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In Situ Arsenic Speciation Using Surface-Enhanced Raman Spectroscopy Mingwei Yang Florida International University, [email protected]

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In Situ Arsenic Speciation Using Surface-Enhanced Raman Spectroscopy Mingwei Yang Florida International University, Minyang@Fiu.Edu Florida International University FIU Digital Commons FIU Electronic Theses and Dissertations University Graduate School 6-30-2017 In Situ Arsenic Speciation using Surface-enhanced Raman Spectroscopy Mingwei Yang Florida International University, [email protected] DOI: 10.25148/etd.FIDC001951 Follow this and additional works at: https://digitalcommons.fiu.edu/etd Part of the Analytical Chemistry Commons Recommended Citation Yang, Mingwei, "In Situ Arsenic Speciation using Surface-enhanced Raman Spectroscopy" (2017). FIU Electronic Theses and Dissertations. 3387. https://digitalcommons.fiu.edu/etd/3387 This work is brought to you for free and open access by the University Graduate School at FIU Digital Commons. It has been accepted for inclusion in FIU Electronic Theses and Dissertations by an authorized administrator of FIU Digital Commons. For more information, please contact [email protected]. FLORIDA INTERNATIONAL UNIVERSITY Miami, Florida IN SITU ARSENIC SPECIATION USING SURFACE-ENHANCED RAMAN SPECTROSCOPY A dissertation submitted in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY in CHEMISTRY by Mingwei Yang 2017 To: Dean Michael R. Heithaus choose the name of dean of your college/school College of Arts, Sciences and Education choose the name of your college/school This dissertation, written by Mingwei Yang, and entitled In situ Arsenic Speciation using Surface-enhanced Raman Spectroscopy, having been approved in respect to style and intellectual content, is referred to you for judgment. We have read this dissertation and recommend that it be approved. _______________________________________ Yi Xiao _______________________________________ Rudolf Jaffe _______________________________________ Bruce McCord _______________________________________ Anthony McGoron _______________________________________ Yong Cai, Major Professor Date of Defense: June 30 2017 The dissertation of Mingwei Yang is approved. _______________________________________ choose the name of dean of your college/school Dean Michael R. Heithaus choose the name of your college/school College of Arts, Sciences and Education _______________________________________ Andrés G. Gil Vice President for Research and Economic Development and Dean of the University Graduate School Florida International University, 2017 ii ACKNOWLEDGMENTS I would like to express my sincere appreciation to Dr Cai−my major Professor, for providing the opportunity to work in his research group and leading me into the right pathway when I was on the wrong tracks many times. Without his patient guidance, financial support and insightful understanding of chemistry, I would not have completed this work. I am also grateful to the rest of my committee members, Dr Yi Xiao, Dr Rudolf Jaffe, Dr Bruce McCord, and Dr Anthony McGoron for their support, critical comments, and suggestions during all these meetings. Special thanks to Dr Anthony McGoron, Dr Wei-chiang Lin and Dr Yun Qian in Biomedical Engineering Department for allowing me to work on the Raman instrument and for financial support to maintain the equipment. This work would have been impossible without Raman spectroscopy. Special thanks to Dr Guangliang Liu (our lab manager and assistant director), Dr Yuzhen Sun (Jianghan University, China) and Dr Changjun Fan (a current postdoc in our research group) for their numerous time input and critical comments and beneficial suggestions. I am grateful to Dr Shannon Matulis and Dr Lawrence Boise from Emory University for their generous providing cell pellets, my research will be less significant without these important samples. I also would like to thank the following persons, Dr Mebel Alexander for beneficial suggestions in theoretical computation, Dr Abuzer Kabir for the discussion of silver nanofilm fabrication, REU student Kelli Sylvers for the help with coffee ring experiments, Dr Vinay Bhardwaj for his help in the use of Raman spectroscopy, Dr iii Daniel Belisario-Lara for his help in Gaussian density functional theory training, Ya-Li Hsu for his help in NMR analysis, Dr Cassian D’Cunha from FIU HPC faculty for the technical support and FIU mass facility for their help in MS analysis. Also I like to thank all members in Dr Cai’s lab for offering a nice academic and pleasant working atmosphere from past to the present, including, Dr Shujuan Sun, Dr Cheng Zhang, Dr Na Zhu, Szabina Stice, Dionne Dickson, Ping Jiang, Wenbin Cui, Yuping Xiang, et al. Lastly, I would like to express my deepest appreciation and gratefulness to all my family members and my fiancée Miss Yan Zhang in China, without their constant and unconditional supports, encouragements and