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101.
Rubén Cordero Miguel Cruz Alberto Molgado Efraín Rojas 《General Relativity and Gravitation》2014,46(7):1-20
In this paper we study the late evolution of Relic Gravitational Waves in coupled dark energy models, where dark energy interacts with cold dark matter. Relic Gravitational Waves are second tensorial order perturbations of the Lemaitre–Friedman–Robertson–Walker metric and experiment an evolution ruled by the scale factor of the metric. We find that the amplitude of Relic Gravitational Waves is smaller in coupled dark energy models than in models with non interacting dark energy. We also find that the amplitude of the waves predicted by the models with coupling term proportional to the dark energy density is smaller than those of the models with coupling term proportional to dark matter density. 相似文献
102.
A QM/MM study on the reaction pathway leading to 2‐Aceto‐2‐hydroxybutyrate in the catalytic cycle of AHAS
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Leslie Sánchez Gonzalo A. Jaña Eduardo J. Delgado 《Journal of computational chemistry》2014,35(6):488-494
The reaction between the intermediate 2‐hydroxyethyl‐thiamin diphosphate (HEThDP?) and 2‐ketobutyrate, in the third step of the catalytic cycle of acetodydroxy acid synthase, is addressed from a theoretical point of view by means of hybrid quantum/molecular mechanical calculations. The QM region includes one molecule of 2‐ketobutyrate, the HEThDP? intermediate, and the residues Arg 380 y Glu 139; whereas the MM region includes the rest of the protein. The study includes potential energy surface scans to identify and characterize critical points on it, transition state search and activation barrier calculations. The results show that the reaction occurs via a two‐step mechanism corresponding to the carboligation and proton transfer in the first stage; and the product release in the second step. © 2014 Wiley Periodicals, Inc. 相似文献
103.
Stereodivergent Carbamate Synthesis by Selective in Situ Trapping of Organic Carbonate Intermediates
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Dr. Eddy Martin Eduardo C. Escudero‐Adán Prof. Dr. Arjan W. Kleij 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(5):1722-1727
Trans carbamates have been prepared in a diastereoselective approach by a judicious one‐pot combination of organic carbonates, prepared in situ, and suitable amine reagents under appropriate reaction conditions. This unprecedented approach allows for stereodivergence from a single oxirane substrate with easy access to both cis and trans carbamate isomers with high stereoselectivity (>19:1 d.r.). Key to the control of the diastereoselective nature of the conversions that lead to the trans carbamates is the in situ formation of trans‐configured oligo/polycarbonates through Al catalysis, which provides the targeted products after aminolysis. The present results demonstrate the valorization of a renewable carbon‐based reagent (CO2) into new valuable scaffolds and an unusual stereocontrol exerted through carbonate intermediates. A series of control experiments support the proposed mechanistic rationale towards the trans carbamate products, which is based on the trapping of an in situ formed trans‐configured oligo/polycarbonate. 相似文献
104.
The controlled synthesis of rhodium (Rh) and iridium (Ir) nanoparticles was carried out by gamma irradiation of aqueous solutions containing the metal precursor salt and polyvinylpyrrolidone (PVP). The nanoparticles were synthesized at various PVP and precursor concentrations with absorbed doses between 20 and 60 kGy. Nanoparticles with average sizes of 2.4 and 2.6 nm and narrow particle size distributions were obtained at metal precursor/PVP concentrations of 6/0.3 and 6/3 mM for Ir and Rh when irradiated at 60 kGy. The interaction of the nanoparticles surfaces with the PVP was studied. 相似文献
105.
106.
