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Full-Text Articles in Physical Sciences and Mathematics

Transient Electrochemical Surface-Enhanced Raman Spectroscopic Study In Electrochemical Reduction Of P-Nitrothiophenol, Yun Ling, Jing Tang, Guo-Kun Liu, Cheng Zong Dec 2019

Transient Electrochemical Surface-Enhanced Raman Spectroscopic Study In Electrochemical Reduction Of P-Nitrothiophenol, Yun Ling, Jing Tang, Guo-Kun Liu, Cheng Zong

Journal of Electrochemistry

P-nitrothiophenol (PNTP) is one of the most common probe molecules studied by surface-enhanced Raman spectroscopy (SERS). The research in electrochemical reduction behavior of PNTP will help understanding the mechanism for the nitrobenzene reduction. In this paper, we used transient electrochemical surface-enhanced Raman spectroscopy (TEC-SERS) to study the SERS of PNTP with cyclic voltammetry and chronoamperometry on gold electrodes. The results show that the TEC-SERS provide a time resolution that equals the transient electrochemical methods, and we concluded that the reaction was so quick that we did not observe the spectral information of intermediate species described in the literatures with a …


Electrochemical Behaviors Of Azopurine On Gold Electrodes, Ming-Xue Li, Hang Shi, Jia Liu, Meng Zhang, Jian-Zhang Zhou, De-Yin Wu, Zhong-Qun Tian Dec 2019

Electrochemical Behaviors Of Azopurine On Gold Electrodes, Ming-Xue Li, Hang Shi, Jia Liu, Meng Zhang, Jian-Zhang Zhou, De-Yin Wu, Zhong-Qun Tian

Journal of Electrochemistry

In this paper, we studied the electrochemical behaviors of azopurine on polished gold electrodes with cyclic voltammetry (CV). On the basis of analyzing scan rate and peak current, it was supposed that the redox process belonged to a reversible process controlled by adsorption in 0.2 mol·L-1 PBS (pH = 4.0 ~ 10.0) solutions. The potentials of redox peaks moved more negatively with increasing pH value. This proved that the H+ proton has participcted in the electrochemical reaction. The further data analysis and the calculation of surface adsorption excess demonstrated that the reaction was a two-proton and two-electron process. …


Bis(Tetra­Phenyl­Arsonium) Hexa­Fluorido­Technetate(Iv) Dihydrate: Preparation, Structure And Spectroscopic Analysis, Samundeeswari Mariappan Balasekaran, Frederic Poineau Nov 2019

Bis(Tetra­Phenyl­Arsonium) Hexa­Fluorido­Technetate(Iv) Dihydrate: Preparation, Structure And Spectroscopic Analysis, Samundeeswari Mariappan Balasekaran, Frederic Poineau

Chemistry and Biochemistry Faculty Research

Reports of quadrivalent transition-metal fluoride salts containing bulky organic cations are limited. In this context, we prepared the bis­(tetra­phenyl­arsonium) hexa­fluorido­technetate(IV) dihydrate salt, (C24H20As)2[TcF6]·2H2O, by a cation metathesis reaction of (NH4)2[TcF6] in water. This is the first report of an arsonium salt of the hexa­fluorido­technetate(IV) dianion. (AsPh4)2[TcF6]·2H2O crystallizes in the triclinic space group P[\overline{1}]. The [TcF6]2− anion adopts a slightly distorted octa­hedral geometry with an average Tc—F bond length of 1.933 Å. The cyclic voltammogram of (AsPh4)2[TcF6]·2H2O in CH3CN shows a one-electron reversible oxidation wave at 1.496 V.


