Chemistry Commons^™

Optimizing Peptide Fractionation To Maximize Content In Cancer Proteomics, Victoria Izumi

USF Tampa Graduate Theses and Dissertations

The purpose of the studies included in this thesis is to develop an effective an efficient method to study the proteome using separation and detection of peptides, when only a limited amount of sample, 10 micrograms of total protein or less, is available. The analysis will be applied to multiple myeloma cancer cells using ultra high-performance liquid chromatography-mass spectrometry for expression proteomics to illustrate utility. To detect low abundance peptides in a complex proteome, we use different strategies, including basic pH reversed-phase liquid chromatography (bRPLC), mass-to-charge fractionation in the mass spectrometer, and various liquid chromatography gradients to increase peptide separation …

Pva/Chitosan/Silver Nanoparticles Electrospun Nanocomposites: Molecular Relaxations Investigated By Modern Broadband Dielectric Spectroscopy, Mohammad K. Hassan, Ahmed Abukmail, Alaa J. Hassiba, Kenneth A. Mauritz, Ahmed A. Elzatahry

Faculty Publications

In this study, we used broadband dielectric spectroscopy to analyze polymer nanofibers of poly(vinyl alcohol)/chitosan/silver nanoparticles. We also studied the effect of incorporating silver nanoparticles in the polymeric mat, on the chain motion dynamics and their interactions with chitosan nanofibers, and we calculated the activation energies of the sub-T_g relaxation processes. Results revealed the existence of two sub-T_g relaxations, the first gets activated at very low temperature (−90 °C) and accounts for motions of the side groups within the repeating unit such as –NH₂, –OH, and –CH₂OH in chitosan and poly(vinyl alcohol). The second …

Information-Driven Inverse Approach To Disordered Solids: Applications To Amorphous Silicon, Dil K. Limbu, Raymond Atta-Fynn, David A. Drabold, Stephen R. Elliott, Parthapratim Biswas

Faculty Publications

© Physical Review Materials

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Molecular Level Interactions And Transformations Of Natural Organic Matter Within The Environment, Benjamin J. Haywood

LSU Doctoral Dissertations

This work was done in order to deepen the understanding of interactions occurring during sorption of anthropogenic organic compounds and dissolved organic matter (DOM) onto soil. As well as the transformation DOM undergoes during the sorption process and the overall transformation OM undergoes in the environment. This was achieved through the use of a “bottom-up” synthetic investigation, “top-down” natural system study, and a combination of these approaches.

The “bottom-up” approach, discussed in Chapter 2, involved the synthesis of a modular multi-tiered engineered soil surrogate (ESS) designed to mimic OM and general trends identified in the literature that impacts sorption behavior. …

‘Cassette’-Ises (In Situ Enzymatic Screening) Identifies Complementary Chiral Scaffolds For Hydrolytic Kinetic Resolution Across A Range Of Epoxides, Sangeeta Dey, Douglas R. Powell, Chunhua Hu, David B. Berkowitz

Department of Chemistry: Faculty Publications

‘Cassette’-ISES (In Situ Enzymatic Screening) Identifies Complementary Chiral Scaffolds for Hydrolytic Kinetic Resolution Across a Range of Epoxides

A new ‘Cassette’-In Situ Enzymatic Screen (ISES) for combinatorial catalysis is introduced. This allows the experimentalist to obtain an information-rich readout, in real time, providing an estimate of the sense and magnitude of enantioselectivity across more than one substrate. In its first iteration, the screen identified Co^III-salen catalysts with β-pinene- and α-naphthylalanine-derived chiral scaffolds with broad, yet complementary, substrate specificities.

Interfacing Nickel Nitride And Nickel Boosts Both Electrocatalytic Hydrogen Evolution And Oxidation Reactions, Fuzhan Song, Wei Li, Jiaqi Yang, Guanqun Han, Peilin Liao, Yujie Sun

Chemistry and Biochemistry Faculty Publications

Electrocatalysts of the hydrogen evolution and oxidation reactions (HER and HOR) are of critical importance for the realization of future hydrogen economy. In order to make electrocatalysts economically competitive for large-scale applications, increasing attention has been devoted to developing noble metal-free HER and HOR electrocatalysts especially for alkaline electrolytes due to the promise of emerging hydroxide exchange membrane fuel cells. Herein, we report that interface engineering of Ni₃N and Ni results in a unique Ni₃N/Ni electrocatalyst which exhibits exceptional HER/HOR activities in aqueous electrolytes. A systematic electrochemical study was carried out to investigate the superior hydrogen …

