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Pdf Version of This Thesis FOLLOWING THE HEADSPACE PRODUCTION OF DIMETHYL TELLURIDE PRODUCED BY PSEUDOMONAS FLUORESCENS AMENDED WITH SODIUM TELLURATE OR SODIUM TELLURITE _______________ A Thesis Presented to The Faculty of the Department of Chemistry Sam Houston State University _______________ In Partial Fulfillment Of the Requirements for the Degree of Master of Science _______________ by Osman Mehmet Akpolat August, 1999 FOLLOWING THE HEADSPACE PRODUCTION OF DIMETHYL TELLURIDE PRODUCED BY PSEUDOMONAS FLUORESCENS AMENDED WITH SODIUM TELLURATE OR SODIUM TELLURITE by Osman Mehmet Akpolat ________________________ Approved: ________________________ Thomas G. Chasteen ________________________ Mary F. Plishker ________________________ Mike P. McCann Approved: ________________________ Christopher Baldwin, Dean College of Arts and Sciences ABSTRACT Akpolat, Osman M. , Following the Headspace Production of Dimethyl Telluride Produced by Pseudomonas fluorescens Amended with Sodium Tellurate or Sodium Tellurite. Master of Science (Chemistry), August, 1999, Sam Houston State University, Huntsville, Texas, 84pp. PURPOSE The purpose of this study was to determine whether a facultative anaerobe, Pseudomonas fluorescens K27, would produce volatile organometalloids when amended with sodium tellurate or sodium tellurite. METHODS Batch bacterial bioreactor experiments were undertaken in order to observe the changes in the headspace of a growth media solution inoculated with Pseudomonas fluorescens and amended with tellurium salts. Gas samples were taken from the bioreactor every hour and were analyzed by gas chromatography to determine the composition of the headspace. Liquid samples were analyzed by a spectrometer to determine their optical densities which were used as an indicator of cell growth. Different concentrations of tellurate and tellurite amendments were tested. As a further verification of the identity of the peak appearing around 7.3 minutes in the gas chromatography, headspace above a tellurate amended culture was analyzed by gas chromatography / mass spectrometry. iii Filtration of the bioreactorÕs solution at the end of the experiments was carried out to determine the amounts of Te present in the bioreactor when cultures of P. fluorescens had reached stationary phase. Both solid particles of Te and Te dissolved in solution were sampled. These filtration samples were analyzed by atomic absorption spectrometry. In addition, the synthesis of dimethyl tellurone, a Te analog of the well- known sulfones, was tried by oxidation of dimethyl telluride. For this purpose two approaches were utilized; a microwave-induced oxidation and a conventional wet oxidation of dimethyl telluride were attempted. FINDINGS The production of dimethyl telluride was observed in the batch bioreactor experiments using Pseudomonas fluorescens. Analyzed headspace gases above the solutions amended with tellurium salts gave increasing concentrations of dimethyl telluride as the cell population increased. The chromatographic peak for dimethyl telluride was identified by using standard gas chromatography and gas chromatography / mass spectrometry. The retention time in our chromatographic temperature program for the dimethyl telluride peak was reported and fragmentation pattern for dimethyl telluride was shown. The concentration of Te left in the solution after the experiments were over was calculated by filtering out the solid and dissolved Te from the solution and measuring the concentration by AAS. The % conversion to gas and % Te that iv had been biomethylated were calculated. For K27 cultures with either 0.2 or 2.0 mM mixed amendments grown into stationary phase in large volume 2.7 L bioreactor experiments, approximately 80% of the added Te was converted to compounds that were volatilized either into culture headspace or lost in subsequent sample handling to determine tellurium in solid or liquid phase. Two different pathways to oxidation of dimethyl telluride were followed in an attempt to synthesize dimethyl tellurone. No product was obtained when microwave-induced oxidation technique was used as measured by thin layer chromatography. The product obtained from classical oxidation of dimethyl telluride was sent for elemental analysis. Percent compositions of possible products were calculated and the results from elemental analysis were compared with the calculated percentages. Apparently dimethyl tellurone was not successfully synthesized. Based on elemental analysis, the most likely product isolated was either CH3-Te(OH)2-OCH3 or CH3-Te(O)(OH)-OCH3. This product was not soluble in any common solvent nor did it melt below 300°C. v ACKNOWLEDGMENTS My sincere thanks go to Dr. Thomas Chasteen, who was not only my graduate advisor through out my studies at Sam, but was also a tutor for me over here in the United States. He has always been there for me and made this long journey seem like a day. I can never forget his enthusiastic approach to research, passion for science and his unmistakable choice of red as his color for everything. His lab full of AppleÕs gave me another chance, after five years, to work with one of the best computer designs to date. Although I must say that they were comparably slow to computers that I own, I will never forget the joy of networking and maintaining the lab Macs. Dr. Verena Van Fleet-Stalder, one of the nicest people I have ever met, I would like to thank you for all your guidance and help in the first year of my study. I wish the best of everything for you. I also like to thank to Lynn Eriksen. This was a hard and long road, but without him it would have been even harder. The twins, Eser Becer and Deger Becer. You guys were like brothers I never had. Without your support and help I couldnÕt have done half of this. Frightening as it sounds, I believe we will always be together. Finally I would like to thank my parents for their love, support, and thrust in me. They should take all the credit for bringing me up here, to this level. I dedicate this thesis to my mom and dad. This is the least I can do to show you how much I love you both. vi TABLE OF CONTENTS ABSTRACT ..........................................................................................................iii ACKNOWLEDGEMENTS.....................................................................................vi TABLE OF CONTENTS ......................................................................................vii LIST OF TABLES ............................................................................................... viii LIST OF FIGURES...............................................................................................ix CHAPTERS I INTRODUCTION ......................................................................... 1 II EXPERIMENTAL ....................................................................... 14 Part 1. Instrumentation ........................................................... 16 Part 2. Bioreactor Experiments............................................... 19 Part 3. Procedures ................................................................. 23 III DATA AND RESULTS ............................................................... 29 IV DISCUSSION AND CONCLUSIONS ......................................... 72 BIBLIOGRAPHY................................................................................................. 78 APPENDIX ......................................................................................................... 83 Chemical Abstract Service Registry Numbers ......................................... 83 VITA ................................................................................................................... 84 vii LIST OF TABLES Table I Classification of elements according to their toxicity................................. 1 Table II Calibration data from direct injection of 1 mL dimethyl telluride solutions of different concentrations. ........................................................................... 30 Table III Te calibration data from the atomic absorption spectroscopy experiments.................................................................................................. 62 Table IV Tellurium found after AA analysis......................................................... 67 Table V Te left in the system after the bacteria reach stationary phase. ............ 67 Table VI Summary of total initial and final Te concentrations in the bioreactor. 68 Table VII Elemental analysis of the oxidation product. ....................................... 70 Table VIII Elemental percentages calculated for some oxidized dimethy telluride compounds................................................................................................... 71 viii LIST OF FIGURES Figure 1. Schematic of biomethylation process. ................................................... 3 Figure 2. Mechanism of biomethylation proposed by Challenger in 1945. ........... 6 Figure 3. Expanded mechanism of biomethylation proposed by Reamer and Zoller. ............................................................................................................. 7 Figure 4. Mechanism of biomethylation of selenium proposed by Doran. ............ 8 Figure 5. Schematic representation of the SCD reaction cell. ............................ 18 Figure 6. Side view of the New Brunswick Bioflow III bioreactor ........................ 21 Figure 7. Top view of of the New Brunswick Bioflow III bioreactor ..................... 22 Figure 8. Schematic representation
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