Experimental And Computational Electrochemistry Of Quinazolinespirohexadienone Molecular Switches – Differential Electrochromic Vs Photochromic Behavior, Eric W. Webb, Jonathan P. Moerdyk, Kyndra B. Sluiter, Benjamin J. Pollock, Amy L. Speelman, Eugene J. Lynch, William F. Polik, Jason G. Gillmore Oct 2019

Experimental And Computational Electrochemistry Of Quinazolinespirohexadienone Molecular Switches – Differential Electrochromic Vs Photochromic Behavior, Eric W. Webb, Jonathan P. Moerdyk, Kyndra B. Sluiter, Benjamin J. Pollock, Amy L. Speelman, Eugene J. Lynch, William F. Polik, Jason G. Gillmore

Faculty Publications

Our undergraduate research group has long focused on the preparation and investigation of electron-deficient analogs of the perimidinespirohexadienone (PSHD) family of photochromic molecular switches for potential application as "photochromic photooxidants" for gating sensitivity to photoinduced charge transfer. We previously reported the photochemistry of two closely related and more reducible quinazolinespirohexadienones (QSHDs), wherein the naphthalene of the PSHD is replaced with a quinoline. In the present work, we report our investigation of the electrochemistry of these asymmetric QSHDs. In addition to the short wavelength and photochromic long-wavelength isomers, we have found that a second, distinct long-wavelength isomer is produced electrochemically. This …


Supercapacitors With Gate Electrodes, Tazima Selim Chowdhury May 2019

Supercapacitors With Gate Electrodes, Tazima Selim Chowdhury

Dissertations

A new approach to improve the capacitance of supercapacitors (SC) is proposed in this study. A typical SC is composed of an anode and a cathode; a separator in between them assures an unintentional discharge of the capacitor. The study focuses on a family of structured separators, either electronically active or passive which are called gates. An active structured separator layer has been fabricated and analyzed. The structured separator has characteristics of electrical diode and is fabricated out of functionalized carbon nanotubes (CNT). Improvement of the overall capacitance of SC, equipped with either active or passive structured separators demonstrated a …


Examining Electrochemical Properties Of O-Quinone And Sulfur Adducts Using Bisphenol A-3,4-Quinone Platform, Barbara Mullen May 2019

Examining Electrochemical Properties Of O-Quinone And Sulfur Adducts Using Bisphenol A-3,4-Quinone Platform, Barbara Mullen

Theses/Capstones/Creative Projects

o-Quinones are toxic electrophiles that can disrupt cellular macromolecules. Whether endogenous or xenobiotic, o-quinones are reactive compounds that are difficult to isolate. This work uses the o-quinone of bisphenol(BPA), bisphenol A-3,4-quinone(BPAQ), which can be efficiently synthesized and isolated, to study the electrochemical properties of o-quinones and their sulfur adducts in order to understand their metabolic fate. Cyclic voltammetry and equilibrium analysis were used to determine the relative oxidation potential of the BPA catechol and adducts, formed by reacting glutathione(GSH) and N-acetylcysteine(NAC) with BPAQ. BPAQ-sulfur adducts with 5-position substitution displayed lower oxidation potentials when compared to the …


Surface Immobilization Of Terpyridine Compounds, Elizabeth Hallett May 2019

Surface Immobilization Of Terpyridine Compounds, Elizabeth Hallett

Chemical Engineering Undergraduate Honors Theses

The deoxydehydration (DODH) of polyols to alkenes is a promising method of producing high-value chemical feedstocks from biomass-derived materials. Current catalytic systems for DODH require the use of costly reducing agents that generate stoichiometric amounts of chemical waste. Immobilizing catalysts on electrode surfaces using chemical linking groups eliminates the need for sacrificial reductants. In this work, glassy carbon electrodes were modified with 4’-(3,4-dihydroxyphenyl)-2,2’:6’,2’’-terpyridine to investigate o-benzoquinone as a potential linking group for DODH, and possibly for other reactions. Previous studies involving electrodes modified with quinone-containing compounds have primarily been focused on catalyzing the oxidation of NADH; the nature or …


Electrochemical Oxidation Of Curcuminoids: An Experimental And Computational Investigation, Zeynep Kalaycioğlu, Nurgül Karadaş, Mehmet Emi̇n Çinar, Si̇bel Ayşil Özkan, Duri̇şehvar Özer Ünal, Ayşegül Gölcü, Fatma Bedi̇a Eri̇m Jan 2019

