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91.
Claudio Tavagnacco Gabriele Balducci Giacomo Costa Karl Tschler Wolfgang von Philipsborn 《Helvetica chimica acta》1990,73(5):1469-1480
In four series of strictly related organocobalt complexes, derived from cobaloximes by replacement of the O…H…O with O…-BF2…O and/or (CH2)3 groups, the trends of 59Co-NMR shielding and electrochemical data are discussed. A largely parallel behaviour of the plots of E1/2(I) values for the first Co(III)/Co(II) electron transfer vs. the 59Co chemical shifts reflects the similar sensitivity of the two parameters to a change in electron affinity of the central metal ion due to a variation of the organic group R. E1/2(II) values for the second Co(II)/CO(I) electron transfer are less sensitive to the change of R, but the trend of the plot vs. δ(59Co) is still parallel in the four series. Consistent deviations from a roughly linear dependence of E1/2(I) on pKa of the hydrocarbon acid corresponding to R, on Taft constant s?* and on 59Co shielding are noticed for the isopropyl derivatives and attributed to a steric effect. This was confirmed in a series of R? Co(DMG)pyridine complexes in which 59Co shielding decreases steadily with increasing steric parameter Es (Taft) of the alkyl group. There is experimental evidence from X-ray data that δ(59Co) decreases with an increase of the Co? C bond length, illustrating steric hindrance in alkyl coordination to be responsible for the decreased shielding of the 59Co nucleus. The relative displacements of the graphic displays for the different series reflect the effect of changes in electron affinity of the redox center, due to the equatorial ligand, which, in turn, is caused by variations in the electron-withdrawing power due to the introduction of the BF2 group and by the change from ?2 to ?1 valence of the (CH2)3-capped ligands. 相似文献
92.
Borba A Gómez-Zavaglia A Simões PN Fausto R 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(7):1461-1470
The preferred conformations of dimethyl sulfate and their vibrational spectra were studied by matrix-isolation FT-IR spectroscopy and theoretical methods (DFT and MP2, with basis sets of different sizes, including the quadruple-zeta, aug-cc-pVQZ basis). Conformer GG (of C2 symmetry and exhibiting OSOC dihedral angles of 74.3 degrees ) was found to be the most stable conformer in both the gaseous phase and isolated in argon. Upon annealing of the matrix, the less stable observed conformer (GT; with C1 symmetry) quickly converts to the GG conformer, with the resulting species being embedded in a matrix-cage which corresponds to the most stable matrix-site for GG form. The highest energy TT conformer, which was assumed to be the most stable conformer in previous studies, is predicted by the calculations to have a relative energy of ca. 10 kJ mol-1 and was not observed in the spectra of the matrix-isolated compound. 相似文献
93.
TG and DTA have been carried out on new anhydrous rare-earth selenites R2SeaO3+2a (a=3.5,4) in order to establish their stability. Decomposition occurs in three steps attributed to successive losses of SeO2. The first process gives rise to other new group of selenites of composition R2Se3O9, which crystallize in two different forms depending on the rare-earth element. The second process leads to isomorphous compounds R2SeO5. The final product of thermal degradation is R2O3. All products were characterized by chemical analysis and X-ray powder diffraction methods. 相似文献
94.
Carlo Costa Antonella Bertazzo Graziella Allegri Silvia Catinella Pietro Traldi 《Journal of mass spectrometry : JMS》1991,26(11):972-976
The electron impact-induced fragmentation processes of pyrrole-2-, -3-, -2,3-, -3,4-, -2,5- and -2,3,4-carboxylic acids were investigated with the aid of metastable ion, collisional and deuterium labelling experiments. The general behaviour of these compounds is discussed in detail, together with the reasonable structures of the more relevant fragment ions. 相似文献
95.
Pedro A. Fernandes Elsa S. Henriques Vineet Pande Maria. J. Ramos Ana R. R. Maia André A. S. Almeida Bruno F. B. Silva Carla M. S. Ribeiro César F. B. Ribeiro David S. M. Ribeiro Diana A. P. Fonseca Eva M. S. Cunha Filipe R. N. C. Maia Joana A. A. Pereira João P. G. Pacheco Joaquim A. A. D. Ferreira Liliana R. C. Matos Manuel A. B. P. Pinto Maria C. S. Borges Paulo J. C. R. Magalhães Pedro F. R. D. Teixeira Pedro N. B. C. Veloso Ricarte J. F. Ferreira Sandro S. Gomes Tiago F. Barros Tiago S. J. T. Selão Virgínia M. M. C. Fernandes 《Theoretical chemistry accounts》2005,113(4):197-204
We present a series of new inhibitors of the association between nuclear factor kappa B (NF-B) and the corresponding B site in DNA. They were designed using the lead compound 15-deoxy-12,14 -prostaglandin J2 (PGJ2), which is a natural product with demonstrated inhibitory efficiency for this system. First, the binding mode of PGJ2 to NF-B was unraveled by GOLD docking calculation. Subsequently, substitutions were made to PGJ2 to optimize its association with NF-B. Care was taken not to strongly increase the reactivity of the new compounds, and to keep the overall shape, size and hydrophilicity of the lead compound, which should render them a similar bioavailability. Molecular mechanics calculations were performed to decide on the suitability of the substitutions, and to evaluate the energies of association with NF-B. Density functional theory calculations were performed also to study the overall reactivity of the substituted drugs towards NF-B. Important general conclusions were obtained, concerning the improvement of these natural inhibitors; namely, a set of rational methodologies were deduced to improve the association between the PGJ2 derivatives and NF-B, and their efficiency demonstrated by generating a set of substituted complexes, some of them with a very much increased affinity for NF-B, opening new doors to enlarge the therapeutic capabilities of this class of drugs. 相似文献
96.
