Chemistry Commons^™

Tranformation Theory, Ronald Lovett

Topics in Quantum Mechanics

No abstract provided.

Insights Into The Roles Of Desolvation And Π-Electron Interactions During Dna Polymerization, Edward A. Motea, Irene Lee, Anthony J. Berdis

Chemistry Faculty Publications

This report describes the use of several isosteric non-natural nucleotides as probes to evaluate the roles of nucleobase shape, size, solvation energies, and π-electron interactions as forces influencing key kinetic steps of the DNA polymerization cycle. Results are provided using representative high- and low-fidelity DNA polymerases. Results generated with the E. coli Klenow fragment reveal that this high-fidelity polymerase utilizes hydrophobic nucleotide analogues with higher catalytic efficiencies compared to hydrophilic analogues. These data support a major role for nucleobase desolvation during nucleotide selection and insertion. In contrast, the low-fidelity HIV-1 reverse transcriptase discriminates against hydrophobic analogues and only tolerates non-natural …

Use Of Soybean Lecithin In Shape Controlled Synthesis Of Gold Nanoparticles, Benjamin Robert Ayres

Dissertations and Theses

The work presented in this dissertation is a composite of experiments in the growth of gold nanoparticles with specific optical properties of interest. The goal is to synthesize these gold nanoparticles using soybean extract for not only shape control, but for propensity as a biocompatible delivery system. The optical properties of these nanoparticles has found great application in coloring glass during the Roman empire and, over the centuries, has grown into its own research field in applications of nanoparticulate materials. Many of the current functions include use in biological systems as biosensors and therapeutic applications, thus making biocompatibility a necessity. …

Soil Chemistry Response To Wollastonite (Casio3) Addition At Hubbard Brook, Chris E. Johnson

Civil and Environmental Engineering - All Scholarship

No abstract provided.

Effects Of The Protein Environment On The Spectral Properties Of Tryptophan Radicals In Pseudomonas Aeruginosa Azurin, Caterina Bernini, Tadeusz AndrunióW, Massimo Olivucci, Rebecca Pogni, Riccardo Basosi, Adalgisa Sinicropi

Chemistry Faculty Publications

Many biological electron-transfer reactions involve short-lived tryptophan radicals as key reactive intermediates. While these species are difficult to investigate, the recent photogeneration of a long-lived neutral tryptophan radical in two Pseudomonas aeruginosa azurin mutants (Az48W and ReAz108W) made it possible to characterize the electronic, vibrational, and magnetic properties of such species and their sensitivity to the molecular environment. Indeed, in Az48W the radical is embedded in the hydrophobic core while, in ReAz108W it is solvent-exposed. Here we use density functional theory and multiconfigurational perturbation theory to construct quantum-mechanics/molecular-mechanics models of Az48W* and ReAz108W* capable of reproducing specific features of their …

Tuning Photophysical Properties And Improving Nonlinear Absorption Of Pt(Ii) Diimine Complexes With Extended Π-Conjugation In The Acetylide Ligands, Rui Liu, Alexander Azenkeng, Dapeng Zhou, Yuhao Li, Ksenija D. Glusac, Wenfang Sun

Chemistry Faculty Publications

Two new Pt(II) 4,4'-di(5,9-diethyltridecan-7-yl)-2,2'-bipyridine complexes (1 and 2,) bearing 9,9-diethyl-2-ethynyl-7-(2-(4-nitrophenyl)ethynyl)-9H-fluorene ligand and N-(4-(2-(9,9-diethyl-7-ethynyl-9H-fluoren-2-yl)ethynyl)phenyl)-N-phenylbenzeneamine ligand, respectively, were synthesized and characterized. Their photophysical properties were investigated systematically by UV vis absorption, emission, and transient absorption (TA) spectroscopy, and the nonlinear absorption was studied by nonlinear transmission technique. Theoretical TD-DFT calculations using the CAM-B3LYP functional were carried out to determine the nature of the singlet excited electronic states and to assist in the assignment of significant transitions observed in experiments. Complex 1 exhibits an intense, structureless absorption band at ca. 397 nm in CH2Cl2 solution, which is attributed to mixed metal-to-ligand charge transfer …

