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University of Nevada, Reno Nanobiocatalytic Degradation Of University of Nevada, Reno Nanobiocatalytic Degradation of Acid Orange 7 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN Materials Science and Engineering by Jason Hastings Dr. Dev Chidambaram / Thesis Advisor December 2010 THE GRADUATE SCHOOL We recommend that the thesis prepared under our supervision by JASON THOMAS HASTINGS entitled Nanobiocatalytic Degradation Of Acid Orange 7 be accepted in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Dev Chidambaram, Ph.D., Advisor Manoranjan Misra, Ph.D., Committee Member Amy Childress, Ph.D., Graduate School Representative Marsha H. Read, Ph. D., Associate Dean, Graduate School December, 2010 i Abstract The catalytic properties of various metal nanoparticles have led to their use in environmental remediation applications. However, these remediation strategies are limited by their ability to deliver catalytic nanoparticles and a suitable electron donor to large treatment zones. Clostridium pasteurianum BC1 cells, loaded with bio‐Pd nanoparticles, were used to effectively catalyze the reductive degradation and removal of Acid Orange 7 (AO7), a model azo compound. Hydrogen produced fermentatively by the C. pasteurianum BC1 acted as the electron donor for the process. Pd‐free bacterial cultures or control experiments conducted with heat‐killed cells showed limited reduction of AO7. Experiments also showed that the in situ biological production of H2 by C. pasteurianum BC1 was essential for the degradation of AO7, which suggests a novel process where the in situ microbial production of hydrogen is directly coupled to the catalytic bio‐Pd mediated reduction of AO7. The differences in initial degradation rate for experiments conducted using catalyst concentrations of 1ppm Pd and 5ppm Pd and an azo dye concentration of 100ppm AO7 was 0.39hr‐1 and 1.94hr‐1 respectively, demonstrating the importance of higher concentrations of active Pd(0). The degradation of AO7 was quick as demonstrated by complete reductive degradation of 50ppm AO7 in 2 hours in experiments conducted using a catalyst concentration of 5ppm Pd. Dye degradation products were analyzed via Gas Chromatograph‐Mass Spectrometer (GCMS), High Performance Liquid Chromatography (HPLC), UltraViolet‐Visible spectrophotometer (UV‐Vis) and Matrix‐Assisted Laser Desorption/Ionization (MALDI) spectrometry. The presence of 1‐amino 2‐naphthol, one of the hypothesized degradation products, was confirmed using mass spectrometry. ii Acknowledgements First, I would like to express my overwhelming gratitude to my advisor Dr. Dev Chidambaram for his leadership and unwavering positive attitude to the completion of this thesis. I am extremely thankful to have such a knowledgeable and available advisor and role model during this process. I am very thankful for Dr. Dev accepting me as a student before he was planning to accept any students. I would like to thank Dr. Amy Childress and Dr. Manoranjan Misra for having accepted to serve on my thesis examination committee and also for their valuable time and patience. I would also like to acknowledge financial support from the Office of the Vice President for Research and the Chemical and Materials Engineering Department at UNR, which was provided to Dr. Chidambaram in the form of his start‐up package. Further, I acknowledge the UNR Graduate School for providing me with an ACCESS graduate student fellowship for the Fall 2010 semester. I would like to thank Narasimharao Kondamudi for his continual advice and services when it came to characterizations of my products and Dr. Manoranjan Misra for providing me with access to the equipment in his laboratory. I thank York Smith for allowing me to bother him on a daily basis for chemicals or supplies at start up. I thank Dr. Mojtaba Ahmadian‐Tehrani for training me on the usage of the SEM. I thank Rebekah Woosley and the Proteomics Center for allowing me to run tests in their facilities. Finally, I would like to thank my fellow graduate students on the fourth floor for their continual humor, advise and availability to converse with. Now I get to the good stuff. I thank Jesse Ruppert and Dharshini Balasubramaniyan for continual support in and out of the laboratory. I am greatly indebted to Dr. Liz Charan iii for her expertise in microbiology and microbial lab techniques. I would like to thank my family for their remarkable support in my decision to continue in higher education. I would like to blame my love, Lisa Loe, for delaying my thesis writing. The support from all of my friends and family makes this process fairly painless. I also would like to thank whoever decided it was ok to make an acknowledgements section because I like that I can write whatever I want. iv Table of Contents Section Page Number Abstract i Acknowledgements ii Table of Contents iv List of Table vi List of Figures vii 1. Introduction 1 1.1 Environmental Contamination 1 1.2 Azo Compounds 1 1.3 Treatment Methods for Azo Dyes 6 2. Material and Methods 14 2.1 Microbial Culture and Growth Medium 14 2.2 Microbial Synthesis of Pd