Synthesis, Characterization And Application Of Structurally Diverse Poly(Chalcogenylene Vinylene)S, Zhen Zhang

Chemistry and Chemical Biology ETDs

Conjugated polymers have found widespread applications in flexible and printable electronic devices, among which poly(thienylene vinylene) (PTV) displays outstanding optoelectronic properties and promising applications. However, further studies of its structure-property-function relationship have been greatly impeded mainly due to the synthetic difficulty of generating new structures beyond its rudimentary form.

To further investigate this class of material, I have developed a facile methodology for the preparation of structurally diverse poly(chalcogenylene vinylene)s (PCVs) through a combination of acyclic diene metathesis (ADMET) polymerization and post-polymerization modification techniques. Specifically, a series of halogenated and cross-conjugated PCVs have been designed and synthesized, followed by complete …

Development Of Betulinic Acid Triazole Conjugates As Potential Anti-Cancer Agents, Gayathri Jampana

Theses and Dissertations

Betulin and betulinic acid are pentacyclic triterpenoid natural product isolated from the bark of birch trees. While betulin is abundantly available in the bark, betulinic acid is present in scarce quantities in nature. However, betulinic acid can be conveniently synthesized from betulin via simple redox manipulations. Betulinic acid shows selective cytotoxicity profile against cancer cells in vitro while being relatively safe for normal cells. One of the challenges for the clinical development of betulinic acid is its lack of aqueous solubility. The three key structural features of betulin/betulinic acid that have been routinely exploited for structural modifications to enhance their …

Several Levels Of Theory For Description Of Isotope Effects In Ozone: Effect Of Resonance Lifetimes And Channel Couplings, Alexander Teplukhin, Dmitri Babikov, Igor Gayday

Chemistry Faculty Research and Publications

In this paper, two levels of theory are developed to determine the role of scattering resonances in the process of ozone formation. At the lower theory level, we compute resonance lifetimes in the simplest possible way, by neglecting all couplings between the diabatic vibrational channels in the problem. This permits to determine the effect of “shape” resonances, trapped behind the centrifugal barrier and populated by quantum tunneling. At the next level of theory, we include couplings between the vibrational channels, which permits to determine the role of Feshbach resonances and interaction of different reaction pathways on the global PES of …

Synthesis Of Some Fossils Of Ferrocene Carboxylic Acid And Their Classification Based On Tif Tn, Н Tulakov,, I. Askarov,, Yu. Isaeva,, K. Otaxonov

Scientific journal of the Fergana State University

The synthesis of some ferrocenecarboxylic acid derivatives and assignment of code numbers for them according to the commodity nomenclature of foreign economic activity (CN FEA) is described in the article.

Comparison Of Theoretical And Experimental Geometric Characteristics Of Betulin, A. Eshimbetov,, Sh Kurbanbaeva,, Sh. Turgunbaev,, A. Xaitbaev

Scientific journal of the Fergana State University

The study of betulin and its derivatives is of great importance, since the programs of mathematical modeling enable a qualitative study of the relationship between structure-spectrum-properties. As a result of the theoretical search, it is possible to determine still non-synthesized highly-biologically active derivatives of betulin

Dependence Of Nmr Chemical Shifts Upon Ch Bond Lengths Of A Methyl Group Involved In A Tetrel Bond, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Four different Lewis acids that might participate in a tetrel bond with a nucleophile (SEt₂Me⁺, NMe₄⁺, SMe₂, NMe₃) are examined. The NMR chemical shifts of the methyl C and H atoms are calculated as the CH bond lengths are systematically stretched and contracted, in the absence of a base. The C shielding diminishes by roughly 2 ppm for a stretch of 0.01 Å, while that of H drops by only 0.3 ppm. The deshieldings caused purely by the bond length changes are far too small to account for the …

Guanidinium Compounds, Stephen Dimagno, Bao Hu

Department of Chemistry: Faculty Publications

The present application provides , inter alia , chemical com pounds useful as synthesis intermediates , said compounds comprising one or more guanidinium moieties and a hyper valent iodine atom . Methods for making these compounds are also provided.

