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81.
Jos R. Ascenso Maria de Deus Carvalho Alberto R. Dias Carlos C. Romo Maria J. Calhorda Luis F. Veiros 《Journal of organometallic chemistry》1994,470(1-2):147-152
The metallocene thioether derivatives [Cp2M(MeSCH2CH2SMe)][PF6]2 (1, M = MO; 2, M = W), [Cp2Mo(SCH2CH2SMe)][PF6] (3) and [Cp2M(SCH2CH2S)] (4, M = Mo; 5, M = W) exhibit temperature-dependent fluxional behavior in solution, owing to the pyramidal sulfur inversion process. The activation energies for this process were determined from proton band-shape analysis in the cases of 1 (54.9 ± 2 kJ mol−1), 2 (51.2 ± 4.6 kJ mol−1) and 3 (30.0 ± 3.1 kJ mol−1). Extended Hückel calculations on related model complexes suggest that local inversion at the sulfur atoms, rather that an inversion of the complete S---C---C---S chain, is responsible for the observed fluxional behaviour. 相似文献
82.
Frontera A Saczewski F Gdaniec M Dziemidowicz-Borys E Kurland A Deyà PM Quiñonero D Garau C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(22):6560-6567
Several structures of pi complexes of isocyanuric acid and of several thio derivatives with anions have been computed by using high level ab initio calculations. The nature of the complexes has been studied by means of the method of molecular interaction potential with polarization (MIPp) and Bader's theory of atoms-in-molecules. These molecules form favorable complexes with anions and can be used as binding units for building receptors for the molecular recognition of anions. In several cases, the anion-pi interaction has been demonstrated experimentally by means of X-ray crystallography. 相似文献
83.
84.
Maria Manfredini 《Rendiconti del Circolo Matematico di Palermo》1992,41(3):441-465
In questo articolo si considerano equazioni differenziali ordinarie del secondo ordine della forma $$\{ A(u')u'\} ' + \delta (r)A(u')u' + f(r,u) = 0,$$ dove cioè la nonlinearità è presente sia nella variabile soluzioneu che nella sua derivata. Si forniscono proprietà di monotonia, oscillazione e un accurato studio del comportamento asintotico all’ infinito delle soluzioni, quandoA, δ,f hanno crescite asintotiche di tipo algebrico. 相似文献
85.
Anna Maria Pastore 《Geometriae Dedicata》1992,43(3):351-361
We study Ambrose-Singer connections with an algebraic curvature tensor on simply connected manifolds carrying a homogeneous Riemannian structure of class 3 in the classification given by F. Tricerri and L. Vanhecke.This work was partially supported by MURST. 相似文献
86.
Dr. Maria Manewa 《Monatshefte für Chemie / Chemical Monthly》1976,107(2):337-343
The infrared and Raman spectra were recorded in the range 4000–160 cm–1 forM(BF4)2·6 H2O whereM=Fe2+, Co2+, Ni2+. The spectroscopic data support the X-ray structural data in showing that in the crystal hydrates studied two kinds of hydrogen bonds are present: H2O...H2O and OH2... F4B–. The energies and molecular force constants (f
OH and fH2O) andr
OH for OH2...F4B– were calculated for the three crystal hydrates. It was found that the bond OH2... F4B– is comparatively weak, with mean energy 3.7–3.3 kcal/mol. Two types of water molecule with different structures are existing as the first are participating in H2O...H–O–H...F4B– and the second in BF4
–...H–O–H...F4B–. 相似文献
87.
M. Carmo Freitas 《Analytical and bioanalytical chemistry》1995,352(1-2):58-60
The IAEA-331 spinach material NIST SRM 1570a Spinach Leaves, submitted to an intercomparison run by the IAEA, has been analysed by k0-based INAA with counting using both low and high energy photon detectors. The results have been compared with (i) the certified values of the NIST SRM 1570a; the agreement is good, taking into account the uncertainties; and (ii) the certified and “consensus” values of the former NIST SRM 1570 Spinach Leaves, their composition in minor and trace-elements are quite similar; however a lower content has been observed for Co, Fe and Sc in the IAEA-331 and for Zn in the SRM 1570. For quality control, the NIST 1573 Tomato Leaves and the NIST 1575 Pine Needles have been analysed using the same conditions as for the IAEA-331. The results agree quite well with the certified and “consensus” values given in the literature. 相似文献
88.
