Chemistry Commons^™

Stereoselective Determination Oftrihexyphenidyl In Human Serum By Lc–Esi–Ms, Vladimı́R Čápka, Yan Xu, Yong Hong Chen

Chemistry Faculty Publications

The antiparkinsonian drug trihexyphenidyl (THP) is currently manufactured and administered as a racemate. However, stereochemistry can play significant role in the drug’s pharmacokinetics, biotransformation, metabolism, interaction with cellular and tissue components and overall effect on human body. It is necessary to consider such a drug as a mixture of two compounds (drug enantiomers), with their own effect on the human body. The present paper describes a simple and sensitive LC–MS method for the stereoselective determination of THP in human serum. In this study, the sample was prepared by a solid-phase extraction (SPE) procedure. The enantiomer separation was done using native …

Method Of Storing Active Zero Valent Zinc Metal, Reuben D. Rieke

Department of Chemistry: Faculty Publications

A novel Zerovalent Zinc species and an organozinc reagent are disclosed. The Zerovalent Zinc species is directly pro duced by reaction of a reducing agent on a Zinc Salt, preferably Zn(CN). The organozinc regent results from the reaction of the Zerovalent Zinc species and an organic compound having one or more stable anionic leaving groups. These organozinc reagents include a wide spectrum of functional groups in the organic radical, and are useful in a variety of reactions Schemes.

Humic Substances As Interferences In The Analysis Of Nitrite In Water, Stephanie Ann Tebault

Chemistry & Biochemistry Theses & Dissertations

Humic substances are of current interest because of their roles in environmental processes involving pollutants. It is also becoming recognized that humic substances may interfere in analysis of environmental samples though the possible adverse effects do not appear to be fully appreciated. The present effort focuses on determining whether humic materials interfere in the analysis of nitrite in water using the Griess reaction. This is a well-known reaction using nitrosation to gjve a diazonium salt followed by coupling with an appropriate reagent to form a dye. This colorimetric method continues to be applied in the laboratory and the field for …

In Situ Ftirs Studies Of The Electrochemically Induced Coupling Of Osmium Nitrido Species In Acetonitrile, Sheng-Pei Chen, Shi-Gang Sun

Journal of Electrochemistry

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Calculation Of Corrosion Rate Of Passive Metals With Charge Curve Analysis Technique, Yuan-Sheng Zhang, Min Gong

Journal of Electrochemistry

This work contains two parts: (1) A charge curve equation having no appro-ximation for passivated metal corrosion systems is derived and compared with the routine charge curve equation, which is virtual only when the polarization is minim(linear range). (2) It is simpler to analyze charge curve data by from of charge differential equation than from charge curve equation. After the charge curve data are measured, the slope of charge curve is computed by numerical differentiation method, then the charge differential equation may be transformed to a set of linear equations using polynomial approximation. The electrochemical parameters of corrosion system would …

The Ac-Impedance Analysis For Pluse Oxide Film Of Aluminium Alloy, Ai-Ling Du, Xi-Cheng Ma, He-Ming Zhang

Journal of Electrochemistry

Bode diagrams for aluminum PC (abbreviated from pulse current) oxide films were first obtained by AC-impedance measurements in a wide range of frequency. The experimental results show that different kinds of electrical equivalent circuits can be used for representing PC films and DC (abbreviated from direct current) oxide films separately, the main differences between them are their porous layers, the PC films are more even with little defects.Those are also verified by SEM and V-I characteristic curve measurements.