love; this work will be pale and less meaningful. iv ABSTRACT OF THE DISSERTATION IN SITU ARSENIC SPECIATION USING SURFACE-ENHANCED RAMAN SPECTROSCOPY by Mingwei Yang Florida International University, 2017 Miami, Florida Professor Yong Cai, Major Professor Arsenic (As) undergoes extensive metabolism in biological systems involving numerous metabolites with varying toxicities. It is important to obtain reliable information on arsenic speciation for understanding toxicity and relevant modes of action. Currently, popular arsenic speciation techniques, such as chromatographic/electrophoretic separation following extraction of biological samples, may induce the alternation of arsenic species during sample preparation. The present study was aimed to develop novel arsenic speciation methods for biological matrices using surface-enhanced Raman spectroscopy (SERS), which, as a rapid and non-destructive photon scattering technique. The use of silver nanoparticles with different surface coating molecules as SERS substrates permits the measurement of four common arsenicals, including arsenite (AsIII), arsenate (AsV), monomethylarsonic acid (MMAV) and dimethylarsinic acid (DMAV). This speciation was successfully carried out using positively charged nanoparticles, and simultaneous detection of arsenicals was achieved. Secondly, arsenic speciation using coffee ring effect-based separation and SERS detection was explored on a silver nanofilm (AgNF), which was prepared by close packing of silver nanoparticles (AgNPs) on a glass v substrate surface. Although arsenic separation using the conventional coffee ring effect is difficult because of the limited migration distance, a halo coffee ring was successfully developed through addition of surfactants, and was shown to be capable of arsenicals separation. The surfactants introduced in the sample solution reduce the surface tension of the droplet and generate strong capillary action. Consequently, solvent in the droplet migrated into the peripheral regions and the solvated arsenicals to migrated varying distances due to their differential affinity to AgNF, resulting in a separation of arsenicals in the peripheral region of the coffee ring. Finaly, a method combining experimental Raman spectra measurements and theoretical Raman spectra simulations was developed and employed to obtain Raman spectra of important and emerging arsenic metabolites. These arsenicals include monomethylarsonous acid (MMAIII), dimethylarsinous acid (DMAIII), dimethylmonothioarinic acid (DMMTAV), dimethyldithioarsinic acid (DMDTAV), S-(Dimethylarsenic) cysteine (DMAIIICys) and dimethylarsinous glutathione (DMAIIIGS). The fingerprint vibrational frequencies obtained here for various arsenicals, some of which have not reported previously, provide valuable information for future SERS detection of arsenicals. vi TABLE OF CONTENTS CHAPTER PAGE Chapter 1 Introduction, Problem Statement, Objectives and Hypotheses ........................ 1 1.1 Relationship between arsenic and human health .............................................. 2 1.2 Cellular stress from arsenic metabolism in human ........................................... 8 1.3 Current analytical techniques for arsenic speciation ...................................... 11 1.4 Surface-enhanced Raman spectroscopy for arsenic detection ........................ 14 1.5 Problem Statement .......................................................................................... 18 1.6 Hypotheses...................................................................................................... 19 1.7 Objectives ....................................................................................................... 21 Chapter 2 Potential Application of SERS for Arsenic Speciation in Biological Matrices............................................................................................................................. 23 2.1 Abstract ........................................................................................................... 24 2.2 Introduction .................................................................................................... 25 2.3 Material and Methods ..................................................................................... 30 2.4 Experimental Procedures ................................................................................ 32 2.5 Results and Discussions.................................................................................. 37 2.6 Conclusions .................................................................................................... 51 Chapter 3 Employing Coffee Ring Effect on Silver Nanofilm for Arsenic Speciation Study ................................................................................................................................. 53 3.1 Abstract ..........................................................................................................
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