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University of Cincinnati UNIVERSITY OF CINCINNATI Date:___________________ I, _________________________________________________________, hereby submit this work as part of the requirements for the degree of: in: It is entitled: This work and its defense approved by: Chair: _______________________________ _______________________________ _______________________________ _______________________________ _______________________________ Characterization of Biologically Important Volatile and Non- Volatile Molecules via Heteroatom Determination Using Chromatography and Mass Spectrometry A dissertation submitted to the Division of Research and Advanced Studies of the University of Cincinnati in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Chemistry of the College of Arts and Sciences 2006 by Monika Shah B.Sc., Chemistry, Banaras Hindu University, 1999 M.Sc., Chemistry, Banaras Hindu University, 2001 Committee Chair: Professor Joseph A. Caruso ABSTRACT OF DISSERTATION Interest in molecule specific characterization of metal and metalloid containing species within a biological system is gaining importance in recent years. This not only facilitates the establishment of toxic or beneficial effects of certain form of elements, but in certain cases paves way to understanding of biotransformation of elements and also helps to assess the fate of the environmental contaminants within a biological system. Coupled techniques involving hyphenation of separation methods such as high performance liquid chromatography and gas chromatography with element/molecule specific detection has become the most powerful tool in determination of metal(loid) containing species. Heteroatom determination using mass spectrometric techniques such as inductively coupled plasma mass spectrometry (based on element selective detection) and others such as ESI, EI and MALDI (based on element specific isotope patterns) have been used for the complete characterization of the species of interest. Heteroelements such as selenium, iodine and phosphorus are known to be important atoms in a wide variety of molecules of biological interest ranging from small volatiles and non-volatile amino acids to the macromolecules such as proteins. The aim of this dissertation is characterization of such species in various complex matrices using the above techniques. These include determination and identification of selenium containing amino acids in green onions, characterization of iodine containing species in commercially available seaweeds, studying the novel selenium volatiles in the green onions and localization of the high molecular weight selenium containing species in the mung bean sprouts. On the basis of the results, conclusions are drawn about their chemical association with biological molecules, both micro (volatile and non-volatile forms), macro molecules and their metabolites in the studied system. Another aspect of this dissertation is method development for the fast and sensitive determination of anthropogenic molecules such as phosphorus containing fire retardants/plasticizer so that their fate from the plastic material to the blood plasma can be studied. ACKNOWLEDGEMENTS The course of my dissertation work at University of Cincinnati (summer of 2002 - spring of 2006) has been nothing but a path to constant learning and growing, not only as a better researcher, but also as a better person. There are many people who I think contributed toward it to make it a very memorable ride. It is a pleasant task that I have now the opportunity to express my gratitude for all of them. The first person I would like to acknowledge is my husband, Arpit Das. He is the one without whom this journey had never been started and also never had come to an end. He strongly supported my decision to join graduate school in the first place and since then he has been nothing but a constant source of inspiration and enthusiasm for me. I learned from him ability to be patient during tough times. I want to thank him for believing in me and constantly stimulating the spark in me to help me accomplish my goals. The second person without whom, I think, I would have never been able to fulfill my dreams is my research advisor, Dr. Joseph A. Caruso. He is a greatest advisor, not only because of his science, but also he is one of the greatest people I have ever met. I acknowledge him for accepting me in his group and giving me opportunities to work on various projects that have become a part of my dissertation. He has always appreciated my contributions and his efforts have been very supportive and kept me challenged enough to get best out of the graduate school experience. Under his guidance, I learned to become an independent researcher and also developed a competitive portfolio, which will help me to become professional chemist. Not only that, he has a great impact on my attitude towards