Chemistry Commons^™

Relating Side Chain Organization Of Pnipam With Its Conformation In Aqueous Methanol, Debashish Mukherji, Manfred Wagner, Mark D. Watson, Svenja Winzen, Tiago E. E. De Oliveira, Carlos M. Marques, Kurt Kremer

Chemistry Faculty Publications

Combining nuclear magnetic resonance (NMR), dynamic light scattering (DLS), and μs long all-atom simulations with two million particles, we establish a delicate correlation between increased side chain organization of PNIPAm and its collapse in aqueous methanol mixtures. We find that the preferential binding of methanol with PNIPAm side chains, bridging distal monomers along the polymer backbone, results in increased organization. Furthermore, methanol–PNIPAm preferential binding is dominated by hydrogen bonding. Our findings reveal that the collapse of PNIPAm is dominated by enthalpic interactions and that the standard poor solvent (entropic) effects play no major role.

Gc Verification Of The Spacecraft Atmosphere Monitor, Jessica S. Castro, Richard D. Kidd, Jeffrey D. Hein

STAR Program Research Presentations

International Space Station crew members face the unique challenge of maintaining air quality due to the volatile organic compounds (VOCs) that have the potential to accumulate at unsafe levels. The Spacecraft Atmosphere Monitor (SAM) is a miniature gas chromatograph/mass spectrometer (GCMS) designed to measure major constituents (such as N₂, O₂ and CO₂) and trace VOCs within the cabin of the spacecraft. The gas chromatograph is responsible for separating the sample into its components in order to be characterized. The oven of the gas chromatograph must reach a temperature of 150°C in order to heat constituents …

Expanding The Applicability Of Raman Spectroscopy For Monitoring Photocatalytic Degradation, Franklyn Wallace

Mahurin Honors College Capstone Experience/Thesis Projects

Compared to other types of wastewater pollutants, dangerous chemical compounds such as pharmaceuticals, pesticides, and herbicides are difficult to remove and consequently being detected (at least in part because detection limits have decreased) in drinking water at increasing concentrations. Photocatalytic degradation degrades harmful compounds to innocuous end products using energy from light. Although it is effective and cost-efficient, the underlying chemical mechanisms are not understood well enough to ensure that dangerous intermediate products are not formed during the degradation process. Raman spectroscopy can be used to analyze photocatalytic degradation reactions in real time, identifying intermediate products based on spectral features. …

A Simplified Direct Lipid Mixing Lipoplex Preparation: Comparison Of Liposomal-, Dimethylsulfoxide-, And Ethanol-Based Methods, Joseph Meisel, George Gokel

Chemistry & Biochemistry Faculty Works

Established transfection methodology often uses commercial reagents, which must be formed into liposomes in a sequence of about half a dozen steps. The simplified method reported here is a direct lipid mixing approach that requires fewer steps, less manipulation, and is less time-consuming. Results are comparable to those obtained with more commonly used methods, as judged by a variety of analytical techniques and by comparisons of transfection results. The method reported here may be applied to non-liposome-forming compounds, thereby greatly expanding the range of structures that can be tested for transfection ability.

First-Principles Calculated Decomposition Pathways For Libh4 Nanoclusters, Zhi-Quan Huang, Wei-Chih Chen, Feng-Chuan Chuang, Eric Majzoub, Vidvuds Ozoliņš

Physics Faculty Works

We analyze thermodynamic stability and decomposition pathways of LiBH4 nanoclusters using grand-canonical free-energy minimization based on total energies and vibrational frequencies obtained from density-functional theory (DFT) calculations. We consider (LiBH4)n nanoclusters with n = 2 to 12 as reactants, while the possible products include (Li)n, (B)n, (LiB)n, (LiH)n, and Li2BnHn; off-stoichiometric LinBnHm (m ≤ 4n) clusters were considered for n = 2, 3, and 6. Cluster ground-state configurations have been predicted using prototype electrostatic ground-state (PEGS) and genetic algorithm (GA) based structural optimizations. Free-energy calculations show hydrogen release pathways markedly differ from those in bulk LiBH4. While experiments have found …

Nmr Analysis Of T‐Butyl‐Catalyzed Deuterium Exchange At Unactivated Arene Localities, Douglas E. Stack, Rachel Eastman

Chemistry Faculty Publications

Regioselective labelling of arene rings via electrophilic exchange is often dictated by the electronic environment caused by substituents present on the aromatic system. Previously, we observed the presence of a t‐butyl group, either covalently bond or added as an external reagent, could impart deuterium exchange to the unactivated, C1‐position of estrone. Here, we provide nuclear magnetic resonance analysis of this exchange in a solvent system composed of 50:50 trifluoroacetic acid and D2O with either 2‐t‐butylestrone or estrone in the presence of t‐butyl alcohol has shed insights into the mechanism of this t‐butyl‐catalyzed exchange. Fast exchange of the t‐butyl group concurrent …

