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Full-Text Articles in Physical Sciences and Mathematics
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
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 …
Electrochemical Carbonylation Of Organoiron Methyl Complex: A Study Of Reaction Intermediates, C. Amatore, Mekki Bayachou, J. N. Verpeaux, L. Pospisil, J. Fiedler
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 FeCH3 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 …