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Articles 391 - 397 of 397

Full-Text Articles in Chemistry

Acid-Base Chemical Mechanism Of Aspartase From Hafnia Alvei, Moon Young Yoon, Kim A. Thayer-Cook, Anthony J. Berdis, William E. Karsten, Klaus D. Schnackerz, Paul F. Cook Jun 1995

Acid-Base Chemical Mechanism Of Aspartase From Hafnia Alvei, Moon Young Yoon, Kim A. Thayer-Cook, Anthony J. Berdis, William E. Karsten, Klaus D. Schnackerz, Paul F. Cook

Chemistry Faculty Publications

An acid-base chemical mechanism is proposed for Hafnia alvei aspartase in which a proton is abstracted from C-3 of the monoanionic form of L-aspartate by an enzyme general base with a pK of 6.3-6.6 in the absence and presence of Mg2+. The resulting carbanion is presumably stabilized by delocalization of electrons into the β-carboxyl with the assistance of a protonated enzyme group in the vicinity of the β-carboxyl. Ammonia is then expelled with the assistance of a general acid group that traps an initially expelled NH3 as the final NH+4 product. In agreement with the function of the general acid …

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Electrochemical Carbonylation Of Organoiron Methyl Complex: A Study Of Reaction Intermediates, C. Amatore, Mekki Bayachou, J. N. Verpeaux, L. Pospisil, J. Fiedler May 1995

Electrochemical Carbonylation Of Organoiron Methyl Complex: A Study Of Reaction Intermediates, C. Amatore, Mekki Bayachou, J. N. Verpeaux, L. Pospisil, J. Fiedler

Chemistry Faculty Publications

The one-electron reduction of CpFe(CO)2CH3 has been investigated by voltammetry and Fourier transform IR spectroelectrochemistry. The reduction initiates the insertion of CO ligand in the FeCH3 bond. The dissociation of a CO group proceeds in a parallel reaction. Reaction intermediates, the acyl derivative and released CO, form the radical anion of a complex CpFe(CO)2(COCH3) which is able to reduce the parent compound. The reversible redox potential − 1.8 V of CpFe(CO)2(COCH3) allows the regeneration of its radical anion which drives a catalytic cycle. The lifetime of intermediates is shortened by side reactions, one of which is the migration of the …

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Dissection Of An Antibody-Catalyzed Reaction, Jon D. Stewart, Joseph F. Krebs, Gary Siuzdak, Anthony J. Berdis, David B. Smithrud, Stephen J. Benkovic Aug 1994

Dissection Of An Antibody-Catalyzed Reaction, Jon D. Stewart, Joseph F. Krebs, Gary Siuzdak, Anthony J. Berdis, David B. Smithrud, Stephen J. Benkovic

Chemistry Faculty Publications

Antibody 43C9 accelerates the hydrolysis of a p-nitroanilide by a factor of 2.5 x 10(5) over the background rate in addition to catalyzing the hydrolysis of a series of aromatic esters. Since this represents one of the largest rate accelerations achieved with an antibody, we have undertaken a series of studies aimed at uncovering the catalytic mechanism of 43C9. The immunogen, a phosphonamidate, was designed to mimic the geometric and electronic characteristics of the tetrahedral intermediate that forms upon nucleophilic attack by hydroxide on the amide substrate. Further studies, however, revealed that the catalytic mechanism is more complex and involves …

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An Ultra-Sensitive Electrochemical Enzyme Immunoassay For Thyroid Stimulating Hormone In Human Serum, Zhengrong Yu, Yan Xu, Michael P.C. Ip Jun 1994

An Ultra-Sensitive Electrochemical Enzyme Immunoassay For Thyroid Stimulating Hormone In Human Serum, Zhengrong Yu, Yan Xu, Michael P.C. Ip