Electrochemical Properties Of Melting Gel Coatings, Lisa C. Klein, Ahmad Dengah, Kutaiba Al-Marzoki, Gabriela Rodriguez, Andrei Jitianu, Jadra Mosa, Mario Amapricio

Publications and Research

Organic-inorganic melting gel coatings were applied to titanium alloy substrates to decrease their corrosion and extend their lifetime in an electrochemical application. Melting gels containing phenyl substitutions were coated onto the substrates. The ratio of diphenyl dimethoxysilane (DPhDMS) to methanol was varied to change the thickness of the coatings. The coatings were inspected visually to see that there is good adhesion between the coating and the substrate. Nanoindenter tests were performed to determine hardness

Capture And Recycle Of Industrial Co2 Emissions Using Mircoalgae, Michael H. Wilson, Daniel T. Mohler, John G. Groppo, Thomas E. Grubbs, Stephanie Kesner, E. Molly Frazar, Aubrey Shea, Czarena L. Crofcheck, Mark Crocker

Center for Applied Energy Research Faculty and Staff Publications

A novel cyclic flow photobioreactor (PBR) for the capture and recycle of CO₂ using microalgae was designed and deployed at a coal-fired power plant (Duke Energy’s East Bend Station). The PBR was operated continuously during the period May–September 2015, during which algae productivity of typically 0.1–0.2 g/(L day) was obtained. Maximum CO₂ capture efficiency was achieved during peak sunlight hours, the largest recorded CO₂ emission reduction corresponding to a value of 81 % (using a sparge time of 5 s/min). On average, CO₂ capture efficiency during daylight hours was 44 %. The PBR at East Bend …

Peroxiredoxin Catalysis At Atomic Resolution, Arden Perkins, Derek Parsonage, Kimberly J. Nelson, O. Maduka Ogba, Paul Ha-Yeon Cheong, Leslie B. Poole, P. Andrew Karplus

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Peroxiredoxins (Prxs) are ubiquitous cysteine-based peroxidases that guard cells against oxidative damage, are virulence factors for pathogens, and are involved in eukaryotic redox regulatory pathways. We have analyzed catalytically active crystals to capture atomic resolution snapshots of a PrxQ-subfamily enzyme (from Xanthomonas campestris) proceeding through thiolate, sulfenate, and sulfinate species. These analyses provide structures of unprecedented accuracy for seeding theoretical studies, and show novel conformational intermediates giving insight into the reaction pathway. Based on a highly non-standard geometry seen for the sulfenate intermediate, we infer that the sulfenate formation itself can strongly promote local unfolding of the active site to …

Room-Temperature Electrochemical Reduction Of Epitaxial Bi₂O₃ Films To Epitaxial Bi Films, Zhen He, Jakub Adam Koza, Ying-Chau Liu, Qingzhi Chen, Jay A. Switzer

Chemistry Faculty Research & Creative Works

This work reports a new facile approach to fabricate high-quality epitaxial Bi thin films by direct electrochemical reduction of epitaxial δ-Bi₂O₃ thin films on Au single crystals in aqueous solution at room-temperature. The as-produced Bi thin films (without any post-annealing process) exhibit large grain sizes, continuous microstructures, and enhanced magnetotransport properties.

The Subject Librarian Newsletter, Chemistry, Fall 2016, Patti Mccall

Libraries' Newsletters

No abstract provided.

A Comparison Of Solvent And Water-Borne Alkyd Coatings And The History Of Voc Regulations In The United States, Molly Elise Burns

Master's Theses

A Comparison of Solvent and Water-Borne Alkyd Coatings Abstract

Conventional solvent based alkyd coatings have gone out of favor due to concerns over volatile organic compound (VOC) content. However, due to recent focus on renewable raw materials, alkyds are making a comeback in waterborne form. Water based alkyd coatings are known to have poor shelf stability and corrosion resistance, as well as other problems during the formulation process. This project focused on comparing solvent borne to two types of water-borne alkyds, water reducible alkyds and alkyds emulsions. The purpose was to understand the differences between the three types of alkyds …

Chromatographic Studies Of Protein-Based Chiral Separations, Cong Bi, Xiwei Zheng, Shiden Azaria, Sandya Beeram, Zhao Li, David S. Hage

