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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
2.
3.
Functional Binding Surface of a β‐Hairpin VEGF Receptor Targeting Peptide Determined by NMR Spectroscopy in Living Cells 下载免费PDF全文
Dr. Donatella Diana Anna Russomanno Dr. Lucia De Rosa Dr. Rossella Di Stasi Dr. Domenica Capasso Dr. Sonia Di Gaetano Dr. Alessandra Romanelli Dr. Luigi Russo Dr. Luca D. D'Andrea Prof. Roberto Fattorusso 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):91-95
In this study, the functional interaction of HPLW peptide with VEGFR2 (Vascular Endothelial Growth Factor Receptor 2) was determined by using fast 15N‐edited NMR spectroscopic experiments. To this aim, 15N uniformly labelled HPLW has been added to Porcine Aortic Endothelial Cells. The acquisition of isotope‐edited NMR spectroscopic experiments, including 15N relaxation measurements, allowed a precise characterization of the in‐cell HPLW epitope recognized by VEGFR2. 相似文献
4.
Particularly-shaped silver nanostructures are successfully applied in many scientific fields, such as nanotechnology, catalysis, (nano)engineering, optoelectronics, and sensing. In recent years, the production of shape-controlled silver-based nanostructures and the knowledge around this topic has grown significantly. Hence, on the basis of the most recent results reported in the literature, a critical analysis around the driving forces behind the synthesis of such nanostructures are proposed herein, pointing out the important role of surface-regulating agents in driving crystalline growth by favoring (or opposing) development along specific directions. Additionally, growth mechanisms of the different morphologies considered here are discussed in depth, and critical points highlighted. 相似文献
5.
Alessandro Morando Paola Trebeschi Tao Wang 《Journal of Differential Equations》2019,266(9):5397-5430
We show the short-time existence and nonlinear stability of vortex sheets for the nonisentropic compressible Euler equations in two spatial dimensions, based on the weakly linear stability result of Morando and Trebeschi (2008) [20]. The missing normal derivatives are compensated through the equations of the linearized vorticity and entropy when deriving higher-order energy estimates. The proof of the resolution for this nonlinear problem follows from certain a priori tame estimates on the effective linear problem in the usual Sobolev spaces and a suitable Nash–Moser iteration scheme. 相似文献
6.
Summary We present an approximation method of a space-homogeneous transport equation which we prove is convergent. The method is very promising for numerical computation. Comparison of a numerical computation with an exact solution is given for the Master equation. 相似文献
7.
The preliminary results of the hydroformylation of 2-phenylsulfonyl substituted norbornene and norbornadiene derivatives catalyzed by the unmodified Rh(CO)2acac system are presented. The reaction, occurring under standard oxo conditions, gives polyfunctionalized exo norbornene- and exo norbornanecarboxaldehydes. The effect of the phenylsulfonyl group has been evaluated: it has been found that the steric properties of the sulfonyl substituent, more than the electronic ones, influence the regioselectivity of the process. 相似文献
8.
On the Application of the Auxiliary Problem Principle 总被引:6,自引:0,他引:6
The auxiliary problem principle (APP) derives from a general theory on decomposition-coordination methods establishing a comprehensive framework for both one-level and two-level methods. In this paper, the results of the two-level methods of APP are specialized for an efficient application to some engineering problems. 相似文献
9.
M. Vedani G. Angella Paola Bassani D. Ripamonti A. Tuissi 《Journal of Thermal Analysis and Calorimetry》2007,87(1):277-284
Equal channel angular
pressing (ECAP) was carried out on solution annealed samples of Al–Mg–Si–Zr
and Al–Mg–Si–Zr–Sc alloys to achieve a substantial
grain refinement of the materials. Post ECAP aging was then investigated on
the ultrafine grained alloys by DSC and TEM analyses.
DSC scans
were carried out with heating rates ranging from 5 to 30°C min–1.
Peak identification was performed by the support of literature information
and TEM analyses. Precipitation kinetics revealed to be similar for both alloys
but the Sc-free alloy showed a recrystallization peak at temperatures ranging
from 310 to 340°C, depending on the strain accumulated during ECAP. On
the contrary, the Sc-containing alloy showed a greater grain stability. Analyses
of peak positions and of activation energies as a function of ECAP passes
experienced by the samples revealed large modifications of precipitation kinetics
in the ultrafine-grained alloys with respect to the coarse-grained materials. 相似文献
10.
Valery Agoshkov Paola Gervasio Alfio Quarteroni 《Mediterranean Journal of Mathematics》2006,3(2):147-176
New domain decomposition methods (DDM) based on optimal control approach are introduced for the coupling of first and second
order equations on overlapping subdomains. Several cost functionals and control functions are proposed. Uniqueness and existence
results are proved for the coupled problem, and the convergence of iterative processes is analyzed.
The work was supported by the Russian Foundation for Basic Research (04-01-00615) and it was partly carried out while the
first author was visiting the IACS at EPFL. 相似文献