Physical Chemistry Commons^™

Novel Algorithms And Instrumentation For Vibrational Spectroscopic Methods Of Analysis, Mohamed F. Abdelkader

Chemistry & Biochemistry Theses & Dissertations

Raman spectroscopy is a form of vibrational spectroscopy that has been increasingly applied to qualitative analysis of chemicals, explosives, pharmaceuticals, and fuels due to its non-invasive and non-destructive nature; its ease of sampling; and its high molecular specificity. These characteristics of Raman spectroscopy also facilitate its use for both in-line and at-line analysis. The principle limitation of Raman spectroscopy is optical interference arising from both analyte and non-analyte fluorescence. In this dissertation, a solution to this problem is presented in the form of a novel spectrometer design which operates in a sequentially shifted excitation mode to eliminate fluorescence backgrounds, fixed …

Patent: Fusion Proteins For Treating Metabolic Disorders, Brian R. Boettcher, Shari L. Caplan, Douglas S. Daniels, Norio Hamamatsu, Stuart Licht, Stephen Craig Weldon

Chemistry Faculty Publications

The invention relates to the identification of fusion proteins comprising polypeptide and protein variants of fibroblast growth factor 21 (FGF21) with improved pharmaceutical properties. Also disclosed are methods for treating FGF21 associated disorders, including metabolic conditions.

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. …

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 …

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 …

Synthesis: What We Have Learned From The East Texas Radiocarbon Database, Robert Z. Selden Jr., Timothy K. Perttula

CRHR: Archaeology

This poster provides a short overview of what we have learned from the East Texas Radiocarbon Database since it became available on the Council of Texas Archeologists’ website in 2011. These successes are numerous and include the advancement of novel methodological approaches; an improvement in our comprehension of the temporal nuances within the East Texas Archaic; the division of the East Texas Woodland period into Early, Middle and Late; the refinement of Caddo temporal chronology – particularly from a geographic perspective -- and it has provided one line of evidence to use to argue for the fluorescence of corn-based agriculture …

Radiocarbon Trends And The East Texas Caddo Tradition (Ca. A.D. 800-1680), Robert Z. Selden Jr., Timothy K. Perttula

CRHR: Archaeology

Through the employment of radiocarbon (¹⁴C) dates as data, we use the date combination process to refine site-specific summed probability distributions for 555 dates from Caddo sites (n = 19) in East Texas with 10 or more ¹⁴C dates. Summed probability distributions are then contrasted across river basins and natural regions with the remainder of the East Texas Caddo Radiocarbon Database (n = 338 dates from 132 other Caddo sites), highlighting the temporal and spatial character of Caddo archaeological sites throughout East Texas.

X-Band Rapid-Scan Epr, Deborah Gale Mitchell

Electronic Theses and Dissertations

The advantages of rapid-scan EPR relative to CW and pulse techniques for samples with long longitudinal relaxation time T₁ (N_s⁰ defects in diamond, N@C₆₀, and amorphous hydrogenated silicon), heterogeneous samples (crystalline 1:1 α,γ-bisdiphenylene-β-phenylallyl (BDPA):benzene), lossy samples (aqueous nitroxyl radicals), and transient radicals (5-tert-butoxycarbonyl-5-methyl-1-pyrroline-N-oxide (BMPO)-superoxide adduct) were studied.

For samples with long relaxation times, CW (continuous wave) EPR is challenging due to power saturation and distortions from passage effects. In rapid-scan EPR, the field is swept through resonance in a time that is short relative to T₂. In rapid-scan EPR, the magnetic field is …

Metastable Nanostructured Metallized Fluoropolymer Composites For Energetics, Hannah A. Miller, Bradley S. Kusel, Seth T. Danielson, James W. Neat, Eryn K. Avjian, Scott N. Pierson, Stephen M. Budy, David W. Ball, Scott T. Iacono, Sharon C. Kettwich

Chemistry Faculty Publications

Fluoropolymers have long served as potent oxidizers for metal-based pyrolant designs for the preparation of energetic materials. Commercial perfluoropolyethers (PFPEs), specifically known as Fomblins®, are well-known to undergo accelerated thermal degradation in the presence of native metals and Lewis acids producing energetically favorable metal fluoride species. This study employs the use of PFPEs to coat nano-aluminum (n-Al) and under optimized stoichiometric formulations, harness optimized energy output. The PFPEs serve as ideal oxidizers of n-Al because they are non-volatile, viscous liquids that coat the particles thereby maximizing surface interactions. The n-Al/PFPE blended combination is required to interface with an epoxy-based matrix …

Exploring Molecular Systems From Chemical Physics To Biochemistry Using Classical And Quantum Mechanics, Brian Thomas Psciuk

Wayne State University Dissertations

Six topic are considered in this dissertation. Chapter 2 is an investigation into the role of ultra-fast hydrogen dynamics in determining fragmentation products of C3H4 following exposure to intense laser fields. Classical dynamics simulations were performed starting from C3H4 isomers with 190 - 240 kcal/mol excess energy distributed randomly as nuclear momenta. Deprotonation events were seen in ca. 50 - 75 % of all trajectories. Roughly one third of all trajectories showed fragmentation involving internal isomerization prior to dissociation. Chapter 3 is a survey of currently popular density functional methods and their ability to calculate accurate excitation energies and intensities …