Chemistry Faculty Publications

A sensitive heterogeneous electrochemical enzyme immunoassay has been developed for thyroid stimulating hormone (TSH) by modifying a commercially available two-site immunoenzymometric assay. p-Aminophenyl phosphate (PAPP) was used as the substrate of alkaline phosphatase, and hydrolysed to p-aminophenol (PAP). The amount of PAP produced from the assay was proportional to the amount of TSH in the sample. Detection of PAP was done by oxidative amperometry in a flow injection system. The working electrode was a glassy carbon electrode whose potential was held at +325 mV (vs Ag/AgCl). The amperometric detection of PAP required only 1 μl of sample (the range of …

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Electrochemical Enzyme Immunoassay Using Sequential Saturation Technique In A 20-Μl Capillary: Digoxin As A Model Analyte, Noriaki Kaneki, Yan Xu, Anu Kumari, H. Brian Halsall, William R. Heineman, Peter T. Kissinger Mar 1994

Electrochemical Enzyme Immunoassay Using Sequential Saturation Technique In A 20-Μl Capillary: Digoxin As A Model Analyte, Noriaki Kaneki, Yan Xu, Anu Kumari, H. Brian Halsall, William R. Heineman, Peter T. Kissinger

Chemistry Faculty Publications

Capillary enzyme immunoassay with flow-injection analysis for digoxin using the sequential saturation technique has been developed. Glass capillary tubes (10 cm × 0.53 mm i.d.) with immobilized digoxin antibody were used as the immunoassay reactor. The product of enzymatic reaction. 4-aminophenol, was detected amperometrically. The digoxin and the labeled digoxin binding reaction with the immobilized digoxin antibody were completed in 2 and 10 min, respectively. Digoxin was determined in a 20-μl sample with a detection limit of 10 pg ml−1 (200 fg or 260 attomoles) and a 3 orders of magnitude range.

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The 2′-Phosphate Of Nadp Is Critical For Optimum Productive Binding To 6-Phosphogluconate Dehydrogenase From Candida Utilis, Anthony J. Berdis, Paul F. Cook Sep 1993

The 2′-Phosphate Of Nadp Is Critical For Optimum Productive Binding To 6-Phosphogluconate Dehydrogenase From Candida Utilis, Anthony J. Berdis, Paul F. Cook

Chemistry Faculty Publications

Initial velocity studies obtained with alternative dinucleotide substrates for the 6-phosphogluconate dehydrogenase reaction suggest that the 2′-phosphate is critical for the optimum productive binding of the dinucleotide substrate. Initial velocity patterns obtained by varying 6-phosphogluconate at different fixed levels of NAD are nearly parallel with apparent competitive substrate inhibition by 6-phosphogluconate at pH 7 and below but intersect to the left of the ordinate at pH 8 and above. Dead-end inhibition studies indicate that the mechanism is random at all pH values. Data are interpreted in terms of a random mechanism with marked antagonism in the binding of NAD and …

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Solid-Phase Electrochemical Enzyme Immunoassay With Attomole Detection Limit By Flow Injection Analysis, Yan Xu, H. Brian Halsall, William R. Heineman Jan 1989

Solid-Phase Electrochemical Enzyme Immunoassay With Attomole Detection Limit By Flow Injection Analysis, Yan Xu, H. Brian Halsall, William R. Heineman

Chemistry Faculty Publications

A sandwich electrochemical enzyme immunoassay with flow injection analysis for the model antigen mouse IgG has been developed with alkaline phosphatase as the enzyme label. The enzyme substrate, 4-aminophenyl phosphate and its enzymatic reaction product, 4-aminophenol have been studied by cyclic and hydrodynamic voltammetry. The determination of 4-aminophenol by flow injection analysis with electrochemical detection (FIAEC) has a linear range of 5.0 × 10−8 to 1.0 × 10−5 M, a detection limit of 2.4 × 10−8 M, and a sample throughput of 72 samples/h. The detection limit is set by a background capacitance response, which depends on the ionic strength …

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