Electrochemical Oxidation Of Curcuminoids: An Experimental And Computational Investigation, Zeynep Kalaycioğlu, Nurgül Karadaş, Mehmet Emi̇n Çinar, Si̇bel Ayşil Özkan, Duri̇şehvar Özer Ünal, Ayşegül Gölcü, Fatma Bedi̇a Eri̇m

Turkish Journal of Chemistry

Curcuminoids, reported to have important biological properties, such as antioxidant, anti-Alzheimer, and antidiabetic properties, comprise curcumin (CRM; 1,7-bis [4-hydroxy-3-methoxyphenyl]-1,6-heptadiene-3,5-dione) and its derivatives demethoxycurcumin (DMC; (E,6E)-1-(3,4-dimethoxy-cyclohexyl)-7-(3,4-dimethoxyphenyl)hepta-1,6-diene-3,5-dione) and bisdemethoxycurcumin (BDMC; 1,7-bis[4-hydroxyphenyl]-1,6-heptadiene-3,5-dione). Their electrochemical oxidations are thoroughly explored by applying cyclic and differential pulse voltammetric techniques. The dependence of current intensities and potentials on pH, concentration, scan rate, and nature of the buffer was investigated. The outcome is supported by density functional theory computations indicating the transfer of 4-e$^{-}$/H$^{+}$, 6-e$^{-}$/H$^{+}$, and 8-e$^{-}$/H$^{+}$ couples involved in the oxidation mechanisms of CRM, DMC, and BDMC, respectively, leading to the formation of the same oxidized product.


In Silico And In Vitro Evaluation Of The Biological Activity Of Some Organic Sulfur-Containing Compounds, Victoria Osipova, Maria Polovinkina, Anastasia Osipova, Yulia Gracheva, Andrey Okhlobystin Jan 2019

In Silico And In Vitro Evaluation Of The Biological Activity Of Some Organic Sulfur-Containing Compounds, Victoria Osipova, Maria Polovinkina, Anastasia Osipova, Yulia Gracheva, Andrey Okhlobystin

Turkish Journal of Chemistry

It was predicted, using the Prediction of Activity Spectra for Substances online software, that organic sulfur-containing compounds 2,6-di-tert-butyl-4-mercaptophenol (1), 2,6-di-tert-butyl-4-(3-mercaptopropyl)phenol (2), bis-3-[3,5-di-tert-butyl-4-hydroxyphenyl)propyl] sulfide (3), bis(3,5-di-tert- butyl-4-hydroxyphenyl) disulfide (4), diphenyl disulfide (5), dibenzyl disulfide (6), dibutyl disulfide (7), di-tert-butyl disulfide (8), diallyl disulfide (9), and methyl propyl trisulfide (10) could possess antioxidant activity and act as active scavengers of oxygen metabolites. The antiradical activity of these species was analyzed and it was shown that they were able to react with electrochemically generated the superoxide anion radical. The rate constants for reactions of 1-10 with the superoxide anion radical were calculated. The …


Amperometric Urea Biosensor Based On Immobilized Urease On Polypyrrole And Macroporous Polypyrrole Modified Pt Electrode, Maliheh Hosseinian, Ghasem Najafpour, Ahmad Rahimpour Jan 2019

Amperometric Urea Biosensor Based On Immobilized Urease On Polypyrrole And Macroporous Polypyrrole Modified Pt Electrode, Maliheh Hosseinian, Ghasem Najafpour, Ahmad Rahimpour

Turkish Journal of Chemistry

Biosensing of urea by a biosensor as a direct detection method at ambient temperature and pressure instead of chromatography leads to a significant reduction in processing costs. Amperometric biosensors based on urease immobilization on macroporous polypyrrole (MPPy) and pyrrole on the surface of a Pt electrode were developed. Applying cyclic voltammetry (CV), we demonstrated the synthesis of MPPy using monodispersed polystyrene spheres (460 nm) as a template. CV and chronoamperometric studies were conducted to evaluate the electrochemical current of the modified electrodes. For the electrode with polypyrrole (PPy), the biosensor response was linear in the range of 1.67--8.32 mM (R$^{2}$ …