David Hage Publications

The development of separation methods for the analysis and resolution of chiral drugs and solutes has been an area of ongoing interest in pharmaceutical research. The use of proteins as chiral binding agents in high-performance liquid chromatography (HPLC) has been an approach that has received particular attention in such work. This report provides an overview of proteins that have been used as binding agents to create chiral stationary phases (CSPs) and in the use of chromatographic methods to study these materials and protein-based chiral separations. The supports and methods that have been employed to prepare protein-based CSPs will also be …

A Study Of Chemistry: For Wind Ensemble, Morgan Duff

Mahurin Honors College Capstone Experience/Thesis Projects

Many musicians have a limited understanding of chemistry, while many chemists aren't familiar with details of music theory or composition. Through the composition of a four-part musical work based entirely on several broad areas of chemistry, certain relationships have been shown between music and chemistry. Because of the overlap between certain scientific concepts and many aspects of music theory, it is possible for members of both fields to use what they already know in order to gain a deeper understanding of the other, very different, subject. Because everyone has learning strengths in differing areas, I believe the use of disciplinary …

Chemistry And Biochemistry News, Georgia Southern University

Biochemistry, Chemistry & Physics: News & Publications (2012-2023)

• Faculty Awards for 2015-2016
• Georgia Southern's Elite 8 for REU-2016

Theoretical Study Of Photoelectrochemical Reactions And Ec-Sers On Spr Metallic Electrodes Of Silver And Gold, Yuan-Fei Wu, Ran Pang, Meng Zhang, Jian-Zhang Zhou, Bin Ren, Zhong-Qun Tian, De-Yin Wu

Journal of Electrochemistry

At present photoelectrochemistry has received much concern back to nanostructures of noble metals from semiconductor electrodes. This is due to the surface plasmon resonance (SPR) effect of metallic nanostructures, which can effectively convert the far-field light to the near-field light and concentrate the photonic energy to the local surface area with high energy density. Thus, the different enhancement mechanisms, such as the local optical field enhancement, the formation of light generated hot carriers (hot electron-hole pairs), or the photothermal effect, have been proposed in literatures. On the basis of the SPR enhancement effect, the surface-enhanced Raman spectroscopy (SERS) can be …

Photoelectrochemical Water Splitting Cells: Methods For Improving Performance Of Electrodes And Recent Progress On Photocathodes, Kai-Jian Zhu, Wen-Jun Luo, Zhong-Jie Guan, Xin Wen, Zhi-Gang Zou, Wei Huang

Journal of Electrochemistry

Photoelectrochemical water splitting can convert solar energy into hydrogen which is an ideal way to utilize and store solar energy. A p-n tandem cell is considered as the most promising solar water splitting cell due to its high theory conversion efficiency, low cost and photoelectrode material flexibility. However, solar conversion efficiency of a tandem cell is still low in the experiment because of poor performance in a single photoelectrode. In this review, we have introduced some effective approaches to improve the performances of photoelectrodes by reducing recombination of photogenerated carriers in the bulk or on the surface, and suppressing back …

Preparations And Photoelectrochemical Properties Of Phosphate Modified Rgo-Biobr Nanocomposites, Shuang-Ying Chen, Zhi-Jun Li, Xu-Liang Zhang, Kang Hu, Rui Yan, Li-Qiang Jing

Journal of Electrochemistry

The RGO-BiOBr nanocomposites have been successfully synthesized by a hydrothermal process, and then modified with phosphorous acids. The photoelectrochemical properties of the fabricated RGO-BiOBr nanocomposite films were studied. The results indicate that the photocurrent densities of RGO-BiOBr were much larger compared with those of the bare BiOBr, and interestingly, the photocurrent densities were further improved after phosphate modification. Based on the analyses of the produced hydroxyl radical amounts, the enhanced photocurrent densities could be attributed to the introduction of RGO and to the formed negative fields of modified phosphate groups, which are favorable for electrons to be transferred and for …

WoX/Pedot:Pss Double-Layered Hole-Transport Layers For Efficient And Stable Planar Heterojunction Perovskite Solar Cells, Wen-Yuan Qiao, Qiang Guo, Cong Li, Shuang Ma, Fu-Zhi Wang, Song-Yuan Dai, Zhan-Ao Tan

Journal of Electrochemistry

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is a commonly used hole-transport material in the perovskite solar cells (PerSCs) structure of perovskite/fullerene planer heterojunction, but it also has a negative effect on the stability of device because of its acidity which will corrode metal oxide transparent electrodes. In this work, a WO_x hole-transport layer with high work function was inserted into the PEDOT: PSS and FTO to enhance the stability and photovoltaic performance. The inserted WO_x layer not only can avoid direct contact between PEDOT:PSS and FTO, but also can further reduce the contact barrier between the electrode interface. We studied the effect …

