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41.
Ana M. Gonzlez‐Noya M. Isabel Fernndez Marcelino Maneiro M. Jesús Rodríguez Rosa Pedrido Miguel Vzquez Manuel R. Bermejo 《无机化学与普通化学杂志》2005,631(11):2167-2173
Interaction of asymmetrical Schiff base ligands H3Ln [where H3Ln are substituted 3–aza–4–(2–hydroxyphenyl)–N– (2–hydroxyphenyl)but–3–enamide] with Mn(acac)3 (acac = acetylacetonate) has been investigated. Two different type of manganese(III) complexes have been obtained depending on the nature of the substituents on the ligand. We have found that ligands containing donor substituents drives to the formation of two different kinds of complexes from the same reaction: Mn(Ln)(H2O)x ( 1a–5a ) and [Mn(HLn)(acac)](H2O)y ( 1b–5b ) (where Ln and HLn signify the ligand in its trianionic and dianionic form, respectively). However, when the substituents are electron withdrawing or poor donor only compounds of the type [Mn(HLn)(acac)](H2O)y ( 6–10 ) are obtained. All these compounds have been characterized by elemental analyses, IR and 1H NMR spectroscopy, FAB mass spectrometry, magnetic measurements and molar conductivities. The electrochemical behaviour of these complexes has also been studied. 相似文献
42.
43.
Fondo M García-Deibe AM Ocampo N Sanmartín J Bermejo MR Llamas-Saiz AL 《Dalton transactions (Cambridge, England : 2003)》2006,(35):4260-4270
The acetylacetonate complexes [Ni(2)L(1)(acac)(MeOH)] x H(2)O, 1 x H(2)O and [Ni(2)L(3)(acac)(MeOH)] x 1.5H(2)O, 2 x 1.5H(2)O (H(3)L(1) = (2-(2-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine and H(3)L(3) = (2-(5-bromo-2-hydroxyphenyl)-1,3-bis[4-(5-bromo-2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine) were prepared and fully characterised. Their crystal structures show that they are dinuclear complexes, extended into chains by hydrogen bond interactions. These compounds were used as starting materials for the isolation of the corresponding [Ni(2)HL(x)(o-O(2)CC(6)H(4)CO(2))(H(2)O)] x n MeOH and [Ni(2)HL(x)(O(2)CCH(2)CO(2))(H(2)O)]x nH(2)O dicarboxylate complexes (x = 1, 3; n = 1-3). The crystal structures of [Ni(2)HL(1)(o-O(2)CC(6)H(4)CO(2))(H(2)O)] x MeOH, 3 x MeOH, [Ni(2)HL(3)(o-O(2)CC(6)H(4)CO(2))(H(2)O)] x 3 MeOH, 4 x 3 MeOH and [Ni(2)HL(1)(O(2)CCH(2)CO(2))(H(2)O)] x 2.5H(2)O x 0.25 MeOH x MeCN, 5 x 2.5H(2)O x 0.25 MeOH x MeCN, were solved. Complexes 3-5 show dinuclear [Ni(2)HL(x)(dicarboxylate)(H(2)O)] units, expanded through hydrogen bonds that involve carboxylate and water ligands, as well as solvate molecules. The variable temperature magnetic susceptibilities of all the complexes show an intramolecular ferromagnetic coupling between the Ni(II) ions, which is attempted to be rationalized by comparison with previous results and in the light of molecular orbital treatment. Magnetisation measurements are in accord with a S = 2 ground state in all cases. 相似文献
44.
Bermejo FJ Taylor JW McLain SE Bustinduy I Turner JF Ruiz-Martin MD Cabrillo C Fernandez-Perea R 《Physical review letters》2006,96(23):235501
Inelastic neutron scattering data from liquid DF close to the melting point show, in addition to spectra comprising quasielastic and heavily damped acoustic motions, an intense, nondispersive band centered at about 27 meV along with a broader higher energy feature. Observation of the former band provides the first direct verification of the existence within the liquid state of collective opticlike excitations as predicted by molecular dynamics simulations. The latter corresponds to mainly reorientational motions assigned from mode eigenvector analysis carried out by computer simulations. 相似文献
45.
H. Aouididi M. Rotger D. Bermejo R.Z. Martínez V. Boudon 《Journal of Raman spectroscopy : JRS》2013,44(4):590-596
The high‐resolution stimulated Raman spectra of the ν1/ν5 C–H stretching bands of C2H4 have been recorded and analyzed by means of the tensorial formalism developed in Dijon for X2Y4 asymmetric‐top molecules. A total of 689 lines (428 for ν5 and 261 for ν1) were assigned and fitted as a dyad including Coriolis coupling constants. We obtained a global root mean square deviation of 4.39 × 10− 3 cm− 1 (4.61 × 10− 3 cm− 1 for ν1, 4.25 × 10− 3 cm− 1 for ν5). The nearby 2ν2 band, extrapolated from ν2, was included in the analysis. However, no interaction parameter involving it could be fitted. The analysis is quite satisfactory, although some parts of ν5 are not very well reproduced, probably indicating some yet unidentified resonances. This region is indeed quite dense, with many interacting dark states that cannot be included at present. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
46.
The spectra of the ν1, 2ν1–ν1, ν2, 2ν2, and 3ν2–ν2 bands of CF4 were obtained with a quasi‐continuous wave stimulated Raman spectrometer. These five bands were studied at a temperature of 135 and 300 K (for the hot bands). The spectrum of ν1 was obtained at a sample pressure of 2 mbar. For the spectra of the other regions, which are much weaker, higher pressures were used. The analysis has been performed thanks to the xtds and spview softwares developed in Dijon for such highly symmetric molecules. Combining the present results with a previous infrared study, we could determine a very accurate value for the C–F equilibrium bond length, i.e. re = 1.31588(6) Å. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
47.