Eimer GA Gómez Costa MB Pierella LB Anunziata OA 《Journal of colloid and interface science》2003,263(2):400-407
The adsorption of aniline on Na-AlMCM-41 synthesized by us has been characterized by infrared spectroscopy, temperature programmed desorption (TPD), and differential thermal analysis methods. Aniline would be mostly bound to the mesostructure through weak pi interactions. On the mesostructure containing adsorbed water, the co-adsorption of aniline could occur by weak hydrogen bonding through surface water molecules. For water, two possible modes of adsorption have been identified. Different associations between aniline and hydrated and nonhydrated mesostructures have been evaluated in order to favor the posterior in situ polymerization of adsorbed aniline. 相似文献
97.
Maria Merces Marques C. Costa F. Lemos F. Ram?a Ribeiro A. R. Dias 《Reaction Kinetics and Catalysis Letters》1997,62(1):9-15
In this paper we present a kinetic approach to the analysis of steady-state homogeneous Ziegler-Natta polymerization activity
data. The influence of the number of monomeric species that are coordinated to the active site on the apparent rate law is
discussed and the equations are fitted to the experimental results. 相似文献
98.
The nucleophilic addition of lithiated allylphenylsulfone to nitrones at −80 °C proceeds exclusively α to the phenylsulfonyl group affording anti adducts in high yield. At 0 °C isoxazolidines are obtained with complete all-trans selectivity. The formation of these compounds involves isomerization of the allylsulphonyl moiety to give a transient vinylsulfone that then undergoes a subsequent intramolecular Michael addition. The addition to several nitrones has been studied and theoretical calculations have been refined to accurately explain the selectivity of the allylation reaction. 相似文献
99.
Costa D Martra G Che M Manceron L Kermarec M 《Journal of the American Chemical Society》2002,124(24):7210-7217
This work reports on the reactivity of coordination vacancies of Ni(II) ions grafted onto the tridentate silica support (Ni(II)(3c) ions) with respect to CO used as a probe molecule. The adsorption of CO at 77 K in the 0.3 to 3.5 Pa CO pressure range is studied by FTIR on two samples differing in the dispersion of nickel. Quantum chemical calculations by the DFT method are performed to investigate, using a cluster approach, the binding of Ni to silica and, after CO adsorption, the geometry of the resulting carbonyl Ni complexes. Silica is modeled by using clusters composed of three types of monodentate ligands, SiO(-), SiOSi and/or SiOH, found on the surface of silica. This work is devoted to the monocarbonyl complexes. Whatever the sample, only one type of monocarbonyl is formed from Ni(II)(3c) ions. It is shown that the charge of the silica cluster is the major parameter influencing the CO IR frequency whereas the nature and the size of the silica cluster do not affect the CO bond length, confirming that local electrostatic interactions predominate. Only the 1- charged silica cluster Si(5)O(3)(-), composed of SiO(-), 2SiOSi fragments, respectively, reproduces the Ni[bond]O distances derived from EXAFS for the Ni(II)(3c) grafted site and gives CO frequencies in good agreement with the experimental values. It is shown that CO is stabilized by a magnetic transition from the (3)Ni(2+) triplet to the (1)Ni(2+) singlet state occurring upon adsorption. 相似文献
100.
A multisite molecular mechanism for Baeyer-Villiger oxidations on solid catalysts using environmentally friendly H2O2 as oxidant 总被引:1,自引:0,他引:1
Boronat M Corma A Renz M Sastre G Viruela PM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(23):6905-6915
The molecular mechanism of the Baeyer-Villiger oxidation of cyclohexanone with hydrogen peroxide catalyzed by the Sn-beta zeolite has been investigated by combining molecular mechanics, quantum-chemical calculations, spectroscopic, and kinetic techniques. A theoretical study of the location of Sn in zeolite beta was performed by using atomistic force-field techniques to simulate the local environment of the active site. An interatomic potential for Sn/Si zeolites, which allows the simulation of zeolites containing Sn in a tetrahedral environment, has been developed by fitting it to the experimental properties of quartz and SnO2(rutile). The tin active site has been modeled by means of a Sn(OSiH3)3OH cluster, which includes a defect in the framework that provides the flexibility necessary for the interaction between the adsorbates and the Lewis acid center. Two possible reaction pathways have been considered in the computational study, one of them involving the activation of the cyclohexanone carbonyl group by Sn (1) and the other one involving hydrogen peroxide being activated through the formation of a tin-hydroperoxo intermediate (2). Both the quantum-chemical results and the kinetic study indicate that the reaction follows mechanism 1, and that the catalyst active site consists of two centers: the Lewis acid Sn atom to which cyclohexanone has to coordinate, and the oxygen atom of the Sn-OH group that interacts with H2O2 forming a hydrogen bond. 相似文献