Nanoparticles 15 2.3 Degradation of Acid Orange 7 16 2.4 Analytical Techniques 17 2.4.1 UV‐visible Spectroscopy 17 2.4.2 Gas Chromatography Mass Spectrometry 18 2.4.3 High Performance Liquid Chromatography 19 2.4.4 Matrix‐Assisted Laser Desorption/Ionization 20 3. Results and Discussion 22 3.1 Proof of Catalyst Formation 22 3.2 Rate of Reaction 28 3.3 Biocatalytic Reduction of Azo Dyes Using Palladium 29 3.4 Degradation Products 32 3.4.1 UV‐Vis 35 3.4.2 Gas Chromatogram 37 3.4.3 HPLC 38 3.4.4 MALDI 40 v 3.5 Effectiveness of Nanobiocatalytic reduction of Azo Dyes 42 4. Conclusions and Future Directions 49 4.1 Implication of Research 50 4.2 Future Directions 51 References 53 vi List of Tables Table Name Page Number 1.1 Classes of dyes and their structures 2 1.2 Comparison of microbial remediation of dyes 8 2.1 Composition of the growth medium for C. pasteurianum BC1 14 2.2 Matrix of palladium‐AO7 experiments 16 3.1 Degradation of 1ppm, 3ppm and 5ppm Pd at 50ppm and 30 100ppm AO7 3.2 Viability tests performed on C. pasuerianum with 3ppm Pd 31 3.3 Table comparing rates and amounts of dye degradation using 44 a multitude of bacteria vii List of Figures Figure Name Page Number 1.1a Chemical dyes being released into the environment in China 6 1.1b China’s yellow river turned red with additions of dye 6 2.1 Anaerobic glove chamber 15 2.2 UV‐1800 spectrophotometer from Shimadzu 17 2.3 Shimadzu GC‐MS QP 2010 19 2.4 Shimadzu LCsolution‐20‐AB 20 3.1 Increasing concentrations of Pd 22 3.2 SEM image of Pd(0) on C.pastuerianum 23 3.3 Proof of experiment for degradation of AO7 with 3ppm Pd and 24 50ppm AO7 3.4 Varying concentrations of AO7 in bacterial growth 25 3.5a Degradation of AO7 (50 and 100ppm) at 1 ppm Pd 27 3.5b Degradation of AO7 (50 and 100ppm) at 3 ppm Pd 27 3.5c Degradation of AO7 (50 and 100ppm) at 5 ppm Pd 27 3.6 The exponential degradation of AO7 and a model generated 29 using a 1st order reaction rate 3.7 Hypothesized breakdown of AO7 32 3.8 Electrochemical pathways for the degradation of AO734 3.9 UV‐Vis spectrum of cultures containing 5ppm Pd and 50ppm 35 AO7 3.10 Comparison of concentrated degradation products with stock 36 dye solution on UV‐Vis 3.11 Mass Spectrometer showing 2‐naphthol as possible 37 degradation product 3.12 The chromatogram of the azo dye degradation products37 3.13 HPLC of the degradation products as compared to spent media 38 and sulfanilic acid standard 3.14 Magnified HPLC of dye degradation products compared to 39 spent media and sulfanilic acid 3.15a MALDI of the matrix background on which the samples were 40 prepared 3.15b MALDI of dye degradation products 40 3.16 MALDI of the spent media of C. pastuerianum BC1 after 19hrs 42 of growth 1 Chapter 1‐Introduction Water supplies (both surface and sub‐surface) at thousands of sites across our country remain contaminated at this time [1]. The Environmental Management (EM) division of the United States Department of Energy (US DOE) reports that only 17 of the 50 states in America do not have remediation sites [2]. Out of the 33 states that have remediation sites, there are 14 host states that are currently under remediation. Within the 14 states with active sites, there are a combined 81 sites that account for a total budget of more than $5.27 Billion [2]. The estimates above do not include the sites or the costs for remediation of radioactive contaminants. Contaminants can be broadly classified into organic, inorganic and radioactive. Organic contamination is the main topic of this study. Organic contamination results from the production, usage and recycling of chemicals with organic structures. Three major classes of organic contaminants are chlorinated organics, pesticides and azo compounds. Azo compounds form the contaminant of interest in this study. Azo Compounds: Azo compounds, the chemicals of interest in this study, are widely used in the textile industry, and account for a little more than half of the world’s production of colorants [3]. Azo compounds may be classified into seven distinct categories: Acid, Basic, Direct, Disperse, Reactive, Sulfur and Vat dyes as shown in Table 1.1. 2 Table 1.1: Classes of azo dyes with characteristic information and their structures. Fixation Dye Class (%)/Fibers Structure Apllied OH 80‐90/Wool Acid and Nylon N N 1-Phenylazo-naphthalen-2-ol H3C N+ S N N 97‐98/Acrylic Basic and some Polyesters N CH3 3-Methyl-2-(1-methyl-2-phenyl-1H- indol-3-ylazo)-thiazol-3-ium 80‐ OH O 92/Polyester, Disperse Acetate and other N N NH synthetics N-[4-(2-Hydroxy-5-methyl-phenylazo)-phenyl]-acetamide SSHO3 CH3 60‐70/Cotton N Sulfur and other H3CO N cellulosics N HO N C6H5 Sulphur Orange 2 3 Table 1.1: (Cont.) HO N N H N 2 SO3Na N 70‐ 95/Cotton, Direct Rayon and O3SNa other cellulosics NH2 H2N N N Direct Black 38 O NaO S O NH N N OH H3C O 60‐90/ Cotton, other Reactive cellulosics and Wool O S O O O S NaO O Reactive Orange 16 4 Table 1.1: (Cont.) O NH O O HN O 80‐95/Cotton Vat other cellulosics N O N O N H H N O O Vat Yellow 10 Acid dyes are water‐soluble anionic compounds that generally have a dye fixation of 80‐90% onto wool or nylon.
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