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41.
The thermodynamic model of inorganic arsenic was validated by comparing the predicted As(III) concentration with the experimentally determined one in several river waters samples of the Basque Country (Spain) collected in two sampling campaigns: spring and autumn 2000. This model takes into account the acid-base equilibria of As(III) and As(V) together with the redox equilibria between the H3AsO3 and H3AsO4 species. A correct prediction of As(III) concentration requires the knowledge of the total concentration of arsenic, pH, redox potential (referred to hydrogen electrode), and ionic strength values of the solution. The estimation of the activity coefficients of the arsenic species was performed by means of the Modified Bromley’s Methodology (MBM).In order to perform the experimental As(III) determination, an analytical method was implemented by using an ion exchange separation of As(III)/As(V) on a continuous FIA-IE-HG-AAS system. The total arsenic concentration was determined together with total concentration of the main alkaline or alkaline-earth metals and anions in the natural waters. Temperature compensated measurements of the pH and redox potentials were made in-situ at the sampling sites.For both seasonal campaigns, the agreement between predicted and experimental As(III) is really high for those samples belonging to non polluted river waters. 相似文献
42.
Marta Filizola Maria Carteni-Farina Juan J. Perez 《Journal of computer-aided molecular design》1999,13(4):397-407
3D models of the opioid receptors , and were constructed using BUNDLE, an in-house program to build de novo models of G-protein coupled receptors at the atomic level. Once the three opioid receptors were constructed and before any energy refinement, models were assessed for their compatibility with the results available from point-site mutations carried out on these receptors. In a subsequent step, three selective antagonists to each of three receptors (naltrindole, naltrexone and nor-binaltorphamine) were docked onto each of the three receptors and subsequently energy minimized. The nine resulting complexes were checked for their ability to explain known results of structure-activity studies. Once the models were validated, analysis of the distances between different residues of the receptors and the ligands were computed. This analysis permitted us to identify key residues tentatively involved in direct interaction with the ligand. 相似文献
43.
Ricardo Baggio Juan Carlos Muoz Mireille Perec 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(10):m498-m500
The title compound, [Dy2(C2H3O2)6(H2O)4]·4H2O, crystallizes in the form of dimeric units related by an inversion centre. Each cation is nine‐coordinate, binding to two water molecules and three acetate groups, two of which are bidentate and the third tridentate. This last acetate group acts as a bridge between neighbouring metal atoms, leading to an intradimer Dy?Dy separation of 4.170 (1) Å. 相似文献
44.
DFT computational study of the mechanism of allyl halides carbonylation catalyzed by nickel tetracarbonyl 总被引:1,自引:0,他引:1
Bottoni A Miscione GP Novoa JJ Prat-Resina X 《Journal of the American Chemical Society》2003,125(34):10412-10419
A theoretical investigation at the DFT(B3LYP) level on the carbonylation reaction of allyl bromide catalyzed by nickel tetra-carbonyl Ni(CO)(4) is discussed. The computational results show the following: (i) Three main steps characterize the catalytic cycle: (a) an oxidative addition step, (b) a carbonylation step, and (c) a reductive elimination step where the acyl product is obtained and the catalyst is regenerated. (ii) Both Ni(CO)(3) and Ni(CO)(4) complexes can behave as "active" catalytic species. (iii) The oxidative addition leads to the formation of either eta(3) or eta(1)-allyl nickel complexes, which are involved in a fast equilibrium. (iv) The carbonylation occurs much more easily on the eta(1) than on the eta(3) intermediates. 相似文献
45.
Paital AR Mitra T Ray D Wong WT Ribas-Ariño J Novoa JJ Ribas J Aromí G 《Chemical communications (Cambridge, England)》2005,(41):5172-5174
Based on a combined theoretical-experimental study, we propose that substituted m-phenylene ligands (m-N-Phi-N) can act as tuneable strong ferromagnetic couplers connecting Cu(II) ions; a new complex presenting that bridge with J close to +15 cm(-1) has been suggested and synthesized. 相似文献
46.
Serrano MC Portolés MT Vallet-Regí M Izquierdo I Galletti L Comas JV Pagani R 《Macromolecular bioscience》2005,5(5):415-423
Tissue engineering offers the potential of providing vessels that can be used to replace diseased and damaged native blood vessels. The endothelization of a synthetic vascular graft minimizes the failures associated with blood clotting and platelet activation. The aim of this study was to culture vascular-derived endothelial and smooth muscle cells on both untreated and NaOH-treated poly(epsilon-caprolactone) (PCL) films, a biocompatible and bio-resorbable polymer, and to evaluate the behavior of both cell types as a preliminary study for vascular graft development. PCL films were prepared by hot pressing; characterized by DSC, IR, SEM, and scanning force microscopy; and treated with NaOH to increase the surface hydrophilicity before cell culture. Endothelial and smooth muscle cells, isolated from pig cava vein, were characterized by immunofluorescence and confocal microscopy studies of endothelial nitric oxide synthase and alpha-smooth muscle actin. Good adhesion, growth, viability and morphology of both the endothelial and smooth muscle cells on PCL films were obtained, but a light stimulation of mitochondrial activity was observed during short culture times. NaOH treatment improved the adhesion and enhanced the proliferation in both cell types. This verified the possible use of this modified polymer as a support in the preparation of a synthetic vascular graft. [Diagram: see text] SEM micrograph of smooth muscle cells cultured on NaOH-treated PCL film. (Original magnification: 1000x). 相似文献
47.
