Chemistry Commons^™

Fabrication And Optical Properties Of Noble Metal Nanostructures, Mark Kinnan

All Dissertations

Experimental and theoretical results are presented in Chapters 2, 3, and 4 on the effects of dielectric medium, particle size, and interparticle distance, respectively, on plasmon coupling in two-dimensional arrays of silver nanoparticles. The arrays were fabricated via the self-assembly of single crystal particles from c.a. 46 nm to 287 nm on PVP-modified glass substrates. Spin-coated poly(methylmethacrylate) layers were used to immobilize the particles and prevent their surface aggregation. Varying the thickness of the PMMA layer made it possible to change the average dielectric medium between the particles. UV-Visible spectra of different arrays were compared to the corresponding electron microscope …

Preparation Of Carboxylic Acid Functionalized Glycopolymers Through Raft And Post-Polymerization Modification For Biomedical Application, Husnu Alp Alidedeoglu

Dissertations

The primary theme of this dissertation involves the synthesis of well-defined primary amine functionalized polymers, subsequent modification of the polymers to produce novel carboxylic acid functionalized glycopolymers and surface polymerization of these systems utilizing controlled polymerization techniques. Additionally, the synthesis of new water-based allylic copolymer latexes is described. Carbohydrates are natural polymers which possess unlimited structural variations. They carry a huge density of information, and play major roles in recognition events and complex biological operations. For example, hyaluronic acid (HA), an anionic glycosaminoglycan, provides lubricating and cushioning properties in the extracellular matrix and has been found to be involved in …

Photopolymerization And Characterization Of Thiol-Enes And Thiourethanes, Qin Li

Dissertations

Compared to conventional acrylic monomer systems, thiol-ene photopolymerization, an efficient click process leading to the formation of dense and uniform molecular networks, has several distinct advantages including relative insensitivity to oxygen inhibition, high monomer conversion and low shrinkage. Although there has been a revival of interest in thiol-enes in the past 6 years, the structure-property relationship of these networks has not been explored in detail. For future applications, thiol-enes with higher shelf-life stability and glass transition temperatures need to be used. Sulfur containing urethanes, thiourethanes and dithiourethanes are a class of widely used materials due to their distinct properties such …

The Relationship Betweeen Dynamic And Chemical Factors On The Morphology In Aot-Water-Polymer Systems, Jolanta Elzbieta Marszalek

Dissertations

Photopolymerization of reverse microemulsion demonstrates strong influences from dynamical and chemical factors on morphology of formed polymer systems. Upon polymerization the clear microemulsion with nanoscale structures transforms into opaque films with larger aggregates that scatter light. Studied here were microemulsions based on acrylate and on thiol-ene chemistries. The difference in the two reaction mechanisms results in the phase separation occurring at different stages of the material formation. Consequently, the morphology of the material demonstrates distinct dissimilarities in the two systems. In addition, the chemical structure of the monomers promotes these morphological differences. When the microemulsion is composed of acrylate and …

The Effect Of The Amide Substituent On The Biodistribution And Tolerance Of Lanthanide(Iii) Dota-Tetraamide Derivatives, Mark Woods, Peter Caravan, Carlos F.G.C. Geraldes, Matthew T. Greenfield, Garry Kiefer, Mai Lin, Kenneth Mcmillan, M. Isabel M. Prata, Ana C. Santos, Xiankai Sun, Jufeng Wang, Shanrong Zhang, Piyu Zhao, A. Dean Sherry

Chemistry Faculty Publications and Presentations

Objectives—Recent advances in the design of MRI contrast agents have rendered the lanthanide complexes of DOTA-tetraamide ligands of considerable interest, both as responsive MR agents and paramagnetic chemical exchange saturation transfer agents. The potential utility of these complexes for in vivo applications is contingent upon them being well tolerated by the body. The purpose of this study was to examine how the nature of the amide substituent, and in particular its charge, affected the fate of these chelates postinjection.

