University of Windsor Scholarship at UWindsor Electronic Theses and Dissertations Theses, Dissertations, and Major Papers 3-10-2019 Oxidative Polymerization of Heterocyclic Aromatics Using Soybean Peroxidase for Treatment of Wastewater Neda Mashhadi University of Windsor Follow this and additional works at: https://scholar.uwindsor.ca/etd Recommended Citation Mashhadi, Neda, "Oxidative Polymerization of Heterocyclic Aromatics Using Soybean Peroxidase for Treatment of Wastewater" (2019). Electronic Theses and Dissertations. 7646. https://scholar.uwindsor.ca/etd/7646 This online database contains the full-text of PhD dissertations and Masters’ theses of University of Windsor students from 1954 forward. These documents are made available for personal study and research purposes only, in accordance with the Canadian Copyright Act and the Creative Commons license—CC BY-NC-ND (Attribution, Non-Commercial, No Derivative Works). 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Oxidative Polymerization of Heterocyclic Aromatics Using Soybean Peroxidase for Treatment of Wastewater By Neda Mashhadi A Dissertation Submitted to the Faculty of Graduate Studies through the Department of Chemistry and Biochemistry in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy at the University of Windsor Windsor, Ontario, Canada 2019 © 2019 Neda Mashhadi Oxidative Polymerization of Heterocyclic Aromatics Using Soybean Peroxidase for Treatment of Wastewater by Neda Mashhadi APPROVED BY: _____________________________ A. Bassi, External Examiner Western University _____________________________ N. Biswas Department of Civil & Environmental Engineering _____________________________ P. Vacratsis Department of Chemistry and Biochemistry _____________________________ J. Gauld Department of Chemistry and Biochemistry _____________________________ K. Taylor, Advisor Department of Chemistry and Biochemistry January 14, 2019 DECLARATION OF CO-AUTHORSHIP / PREVIOUS PUBLICATION I. Co-Authorship I hereby declare that this thesis incorporates material that is result of joint research, as follows: Section 4.4 of the thesis was co-authored with Paul Meister under the supervision of professor James Gauld. In all cases, the key ideas, data analysis, interpretation, and writing were performed by the author, and the co-authors contribution was primarily through the provision of computational calculations. The co-author, Paul Meister, contributed by conducting all computational calculations presented in this dissertation and Dr. Gauld provided feedback on the results. I am aware of the University of Windsor Senate Policy on Authorship and I certify that I have properly acknowledged the contribution of other researchers to my thesis, and have obtained written permission from each of the co-author(s) to include the above material(s) in my thesis. I certify that, with the above qualification, this thesis, and the research to which it refers, is the product of my own work. II. Previous Publication This thesis includes one original paper that has been previously published/submitted for publication in peer reviewed journals, as follows: iii Thesis Chapter Publication title/full citation Publication status* Chapter 4 N. Mashhadi, K. E. Taylor, N. Biswas, P. In Peer Review Meister, J. W. Gauld, “Oligomerization of 3- substituted quinolines by catalytic activity of soybean peroxidase as a wastewater treatment. Product formation and computational studies”, Chem. Eng. J. 2018. I certify that I have obtained a written permission from the copyright owner(s) to include the above published material(s) in my thesis. I certify that the above material describes work completed during my registration as a graduate student at the University of Windsor. III. General I declare that, to the best of my knowledge, my thesis does not infringe upon anyone’s copyright nor violate any proprietary rights and that any ideas, techniques, quotations, or any other material from the work of other people included in my thesis, published or otherwise, are fully acknowledged in accordance with the standard referencing practices. Furthermore, to the extent that I have included copyrighted material that surpasses the bounds of fair dealing within the meaning of the Canada Copyright Act, I certify that I have obtained a written permission from the copyright owner(s) to include such material(s) in my thesis. I declare that this is a true copy of my thesis, including any final revisions, as approved by my thesis committee and the Graduate Studies office, and that this thesis has not been submitted for a higher degree to any other University or Institution. iv ABSTRACT Along with other contaminants, heterocyclic aromatic compounds have found their way to our water sources in concentrations up to tens of µg/L. Contrary to their carbon counterparts, there is a gap of information regarding nitrogen, sulfur and oxygen heterocyclic aromatic contaminants. This information gap also extends to the feasibility of enzymatic treatment of such compounds. In this dissertation, a survey of various heterocyclic aromatic families has been conducted to explore the possibility of removing them from synthetic wastewater by the oxidative polymerization action of soybean peroxidase enzyme. The experiments were designed for ≥ 95% removal of the target compound as the most important parameters pH, enzyme activity, peroxide concentration and reaction time were optimized. In most cases, 85-90% removal efficiency was achieved under the studied conditions. In some cases, the cost of enzyme and peroxide used was considered in determining the optimal treatment conditions. Mass spectral (MS) analysis was conducted on the supernatant and precipitate of the reaction under optimal conditions for preliminary identification of reaction products. Plausible structures were assigned to related empirical formulae derived from MS analysis. Lastly, computational tools were applied to investigate the most favored polymerization positions on the substrates and were compared to structurally related non-substrates. Furthermore, using computational studies, ionization energies and standard reduction potentials of all substrates and some non-substrates were calculated and ranked to investigate a possible trend in SBP specificity based on these two factors. v DEDICATION This dissertation is dedicated to my parents: Mohsen Mashhadi & Monireh Yousefi And to my siblings: Mona, Ali & Zizi It does not matter how slowly you go as long as you do not stop. Confucius vi ACKNOWLEDGEMENTS I would like to thank my advisor, Dr. Keith E. Taylor, for his patience, motivation, enthusiasm, and immense knowledge. I have been extremely lucky to have his guidance, support and encouragement throughout these years. Similarly, profound gratitude goes to my co-adviser, Dr. Nihar Biswas, who has been a truly dedicated mentor and supporter to make this dissertation possible. For many valuable encouragements and discussions, I am indebted to Dr. J. K. Bewtra. I am also grateful to the rest of my committee: Dr. Vacratsis and Dr. Gauld for their time and suggestions. I extend my gratitude to Dr. Gauld and his Ph.D. student Paul Meister, for conducting the computational analysis presented in section 4.3 of this work and for their assistance and guidance provided throughout the collaboration. I would also like to thank Dr. Bassi for giving me the honor to be on my committee. I would also like to extend my gratitude to Mr. Bill Middleton for all his support and technical training provided during this work. I am very grateful to Dr. Auld for MS analysis and sparing the time to answer my never ending questions. To the best lab coordinators and technicians Una, Tina, Nedhal and Ronan, thank you for making these years so joyful. I wish to thank my best friend and soul sister, Dr. Laura Cordova, for all the support she has given me and for all the fun we have had in the past couple of years. A special thanks to my colleagues, Miao Chen, Dr. Samar Mazloum, Dr. Wei Feng, Andrew Schoof, Debjani Mukerjee, and Baturh Yarkwan for their help and support. vii My very sincere thanks to Dr. Elodie Heyer for her help editing the manuscript and her advice and support when I was writing up my dissertation. To the volunteer students Nathalie, Sherin, Vinay, Chris, Kiruthika and Nicola, your help is greatly appreciated and thanks for all those fun conversations. Finally, I express the profound gratitude to my beloved parents and my siblings for their love and continuous support, this would not have been possible without your encouraging words. viii TABLE OF CONTENTS DECLARATION OF CO-AUTHORSHIP / PREVIOUS PUBLICATION ........... iii ABSTRACT .............................................................................................................. v DEDICATION ......................................................................................................... vi ACKNOWLEDGEMENTS .................................................................................... vii LIST OF TABLES ................................................................................................