Cárdenas F Caba JM Feliz M Lloyd-Williams P Giralt E 《The Journal of organic chemistry》2003,68(25):9554-9562
Aplidine (dehydrodidemnin B), a natural product with potent antitumor activity currently in multicenter phase II clinical trials, exists in DMSO as a mixture of four slowly interconverting conformations in a ratio of 47:33:13:7. NMR spectroscopy shows that these arise as a consequence of cis/trans isomerization about the NMe-Leu(7)-Pro(8) and Pro(8)-Pyr amide bonds of the molecule's side chain. Two major conformations account for 47% and 33% of the total population, a ratio of 60:40 between the two. They correspond to the cis- and trans-isomers, respectively, about the Pro(8)-Pyr amide bond. Two minor conformers arise as a consequence of similar isomerism about the Pro(8)-Pyr amide bond, but in structures in which the NMe-Leu(7)-Pro(8) amide bond is cis rather than trans. These account for approximately 13% and 7% of the total population, corresponding to a ratio of 65:35 cis/trans, respectively. Molecular dynamics simulations show that the three-dimensional structures of all four conformational isomers are similar in the macrocycle and that all are essentially unchanged with respect to the macrocycle of didemnin B. Significant differences in the conformation of the molecule's side chain are, however, observed between major and minor pairs. Analysis of hydrogen-bonding patterns shows that each major conformer exhibits a beta-turn like structure and is stabilized by hydrogen bonding between a different carbonyl group of the pyruvyl unit of the molecule's side chain and the NH of the Thr(6) residue. The minor isomers have a cis-amide bond between the NMe-Leu(7) and Pro(8) residues that obliges the side chain to adopt an extended disposition where hydrogen bonding to the macrocycle is absent. These results suggest that the ability of the molecule's side chain to adopt a beta-turn-like conformation may not be a prerequisite for biological activity in the didemnins and that conformations having an extended side-chain may play a role in the biological activity of aplidine. 相似文献
89.
As is well known ammunitions containing depleted uranium (DU) were used by NATO during the Balkan war. The paper deals with the determination of uranium alpha emitting radiosotopes in Kosovo soils by chemical separation and alpha spectrometry. The samples were collected by CISAM (Centro Interforze Studi ed Applicazioni Militari, S. Piero a Grado, Livorno) in the period November 1999-April 2000. The DU distribution in soil appeared very disomogeneous; the isotope weight percentages for U-238, U-235 and U-234 resulted 99.76, 0.24 and 7.24.10(-4) respectively; consequently the activity distribution was 86.42%, 1.31%, 11.63% and the isotope ratios were 1.52.10(-2) and 0.134 for U-235/U-238 and U-234/U-238 showing clearly the presence of DU. A small peak at 4.49 MeV (U-236) in the alpha spectrum indicated that the used DU was the by-product of exhausted uranium reprocessing. In order to determine the chemical and physiological solubility of uranium a fractionation study was carried out by using the Tessier method: 55% of uranium showed a fair solubility, but 45% was solubilized only by 8 M HNO3. 相似文献
90.
An analytical potential energy surface for the gas-phase CCl4 + H --> CCl3 + ClH reaction was constructed with suitable functional forms to represent vibrational modes. This surface is completely symmetric with respect to the permutation of the four chlorine atoms and is calibrated with respect to experimental thermal rate constants available over the temperature range 297-904 K. On this surface, the thermal rate constants were calculated using variational transition-state theory with semiclassical transmission coefficients over a wider temperature range 300-2500 K, therefore obtaining kinetics information at higher temperatures than are experimentally available. This surface was also used to analyze dynamical features, such as tunneling and reaction-path curvature. In the first case, the influence of the tunneling factor is very small since a heavy chlorine atom has to pass through the barrier. In the second, it was found that vibrational excitation of the Cl-H stretching mode can be expected in the exit channel. 相似文献