Oxidation Of Adenosine And Inosine: The Chemistry Of 8-Oxo-7,8-Dihydropurines, Purine Iminoquinones, And Purine Quinones As Observed By Ultrafast Spectroscopy, Denis I. Nilov, Dmitry Y. Komarov, Maxim S. Panov, Kanykey E. Karabaeva, Andrey S. Mereshchenko, Alexander N. Tarnovsky, R. Marshall Wilson

Chemistry Faculty Publications

Oxidative damage to purine nucleic acid bases proceeds through quinoidal intermediates derived from their corresponding 8-oxo-7,8-dihydropurine bases. Oxidation studies of 8-oxo-7,8-dihyroadenosine and 8-oxo-7,8-dihydroinosine indicate that these quinoidal species can produce stable cross links with a wide variety of nucleophiles in the 2-positions of the purines. An azide precursor for the adenosine iminoquinone has been synthesized and applied in ultrafast transient absorption spectroscopic studies. Thus, the adenosine iminoquinone can be observed directly, and its susceptibility to nudeophilic attack with various nucleophiles as well as the stability of the resulting cross linked species have been evaluated Finally, these observations indicate that this …

Site-Specific Inter-Strand Cross-Links Of Dna Duplexes, Miao Ye, Johan Guillame, Yu Liu, Ruojie Sha, Risheng Wang, Nadrian C. Seeman, James W. Canary

Chemistry Faculty Research & Creative Works

We report the development of technology that allows inter-strand coupling across various positions within one turn of DNA. Four 2'-modified nucleotides were synthesized as protected phosphoramidites and incorporated into DNA oligonucleotides. The modified nucleotides contain either 5-atom or 16-atom linker components, with either amine or carboxylic acid functional groups at their termini, forming 10 or 32 atom (11 or 33 bond) linkages. Chemical coupling of the amine and carboxylate groups in designed strands resulted in the formation of an amide bond. Coupling efficiency as a function of trajectory distance between the individual linker components was examined. For those nucleotides capable …

Observation Of Ground-State Two-Neutron Decay, M Thoennessen, Z Kholey, A Spyrou, E Lunderberg, Paul A. Deyoung, H Attanayake, T Baumann, D Bazin, B A. Brown, G Christian, D Divaratne, S M. Grimes, A Haagsma, J E. Finck, N Frank, B Luther, S Mosby, T Nagi, Graham F. Peaslee, W A. Peters, A Schiller, J K. Smith, J Snyder, M Strongman, A Volya

Faculty Publications

Neutron decay spectroscopy has become a successful tool to explore nuclear properties of nuclei with the largest neutron-to-proton ratios. Resonances in nuclei located beyond the neutron dripline are accessible by kinematic reconstruction of the decay products. The development of two-neutron detection capabilities of the Modular Neutron Array (MoNA) at NSCL has opened up the possibility to search for unbound nuclei which decay by the emission of two neutrons. Specifically, this exotic decay mode was observed in¹⁶Be and ²⁶O.

Immunological And Reproductive Health Assessment In Herring Gulls And Black-Crowned Night Herons In The Hudson-Raritan Estuary, Keith A. Grasman, Kathy R. Echols, Thomas M. May, Paul H. Peterman

University Faculty Publications and Creative Works

Previous studies have shown inexplicable declines in breeding waterbirds within western New York/New Jersey Harbor between 1996 and 2002 and elevated polychlorinated dibenzo-p-dioxins and polychlorinated biphenyls (PCBs) in double-crested cormorant (Phalacrocorax auritus) eggs. The present study assessed associations between immune function, prefledgling survival, and selected organochlorine compounds and metals in herring gulls (Larus argentatus) and black-crowned night herons (Nycticorax nycticorax) in lower New York Harbor during 2003. In pipping gull embryos, lymphoid cells were counted in the thymus and bursa of Fabricius (sites of T and B lymphocyte maturation, respectively). The phytohemagglutinin (PHA) skin response assessed T cell function in …

Variational Principle Variational Calculations Of Energy Eigenstates, Ronald Lovett

Topics in Quantum Mechanics

No abstract provided.