Fundamental Studies And Applications Of Strong Field Ionization, Lu Yan

Wayne State University Dissertations

In an intense laser field, atoms and molecules experience tunneling ionization directly to the continuum. We used this method to study several aspects and applications of strong field ionization (SFI) in atoms and molecules. One study used SFI to probe the photofragments produced by photodissociation using DC sliced imaging. The photodissociation mechanism of two polyatomic molecules (sulfur dioxide and nitromethane) were investigated. In a second study, we show the strong field ionization rate depends on the sign of the magnetic number distribution. We detect the signal of sequential double ionization of argon dications by a pump-probe method to investigate the …

Preparation Of Phosphonoterephthalic Acids Via Palladium-Catalyzed Coupling Of Aromatic Iodoesters, Nathaniel Ivan, Vladimir Benin, Alexander Morgan

Chemistry Faculty Publications

The current article reports in detail the preparation of two phosphonoterephthalic acids: 2-phosphonoterephthalic acid (1) and 2,5-diphosphonoterephthalic acid (2). Efficient, scalable syntheses have been developed for both compounds based on Pd-catalyzed coupling reactions of iodinated terephthalate esters. Phosphonoterephthalic acids are potentially useful as flame-retardant additives or as monomers for the construction of acid-pendant polymer chains.

The Bench Synthesis Of Silver Nanostructures Of Variable Size And An Introductory Analysis Of Their Optical Properties, Aoife Power, Tony Betts, John Cassidy

Articles

A laboratory practical was designed for use by both undergraduate and second level students to demonstrate the synthesis and characterisation of tuneable silver colloids. It clearly illustrates the novel optical properties of silver nanoparticles compared to the bulk metal. The synthesis is both rapid and repeatable, and can be conducted on the laboratory bench at room temperature.

Specific Salt Effects On The Formation And Thermal Transitions Among Β-Lactoglobulin And Pectin Electrostatic Complexes, Stacey Ann Hirt

Open Access Theses

Factors of ion specificity and ionic strength (I~0-100) were studied in the electrostatic complex formation and protein particle formation by thermal treatment for a β-lactoglobulin and pectin system. ζ-potential showed β-lactoglobulin and pectin began to interact near pH 5.50 and interactions were strengthened with decrease in pH. Visible light turbidimetry and light scattering at 90° revealed a trend in critical pH transitions for electrostatic complex formation based on both the ionic strength and the anion of the salt species, while effects of the monovalent cation was insignificant. Critical pH values for complex formation and separation (pHc and pHΦ) decreased with …

Pickering Stabilization Of Oil-Water Interfaces By Heated B-Lactoglobulin/Pectin Particles, Laura Kathryn Zimmerer

Open Access Theses

The use of natural biopolymer particles as Pickering stabilizers for oil-in-water emulsions was investigated. B-lactoglobulin microgels and B-lactoglobulin/pectin complexes were created by heating appropriate biopolymer solutions at pH 5.8 and 4.75, respectively. Resultant particles exhibited spherical morphology with diameters of 100-300 nm and possessed significant negative surface charge. Particles were first homogenized with 1% corn oil at 0.05%, 0.1% or 0.25% (wt/ wt) particle concentrations. All emulsions appeared stable over seven days with only a thin, creamed ring forming after several hours. Corn oil emulsions were most stable with 0.25% heated complexes, with volume-weighted mean droplet diameter remaining around 480 …

The Critical Role Of Mechanism-Based Models For Understanding And Predicting Liposomal Drug Loading, Binding And Release Kinetics, Sweta Modi

Theses and Dissertations--Pharmacy

Liposomal delivery systems hold considerable promise for improvement of cancer therapy provided that critical formulation design criteria can be met. The main objective of the current project was to enable quality by design in the formulation of liposomal delivery systems by developing comprehensive, mechanism-based mathematical models of drug loading, binding and release kinetics that take into account not only the therapeutic requirement but the physicochemical properties of the drug, the bilayer membrane, and the intraliposomal microenvironment.

Membrane binding of the drug affects both drug loading and release from liposomes. The influence of bilayer composition and phase structure on the partitioning …

Reaction Between Polyol-Esters And Phosphate Esters In The Presence Of Metal Carbides, David W. Johnson, Carolyn Iacullo, John E. Hils

Chemistry Faculty Publications

The reaction of metal carbides with polyol esters found in aerospace lubricants and phosphate esters commonly used as additives was investigated. Carbides were of particular interest since modern materials under consideration at high temperature bearings have surfaces that are primarily metal carbides. Vanadium and chromium carbide were found to react with the ester and phosphate ester by a transesterification reaction, producing an alkyl phosphate which is less stable than the aromatic phosphate esters. In the process, the metal carbide is converted to the metal phosphate and metal polyphosphate, evidenced by the infrared and Raman spectra of the solid residue and …

Brust-Schiffrin Synthesis Of Catalytic Bipodal Pdpt Nanoparticles With Some Mechanistic Insights, Sangbum Han, Vara P. Sheela, Wei Cao, Balasubramanian Ramjee

Applied Research Center Publications

Brust–Schiffrin reduction of Pd and Pt precursors in the presence of resorcinarene amine surfactant led to the formation of substantially Pt rich, PdPt bimetallic nanoparticles of a V-shape or variants on the V-shape. New insights into this reaction are provided on the basis of reversed Brust–Schiffrin syntheses, DLS, UV-vis, and NMR analysis. Based on our experiments we conclude that the resorcinarene amine surfactant is part of the inverse micelle formed from TOABr and it also selectively complexes with the Pd salts prior to their reduction. Remarkably, the composition of the bipodal nanoparticles could be varied substantially by varying the reaction …