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41.
N Fernandez M Labeta M Kurpisz T Nakatsuji J Sachs H Festenstein 《Electrophoresis》1990,11(2):167-174
Human histocompatibility molecules HLA-Class I and Class II (DR, DQ, DP) were analysed using three two-dimensional protocols: nonequilibrium pH gradient electrophoresis (NEPHGE), isoelectric focusing-acidic gradient (IEF-AG) and isoelectric focusing-basic gradient (IEF-BG). The three methods differ in their carrier ampholyte combinations and electrophoretic conditions. They provide different pH gradients and therefore different electrofocusing profiles. The NEPHGE protocol was adequate for separating proteins across a broad range of pI mobilities, i.e. 4.4 pH units between the acidic and the basic end. In contrast, the IEF-AG and the IEF-BG protocols gave a separation power across a narrow pH range, 1.9 and 1.7 pH units respectively. Thus, whereas the NEPHGE protocol provides a tool for a global major histocompatibility complex (MHC) antigen profile analysis, the IEF-AG and -BG allows one to investigate subcomponents of the individual MHC chains. For example, NEPHGE analysis of the HLA Class I heavy chain revealed a single spot. However, IEF-BG revealed the presence of six equidistantly spaced spots spanning a short pH gradient with identical molecular weight. Similar improved resolution was seen for the HLA-DR, DQ, and DP molecules. The IEF acidic gradient was adequate for separating the alpha chain; the IEF basic gradient gave better resolution of the beta chains. This data provides a baseline set of conditions for both analytical and preparative MHC protein studies prior to amino acid sequencing. 相似文献
42.
de Oliveira MC Scarpellini M Neves A Terenzi H Bortoluzzi AJ Szpoganics B Greatti A Mangrich AS de Souza EM Fernandez PM Soares MR 《Inorganic chemistry》2005,44(4):921-929
The crystal structures and redox and UV-vis/EPR spectroscopic properties of two new mononuclear copper(II) complexes, [Cu(HL1)Cl2] (1) and [Cu(L1)Cl] (2), prepared through the reaction between copper(II) chloride and the ligand 2-[(bis(pyridylmethyl)amino)methyl]-4-methyl-6-formylphenol (HL1) under distinct base conditions, are reported along with solution studies. Also, we demonstrate that these CuII complexes are able to cleave unactivated peptide bonds from bovine serum albumin (BSA) and the thermostable enzyme Taq DNA polymerase at micromolar concentration, under mild pH and temperature conditions. The cleavage activity seems to be specific with defined proteolytic fragments appearing after protein treatment. The location of the specific cleavage sites was tentatively assigned to solvent-accessible portions of the protein. These are two of the most active Cu(II) complexes described to date, since their cleavage activity is detected in minutes and evidence is here presented for a hydrolytic mechanism mediating protein cleavage by these complexes. 相似文献
43.
Quantitative investigation of the reaction of the ferri-heme model compound Fe(III)(TPPS)(H(2)O)(2) (1) to give Fe(II)(TPPS)(NO) (2) (TPPS = tetra(4-sulfonato-phenyl)porphinato) in buffered aqueous solution demonstrates a slow pH-independent reductive nitrosylation pathway in the pH range 4-6. The rate of this reaction is subject to modest general base catalysis. In the course of this study, a surprising catalytic pathway whereby nitrite ion (NO(2)(-)) strongly catalyzes the reduction of 1 to 2 under reductive nitrosylation conditions was demonstrated. 相似文献
44.
Fernandez Romero AJ López Cascales JJ Fernandez Otero T 《The journal of physical chemistry. B》2005,109(2):907-914
Polypyrrole/poly(vinyl sulfonate) (PPy/PVS) films in acetonitrile containing 0.1 M LiClO4 were studied by cyclic voltammetry. Consecutive voltammograms pointed to a continuous increase in the charge involved in the process, suggesting a rise in the number of the electroactive participants involved in the redox process. However, voltammograms obtained for the PPy/ClO4 films in analogous conditions pointed to a steady-state behavior from the very early cycles. Theoretical studies based on the Nernst and Butler-Volmer equations indicated that perchlorate ions are involved during the oxidation/reduction process of the PPy/PVS films when the steady state is reached. This result was confirmed by "ex situ" energy-dispersive X-ray analysis of the films. In this regard, the electrochemical behavior of PPy/PVS polymers was similar to that of PPy/ClO4 films when a high number of cycles were carried out. The exchange of ClO4- during the redox reaction of the PPy/PVS films made it necessary to incorporate Li+ cations inside the polymer during the initial voltammetric cycles to compensate for the negative charges of PVS polyanions. Li+ cations are mainly stabilized inside the polymer by the ion pairs formed with the sulfonated groups of the PVS. An increase and shift of the voltammetric cycles indicated a restructuring of the polymeric chains with consecutive scans. 相似文献
45.