A Novel Flexible Dye-Sensitized Solar Cell Based On Pt Networks Counter Electrode, Zi-Jie Xu, Fa-Yin Zhang, Xiao-Dan Hong, Wen-Xi Guo, Xiang-Yang Liu, Chang-Jian Lin

Journal of Electrochemistry

Flexible dye-sensitized solar cells (DSSCs) have received widespread attentions in recent years because of their ease of fabrication, low production cost, relatively high chemical stability and flexibility. We report the fabrication of ZnO DSSCs based on the highly flexible, conducting, catalytic and transparent Pt networks counter electrode, and the performance of this solar cell was characterized by SEM, XRD, polarized fluorescence microscope, motor, I-V test station and electrochemical workstation. Compared to Pt nanofiber arrays (NFs), Pt networks not only show a better conductivity, but also exhibit superior transparency and catalytic activity. Furthermore, Pt networks electrode could be constructed on arbitrary …

Fabrications Of Three Copper Sulfide Counter Electrodes And Their Influences On Photovoltaic Properties In Qdsscs, Xiao-Dan Hong, Zi-Jie Xu, Fa-Yin Zhang, Yu-Peng Li, Mei-Dan Ye, Chang-Jian Lin, Wen-Xi Guo

Journal of Electrochemistry

Quantum dot-sensitized solar cells (QDSSCs) have attracted intensive attention in scientific and industrial fields due to their high molar extinction coefficient, spectral tunability by particle size, ease of fabrication, and low cost. In the past years, semiconductor metal sulfides have attracted extensive attention because of their attractive physical and chemical properties for potential applications in many fields,such as PbS, CuS, CoS and CdS. In particular, copper sulfides have become a promising candidate for counter electrode materials in QDSSCs for their outstanding electrochemical and catalytic properties. In order to explore more stable and efficient copper sulfide counter electrode materials, in this …

Hydrothermal One-Step Synthesis Of Layered Nickel/Cobalt Double Hydroxide With Using Shape-Directing Agent And Homogeneous Precipitating Agent, Li-Wei Zhu, Yun-Hai Yan, Hui Jia, Run-Fen Liang

Journal of Electrochemistry

Nickel/cobalt double hydroxide (Ni/Co-DH) has been prepared by facile hydrothermal one-step synthesis method using hexamethylene tetramine (HMT) as a homogeneous precipitating agent and cetyltrimethylammonium bromide (CTAB) as a shape-directing agent. With the hydrolysis of HMT and the use of CTAB, the Ni/Co-DH could be synthesized without additional alkali source, and in the meantime, the Ni/Co-DH exhibited a controlled mesopore size of 13.4 nm and a large BET surface area of 93.6 m² •g^-1 . The X-ray diffraction (XRD) pattern displays that the Ni/Co-DH existed as a mixture of α-Ni(OH)₂-β-Co(OH)₂. The scanning electron microscope (SEM) …

Special Issue: Photoelectrochemistry And New Types Of Solar Cells, Chang-Jian Lin, Yong-Fang Li

Journal of Electrochemistry

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Prospects Of D-Π-A Structured Porphyrins And Their Photoelectrochemical Application, Shuang-Shuang Liu, Jian-Feng Lu, Ming-Kui Wang

Journal of Electrochemistry

Porphyrins and their metalloderivatives are a class of compounds exhibiting a wide variety of interesting and highly useful properties, such as chlorophyll. Porphyrins are particularly interesting in photoelectrochemical applications due to their structural similarity to chlorophylls in natural photosynthetic systems, as well as their strong and tunable absorption properties. Recently, various porphyrins have been extensively studied for their applications in solar cells, photocatalytic hydrogen production, optical information storage and others. This review will focus on the unique physical and chemical properties of D-π-A structured porphyrins, and their photovoltaic performances in dye-sensitized solar cells. A brief discussion in the future development …

Solvent Effect On The Anticorrosive Properties And Active Coating Area Of A Long Alkyd Varnish, Saadawy M., Abd-El-Nabey B.A., Gomaa A.Z., Ashour M.

Journal of Electrochemistry

The effects of solvent nature and composition on the anticorrosive properties of a long alkyd varnish after different days of immersion in 0.5 mol•L^-1 NaCl were studied using electrochemical impedance spectroscopy. The protection efficiencies of the long alkyd varnishes containing different solvents increased with increasing the volatility of solvent or the composition of a given volatile solvent, which was confirmed with the observations using scanning electron microscopy and energy-dispersive X-Ray spectroscopy. The delaminated area, the area where the organic coating is detached from the metal surface leaving it unprotected, was found to decrease by increasing the volatility of solvent.

