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Characterization of DNA Damaging Intermediates by EPR

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Characterization of DNA Damaging Intermediates by EPR Chromium Carcinogenesis: Characterization of DNA damaging Intermediates by EPR 31P NMR, HPLC, ESI-MS and Magnetic Susceptibility A dissertation presented to the faculty of the College of Arts and Sciences of Ohio University In partial fulfillment of the requirements for the degree Doctor of Philosophy Roberto Marín Córdoba March 2010 2 This dissertation titled Chromium Carcinogenesis: Characterization of DNA damaging Intermediates by EPR 31P NMR, HPLC, ESI-MS and Magnetic Susceptibility by ROBERTO MARÍN CÓRDOBA has been approved for the Department of Chemistry and Biochemistry and the College of Arts and Sciences by Rathindra N. Bose Professor of Chemistry and Biochemistry Benjamin M. Ogles Dean, College of Arts and Sciences 3 ABSTRACT MARÍN CÓRDOBA, ROBERTO, Ph.D., March 2010, Chemistry and Biochemistry Chromium Carcinogenesis: Characterization of DNA damaging Intermediates by EPR 31P NMR, HPLC, ESI-MS and Magnetic Susceptibility (150 pp.) Director of Dissertation: Rathindra N. Bose The hydrolytic cleavage and oxidative degradation mechanisms of dGDP by the oxochromate-(V) complexes bis(2-ethyl-2-hydroxybutanoato)oxochromate(V) (I) and bis(hydroxyethyl)-amino-tris((hydroxymethyl)methane)oxochromate(V) (II) in the presence of H2O2 were investigated at neutral pH. The products of the reactions were separated and characterized by chromatographic and spectroscopic methods. The oxidative degradation is supported by the detection of free G, furfural, phosphoglycolate, pyrophosphate, guaninepropenal, 8OHdG and guanidinohydantoin. These products are formed through two parallel mechanisms that start with a common Cr-dGDP intermediate in which the oxochromate binds the α phosphate moiety followed by abstraction of H from C4’ and C5’ from the ribose. The detection of inorganic phosphate and dGMP suggests that when the oxometal binds the β phosphate it mainly promotes hydrolytic cleavage of the phosphate diester bond. By estimating the amount of each catabolite it was concluded that the oxo metal ion does not show selectivity during the hydrogen abstraction and that oxidation of the substrate is preferred over its hydrolysis. The reaction between diperoxoaquaethylendiamine chromium(IV) (III) and glutathione (GSH) at neutral pH was studied by EPR and ESI-MS. The ions of m/z ratios of 450 and 757 were identified as intermediates while the ions of m/z ratios of 484 and 775 were identified as products. Three EPR signals detected at g = 1.996, 1,986 and 1.983 were attributed to Cr(V) intermediates while a signal at g = 1.975 (peak to peak line width = 259.72 G) that appeared after the Cr(V) signals had disappeared was 4 attributed to Cr(IV). Spin trapping experiments with DMPO and DEPMPO revealed that the GS radical but not OH radical was formed during this reaction. The GS radical and the Cr(V) intermediates detected by EPR confirmed that the reaction occurs in a series of one electron transactions. Overall this reaction proceeds in cycles. The reaction produces Cr(V) intermediates followed by accumulation of a chromium(IV) second intermediate that decays slowly to a Cr(III) product. The DNA damage assay suggests that during its reaction with glutathione, III becomes a DNA damaging agent. The mixture of intermediates of the reaction between chromate and glutathione in glycine buffer (pH 2.8) was investigated with a SQUID susceptomer. The saturation magnetic moment was calculated to be 1.39 µB while the effective magnetic moment was 2.55 µB. Based on the saturation magnetic moment, the intermediates were characterized as 30 % Cr(IV) and 69 % Cr(V). Using the effective magnetic moment the mixture was characterized as 58 % Cr(IV) and 42 % Cr(V). The spin only formula gave a total spin angular momentum of 0.88 which supports Cr(IV) as the predominant intermediate. As previous studies did not detect Cr(V) EPR signals, it was assumed that only a Cr(IV) intermediate was formed. In light of the present work and stoichiometric data from previous work, the silent part of the mixture of intermediates was interpreted as a Cr(V) dimer in which the Cr centers are diamagnetically coupled. With this data in consideration, the proportion of Cr(IV) in the mixture of intermediates should be at least 65%. Approved: _____________________________________________________________ Rathindra N. Bose Professor of Chemistry and Biochemistry 5 ACKNOWLEDGMENTS The end of this journey would not be possible without the people that helped me throughout it. First to Dr. Gisell Sandi, who encouraged me to apply to the graduate school and to the Department of Chemistry at Northern Illinois University. Also the NIU chemistry graduate committee that accepted my application and awarded me a teaching assistantship throughout my