Resurrecting The Regulatory Properties Of The Ostreococcus Tauri Adp-Glucose Pyrophosphorylase Large Subunit, Carlos M. Figueroa, Misty L. Kuhn, Benjamin L. Hill, Alberto A. Iglesias, Miguel A. Ballicora

Chemistry: Faculty Publications and Other Works

ADP-glucose pyrophosphorylase (ADP-Glc PPase) catalyzes the first committed step for the synthesis of glycogen in cyanobacteria and starch in green algae and plants. The enzyme from cyanobacteria is homotetrameric (α4), while that from green algae and plants is heterotetrameric (α2β2). These ADP-Glc PPases are allosterically regulated by 3-phosphoglycerate (3PGA, activator) and inorganic orthophosphate (Pi, inhibitor). Previous studies on the cyanobacterial and plant enzymes showed that 3PGA binds to two highly conserved Lys residues located in the C-terminal domain. We observed that both Lys residues are present in the small (α) subunit of the Ostreococcus tauri enzyme; however, one of these …

Acidity And Antioxidant Activity Of Cold Brew Coffee., Niny Z. Rao, Megan Fuller

College of Life Sciences Faculty Papers

The acidity and antioxidant activity of cold brew coffee were investigated using light roast coffees from Brazil, two regions of Ethiopia, Columbia, Myanmar, and Mexico. The concentrations of three caffeoylquinic acid (CQA) isomers were also determined. Cold brew coffee chemistry was compared to that of hot brew coffee prepared with the same grind-to-coffee ratio. The pH values of the cold and hot brew samples were found to be comparable, ranging from 4.85 to 5.13. The hot brew coffees were found to have higher concentrations of total titratable acids, as well as higher antioxidant activity, than that of their cold brew …

Heme Dissociation From Myoglobin In The Presence Of The Zwitterionic Detergent N,N-Dimethyl-N-Dodecylglycine Betaine: Effects Of Ionic Liquids, Eric M. Kohn, Joshua Y. Lee, Anthony Calabro, Timothy Vaden, Gregory A. Caputo

College of Science & Mathematics Departmental Research

We have investigated myoglobin protein denaturation using the zwitterionic detergent Empigen BB (EBB, N,N-Dimethyl-N-dodecylglycine betaine). A combination of absorbance, fluorescence, and circular dichroism spectroscopic measurements elucidated the protein denaturation and heme dissociation from myoglobin. The results indicated that Empigen BB was not able to fully denature the myoglobin structure, but apparently can induce the dissociation of the heme group from the protein. This provides a way to estimate the heme binding free energy, ΔGdissociation. As ionic liquids (ILs) have been shown to perturb the myoglobin protein, we have investigated the effects of the ILs 1-butyl-3-methylimidazolium chloride (BMICl), 1-ethyl-3-methylimidazolium acetate (EMIAc), …

Synthesis And Characterization Of A Series Of Vanadium ( Iv ) Complexes With The Kläui Ligand, Xiao Wu

Theses and Dissertations

Cyclopentadienyltris (dibutyl phosphito-P) cobaltate, {(C5H5)Co[(OR)2PO]3}– (R=Bu), is a tripodal ligand and also called Kläui ligand (R=Bu). The synthesis and characterization of several vanadium(III) and vanadium(IV) complexes containing Kläui ligand (R=Bu) as the catalytic models to catalyst the oxidation reaction of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butyl-o-benzoquinone (3,5-DTBQ) are detailed here. Chapter II details the synthesis of the supersandwiches and Kläui ligand (R=Bu). Chapter III details the synthesis of vanadium monomeric complexes containing Kläui ligand (R=Bu). Chapter IV details the vanadium dimeric bridging complexes synthesized by different vanadium monomers from Chapter III. Chapter V details the catalytic activities of these vanadium complexes.

Recent Process In Transition-Metal-Oxide Based Catalysts For Oxygen Reduction Reaction, Yao Wang, Zi-Dong Wei

Journal of Electrochemistry

Transition metal oxides (TMOs) based catalysts have become the most promising catalysts to be employed in anion exchange membrane fuel cell for the sluggish oxygen reduction reaction (ORR). However, their ORR activity is still far from that of the Pt-based catalysts. Therefore, it is important to develop high performance TMO based catalysts. Electrical conductivity and intrinsic activity have been regarded as the two keys to affect the ORR activity of the TMOs based catalysts. In this review, we focused on the recent progresses in the fundamental viewpoints on the electrical conductivity and intrinsic activity of the TMOs based ORR catalysts. …

Conference Information, Editorial Office Of J.Electrochem.