Iapp Aggregation And Cellular Toxicity Are Inhibited By 1,2,3,4,6-Penta-O-Galloyl-Β-D-Glucose, Edward Bruno, Catalina Pereira, Karla P. Roman, Marisa Takiguchi, Pei-Yu Kao, Luiza A. Nogaj, David A. Moffet

Chemistry and Biochemistry Faculty Works

The polyphenol, 1,2,3,4,6-penta-O-galloyl-β-D-glucose (PGG) has been found to exhibit a host of positive pharmacologic activities, including anti-cancer and anti-diabetic. Little is known about the mode of action of PGG in yielding these positive activities. We show here that PGG is a potent inhibitor of IAPP (islet amyloid polypeptide, amylin) aggregation. Preventing the initial aggregation event of IAPP is one strategy for slowing, and possibly preventing, the toxic effects of IAPP oligomeric intermediates. Equal molar ratios of PGG to IAPP substantially reduced the ability of IAPP to bind thioflavin T. Atomic force microscopy revealed that PGG prevented amyloid-based fiber formation under …

Affinity Monolith Chromatography: A Review Of Principles And Recent Analytical Applications, Erika L. Pfaunmiller, Marie Laura Paulemond, Courtney M. Dupper, David S. Hage

David Hage Publications

Affinity monolith chromatography (AMC) is a type of liquid chromatography that uses a monolithic support and a biologically-related binding agent as a stationary phase. AMC is a powerful method for the selective separation, analysis or studies of specific target compounds in a sample. This review discusses the basic principles of AMC and recent developments or applications of this method, with particular emphasis being given to work that has appeared in the last five years. Various materials that have been used to prepare columns for AMC are examined, including organic monoliths, silica monoliths, agarose monoliths and cryogels. These supports have been …

Density Functional Theory And The Calculation Of Tcmg2O4 Spinel Lattice Parameters, Jon Karlo Macias

Physics

The cohesive energy, lattice constant and bulk modulus of two simple HCP crystal structures of magnesium and technetium were calculated using the vienna ab initio simulation package (VASP) which is based on density functional theory (DFT). The same properties were determined for TcMg₂O₄ spinel. The theoretical results of the lattice constant of the pure crystals were compared to experimental results and found to be in excellent agreement with a difference of less than 2%. The results for the lattice constant of the TcMg₂O₄ spinel were found to be in excellent agreement as well with …

Kinetic And Spectroscopic Studies Of Bicupin Oxalate Oxidase And Putative Active Site Mutants, Ellen W. Moomaw, Eric Hoffer, Patricia Moussatche, John C. Salerno

Faculty Articles

Ceriporiopsis subvermispora oxalate oxidase (CsOxOx) is the first bicupin enzyme identified that catalyzes manganese-dependent oxidation of oxalate. In previous work, we have shown that the dominant contribution to catalysis comes from the monoprotonated form of oxalate binding to a form of the enzyme in which an active site carboxylic acid residue must be unprotonated. CsOxOx shares greatest sequence homology with bicupin microbial oxalate decarboxylases (OxDC) and the 241-244DASN region of the N-terminal Mn binding domain of CsOxOx is analogous to the lid region of OxDC that has been shown to determine reaction specificity. We have prepared a series of CsOxOx …

Student Named Acs Scholar, Mallika Kavadi

News and Events (Discontinued Series)

No abstract provided.