Materials and Methods—Complexes of 6 DOTA-tetraamide ligands were prepared in which the nature of the amide substituent was systematically …

Evaluation Of Electron Donor Materials Used To Create Subsurface Permeable Reactive Barriers For Enhanced Reductive Dechlorination Of Chlorinated Ethenes, Elizabeth S. Semkiw

Dissertations

Chlorinated ethenes (CEs) are widespread ground water contaminants, apparently due to their extensive migration from numerous contamination source points. In this study, a long-term field investigation and aquifer microcosm experiments were combined to evaluate the effectiveness of electron donor materials used to create and maintain subsurface permeable reactive barriers (PRBs) for the enhanced in-situ biodegradation of CEs. The laboratory component includes the first side-by-side comparison of electron donor materials dairy whey, lactate syrup, and Hydrogen Release Compound® (HRC), in which dechlorination rates, fermentation product distributions, and H₂ production were monitored as measures of substrate efficiency. Field study allowed the …

Switch On And Switch Off Nanosensors For The Detection Of Nerve Gas Agents, Shankar Varaganti

Dissertations

The central hypothesis of this research is the development of novel nanosensors by a bottom-up approach for the detection of nerve gas agents. The nanosensor assembly consists of four main parts; nanoparticles (N), Monomer (M), Complex (C) and Receptor (R). Two novel Ru (II)-bipyridyl and zinc complexes with tryptophan receptors either in 4,4' or 5,5' position of the bipyridyl ring have been synthesized and characterized by using ¹H NMR, ¹³C NMR, mass spectrometry and absorption spectroscopy. Silica nanoparticles or quantum dots are used as a platform for the nanosensors. Highly conjugated stilbene type compounds are used as monomers. …

Fluorescent Conjugated Polymer Dots For Single Molecule Imaging And Sensing Applications, Changfeng Wu

All Dissertations

While single molecule imaging and sensing hold the promise of providing unprecedented detail about cellular processes, many advanced applications are limited by the lack of appropriate fluorescence probes. In many cases, currently available fluorescent labels are not sufficiently bright and photostable to overcome the background associated with various autofluorescence and scattering processes. This dissertation describes research efforts focused on the development of a novel class of fluorescent nanoparticles called conjugated polymers dots (CPdots) for single molecule fluorescence detection. The CPdots contain highly fluorescent π-conjugated polymers that have been refined over the last decades as the active material in polymer light-emitting …

Synthesis, Characterization, And Application Of Ag Nanostructures, Stephen Hudson

All Dissertations

Noble metal nanoparticles (NPs) have been used for many centuries; however their properties were not truly scrutinized until Michael Farady's investigations in the 1850's. Advances in the field of nanotechnology over the last three decades have enabled insights into the properties of materials as their dimensions are reduced to the nanoscale. The repercussions of these insights are seen in many modern applications.
In this dissertation, properties of novel nanostructures based on Ag NPs are presented and discussed. The exceptional optical properties of Ag NPs stem from the collective oscillations of the conduction electrons known as plasmon resonances. The excitation of …

Novel Lactide Derived Polymers; Synthesis, Properties And Applications, Dahlia Haynes

All Dissertations

This dissertation primarily encompasses the synthesis, characterization, properties and discussion of applications for lactide derived polymers. The methodology focuses on altering polylactide's (PLA's) dynamic and physical properties increasing its broad market utility in both traditional and non-traditional applications. The fundamentals of this work include understanding and enhancing the polymer chemistry and materials related processes through the use of copolymerization, fluorination, composite chemistry and materials science.
The first chapter discusses the important of this research with emphasis on current world issues that focuses on the feasibility of renewable resources and sustainability implementation. Modification of renewable resource materials like lactic acid is …

Analysis Of Chemical Bonding In Clusters By Means Of The Adaptive Natural Density Partitioning, Dmitry Yu Zubarev

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Models of chemical bonding are essential for contemporary chemistry. Even the explosive development of the computational resources including, both hardware and software, cannot eliminate necessity of compact, intuitive, and efficient methods of representing chemically relevant information. The Lewis model of chemical bonding, which was proposed eleven years before the formulation of quantum theory and preserves its pivotal role in chemical education and research for more than ninety years, is a vivid example of such a tool. As chemistry shifts to the nanoscale, it is becoming obvious that a certain shift of the paradigms of chemical bonding is inescapable. For example, …