Activation Effect Of Nano-Carbon Derived From Co2 On Lead Electrode In Sulfuric Aqueous Solution, Yu-Qiao Song, Hua Zhu, Guang-Jin Zhao, Wen-Long Wu, Shou-Bin Zhou, Di-Hua Wang

Journal of Electrochemistry

Serious sulfation of the negative plate is one of the most popular reasons of the early failure of lead-acid battery. Addition of nano-carbon was proved to be effective for recovering the sulfated electrode and the property of the carbon material always plays an important role. In this work, a new kind of nano-carbon material with high electrical conductivity and good adsorption capability for heavy metal cations, which is electrochemically prepared from CO₂ in molten carbonates, was tested as activation additive for the sulfated lead electrode by cyclic voltammetry and SEM measurements. The results showed that the as-prepared carbon can …

Cathode Buffer Layer For Improving Photovoltaic Performance Of Planar P-I-N Perovskite Solar Cells, Xiao-Dong Liu, Yong-Fang Li

Journal of Electrochemistry

Organic/inorganic hybrid metal halide perovskite semiconductor materials have drawn great attention for the application in solar cells in recent years because of their combined superior photoelectrical properties of inorganic semiconductors (with high dielectric constant and high charge carriers mobility) and organic semiconductors (with good solution processability and high absorbance). The power conversion efficiency (PCE) of the organometal halide perovskite solar cells (pero-SCs) based on CH₃NH₃PbI₃ has been increased dramatically in a few years from 3.8% to a certified 22.1%, primarily owing to the development of new interfacial materials, careful optimization of morphology, and perovskite crystallization …

Application Of Metal-Organic Frameworks In Dye-Sensitized Solar Cells, Ya-Feng Li, Qing-Qing Sun, Ming-Deng Wei

Journal of Electrochemistry

To assemble dye-sensitized solar cells (DSSCs) with high efficiencies, their photoanodes should have large specific surface area to establish a large adsorption amount of dyes and good light-harvesting ability. From this point of view, it will be an interesting topic to explore the application of metal-organic frameworks (MOFs) in the field of DSSCs due to their huge specific surface area. This paper introduces the application of MOFs in photovoltaic devices briefly, and then summaries our approaches in using MOFs in the study of DSSCs, including the pre-treatment and the post-treatment of photoanode, the preparation of photoanode materials and the light …

Discrimination Of Chiral Copper(Ii) Complexes Upon Binding Of Galactonoamidine Ligands, Susanne Striegler, Jessica Pickens

Chemistry & Biochemistry Faculty Publications and Presentations

The coordination between N-p-methylbenzyl-D-galactonoamidine, a putative transition state analogue of the hydrolyis of glycosidic bonds, and symmetric and chiral binuclear copper(II) complexes was characterized by spectroscopic titration, isothermal titration calorimetry, circular dichroism spectroscopy, and DFT calculations to elucidate the binding sites in the carbohydrate upon coordination to selected metal complexes. For the formation of metal complex-glyconoamidine assemblies, contributions of the amidine site and of the hydroxyl group at C-2 in the glycon of the amidine are noted. The chiral complexes S- and R-Cu2bpdbo are discriminated by a third binding site in the carbohydrate that leads to higher stability of complexes …

Selective Oxygen Atom Insertion Into An Aryl-Palladium Bond, Ava Behnia, Paul D. Boyle, Johanna M. Blacquiere, Richard J. Puddephatt

Chemistry Publications

The chemistry of a palladium(II) complex containing both an alkyl- and an aryl-palladium bond is reported. The reaction of [Pd(CH2CMe2C6H4)(MesN=CHCH=NMes)] with bromine or iodine leads to reductive elimination of 1,1-dimethylcyclobutabenzene with formation of [PdX2(MesN=CHCH=NMes)] (X = Br, I). However, the reaction with hydrogen peroxide gives [Pd(CH2CMe2C6H4O)(MesN=CHCH=NMes)] by overall oxygen atom insertion into the aryl-palladium rather than the alkyl-palladium bond. This complex [Pd(CH2CMe2C6H4O)(MesN=CHCH=NMes)] reacts with bromine, iodine, or hydrogen peroxide to give 3,3-dimethyl-2,3-dihydrobenzofuran and the corresponding complex [PdX2(MesN=CHCH=NMes)]. The mechanisms of reaction and basis for selectivity are discussed. The results support the view that oxygen atom insertion is a mechanistically viable …