life. One of the most important things he has taught me is to believe in myself and to believe in best of others. He has always tried to instill great deal of confidence in me, which has helped me to make right decisions for my future. I will always try to emulate his working style and consider him as my role model for rest of my life. I would like to thank Dr. Patrick Limbach and Dr. Theresa Reineke for serving on my committee. I want to thank them for their insightful suggestions during presentations I have given. Not only that, I am fascinated by their accomplishments and achievements in their career and am constantly motivated by these. Another faculty member I would like to acknowledge is Dr. Thomas Ridgway for giving me opportunities to teach various day and evening classes. These assignments have helped me to improve my teaching as well as communication skills. I would also like to pay many thanks to many colleagues past and present. I want to thank Dr. Sasi Kannamkumarath, Dr. Rodolfo Wuilloud, Dr. Sandra Mounicou, Dr. Juris Meija for many discussions and giving me valuable advice on various research projects I have worked on and on which we have collaborated. I would like to thank Douglas Richardson, Kevin Kubachaka, Scott Afton, Jenny Ellis, Allison Krentz, Santha Ketaverapu and Heather Ternary for their constant support and also keeping very friendly environment in the lab which I think is one of the most important things to remain productive in any field. I would also like to thank University of Cincinnati - Department of Chemistry and the National Institute of Environmental Health Sciences for financial support of my work. Agilent Technologies is to be recognized for their continuing support with the instrumentation central to my dissertation studies. I cannot end this without paying my gratitude to my parents, Ashok and Abha Shah, my brothers Avanish and Ankit Shah and my grandfather, the Late Shri Madhusudan Das Shah. Without them and their support, I would have not been able to come so far in my life and also in my career. --- Monika Shah TABLE OF CONTENTS CHAPTER 1: INTRODUCTION…………………………………………………………4 1.1. Heteroatom containing molecules 1.2. Characterization of heteroatom containing molecules 1.2.1. ICP-MS for heteroatom determination 1.2.2. Coupling of chromatography and ICP-MS 1.2.2.1. LC-ICP-MS 1.2.2.2. GC-ICP-MS 1.2.3. Molecular mass spectrometry in speciation analysis 1.3 References CHAPTER 2: IDENTIFICATION AND CHARACTERIZATION OF SELENIUM SPECIES IN ENRICHED GREEN ONIONS USING HPLC-ICP-MS AND ESI-ITMS …………………………………………………………………..25 2.1. Abstract 2.2. Introduction 2.3. Experimental 2.3.1. Instrumentation 2.3.2. Reagents and Standards 2.3.3. Cultivation and preparation of selenium enriched green onions 2.3.4. Total Selenium determination 2.3.5. Chromatographic speciation analysis 2.3.6. ESI-ITMS analysis 2.4. Results and Discussions 2.4.1. Plant growth and total selenium accumulation 2.4.2. Molecular weight distribution of selenium in green onions 2.4.3. Speciation studies of selenium by HPLC-ICP-MS 2.4.4. Investigation of unknown selenium species by ESI-ITMS 2.5. Conclusions 2.6. References CHAPTER 3: CHARACTERIZATION OF IODINE CONTAINING SPECIES IN COMMERCIALLY AVAILABLE SEAWEEDS………………………46 3.1. Abstract 3.2. Introduction 3.3. Experimental 3.3.1. Instrumentation 3.3.2. Reagents and Standards 3.3.3. Procedures 3.3.3.1. Sample collection and preparation 3.3.3.2. Total iodine determination 1 3.3.2.3. Extraction of iodine from seaweed in various media 3.3.2.4 Extraction of high M.W. iodine species from Wakame 3.3.3.5. Extraction of polyphenol-bound iodine from Wakame 3.3.4 Chromatographic Conditions 3.4. Results and Discussion 3.4.1. Total iodine concentration in samples and extracts 3.4.2. Optimization of SEC-ICP-MS 3.4.3. Fractionation studies of iodine in seaweed extracts 3.4.3.1. SEC-ICP-MS of Wakame extracts 3.4.3.2. Study of the association of iodine to biological molecules 3.4.3.3. SEC-ICP-MS of Kombu extracts 3.4.4. IC-ICP-MS for speciation of inorganic iodine 3.4.5. RP-HPLC-ICP-MS for studying iodine species 3.5. Conclusions 3.6. References CHAPTER 4: DETERMINATION OF PHOSPHORIC ACID TRIESTERS IN HUMAN PLASMA USING SPME AND GC-ICP-MS…………………………………71 4.1. Abstract 4.2. Introduction 4.3. Experimental 4.3.1. Chemicals and Standards 4.3.2. Instrumentation 4.3.3. SPME fibers 4.3.4. Sample Preparation 4.4. Results and Discussion 4.4.1. Injection and gas chromatography conditions 4.4.2. ICP-MS conditions i. Forward Power and argon carrier gas flow rate ii. Optimization of ICP collision cell gas flow rate 4.4.3. Solid Phase micro-extraction i. Selection of SPME coating 4.4.4. Optimization of extraction procedure i. Influence of plasma matrix and deproteinization ii. Effect of Salt iii. Effect of pH iv. Effect of extraction temperature v. Effect of extraction and desorption time 4.5.
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