Rearrangement Of Cyclotriveratrylene (Ctv) Diketone: 9,10-Diarylanthracenes With Oled Applications, Samuel R. Sarsah, Marlon R. Lutz Jr., Matthias Zeller, David S. Crumrine, Daniel Becker

Chemistry: Faculty Publications and Other Works

Electroluminescent 9,10-diaryl anthracenes have been shown to be promising host and hole-transporting materials in organic electroluminescence due to their high thermal stability, electrochemical reversibility, and wide band gap useful for organic light-emitting diodes (OLEDs), especially blue OLEDs. Oxidation of cyclotriveratrylene (CTV) to the corresponding diketone and subsequent bromination resulted in an unexpected rearrangement to a highly functionalized 9-aryl-10-bromoanthracene derivative, which was employed in Suzuki couplings to synthesize a series of 9,10-diaryl compounds that are structural analogues of anthracene derivatives used in the preparation of OLEDs but are more highly functionalized, including electron-donating methoxy groups in addition to substitution by a …

Physical Essentials Of Rotating Complex Impedance Diagram In Some Electrochemical Systems, Bing-Liang Wu

Journal of Electrochemistry

The essential of the rotation of complex impedance diagram in some electrochemical systems is discussed. It is attributing to that the electrochemical capacitance usual is not simple real capacitor but must be complex number capacitance. As the examples: 1, the metal/support electrolyte electrode in the ideal polarization condition, the capacitance must be that of the electrochemical double layer and represents complex number properties. Its complex impedance diagram was not a line parallel to imaginary axis but rotated clockwise α=arctgC"/C'. 2, In the case of insertion/desertion electrodes, the capacitance must be that of the solid electrolyte interphase (SEI). The rotation of …

Combination And Applications Of Time-Resolved Surface Plasmon Resonance Spectroscopy And Electrochemical Methods, Yu Bao, Yan Mao, Wei Wang, Zheng-Gang Li, Li Niu

Journal of Electrochemistry

Electrochemical-surface plasmon resonance (EC-SPR) technique, developed in recent years, is a new technology which combines time-resolved surface plasmon resonance spectroscopy and electrochemical methods. Surface plasmon resonance (SPR) is a physical phenomenon generated by optical coupling using a metallic thin film and is very sensitive to optical analysis. The principles of SPR and EC-SPR are briefly introduced and the applications of the combination of SPR spectroscopy with electrochemical techniques are reviewed in this paper. This new technology has been widely used in such research areas as reaction dynamics, biochemical sensors, electrode/electrolyte interfaces, kinetic parameters and bimolecular interactions.

High Performance Membrane Electrode Assembly With Low Platinum Loadings Prepared By Atomic Layer Deposition For Pemfc Application, Ting Shu, Shi-Jun Liao, Chien-Te Hsieh, Ay Su

Journal of Electrochemistry

A high performance membrane electrode assembly (MEA) with low platinum loadings was successfully prepared with atomic layer deposition (ALD) technique. The anode of the MEA was prepared by depositing platinum on the carbon paper substrate, which was prepared by coating the slurry of carbon black (XC-72R) and Teflon, followed by drying and calcining at 350 °C. The MEAs consisted of the ALD anode or commercial catalyst anode, pretreated Nafion membrane (Nafion-117) and commercial cathode. Performances of MEAs were measured by single cell testing, and the anodes and MEAs were characterized by CV, SEM, TEM and XRD. The results revealed that …

Electrochemical Performance Of Fe3O4/C Composites As Negative Material For Lithium-Ion Batteries, Jun-Jie Cai, Shu Yao, Ze-Sheng Li, Hui Meng, Pei-Kang Shen

Journal of Electrochemistry

The Fe₃O₄/Carbon composites have been synthesized through coprecipitation pathway and by insitu aniline polymerization as a carbon source. Structural characterization and morphological study of the composites were investigated by using XRD, SEM and TEM techniques. The results showed that the nanosized Fe₃O₄ particles (40 ~ 80 nm) were encapsulated in the amorphous carbon. During the electrochemical tests, the Fe₃O₄/C composites exhibited high capaticity and excellent cycle ability, the retention of capaticity was about 1000 mAh·g^-1 after 30 cycles of charge/discharge tests at 50 mA·g^-1.