Denise Tofanello Gimenes Polyana Fernandes Pereira Rafael Rodrigues Cunha Rodrigo Amorim Bezerra da Silva Rodrigo Alejandro Abarza Munoz Eduardo Mathias Richter 《Electroanalysis》2012,24(9):1805-1810
In this study, we describe for the first time the application of an internal standard method to compensate for random errors associated with the injection procedure in batch injection analysis (BIA) systems with multiple pulse amperometric detection. A sequence of potential pulses was selected in such a way that the internal standard (IS) compound was detected individually at one potential pulse and both the IS and analyte, were detected at another potential pulse. The current ratio (IIS+analyte/IIS) was used in the construction of the calibration curve and then to compensate for random errors. The use of disposable syringes or manual pipettes in BIA systems increases the robustness of the method and dispenses with skilled operators. 相似文献
107.
108.
Hydroxyl Radical Generation and DNA Nuclease Activity: A Mechanistic Study Based on a Surface‐Immobilized Copper Thioether Clip‐Phen Derivative
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Adolfo I. B. Romo Dieric S. Abreu Dr. Tércio de F. Paulo Dr. Marta S. P. Carepo Prof. Eduardo H. S. Sousa Prof. Luis Lemus Prof. Carolina Aliaga Prof. Alzir A. Batista Prof. Otaciro R. Nascimento Prof. Héctor D. Abruña Prof. Izaura C. N. Diógenes 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):10081-10089
Coordination compounds of copper have been invoked as major actors in processes involving the reduction of molecular oxygen, mostly with the generation of radical species the assignment for which has, so far, not been fully addressed. In the present work, we have carried out studies in solution and on surfaces to gain insights into the nature of the radical oxygen species (ROS) generated by a copper(II) coordination compound containing a thioether clip‐phen derivative, 1,3‐bis(1,10‐phenanthrolin‐2‐yloxy)‐N‐(4‐(methylthio)benzylidene)propan‐2‐amine (2CP‐Bz‐SMe), enabling its adsorption/immobilization to gold surfaces. Whereas surface plasmon resonance (SPR) and electrochemistry of the adsorbed complex indicated the formation of a dimeric CuI intermediate containing molecular oxygen as a bridging ligand, scanning electrochemical microscopy (SECM) and nuclease assays pointed to the generation of a ROS species. Electron paramagnetic resonance (EPR) data reinforced such conclusions, indicating that radical production was dependent on the amount of oxygen and H2O2, thus pointing to a mechanism involving a Fenton‐like reaction that results in the production of OH.. 相似文献
109.
110.
Carlos Camacho‐Camacho Irma Rojas‐Oviedo Ariadna Garza‐Ortiz Jorge Cárdenas Rubén Alfredo Toscano Rubén Gaviño 《应用有机金属化学》2013,27(1):45-51
Two novel triorganotin carboxylate complexes of the biologically active urocanic acid have been synthesized and characterized. Elemental analysis, melting point, spectroscopic techniques – IR, 1H, 13C and 119Sn NMR – mass spectrometry and X‐ray diffraction studies have been used for structural characterization. Crystal structures of the tin(IV) derivatives show that urocanic acid acts as a bridging bidentate ligand through its imidazole nitrogen atom and its carboxylic group, producing a polymeric one‐dimensional chain. The molecular structures of the complexes, catena‐poly‐tri(n‐butyl)tin(IV) 3‐(3H‐imidazol‐4‐yl)prop‐2‐enoate (1) and catena‐poly‐triphenyltin(IV) 3‐(3H‐imidazol‐4‐yl)prop‐2‐enoate (2), present a distorted trigonal–bipyramidal configuration. This is further confirmed by 119Sn NMR in the solid state. The tin(IV) derivatives form double‐stranded ribbons via N―H…O―H bonds. Nevertheless, the compounds are essentially monomeric in solution, with a tetrahedral configuration as observed by 119Sn NMR in solution. The cytotoxic activity of the titled compounds has been tested against six human cell lines and the corresponding IC50 values are reported. Both tin(IV) compounds have a high to very high in vitro cytotoxic activity against the tumor cell lines K562, HCT‐15 and MCF‐7. Compound 1 is 86 times more active than cisplatin in the HTC‐15 cell line. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献