Study On The Microband Array Electrode-Based Glucose Microsensor, Neng-Qin Jia, Chui-Jue Sun, Lin Gao, Zong-Rang Zhang, Jian-Zhong Zhu, Guo-Xiong Zhang

Journal of Electrochemistry

The microband array electrode (MAE) consisting of 11 Pt microband of 5 m in wide, 2000 m long and 85 m gap was fabricated with a thin film techology. The MAE was characterized by means of cyclic voltammetry in a solution of K₃Fe(CN)₆ and H₂O₂. The results showed higher current density on MAE than on conventional Pt eletrode due to the strong edge effect of the former. A glucose microsensor was constructed with the substrate electrode of microband array. Microband array electrode was modified by Nafion followed by the immobilization of ferrocene onto …

In Situ Ftir Spectroelectrochemical Study Of Palladium Hexacyanoferrate Thin Film Deposited On Glassy Carbon Electrode, Ai-Li Bo, Xiang-Qin Lin

Journal of Electrochemistry

The electrochemically deposited Palladium hexacyanoferrate thin film on Glassy Carbon electrode (PdHCF|GC) has been studied in HCl, KCl and NaCl solutions by in-situ external reflection FTIR spectroelectrochemical technique. It is found that the behavior of the electroactive PdHCF film can be understood in terms of two states: Pd₂Fe(II)(CN)₆ formed in the inner layer and (M⁺)2Fe(II)(CN)₆ (M⁺: electrolyte cation) formed in the outer layer. The inner layer is oxidized at E_m=0.87 V in 1 mol/L KCl, while for the outer layer Em=0.77 V(vs. Ag/AgCl). In 1 mol/L NaCl or HCl solutions, …

Molecular Composition Of The Louse Sheath, Craig N. Burkhart, B Artur Stankiewicz, Irene Pchalek, Michael A. Kruge, Craig G. Burkhart

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Flash pyrolysis-gas chromatography/mass spectrometry was used to assess the chemical composition of the head louse's nit sheath. The pyrolyzate of the female insect's secretions, which form a cement-like cylinder holding the egg onto the hair, is dominated by amino acid derivatives and fatty acids. No chitin-specific compounds were detected in the sheath. These results, contrary to previous reports, show that the polymeric complex of the sheath is composed of proteinaceous moieties, possibly cross-linked to aliphatic components. This study constitutes the first chemical characterization of the pyrolysis products of insect (louse) glue and unequivocally confirms that louse sheaths are not chitinous, …

A Biogeochemical Comparison Of Fossil (Carboniferous) And Modern Crustose Red Algae, Michael A. Kruge, John E. Utgaard, William Ferry

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The nature of the contribution of the various types of algae to sedimentary organic matter continues to be a topic of research interest. Crustose red algae have however received less attention than other types. The fossil calcareous red algae (Rhodophyta) analyzed in this study are two relatively unrecrystallized specimens of Parachaetetes (Family Solenoporacea) from the lower part of the Ste. Genevieve Formation (Carboniferous, Visean) in Union County, Illinois, USA. They occurred in the patch reef phase of a small carbonate mudmound-patchreef. The three modern specimens (collected and identified by F. Collier) are the crustose algae Lithothamnion, Clathromorphum and Phymatolithon …

Chemistry Of Maceral And Groundmass Density Fractions Of Torbanite And Cannel Coal, Zhiwen Han, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Microscopically, torbanite and cannel coal are composed of coarser macerals set in a fine-grained to amorphous groundmass. It is often assumed that the amorphous groundmass is genetically related to the distinct macerals. The separation of macerals and groundmass from 14 late Paleozoic torbanite, cannel, and humic coals permits the analysis of individual constituents using elemental analysis and flash pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Cluster and principal component analyses of the Py-GC/MS data further reveal the chemical similarities and differences between the various constituents. Pyrolyzates of Botryococcus-related alginites are characterized by an abundance of normal alkadienes, alkenes, and alkanes. Even their …

Classification Of Torbanite And Cannel Coal. Ii. Insights From Organic Geochemical And Multivariate Statistical Analysis, Zhiwen Han, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Petrographic and megascopic criteria have traditionally been used as the basis for the classification of torbanite and cannel coal. For this study, it was hypothesized that modern analytical organic geochemical and multivariate statistical techniques could provide an alternative approach. Towards this end, the demineralized residues of 14 torbanite (rich in Botryococcus-related alginite) and cannel (essentially, rich in organic groundmass and/or sporinite) coal samples were analyzed by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Cluster analysis performed on the Py-GC/MS data clearly distinguished the torbanite from the cannel coal, demonstrating a consistency between the chemical properties and the petrographic composition. All the torbanite …