Pulse-Laser Infrared Photothermal Spectrometry Of Condensed-Phase Aerosols Based On Photothermal Deflection Spectroscopy, Oluwatosin Olubunmi Dada

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The research reported in this dissertation is aimed at development of photothermal deflection detector that is consistent with constraints imposed by aerosols sampling and analysis. The main objectives of this project are: 1) the design and evaluation of initial apparatus prototypes and 2) a test of the prototype apparatus with surrogate substances using conventional mid-infrared gas lasers.

Experimental evaluation of reduced size photothermal apparatus is first performed with gaseous samples. Analysis of trichlorofluoromethane (CFC-11) and ethanol vapors is performed with both conventional large apparatus and the prototype small apparatus. Comparison studies in terms of photothermal signal from both apparatuses are …

Synthetic Complexes Of Relevance To Ni(Ii)-Containing Enzymes, Katarzyna Rudzka

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The work outlined herein presents an investigation of synthetic model complexes of relevance to the active sites of Ni(II)-containing enzymes, particularly urease, glyoxalase I, and acireductone dioxygenase. The research focuses on studying the structural and reactivity features of nickel complexes with biologically relevant substrates. The anion of acetohydroxamic acid is a well-known inhibitor of urease enzymes, including those isolated from Klebsiella aerogenes and Bacillus pasteurii. A precursor to the acetohydroxamate coordination in ureases is proposed to be an interaction between Ni(II) and acetohydroxamic acid. By using a novel supporting chelate ligand capable of secondary hydrogen bonding interactions a novel …

Sources And Source Processes Of Organic Nitrogen Aerosols In The Atmosphere, Mark E. Erupe

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The research in this dissertation explored the sources and chemistry of organic nitrogen aerosols in the atmosphere. Two approaches were employed: field measurements and laboratory experiments. In order to characterize atmospheric aerosol, two ambient studies were conducted in Cache Valley in Northern Utah during strong winter inversions of 2004 and 2005. The economy of this region is heavily dependent on agriculture. There is also a fast growing urban population. Urban and agricultural emissions, aided by the valley geography and meteorology, led to high concentrations of fine particles that often exceeded the national ambient air quality standards. Aerosol composition was dominated …

The Performance Of Maize Crop During Acid Amelioration With Organic Residues In Soils Of Mtwara, Tanzania, Ae Majule, Jo Omollo

Tanzania Journal of Science

This study evaluated acid ameliorative potential and their effects on maize growth of four organic residues namely wild spikenard, cordia, cowpea and pigeon peas through incubations with or without sulphur. This was done in order to recommend potential organic residue source that could ameliorate soil acidity associated with sulphur dusting. Increased levels of sulphur in the soils reduced the growth and dry matter yields of maize due to intense acidification while maize growth and dry matter yields in soils which organic residues were incorporated was enhanced. Enhancement in maize performance may be a result of reduced soil acidity due to …

Geochemistry And Nd - Isotopic Composition Of High Silica Rhyolites In The Neoarchaean Musoma-Mara Greenstone Belt, Northern Tanzania: Evidence For The Presence Of Older Continental Crust, S Manya

Tanzania Journal of Science

The high silica rhyolites of the Kibasuka Hill, although volumetrically minor, constitute a part of the greenstone sequence in the northern Musoma-Mara Greenstone Belt (MMGB). They are characterized by high silica contents (63.38 – 81.65 wt %), very low CaO (! 0.05 wt %), variable to unusually high K2O (2.24 – 13.43 wt %) most likely attributed to strong sericite alteration, and their major element composition are similar to those of melts derived from partial melting of metapelites. The samples have very low concentration of the transition elements, Sr (3.13 – 48.4 ppm) and very large negative Europium anomalies (Eu/Eu* …

Effect Of Ch2Cl2 On The Redox Behavior Of Ferrocene In Ionic Liquid Bmimpf6, Wei-Wei Ji, Li-Qun Xu, Dong-Mei Li, Rong Wang, Xia-Qin Wu, Zong-Rang Zhang