A Comparative Study Of Charge-Discharge Behaviors Of α-Pbo2 And β-Pbo2 Cathodes, Cong-Ying Cui, Xue-Mei Ma, De-Long Kong, Hou-Yi Ma

Journal of Electrochemistry

The α-PbO₂ and β-PbO₂ powders were prepared using simple chemical synthetic methods, and their crystalline structures and surface morphologies were characterized with X-ray powder diffraction spectroscopy and scanning electron microscopy. Using the as-synthesized α-PbO₂ and β-PbO₂ powders as positive active materials, the electrochemical performance of the two PbO₂ materials was investigated by means of cyclic voltammetry, galvanostatic charge-discharge tests, and electrochemical impedance spectroscopy. The results indicate that the discharge capacity of α-PbO₂ electrode is larger than that of β-PbO₂; moreover, the composite electrodes made by α-PbO₂ and β-PbO₂ mixtures with …

An In Situ Ftir Spectroelectrochemical Study On Methanol Oxidation At Pt-Mo2C/Gc Catalyst, Hai-Ping Huang, Xi-Yu Yao, Pei-Kang Shen

Journal of Electrochemistry

A 40% Pt on Mo₂C/GC catalyst has been prepared by ion exchange method. The mechanism of methanol electrooxidation on Pt-Mo₂C/GC and commercial Pt/C catalysts in acidic media was studied by cyclic voltammetry, XRD measurements and in-situ Fourier transform infrared spectroelectrochemistry. The results revealed that the Pt nanoparticles were uniformly dispersed on Mo₂C/GC with an average particle size of 3 nm. The cyclic voltammetric and chronopotentiometric experiments indicated that Pt-Mo₂C/GC catalyst exhibited a better performance for methanol oxidation than that of Pt/C in acid solution. A negative shift over 90 mV of the …

Recent Experimental Progresses On Electrochemical Atr-Seiras, Yao-Yue Yang, Han-Xuan Zhang, Wen-Bin Cai

Journal of Electrochemistry

Technical aspects on developing electrochemical ATR surface-enhanced infrared absorption spectroscopy are briefly accounted mainly based on our recent investigations, including wet-fabrication of metallic film electrodes on Si prism, design and construction of a wide-frequency combination optical window and a spectroelectrochemical cell switchable for external and internal reflection modes.

Applications Of Ellipsometry In The Investigations Of Electrode-Solution Interface, Jing-Lei Lei, Liang-Liu Wu, Ling-Jie Li, Sheng-Mao Wu, Sheng-Tao Zhang

Journal of Electrochemistry

Ellipsometry is an optical technique with high-sensitivity to quantitatively obtain surface/interface properties such as thickness andrefractive index by analyzing the changes in polarized light reflected from the surface/interface. Its noncontacting and nondestructivenature makes it possible to acquire thein situreal-time information of the change at the surface/interface. Therefore, ellipsometry has been used widely in the electrochemical investigations. In this paper, based on the brief introduction of the measurementprinciple of ellipsometry, the current progress and the future trends of ellipsometry in electrochemistry arediscussed. The applications of ellipsometry in the fields of conversion and storage of electrochemical energy, electrochemistry ofmaterials science,electroanalysisand bioelectrochemistry are …

Oxygen Reduction Reaction On Glycin Modified Pt(111) Electrode, Ming-Fang Li, Jing Kang, Ling-Wen Liao, Yan-Xia Chen, Shen Ye