Molecular Organic Geochemistry Of New York Bight Sediments. Sources Of Biogenic Organic Matter And Polycyclic Aromatic Hydrocarbons, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

As part of a multidisciplinary evaluation of the environmental impact of waste disposal in the New York Bight, a preliminary effort was undertaken to assess the molecular geochemistry of its sedimentary organic matter (OM). For this initial phase of the study, samples were taken from two New York Bight cores collected outside the area of known dumping [in Sandy Hook Bay, NJ], to establish the environmental context for future work on sediments from within dumpsite zones. The method employed was flash pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), which is an organic microanalysis technique suitable for solid samples, in this case dried, raw …

New Polyether Toxins From Shellfish And Marine Phytoplankton: Isolation Studies And Development Of Analytical Methods, Alan G. Bishop

Theses

There are three classes of polyether toxins responsible for Diarrhetic Shellfish Poisoning (DSP) world-wide. The causative toxins are okadaic acid (OA) and derivatives (DTXs), pectenotoxins (PTXs) and yessotoxins (YTXs). The origin of these toxins are phytoplankton from Dinophysis or Prorocentrum spp. OA has been demonstrated for most outbreaks in Europe and more recently a new isomer DTX-2 has been reported in Ireland.

Marine phytoplankton biomass samples consisting predominantly of Dinophysis acuta, were acquired using a large double plankton net from waters off the South-west coast of Ireland. Analysis of unialgal samples using high performance liquid chromatography (HPLC) with fluorescence and …

Reply To Comment On ‘Nondipole Resonant X-Ray-Raman Spectroscopy: Polarized Inelastic Scattering At The K Edge Of Cl2,’, J. D. Mills, J. A. Sheehy, T. A. Ferrett, S. H. Southworth, R. Mayer, Dennis W. Lindle, P. W. Langhoff

Chemistry and Biochemistry Faculty Research

Mills et al. Reply: In their Comment on our Letter [1], Gel’mukhanov and Ågren [2] reiterate recent assertions [3] based on their earlier theoretical studies [4]. The primary purpose of their Comment is apparently to refute our stated conclusion that core-excited-state localization/ delocalization mechanisms are irrelevant to interpretations of reported Raman scattering experiments on homonuclear diatomic molecules.

Studies On The Amylolytic Breakdown Of Damaged Starch In Cereal And Non-Cereal Flours, Karen Bailey

Masters

The term starch damage refers to a number of changes to the starch granule structure, which are detectable by different analytical techniques. Damaged starch is the substrate for amylases, which in turn provides carbohydrates that are used in the production of certain foods and food ingredients; as a result, therefore, determination of levels in flours is a procedure carried out routinely by many manufacturers of starch based products. Enzymatic assay methods emulate the susceptibility of damaged starch granules to enzymatic attack. The first aim of this study was to evaluate enzymatic methods(1,2) to determine damaged starch in wheat flours and …

Study Of The Effect Of Rare Earth Ions On Dna Using Cyclic Voltammetry And Spectroscopy, Hei-Bai Shen, Yu-Zhuan Kang, Hai-Feng Yang, Lin Yu, Zong-Rang Zhang

Journal of Electrochemistry

The interaction between rare earth ions(e.g. Eu³⁺ ,Ce³⁺, Er³⁺, Sm³⁺, Tb³⁺, La³⁺ and Nd³⁺) and DNA had been investigated by using Cyclic Voltammetry, Ultraviolet and Raman Spectroscopy. After the adding of Ce³⁺ ion to DNA solution, the cathodic peak current of Ce³⁺ ion reduction was found to decrease obviously, and the anodic peak current to decrease even more significantly. Differential UV spectra of Ce³⁺ ion depicted hyperchromic effect after the reaction of these two species and a new peak of 272 nm was found. Differential …

Direct Electro-Oxidation Synthesis Of D-Arabinose On Spectroscopic Graphite Electrode, Hei Wei, Huang Ying

Journal of Electrochemistry

D Arabinose synthesized by direct electro-oxidative decarboxylation of D gluconate on graphite electrode from aqueous solutions. The effects of D gluconate concentration, electrolysis potential, temperature and electrolyte composition on the current efficiency and product yield of electrosynthsis are discussed. The laboratory scale electrosynthesis was achieved with flow through cell. The optimum technology conditions for electrosynthesis were obtained with orthogonal design method. Both galvanostatic and potentionstatic conditions have been exploited, the later was found to be more effective.