Journal of Electrochemistry

No abstract provided.

Preparation Of Nanoprobes And Their Possible Applications In Nanoscale Scanning Electrochemical Microscopy For Studying Electrocatalytic Oxygen And Hydrogen Reactions, Xing-Xing Chen

Journal of Electrochemistry

Scanning electrochemical microscopy (SECM) is a type of scanning probe microscopy, which can not only provide the topographical information, but also offer the electrochemical properties of different samples. The interrelationship of physical and electrochemical properties of a sample can be searched at a high-resolution scale due to the introduction of ultramicroelectrode (UME). With the continuous development of modern nanotechnology, the SECM probe has been improved with drastically decreasing its size down to nanometer. Meanwhile, to evaluate and understand the electrochemical performance of various electrocatalysts for both oxygen and hydrogen reactions with high-efficiency is highly demanded in the research area of …

Recent Advances In Continuous Models Of Electrochemical Supercapacitors, Hao-Tian Lu, Jing-Hong Zhou, Guang-Hua Ye, Xing-Gui Zhou

Journal of Electrochemistry

Electrochemical capacitors (supercapacitors) have been developed as a new type of energy storage device with high energy and power densities, which have the advantages of both fast charging-discharging as traditional capacitors and high energy density as batteries. Notable improvements in their electrochemical performance have been achieved in recent years owing to the recent advances in understanding of charge storage mechanisms and the development of advanced nanostructured materials. Recently, modeling and simulation of these supercapacitors has been applied as a useful approach to better understand the working mechanisms of the supercapacitors by describing the concentrations and electric fields inside the capacitors. …

Recent Advances In Non-Noble Metal Nanomaterials For Oxygen Evolution Electrocatalysis, Dan-Dan Zhao, Nan Zhang, Ling-Zheng Bu, Qi Shao, Xiao-Qing Huang

Journal of Electrochemistry

Hydrogen is a kind of renewable energies with the merits of environmentally friendly, abundance and high weight energy density, which can replace the fossil energy. The electrolysis of water is regarded as the most effective way to generate hydrogen. Owing to the sluggish kinetics and large overpotential of the anode oxygen evolution reaction (OER), the efficiency of the cathode hydrogen evolution reaction is greatly limited. Therefore, it is highly desirable to explore efficient, stable and low cost electrocatalysts to reduce the overpotential of OER and improve the efficiency of hydrogen evolution. Based on the natural characteristics of non-noble metal catalysts …

Recent Progress In Organic Redox Flow Batteries, Li-Xing Xia, Hao Liu, Lin Liu, Zhan-Ao Tan

Journal of Electrochemistry

Redox flow batteries (RFBs) are promising candidate for balancing instability of grids caused by integration of intermittent renewable energies such as solar energy and wind energy. Along with wide deployments in solar energy and wind energy due to abundance and declining installation cost, it can be predicted that RFBs will enter a period of rapid development. Basically,RFBs are electrochemical energy storage devices that decouple energy and power of the system by storing liquid electrolyte in tanks outside battery system itself. Such a unique framework makes RFBs flexible and fulfills the various demands of grids. During battery operation, redox-active species are …

Preface For The Special Issue Of The Award Winners, Shi-Gang Sun

Journal of Electrochemistry

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The New Application Of Battery-Electrode Reaction: Decoupled Hydrogen Production In Water Electrolysis, Yuan-Yuan Ma, Zhao-Wei Guo, Yong-Gang Wang, Yong-Yao Xia

Journal of Electrochemistry

Hydrogen has been considered as a promising alternative to unsustainable fossil fuels because of its high calorific value, clean and abundant resources. Water electrolysis combined with renewable energy is regarded as the best way for hydrogen production, which will become the foundation of future hydrogen economy. For the past few years, many efforts have been employed to develop the cheap and high-performance catalyst for hydrogen evolution reaction and oxygen evolution reaction. However,the coupled hydrogen and oxygen evolution and the use of the expensive membrane have greatly restricted the flexibility of the conventional water electrolysis, and hindered the utilization of renewable …