Journal of Electrochemistry

O

xygen reduction reaction (ORR) on glycin (NH₂CH₂COOH) modified Pt(111) electrode has been investigated using hanging meniscus rotating disk electrode system (HMRD) in 0.05 mol•L^-1 H₂SO₄ and 0.1 mol•L^-1 HClO₄ solutions, respectively. Cyclic voltammograms of the glycin modified Pt (111) electrode measured in 0.05 mol•L^-1 H₂SO₄ solution similar to that of CN^- modified Pt(111) electrodes, demonstrating that sulfate adsorption is strongly inhibited at the glycin modified Pt(111). From the polarization curve of ORR recorded in 0.05 mol•L^-1 H₂SO₄ solution, it is …

Porous Electrodes With High Pt Utilization Obtained By Ion-Exchange/Electrodeposition, Si-Guo Chen, Wei Ding, Xue-Qiang Qi, Li Li, Zi-Hua Deng, Zi-Dong Wei

Journal of Electrochemistry

We report a novel method based on ion-exchange/electrodeposition (IEE) for constructing high Pt utilization porous electrodes. The electrode prepared using IEE was assessed by linear sweep voltammetry (LSV), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and single cell test. The preliminary results show that the undesired ion-exchange between Pt anion and surface functional group in carbon black can be eliminated through the electrode preparation process, and every Pt particle prepared by IEE is expected to be deposited on the three-phase reaction zone and thus can be fully utilized in fuel cell reactions. The Pt particle size, shape and distribution …

Effect Of Ti/Pbo2 Electrodes Doped With Different Elements On Electrocatalytic Oxidation Characteristics Of Phenol, Xiao-Lei Liu, Yuan-Yuan Dan, Hai-Yan Lu, Hai-Bo Lin, Ming-Li Ouyang, Chuan-Jun Yun

Journal of Electrochemistry

Three types of electrodes, namely, Ti/PbO₂, F-doped PbO₂ (Ti/PbO₂-F) and nano-Co₃O₄-doped PbO₂ (Ti/PbO₂+Nano-Co₃O₄) electrodes, were prepared by electro-deposition method on the Ti substrate with the interlayer of SnO₂-Sb₂O₅. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to study the compositions, structures and film morphologies of the electrodes. Electrocatalytic oxidation characteristics to phenol on the prepared electrodes were investigated by electrochemical method. The experimental results showed that compared with the Ti/PbO₂ electrode, the potentials of oxygen …

A Dft Calculation Screening Of Pt-Based Bimetallic Catalysts For Oxygen Reduction, Li-Hui Ou, Sheng-Li Chen

Journal of Electrochemistry

Developing Pt-lean catalysts for oxygen reduction reaction (ORR) is the key for large-scale application of proton exchange membrane fuel cell (PEMFC). In this paper, we have proposed a multiple-descriptor strategy for screening efficient and durable ORR alloy catalysts of low Pt content. We argue that an ideal Pt-based bimetallic alloy catalyst for ORR should possess simultaneously negative alloy formation energy, negative surface segregation energy of Pt and a lower oxygen binding ability than pure Pt. By performing detailed DFT calculations on the thermodynamics, surface chemistry and electronic properties of various Pt-M alloys (M refers to non-precious transition metals in the …

Sodium Carbonate Catalyzed Photoelectrochemical Water Splitting Over Tio2 Nanotubes Photoanode, De-Sheng Kong, Jing Wang, Xue-Di Zhang, Xi Zhao, Chao Wang, Yuan-Yuan Feng, Wen-Juan Li

Journal of Electrochemistry

Surface recombination of the photogenerated electron-hole pairs at semiconductor/electrolyte interface is one of the most essential reasons responsible for lowering photoconversion efficiency (Φ) of light to chemical energy for photoelectrochemical (PEC) water splitting reaction. In this paper, the catalytic effect of sodium carbonate on the oxygen evolution reaction (OER) over TiO₂ nanotubes photoanode during PEC water splitting was investigated by performing photocurrent and ac impedance measurements. It was demonstrated that the addiction of 1 mmol•L^-1 Na₂CO₃ in 0.5 mol•L^-1 NaClO₄ electrolyte can effectively improve the charge transfer properties for the photogenerated holes across …