Auger Resonance Decay Process In Ar 2p Shell Excitation And Ionization, Y. Lu, Wayne C. Stolte, J.A. R. Samson

Chemistry and Biochemistry Faculty Research

The production and subsequent autoionization of the Ar⁺ (¹D₂)6d¹ satellite state that is formed either by shake-up or recapture during the Auger decay of a 2p vacancy in Ar has been studied by photoelectron spectroscopy in the energy region from 243 to 256 eV. The creation of near zero energy electrons below and immediately above the Ar 2p ionization threshold is discussed. Some ambiguous points in previous studies are clarified.

Electrochemical Determination Of Trace Amouns Of Gold(Ⅲ)By Cathodic Sptripping Voltammetry Using A Carborn Paste Electroele Modified With Bacteria, Rong-Zong Hu, Hao Xu, Jin-Kun Fu, Wen-Yun Hu, Yan-Zhen Chen

Journal of Electrochemistry

An electrochemically pretreated carbon paste electrode modified with bacteria has been studied and used for determination of trace amounts of gold(Ⅲ). A detection limit of 1 ng/mL was obtained by applying cathodic stripping valtammetry. There is a linear relationship between the concentration and peak height in the range of 10～100 μg/mL. The ralative standard deviation of the response to 84.7 μg/mL Au(Ⅲ) is 3.43%.

In-Situ Raman Spectroscopic Study Of The Oxidation And Reduction Of Ag Electrode In Na2So4, Yan-Xia Chen, Kai-Qi Huang, Zhong-Qun Tian

Journal of Electrochemistry

In-situ Raman spectroscopy combined with cyclic voltammogram measurements was used to investigate formation of oxygen species at Ag electrode surfaces during the oxidation and reduction process in 0.1 mol/L Na₂SO₄ solution. The time dependent Raman spectra show that at potentials positive of 0.2 V, adsorption of oxygen atom occurs, while at the potentials positive of 0.4 V, some oxygen atoms migrate into subsurface of the Ag electrode and the other form strongly bound oxygen on the surface through chemical bond. At the same potentials, part of the silver atoms are oxidized and form Ag₂SO_{4 …}

Explosive Vapor Generation And Sampling In Conjunction With Ion Mobility Spectrometry, Saeed H. Almeer

Chemistry & Biochemistry Theses & Dissertations

The primary objective of this research is to develop an inexpensive and reliable method to generate vapor pulses of explosives using 2,4,6-trinitrotoluene TNTl for proof of concept. A secondary objective is to demonstrate the use of the vapor generator in various applications keeping in mind potential field scenarios involving explosives. A vapor generator/collector system was developed which gives reproducible pulses of TNT vapors at nanogram levels. The use of this technology was demonstrated in evaluating different surfaces for vapor adsorption of TNT in conjunction with ion mobility spectrometry as the primary analytical tool. Of the materials examined, Teflon was by …

Neutral Dissociation Of Hydrogen Following Photoexcitation Of Hcl At The Chlorine K Edge, D. L. Hansen, J. Cotter, G. R. Fisher, K. T. Leung, R. Martin, Paul Neill, Rupert C. Perera, I. A. Sellin, Marc Simon, Y. Uehara, B. Vanderford, S. B. Whitfield

Chemistry and Biochemistry Faculty Research

Time-of-flight mass spectroscopy was used to study the relaxation dynamics of HCl following photoexcitation in the vicinity of the Cl K edge (~2.8 keV) using monochromatic synchrotron radiation. At the lowest resonant excitation to the 6ơ* antibonding orbital, almost half of the excited molecules decay by emission of a neutral H atom, mostly in coincidence with a highly charged Cln1 ion. The present work demonstrates that neutral-atom emission can be a significant decay channel for excited states with very short lifetimes (1 fs). [S1050-2947(98)03604-X]