Velázquez MM Ortega F Monroy F Rubio RG Pegiadou S Pérez L Infante MR 《Journal of colloid and interface science》2005,283(1):144-152
We report the formation of Langmuir monolayers of pure zwitterionic hexadecyl 1-N-L-tryptophan glycerol ether (C(16)-TGE) surfactant and mixed monolayers of cationic-zwitterionic surfactant obtained modifying the pH of the subphase. The pressure-area and surface potential-area isotherms and fluorescence microscopy measurements have been used to characterize the surface phase transitions in the monolayers. These transitions appeared at larger areas as the pH decreased from 6.0 to 2.0 and almost disappeared as the pH decreased further. The analysis of the surface potential and the infrared reflection-absorption spectroscopy data suggests that the phase transition is associated with a change of orientation of both the hydrocarbon chain and the aromatic group of the surfactant with respect to the air-water surface. The surface rheology of the monolayers was studied by quasielastic light scattering and by the oscillatory barrier technique. The results indicate that there is at least one relaxation process in the monolayer. 相似文献
46.
H-bonding motifs for pyrazoles and oximes have been examined in the Cambridge Structural Database. The accessible surface of the N atoms has been found to be useful as a discriminator to divide structures into dimer and catemer motifs for both pyrazoles and oximes. Low accessibility favors dimers and tetramers and high values favor catemers and trimers. Total molecular volume shows some correlation for oximes, while high values favor dimers. Empirical rules were successfully applied to predict the motifs of eight new structures in the subsequent release of the CSD. 相似文献
47.
Iván da Silva Cristina González-Silgo Juan Rodríguez-Carvajal Lourdes Mestres 《Journal of solid state chemistry》2005,178(5):1601-1608
The crystal structure of potassium, rubidium and caesium fluoroberyllates have been re-examined by neutron powder diffraction at room temperature and at 1.5 K. Previously, their structures, obtained from X-ray data, were described in the Pn21a space group. However, the results obtained from Rietveld refinements, using powder neutron diffraction, at both temperatures, indicated that all structures are orthorhombic with space group Pnma. The known phase transition at high temperature is probably related to the appearance of a hexagonal pseudo-symmetry instead of the elimination of the mirror plane between the above mentioned orthorhombic space groups. A possible phase transition, at very low temperature, was discarded considering the stereochemical criteria concerning the structural stability of A2BX4 compounds. This was confirmed by thermal analysis. On the other hand, a modulated background has been detected in all samples during the refinements. This is compatible with the presence of an amorphous phase, coexisting with the crystalline phase, or with a disordered component within the main crystalline phase. Instead of using a polynomial function, the background was modelled by Fourier filtering improving the fit for all patterns. The radial distribution function (RDF) was obtained from the analysis of the calculated background and compared with the RDF from the average crystal structure. The advantages of neutron with respect to X-ray diffraction were evidenced for this type of compound with β-K2SO4-type structure. 相似文献
48.
Inmaculada Fernandez Robert Greatrex Norman N. Greenwood 《Journal of solid state chemistry》1980,34(1):121-128
99Ru Mössbauer spectra have been recorded at 4.2 K for the quaternary oxides Ba3Ru2MO9 (M = Mg, Ca, Sr; Co, Ni, Cu, Zn; and Cd), all of which crystallize with the hexagonal barium titanate structure. The Ca, Sr, and Cd compounds give sharp symmetrical singlets with chemical isomer shifts typical of ruthenium in the +5 oxidation state. The absence of magnetic hyperfine splitting is consistent with the published interpretation of magnetic susceptibility data in terms of binuclear intracluster spin pairing which leads to an S = 0 ground state. In contrast, magnetic hyperfine splitting is seen for the Mg, Zn, Co, Ni, and Cu compounds; this can be interpreted only in terms of long-range magnetic order and the absence of such an S = 0 ground state at 4.2 K. This differs from the published interpretation of the magnetic susceptibility data for Ba3Ru2MgO9 in the low-temperature region. The magnetic flux densities at the ruthenium nuclei in the magnetically ordered compounds (32.5–51.6 T) are lower than those normally associated with ruthenium(V), and the spectra cannot be curve fitted satisfactorily with single hyperfine patterns having the natural linewidth. Possible reasons for these observations are discussed. 相似文献
49.
The structure of five conformations of the-lac inhibitor clavulanic acid have been optimized using ab initio gradient methods at the 4-21G level. The conformations of lowest energy possess an intramolecular H bond and also have the lowest pyramidization of N1. Different side-chain conformations lead to (i) differences in anomeric interactions and variations of the hydroxyethylidene geometry and (ii) changes in the geometry of the ring skeleton, which are smaller in the four- than in the five-membered ring.On leave from Universidad de Santiago de Compostela, Departamento de Química Física, Facultad de Química, Galicia (Spain). 相似文献
50.
A routing R of a graph G is a set of n(n ? 1) elementary paths R(u, v) specified for all ordered pairs (u, v) of vertices of G. The vertex-forwarding index ξ(G) of G, is defined by Where ξ(G, R) is the maximum number of paths of the routing R passing through any vertex of G and the minimum is taken over all the routings of G. Let Gp denote the random graph on n vertices with edge probability p and let m = np. It is proved among other things that, under natural growth conditions on the function p = p(n), the ratio Tends to 1 in probability as n tends to infinity. 相似文献