We study estimates for proper orthogonal decomposition eigenvectors and eigenvalues as well as error estimates between the
exact solution of a 2D Navier–Stokes model and the numerical approach when the proper orthogonal decomposition method is considered.
These estimates are also extended when bifurcation diagram are calculated using the so called p-POD or SPOD methods with a
new cut-off criterion to minimize noisy modes produced by the p-POD method. 相似文献
48.
Pedrido R Romero MJ Bermejo MR González-Noya AM García-Lema I Zaragoza G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(2):500-512
The coordination behaviour of a new thiosemicarbazone Schiff-base building block, N-{2-([4-N-ethylthiosemicarbazone]methyl)phenyl}-p-toluenesulfonamide, H2L1 (1), incorporating a bulky tosyl group, towards Mn II, Fe II, Co II, Ni II, Cu II, Zn II, Cd II, Ag I, Sn II, and Pb II has been investigated by means of an electrochemical preparative procedure. Most metal complexes of L1 have the general formula [M(L1)]2.nX (M=Mn, Fe, Co, Ni, Cu, Cd, Pb; n=0-4, X=H2O or CH3CN), as confirmed by the structure of [Pb(L1)]2 (15), in which the lone pair on lead is stereochemically active. This lead(II) complex shows an intense fluorescence emission with a quantum yield of 0.13. In the case of silver, the complex formed was found to possess a stoichiometry of [Ag2(L1)]2.3H2O. During reactions with manganese and copper metals, interesting catalysed processes have been found to take place, with remarkable consequences regarding the ligand skeleton structure. In synthesising the manganese complex, we obtained an unexpected dithiolate thiosemicarbazone tosyl ligand, H2L2, as a side-product, which has been fully characterised, including by X-ray diffraction analysis. In the case of copper, the solid complex has the formula [CuL1]2, but the crystallised product shows the copper atoms coordinated to a new cyclised thiosemicarbazone ligand, H2L3, as in the structures of the complexes [Cu(L3)]2.CH3CN (8) and [Cu(L3)(H2O)]2.CH3CN.H2O (9). The zinc complex [Zn(L1)]4 (12) displays a particular tetranuclear zeolite-type structure capable of hosting small molecules or ions, presumably through hydrogen bonding. 相似文献
49.
We demonstrate the feasibility of determining the global fold of a highly deuterated protein from unassigned experimental NMR nuclear Overhauser effect (NOE) data only. The method relies on the calculation of a spatial configuration of covalently unconnected protons-a "cloud"-directly from unassigned distance restraints derived from 13C- and 15N-edited NOESY spectra. Each proton in the cloud, labeled by its chemical shift and that of the directly bound 13C or 15N, is subsequently mapped to specific atoms in the protein. This is achieved via graph-theoretical protocols that search for connectivities in graphs that encode the structural information within the cloud. The peptidyl HN chain is traced by seeking for all possible routes and selecting the one that yields the minimal sum of sequential distances. Complete proton identification in the cloud is achieved by linking the side-chain protons to proximal main-chain HNs via bipartite graph matching. The identified protons automatically yield the NOE assignments, which in turn are used for structure calculation with RosettaNMR, a protocol that incorporates structural bias derived from protein databases. The method, named Sparse-Constraint CLOUDS, was applied to experimental NOESY data on the 58-residue Z domain of staphylococcal protein A. The generated structures are of similar accuracy to those previously reported, which were derived via a conventional approach involving a larger NMR data set. Additional tests were performed on seven reported protein structures of various folds, using restraint lists simulated from the known atomic coordinates. 相似文献
50.
Bermejo JF Ortega P Chonco L Eritja R Samaniego R Müllner M de Jesus E de la Mata FJ Flores JC Gomez R Muñoz-Fernandez A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(2):483-495
Novel amine- or ammonium-terminated carbosilane dendrimers of type nG-[Si{OCH2(C6H3)-3,5-(OCH2CH2NMe2)2}]x, nG-[Si{O(CH2)2N(Me)(CH2)2NMe2}]x and nG-[Si{(CH2)3NH2}]x or nG-[Si{OCH2(C6H3)-3,5-(OCH2CH2NMe3 +I-)2}]x, nG-[Si{O(CH2)2N(Me)(CH2)2NMe3 +I-}]x, and nG-[Si{(CH2)3NH3 +Cl-}]x have been synthesized and characterized up to the third generation by two strategies: 1) alcoholysis of Si--Cl bonds with amino alcohols and subsequent quaternization with MeI, and 2) hydrosilylation of allylamine with Si--H bonds of the dendritic systems and subsequent quaternization with HCl. Quaternized carbosilane dendrimers are soluble in water, although degradation is apparent due to hydrolysis of Si--O bonds. However, dendrimers containing Si--C bonds are water-stable. The biocompatibility of the second-generation dendrimers in primary cell cultures of peripheral blood mononuclear cells (PBMCs) and erythrocytes have been analyzed, and they show good toxicity profiles over extended periods. In addition, we describe a study on the interactions between the different carbosilane dendrimers and DNA oligodeoxynucleotides (ODNs) and plasmids along with a comparative analysis of their toxicity. They can form complexes with DNA ODNs and plasmids at biocompatible doses via electrostatic interaction. Also a preliminary transfection assay has been accomplished. These results demonstrate that the new ammonium-terminated carbosilane dendrimers are good base molecules to be considered for biomedical applications. 相似文献