Journal of Electrochemistry

The effects of CH₂Cl₂ on the room temperature redox behaviors of ferrocene in ionic liquid,BmimPF₆,were studied by cyclic voltammetry and AC Impedance.The results suggested that the presence of CH₂Cl₂,accelerated the dissociation of ionic liquid,leading to lower viscosity and larger ionic conductovity,hence,the diffusions of ferrocence in BmimPF₆ were enhanced and the peak currents of redox reactions were increased.The changes in the double-layer structure at the electrode interface resulted in larger capacitance,which reduced the electrode recution resistances,accordirgly,the reaction kinetics of ferrocene were enhanced.

Primary Study Of Tiron As Active Materials For The Redox Flow Battery, Yan Xu, Yue-Hua Wen, Jie Cheng, Yu-Sheng Yang, Zi-Li Xie

Journal of Electrochemistry

Effects of solution pH on the electrochemical behavior of tiron(sodium 4,5-dihydroxy-1,3-benzendisulfonic) couple(on a graphite electrode) were studied by cyclic voltammetry in aqueous solutions.It is shown that at pH<4,tiron exhibited a redox process at a relatively high potential with a good reversibility.A redox flow battery was formed employing tiron as the positive active species and V(III)/V(II) as the negative redox couple.In sulfuric acid medium,the coulombic efficiency of the tiron-V redox flow cell was more than 90% with a good cycle life.The decay in the cycle performance was minimal.Therefore,the feasibility of tiron as active materials for redox flow battery application is demonstrated.

Study On The Texturization Of C-Si Wafers By Different Kinds Of Alkaline For Heterojunction Solar Cells, Yu-Hua Dou, Yu-Qin Zhou, Mei-Fang Zhu, Shuang Song, Feng-Zhen Liu, Jin-Long Liu, Zhan-Jun Zhang

Journal of Electrochemistry

The texturization of(100) crystalline silicon(c-Si) wafer was studied by field-emission scanning electron microscope using different kinds of etchant: sodium hydroxide,sodium carbonate and tribasic sodium phosphate.By optimizing the etching parameters,the lowest values of averaged reflectance(Rav) were obtained to be 9.70% for NaOH,9.76% for Na₂CO₃ and 8.63% for Na₃PO₄·12H₂O,which is comparable to that of the wafer with textured surface covered with an anti-reflection coating of either silicon nitride or thermally grown silicon dioxide.The relation of Rav and surface morphology of textured wafer was analyzed.Moreover,special emphasis was put on the role of isopropyl alcohol(IPA) …

The Hydrothemal Synthesis Of Nanoscale Lifepo4 And Its Electrochemical Performance, Si-Min Wang, Ming-Sen Zheng, Quan-Feng Dong

Journal of Electrochemistry

The cathode materials of LiFePO₄ were prepared via a hydrothermal reduction method using FeCl₃ as Fe source and iron as a reducing agent.The results showed that ferric salt could be reduced to ferrous salt completely under the hydrothermal condition and pure-phase LiFePO₄ was obtained based on the test results of XRD and FTIR. Carbon-coated LiFePO₄ was synthesized by pyrolysisng glucose at high temperature. The morphologies of pure LiFePO₄ displayed cluster-like while the LiFePO₄/C displayed sphere-like particles. The electrochemical test showed that the LiFePO₄/C had good rate performance,while LiFePO₄ delivered much …

Combustion Product Characterization Of The Iron-Heated Powders In Thermal Batteries, Jin Chong, Xue-Ping Gao, Ji-Qiang Wang

Journal of Electrochemistry

The combustion products of thermal battery used iron-heated powders have been studied.It is identified by X-ray diffraction (XRD) analysis that the main compositions of the combustion products are Fe, FeO and KCl. The transmission electron microscopy(TEM) shows a typical core-shell structure with un-reacted Fe particle core coated by FeO shell with a shell thickness of around 200 nm. The combusted iron-heated powders exhibit no metal property, which is contrast to previous assumption. Further measurement indicates that at the ambient temperature the combustion products show semiconductor property of the p-type with conductivity in the order of 103 S·cm^-1, which …

