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1.
Triesterase and Promiscuous Diesterase Activities of a Di‐CoII‐Containing Organophosphate Degrading Enzyme Reaction Mechanisms 下载免费PDF全文
Dr. Marta E. Alberto Gaspar Pinto Prof. Nino Russo Dr. Marirosa Toscano 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(9):3736-3745
The reaction mechanism for the hydrolysis of trimethyl phosphate and of the obtained phosphodiester by the di‐CoII derivative of organophosphate degrading enzyme from Agrobacterium radiobacter P230(OpdA), have been investigated at density functional level of theory in the framework of the cluster model approach. Both mechanisms proceed by a multistep sequence and each catalytic cycle begins with the nucleophilic attack by a metal‐bound hydroxide on the phosphorus atom of the substrate, leading to the cleavage of the phosphate‐ester bond. Four exchange‐correlation functionals were used to derive the potential energy profiles in protein environments. Although the enzyme is confirmed to work better as triesterase, as revealed by the barrier heights in the rate‐limiting steps of the catalytic processes, its promiscuous ability to hydrolyze also the product of the reaction has been confirmed. The important role played by water molecules and some residues in the outer coordination sphere has been elucidated, while the binuclear CoII center accomplishes both structural and catalytic functions. To correctly describe the electronic configuration of the d shell of the metal ions, high‐ and low‐spin arrangement jointly with the occurrence of antiferromagnetic coupling, have been herein considered. 相似文献
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Vieira Renata Leia Demario Gaglieri Caroline de Oliveira Cristina Soltovski Ferreira Laura Teófilo Schnitzler Egon Bannach Gilbert 《Journal of Thermal Analysis and Calorimetry》2021,144(3):689-697
Journal of Thermal Analysis and Calorimetry - Buckwheat starch is an alternative source to supply the high global demand for starch. The properties of starch can be modified through chemical and... 相似文献
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Probing the Catalytic Activity of Reduced Graphene Oxide Decorated with Au Nanoparticles Triggered by Visible Light 下载免费PDF全文
Dr. Jiale Wang Dr. Fabiane J. Trindade Caroline B. de Aquino Joana C. Pieretti Prof. Dr. Sergio H. Domingues Prof. Dr. Romulo A. Ando Prof. Dr. Pedro H. C. Camargo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9889-9894
Hybrid materials in which reduced graphene oxide (rGO) is decorated with Au nanoparticles (rGO–Au NPs) were obtained by the in situ reduction of GO and AuCl4?(aq) by ascorbic acid. On laser excitation, rGO could be oxidized as a result of the surface plasmon resonance (SPR) excitation in the Au NPs, which generates activated O2 through the transfer of SPR‐excited hot electrons to O2 molecules adsorbed from air. The SPR‐mediated catalytic oxidation of p‐aminothiophenol (PATP) to p,p′‐dimercaptoazobenzene (DMAB) was then employed as a model reaction to probe the effect of rGO as a support for Au NPs on their SPR‐mediated catalytic activities. The increased conversion of PATP to DMAB relative to individual Au NPs indicated that charge‐transfer processes from rGO to Au took place and contributed to improved SPR‐mediated activity. Since the transfer of electrons from Au to adsorbed O2 molecules is the crucial step for PATP oxidation, in addition to the SPR‐excited hot electrons of Au NPs, the transfer of electrons from rGO to Au contributed to increasing the electron density of Au above the Fermi level and thus the Au‐to‐O2 charge‐transfer process. 相似文献
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Anatoliy Samoilenko Manuel Pinto Sergei Trofimchuk 《Proceedings of the American Mathematical Society》2005,133(1):145-154
We apply the Krylov and Bogolyubov asymptotic integration procedure to asymptotically autonomous systems. First, we consider linear systems with quasi-periodic coefficient matrix multiplied by a scalar factor vanishing at infinity. Next, we study the asymptotically autonomous Van-der-Pol oscillator.
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O.M. Hussain A.S. Swapnasmitha J. John R. Pinto 《Applied Physics A: Materials Science & Processing》2005,81(6):1291-1297
The structure and surface morphology of WO3 thin films deposited by a laser-ablation technique have been found to be strongly dependent on the deposition conditions and the nature of the substrate. By precisely controlling the substrate temperature and the oxygen partial pressure, amorphous, polycrystalline, nano-crystalline and iso-epitaxial WO3 thin films were successfully grown. The structure and surface morphological features of the films from X-ray diffraction and atomic force microscopy data are described in relation to the deposition conditions. PACS 81.15.Fg; 68.55.-a; 68.37.Ps 相似文献
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Gianluigi Luppi Rodrigo J. Corrêa Angelo C. Pinto Quirinus B. Broxterman Claudia Tomasini 《Tetrahedron》2006,62(51):12017-12024
The first total synthesis of (R)-convolutamydine A has been achieved by the organocatalytic addition of acetone to 4,6-dibromoisatin. The absolute configuration was determined by single crystal X-ray diffraction. DFT studies were used to model the transition states for the aldol reaction and equilibrium geometries of the post-aldol reaction intermediates. The DFT study revealed that the aldol bond forming reaction was considerably endothermic. 相似文献