ZHOU Cheng-He Juan F.Miravet M.Isabel Burguete Santiago V.Luis BAI Xue YUAN Yong 《有机化学》2004,24(Z1):380
Polynitrogen receptors such as bis-histidine peptides possess strong ability to bind metals, which play much important roles in medicinal, bioinorganic, bioorganic, biomimetic and supramolecular chemistry. In order to investigate the interaction of these hosts with a variety of neutral, cationic and anionic guests, several techniques, for example, NMR,potentiometric tirations and monocrystal X-ray diffraction have been employed. Among them NMR is a powerful technique for unraveling the structure of polynitrogen receptors as long as they are in solution where the rapid tumbling of molecules averages out the anisotropies such as chemical shift and dipole-dipole interactions. General 1H NMR approach has been widely used for the study of host-guest interaction, but it is difficult for the accurate measurement in complexes structures, particularly metal complexes structures in which how the polynitrogen receptors bind metal, and which nitrogen binds metal and so on. 相似文献
48.
Héctor Beltrán Nahum Masó Beatriz Julian Eloisa Cordoncillo Juan B. Carda Purificación Escribano Anthony R. West 《Journal of Sol-Gel Science and Technology》2003,26(1-3):1061-1065
Lead Magnesium Niobate, Pb(Mg1/3Nb2/3)O3 (PMN), is an important relaxor ferroelectric material. A significant problem exists, however, in the preparation of this material: it is very difficult to prepare pure phase, without the presence of a pyrochlore impurity phase which degrades the dielectric properties. Depending on the processing conditions, the amount of pyrochlore phase varies.Considering the ternary diagram PbO-MgO-Nb2O5, different compositions have been prepared by a simple sol-gel method at room temperature using Pb(CH3COO)2, Mg(CH3COO)2, Nb(OC2H5)5 as precursors. After the heat treatment, the samples obtained were analyzed by XRD and EPMA with the purpose of studying the compositions formed.From the analysis of these results, it seems to be that the appearance of pyrochlore can be related to the reactivity of the MgO and/or the presence of other phases of the binary system PbO-Nb2O5. An excess of Pb and Mg is necessary for compositions to be formed near the PMN. The control of the amount of these two elements is very important because an excess of MgO would lead to rich compositions in Mg as a secondary phase. 相似文献
49.
Ignacio Gimeno Ainhoa Urtizberea Juan Romn-Roche David Zueco Agustín Camn Pablo J. Alonso Olivier Roubeau Fernando Luis 《Chemical science》2021,12(15):5621
We explore how to encode more than a qubit in vanadyl porphyrin molecules hosting a S = 1/2 electronic spin coupled to a I = 7/2 nuclear spin. The spin Hamiltonian and its parameters, as well as the spin dynamics, have been determined via a combination of electron paramagnetic resonance, heat capacity, magnetization and on-chip magnetic spectroscopy experiments performed on single crystals. We find low temperature spin coherence times of micro-seconds and spin relaxation times longer than a second. For sufficiently strong magnetic fields (B > 0.1 T, corresponding to resonance frequencies of 9–10 GHz) these properties make vanadyl porphyrin molecules suitable qubit realizations. The presence of multiple equispaced nuclear spin levels then merely provides 8 alternatives to define the ‘1’ and ‘0’ basis states. For lower magnetic fields (B < 0.1 T), and lower frequencies (<2 GHz), we find spectroscopic signatures of a sizeable electronuclear entanglement. This effect generates a larger set of allowed transitions between different electronuclear spin states and removes their degeneracies. Under these conditions, we show that each molecule fulfills the conditions to act as a universal 4-qubit processor or, equivalently, as a d = 16 qudit. These findings widen the catalogue of chemically designed systems able to implement non-trivial quantum functionalities, such as quantum simulations and, especially, quantum error correction at the molecular level.We show that a sizeable electronuclear entanglement of the S = 1/2 and I = 7/2 spins of a vanadyl porphyrin provides the conditions to act as a universal 4-qubit processor, and thus implement quantum error correction at the molecular level. 相似文献
50.
Sanz V de Marcos S Castillo JR Galbán J 《Journal of the American Chemical Society》2005,127(3):1038-1048
In this paper an in depth study is presented of the use of the horseradish peroxidase (HRP) enzyme as a self-indicating biorecognition reagent in UV-vis molecular absorption spectrometry. The HRP/H2O2 reaction mechanism in the absence of an external substrate has been clarified, and the interaction between HRP and glucose oxidase (GOx) has been studied. It has been demonstrated that GOx can act as a substrate of HRP; in both cases the kinetic constants have been obtained and mathematical models have been developed. Second, the HRP/H2O2 reaction is used to follow a H2O2-producing enzymatic reaction, the glucose reaction with GOx being used as a model. As an application of this, two methodologies have been proposed for glucose determination: with or without previous incubation of glucose with GOx. In both cases mathematical models relating HRP absorbance changes to glucose concentration have been developed and tested; both methods have been optimized, analytically characterized, and tested for glucose determination in samples. The methodology described could be applied to other heme-proteins and to other H2O2-producing enzymatic reactions. The models permit the reaction constants to be calculated. From the analytical chemistry point of view the models allow the prediction of the method sensitivity for other analytes involved in this type of reaction if the kinetic constants are known and can be used in the design of optical sensors. 相似文献