Synthesis Of The Lifepo4 By Co Reduction: Reaction Mechanism And Kinetics, Yun-Hua Chen, Yong Yang

Journal of Electrochemistry

LiFePO₄ cathode material was synthesized by CO reducing FePO₄ and LiOH precursors.The structure,morphology and electrochemical performances of such LiFePO₄ material were characterized by XRD,SEM and charge-discharge tests.It was shown that the particle size of the LiFePO₄ synthesized with 5% excess of LiOH in the precursor was about 200 nm.By carbon coating,the LiFePO₄ electrode was able to deliver a reversible capacity of 158 mAh·g^-1 at 0.1C discharge rate.Temperature-programmed X-ray diffraction was employed to monitor the reaction during the formation of LiFePO₄,and Li₃Fe₂(PO₄)₃ was found to be …

Preparation And Optical Transmission Of The Zno Nanorod Array Films, Feng Ye, Jing-Jing Li, Tong-Tao Wang, Yong-Liang Wang, Yun Liu, Xin-Dong Wang

Journal of Electrochemistry

By using a galvaostatic electrodeposition method in the ZnCl₂ solution,the highly oriented ZnO nanorod array films have been successfully prepared on ITO substrate after the pretreatment with ZnO nanoparticles.And they were characterized by scanning electron microscope,X-ray diffraction and transmittance spectra.The results indicated that the ZnO nanorod arrays grew along(001) direction with an orientation perpendicular to the substrate.When the wavelength of incident was over 380 nm,the ZnO nanorod arrays showed high optical transmission of above 95%.Furthermore,the band gap became narrower.

Preparations Of Composite Electrodes Of Pt With HXWo3 And Catalytic Activity Toward Oxygen Reduction Reaction, Pan-Pan Guo, You-Ju Huang, Hong-Yan Yang, Wei Li, Qing-Long Zhang, Wei-Shan Li

Journal of Electrochemistry

Three composite electrodes of platinum with hydrogen tungsten bronze(H_xWO₃)were prepared by voltammetry: hydrogen tungsten bronze deposited on platinum(H_xWO₃/Pt);platinum deposited on hydrogen tungsten bronze(Pt/H_xWO₃) and codeposited platinum and hydrogen tungsten bronze(Pt-H_xWO₃).The eletro-catalytic activities of three electrodes toward oxygen reduction reaction were studied.It is found that the catalytic activity of platinum can be improved by introducing with hydrogen tungsten bronze.Among these composite electrodes Pt/H_xWO₃,and the electrode shows the best eletro-catalytic activity toward oxygen reduction reaction,hence,provides a new way for reducing loading of …

High Performance Fuel Cell Catalyst And 5kw Pemfc Stack Without Humidification At Room Temperature And Atmosphere, Xin-Fa Hu, Min Chen, Shi-Jun Liao

Journal of Electrochemistry

The Pt/C catalyst with high dispersion and high performance was prepared successfully by an organic colloidal method and small batch production(10g) of Pt/C catalyst has been realized.The particle sizes of the active components in the catalyst could be as small as 2.8 nm and the active surface area was up to 450 m²/g.A high performance membrane-electrode assembly(MEA) with surface area of 275 cm² has been prepared by using the home-made catalyst with a catalyst coated membrane method invented in the lab,and a 5 kW stack has been assembled.The stack showed working 10 h at room temperature,atmosphere and …

Ceo2/Pt Composite Electrodes And Their Catalytic Performance, Ying Fu, Zi-Dong Wei, Yong-Chao Feng, Xin-Li Ma, Ming-Jia Liao, Chao Liao, Jie Zhang, Huan Zhang