Design Strategies Toward Highly Active Electrocatalysts For Oxygen Evolution Reaction, Tang Tang, Wen-Jie Jiang, Shuai Niu, Jin-Song Hu

Journal of Electrochemistry

Electrocatalytic water splitting is pivotal for efficient and economical production of hydrogen and oxygen gasses. However, the efficiency of the whole device is largely limited by the oxygen evolution reaction (OER) at the anode due to its sluggish kinetics. Thus, it is imperative to develop inexpensive, highly active OER catalysts to lower the reaction barriers. By examining the underlying critical factors for OER performance, this review outlines general principles for designing efficient nanosized OER catalysts, including (1) enhancing the intrinsic activity of active site by electronic modulation, crystallinity modulation, phase control, defect engineering and spin state engineering; (2) designing appropriate …

Research Progresses In Improvement For Low Temperature Performance Of Lithium-Ion Batteries, Yue-Ru Gu, Wei-Min Zhao, Chang-Hu Su, Chuan-Jun Luo, Zhong-Ru Zhang, Xu-Jin Xue, Yong Yang

Journal of Electrochemistry

Lithium-ion batteries (LIBs) have become a new research hotspot due to their high energy density and long service life. However, the temperature characteristics, especially the poor performance at low temperatures, have seriously limited their wider applications. In this report, the research progresses in the low temperature performance of LIBs are reviewed. The main existing limitations of LIBs at low temperatures were systematically analyzed, and followed by discussion on the recent improvements in low temperature performances by developing novel cathode, electrolyte, and anode materials. The developments for improving the low temperature performance of LIBs are prospected. The three most important factors …

An Investigation On The Structure Of Au(111)/Imidazolium-Based Ionic Liquid Interface: Effect Of Alkyl Side Chain Length, Li Chen, Shuai Liu, Mian-Gang Li, Jian-Jia Su, Jia-Wei Yan, Bing-Wei Mao

Journal of Electrochemistry

In this work, we comparatively investigated the interfacial structures at Au(111) electrode surfaces in two ionic liquids (ILs) with different alkyl chain lengths by combining AFM force curve technique and electrochemical methods. The number and stability of the layering structures, and their potential-dependency were analyzed. The experimental results indicated that the tendencies of force-potential curves in the two ILs behave the same way. At potentials close to PZC, the ions arrange loosely, which lowers the stability of the layering structure. As the potential shifting away from PZC, more ions attach to electrode surface, which increases the stability of layering structure, …

Synthesis Of Keggin Polyoxometalates Modified Carbon Paste Electrode As A Sensor For Dopamine Detection, Peng-Fei Dong, Na Li, Hai-Yan Zhao, Min Cui, Cong Zhang, Ju-Jie Ren, Xue-Ping Ji

Journal of Electrochemistry

Polyoxometalates, a class of anionic clusters with structure diversity and size variability, make them very attractive in many fields such as electrochemistry, catalysis and medicine. The Co(C₁₅N₆H₁₂)₂[PW₁₂O₃₈]·5H₂O(Co[PW₁₂O₃₈]) modified carbon paste electrode was prepared in this work, and its electrochemical performances as the sensor for dopamine detection were characterized with electrochemical impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry. The preparation conditions and test conditions were optimized respectively. Under the optimized conditions, the POMs modified carbon paste electrode exhibited good selectivity and sensitivity …

Effects Of Sulfur-Containing Additive On Low Temperature Performance Of Graphite Anode, Ze-Li Wu, Ye-Zhen Zheng, Zhong-Ru Zhang, Yong Yang

Journal of Electrochemistry

The low temperature performance of lithium ion battery mainly depends on the graphite anode, and one of the research focuses is to improve the low temperature performance of the anode by additives. In this paper, the effects of different sulfur-containing functional groups such as DTD (ethylene sulfate), 1,3-PS (1,3-propane sultone) and ES (ethylene sulfite) on low temperature performances of artificial graphite materials were systematically studied. The results in density functional theory (DFT) calculations, cyclic voltammetry (CV), scanning electron microscopy (SEM) and charge-discharge measurement clearly demonstrated that all three sulfur-containing additives could participate in formation of films on the surface of …