entire stay. In this regard I would like to thank the tax payers of the United States of America, who made possible the research and the teaching activities involved in this process. From the very beginning Dr. Gerardo Chacon and Dr. Jorge Alvarado awarded to me their friendship and help in many situations. For this I am thankful. Soon after my arrival to the United States of America, the Highlands made me part of their family, in particular John, Mrs. Rose Mary Highland, Angelo, Mary, Rita and Sheila. To them I give my gratitude. Thank you John for helping me to run my errands when I did not have a car, for picking up my recyclables, for introduce me to your lovely family and for your friendship. Also thank you Dr. Gregory Ross for allowed me to participate during the school year of 2005 in the Foreign Language Residence Program at NIU. Special thanks to Leslie and Brad Shive, who I am sure have helped hundreds of international students personally and through the Network of Nations and other organizations and activities. And thanks also to Cliff Golden and the scouts of the Troop 33 of Dekalb Illinois for accepting me as scout leader and for sharing with me the camaraderie that makes boy scouts an international community. 6 Of great help were, and still are Dr. James Erman and Dr. Lidia Vitello. From them not only did I obtain good advice and friendship, but a model upon which to look. A particular joyful memory was to watch my first snow fall in Dr. Erman’s office. Dr. Morley and Mrs. Maureen Russell are two sincere friends who still follow my well being, - my heartfelt thanks. I would like also to thank all the members of Dr. Bose and Dr. Anima Bose research groups whose company, friendship, and help I enjoyed over the last five years, and in particular to Dr. Leila Maurman, Dr. Robert Mishur, Dr. Shadi Moghadas, Raghu Kumar and Pradeep Babbury, This dissertation was performed in the research laboratories of Northern Illinois University and the Konneker Research Laboratory of Ohio University. Also, the EPR studies were performed at the EPR and Imaging Center of Ohio State University. To the staff members of these institutions and their Chemistry and Biochemistry Departments, I give sincere thanks. In particular I would like to mention Dr. Jon Carnahan, graduate chair of the NIU Chemistry and Biochemistry Department at my arrival in 2004 and Dr. Periannan Kuppusamy, head of the EPR center at Ohio State University. During the last two years of my doctoral work I also participated in the study of a catalyst for the reaction of oxygen reduction for applications in fuel cells. I would like to thank to Dr. Anima Bose for accepting me as part of her research group and for her guidance on such an important subject. Finally I would like to thank Dr. Rathindra Bose for allowing me to work on his research projects and for his guidance and thoughtful suggestions. Few graduate 7 students, regardless of the name of the institution, have the opportunity that was given to me, and that I vigorously took. During my dissertation I had the opportunity to work with the most relevant instrumental techniques to perform state of the art science, including NMR, EPR, HPLC, ESI-MS, magnetic susceptibility, electrochemical analysis and UV spectroscopy. And through my participation in the catalyst for fuel cells project and the synthesis and chemical analysis of pyrodach-2 and 4, I also gained knowledge in GFAA, ICP-OES and surface science techniques that include SEM, EDX, XPS and fuel cell testing. More importantly, working with and witnessing Dr. Bose’s performance as both administrator of science and as scientist. I also refined my soft skills, in particular courage, creativity, commitment and compassion. A very important lesson that I am taking with me comes from Dr. Bose own story as scientist. I quickly noticed that his work from twenty years or more is giving fruits today, thanks to his perseverance and courage as a deep thinker. It is of the popular domain that science is about trial and error; but what most do not know is that intelligently designed and carefully performed experiments are most likely to give more meaningful data than errors, with less trials. Dr. Bose’s guidance led me to comprehend the depth of this statement. 8 Dedicated to little Robin bird and all the young little faces of our families 9 TABLE OF CONTENTS Page Abstract ............................................................................................................................... 3 Acknowledgments............................................................................................................... 5 List of Tables .................................................................................................................... 12 List of Figures ..................................................................................................................
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