Double Photoionization Of Helium, James A.R. Samson, Wayne C. Stolte, Z. X. He, Y. Lu, J. N. Cutler, R. J. Bartlett

Chemistry and Biochemistry Faculty Research

The cross sections for double photoionization of helium and the ratios of double to single ionization have been measured from the double-ionization threshold to 820 eV. The results are in very good agreement with several recent calculations.

Spectroscopic Investigation Of Ion Transport Mechanisms In Polyacrylonitrile Based Electrolytes, Zhaoxiang Wang, Biying Huang, Rongjian Xue, Xuejie Huang, Liquan Chen

Journal of Electrochemistry

Raman, IR, X-ray photoelectron (XPS), and NMR spectra of components in polyacrylonitrile based electrolytes have been studied. It is found that there are strong interactions among the components though different systems show different interaction characteristics. A concept of competition is proposed between the polymer matrix and the plasticizer on associating with the Li⁺ ions. By analyzing the important functions of the plasticizer, a possible mechanism of the ions transport in the polymer electrolyte is suggested.

Investigation On The Ellipsometry For The Detection Of Nickel Through Anodic Stripping Voltammetry, Wei Zhu, Yu-Ru Yang, Zong-Qing Huang

Journal of Electrochemistry

The ellipsometry with a new parameter Vop and anodic stripping voltammetry are used to analyze the nickel ions solutions with different concentration of 10^-6～10^-9 mol/L. It is shown that the results given by both methods are identical and the sensitivity and accuracy of ellipsometry are higher than anodic stripping voltammety.

Method For The Synthesis Of Α-Oxranyl Amino Acids, David B. Berkowitz, Michelle L. Pedersen

Department of Chemistry: Faculty Publications

The present invention is related to a novel class of decar-boxylase enzyme inhibitors consisting of α-oxiranyl amino acids and derivatives thereof and a method of synthesizing Such compounds.

Pyrrolic Compounds, Michael J. Therien, Stephen Dimagno

Department of Chemistry: Faculty Publications

Novel methylpyrroles are provided, as well as processes for their preparation.

Environmental And Botanical Controls On Peatification - A Comparative Study Of Two New Zealand Restiad Bogs Using Py-Gc/Ms, Petrography And Fungal Analysis, Tomasz K. Kuder, Michael A. Kruge, J C. Shearer, S L. Miller

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

This study shows that chemical properties of two restiad species, Empodisma minus and Sporadanthus traversii, may contribute to their success as peat-formers in a climate of the North Island of New Zealand which is not conducive to raised mire development. Unlike Sphagnum, the equivalent northern hemisphere peat-former, restiads possess lignin in their tissues. In addition, the presence of non-lignin polyphenols (including tannins and phenolic acids) in restiads may be an important factor in peat formation due to the allelopathic decay retardation. Patterns of degradation of plant biopolymers have been examined and the pathway of degradation of monocotyledons (loss …

A Molecular Evaluation Of Contaminants And Natural Organic Matter In Surface Sediments From Western Lake Ontario, Michael A. Kruge, Prasanta K. Mukhopadhyay, C.F. Michael Lewis

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) analysis of bottom sediment from Lake Ontario was shown to be effective in assessing organic contaminants, especially attractive as it is a rapid technique requiring little sample preparation. Pyrolyzates of samples richer in organic matter (OM) were relatively enriched in aliphatic hydrocarbons and pyrrolic nitrogen compounds, while leaner samples were more aromatic and pyridinic. Alkylbenzene and alkylphenol distributions in the pyrolyzates were most compatible with derivation from aquatic (algal, bacterial) OM. The organonitrogen compounds indicated the presence of degraded proteinaceous material from aquatic sources and/or sewage. Normal and polycyclic aromatic hydrocarbon distributions indicate, at least in …