1 - 4-chloro-7-nitrobenzo-2-oxa-l,3-diazole Dimedone - 5,5’-Dimethyl-1,3-cyclohexanedione RSO-NBD - sulfenic acid adduct - sulfoxide or sulfenate ester - product of NBD bonding to protein sulfenic acid RS-NBD - thiol adduct - thioether - product of NBD bonding to the protein sulfhydryl LIST OF STRUCTURES AND OBSERVED MAXIMUM ABSORBANCES DTNB Related Structures DTNB s—s pH 7.4 - 328 nm Acid - 328 nm o=c c=o OHHO Thiosulfinate pH 7.4 - 268 nm Acid - 320 nm 0 = C c = o / XOH HO N+- Thiosulfonate pH 7.4 - ? Acid - ? 0= C C = 0 OH HO TNB Sulfinic Acid S- pH 7.4 - 409 nm pH 7.4 - ? Acid - 332 nm Acid - ? 0=C 0 = 0 \ \ OH OH Sulfonic Acid Sulfenic Acid pH 7.4 - 260 nm pH 7.4 - 405 nm / + Acid - 263 nm \ Acid - 319 nm -O OH OH o=c 0= C \ OH OH X DTNP Related Structures DTNP pH 7.4 - 316 nm Acid - 316 nm Thiosulfinute pH 7.4 - 340 nm Acid - 340 nm Thiosulfonate pH 7.4 - ? Acid - ? TNP Sulfinic Acid S- pH 7.4 - 392 nm pH 7.4 - ? Acid - 374 nm Acid - ? -OKM X= N OH Sulfonic Acid Sulfenic Acid pH 7.4 - 276 nm pH 7.4-402 nm Acid - 276 nm \ Acid - 380 nm -OKM X= N OH OH Other Structures NBD-Cl pH 7.4 - 342 nm Acid - 342 nm < / S > Dimedone pH 7.4 - 260 nm Acid - 260 nm 0| - Na+m 0 = S = 0 3-Nitrobenzenesulfonic acid pH 7.4 - 260 nm Acid - 260 nm N+ xii ABSTRACT The oxidation of thionitrobenzoic acid (TNB) yielded multiple unexpected oxidation products. As this prevented its use in a competition assay to calculate the rate constants for oxidation of protein thiols, the oxidation of this compound was studied. The expected product was dithionitrobenzoic acid (DTNB), and this was found to be the major product formed when TNB was oxidized using peroxynitrite. HPLC separation of oxidation products implied the presence of two other products. The
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