Journal of Electrochemistry

In this paper,the cerium oxide(CeO₂) nanoparticles were electrochemically deposited on a Pt electrode by potentiostatic deposition(psd) and potential pulse deposition(ppd) to form CeO₂/Pt composite electrodes,CeO₂/Pt(psd) and CeO₂/Pt(ppd).The properties of the CeO₂ were characterized by field emission scanning electron microscope(FESEM) and X-ray diffraction(XRD).The results showed that the CeO₂ nanoparticles prepared by psd and ppd were homogeneous and dense.The methanol oxidation reaction(MOR) and oxygen reduction reaction(ORR) on the Pt electrode were enhanced with the introduction of CeO₂ into Pt.In addition,the catalytic capability of the CeO₂/Pt electrode can be further …

Ec-Pt/Cnts Glucose Oxidative Electrode, Jia-Hua Liang, Chun-Mei Zhou, Hong-Juan Wang

Journal of Electrochemistry

A glucose oxidative electrode(GOD),EC-Pt/CNTs glucose oxidative electrode,was constructed by ethyl cellulose(EC) and Pt/CNTs.The sensitivity of the EC-Pt/CNTs GOD is 0.85 μA/mM in the concentration range of 0～4 mmol/L of glucose.After dipped in PBS(4℃) for 18 days,the activity of the EC-Pt/CNTs GOD can reach 80%.It is promising for the EC-Pt/CNTs GOD to be used to construct glucose biosensor.

Corrosion Inhibition Of Magnesium Alloy In 3.5% Nacl Medium By Tungstate, Ling-Jie Li, Zhi-Ming Yao, Jing-Lei Lei, Dong-Hai He, Sheng-Tao Zhang, Fu-Sheng Pan

Journal of Electrochemistry

Electrochemical impedance spectroscopy(EIS),Tafel polarization curves and scanning electron microscopy(SEM) were used to study the corrosion inhibition of AZ61 magnesium alloy in 3.5% NaCl medium with tungstate.Results showed that tungstate demonstrates strong inhibition to the corrosion of AZ61 magnesium alloy.At the concentration of 0.01 mol/L,tungstate has a high inhibition efficiency 75.5%.Tungstate is an anodic inhibitor that mainly inhibited the anodic reactions of magnesium alloy through forming a compact protective layer that covered the magnesium alloy surface active sites.

Voltammetric Determination Of Iodate Ion In Table Salt By Carboxylic Carbon Nanotubes Modified Carbon Paste Electrode, Jun-Hua Li, Fu-Xing Zhang, Jian-Qiu Wang, Zhi-Feng Xu, Rong-Ying Zeng, Yan Yu

Journal of Electrochemistry

A highly-sensitive and mercury-free method of determining iodate ion in table salt was established based on carboxylic carbon nanotubes modified carbon paste electrode.In 0.1 mol/L NaOH solution,there was a sensitive cathodic stripping peak on voltammograms.The stripping peak potential was-0.52 V when accumulation time of IO-3 at the modified electrode was 60 s and the potential scan rate was 300 mV/s.There was a good liner relationship between the peak current and IO-3 concentration in the range of 8.0×10^-10 ～ 5.0×10^-8 mol/L and 1.0×10^-7 ～ 3.0×10^-6 mol/L with the correlation coefficient of 0.999 and 0.998,respectively.The detection limit was …

Electrochemical Behavior And Determination Of Paracetamol On Activated Glassy Carbon Electrode, Bao-Yu Tan, Fang Liao, Xiao-Ying He, Qing-Tao Zhu, Jun Hua, Xiao-Li Jiang

Journal of Electrochemistry

The electrochemical behavior of paracetamol(PCT) was studied at glassy carbon electrode activated by cyclic voltammetry.In HAc-NaAc buffer solution(pH=4.00),a couple of sensitive redox peaks were recorded about 0.54 V in the cyclic voltammograms.The result indicated that the process was controlled by adsorption and nearly reversible.The reaction electron and proton numbers were estimated,respectively,to be two.Excllent linearity was observed in the correlation between the oxidation peak current and the concentration of PCT in the range of 8.00×10^-6～2.00×10^-4 mol·L-1.The correlative coefficient was-0.999 18.The detection limit was 6.34×10^-6 mol·L^-1.This method can be used for the determination of PCT real …