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61.
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   
62.
自六十年代以来陆续发现稀土化合物具有一系列特殊的药效作用 ,使稀土元素在药物上的应用展现出广阔前景。目前 ,已有不少稀土化合物应用于临床 ,如抗凝血药物 3 磺酸异烟酸钕、左旋糖酸镨、钕混合物 ;消炎药水杨酸钐等。合成具有生物活性配体的稀土配合物是寻找有效稀土药物的一条途径。瑞香素是一具有抗菌、抗炎、抗凝血等生物活性的香豆素类化合物 ,其分子结构为 :稀土与香豆素类的配合物的合成与性质研究己有不少报道[1,2 ] 。为了进一步研究这类配合物的性质和生物活性 ,我们合成了六种瑞香素稀土配合物。1 实验部分1 .1 仪器及试剂…  相似文献   
63.
A systematic study of the bulk and surface geometrical and electronic properties of a series of transition-metal carbides (TMC with TM = Ti, V, Zr, Nb, Mo, Hf, Ta, and W) by first-principles methods is presented. It is shown that in these materials the chemical bonding is strongly covalent, the cohesive energies being directly related to the bonding-antibonding gap although the shift of the center of the C(2s) band related peak in the density of states with respect to diamond indicates that some metal to carbon charge transfer does also take place. The (001) face of these metal carbides exhibits a noticeable surface rumpling which grows along the series. It is shown that neglecting surface relaxation results in very large errors on the surface energy and work function. The surface formation induces a significant shift of electronic energy levels with respect to the corresponding values in the bulk. The extent and nature of the shift can be understood from simple bonding-antibonding arguments and is enhanced by the structural rippling of this surface.  相似文献   
64.
An on-line time based injection system used in conjunction with cold vapor generation atomic absorption spectrometry and microwave-aided oxidation with potassium persulfate has been developed for the determination of the different mercury species in fish-eggs oil samples. A three-phase surfactant-oil-water emulsion produced an advantageous flow when a peristaltic pump was used to introduce the highly viscous sample into the system. The optimum proportion of the oil-water mixture ratio was 2:3 v/v with a Tween 20 surfactant concentration in the emulsion of 0.008% v/v. Inorganic mercury was determined after reduction with sodium borohydride while total mercury was determined after an oxidation step with persulfate prior to the reduction step to elemental mercury with the same reducing agent. The difference between total and inorganic mercury determined the organomercury content in samples. A linear calibration graph was obtained in the range 0.1-20 micrograms l-1 of Hg2+ by injecting 0.7 ml of samples. The detection limits based on 3 sigma of the blank signals were 0.11 and 0.12 microgram l-1 for total and inorganic mercury, respectively. The relative standard deviation of ten independent measurements were 2.8 and 2.2% for 10 micrograms l-1 and 8.8 and 9.0% for 0.1 microgram l-1 amounts of total and inorganic mercury, respectively. The recoveries of 0.3, 0.6 and 8 micrograms l-1 of inorganic and organic mercury added to fish-eggs oil samples ranged from 93.0 to 94.8% and from 100 to 106%, respectively. Good agreement with those values obtained for total mercury content in real samples by electrothermal atomic absorption spectrometry was also obtained, differences between mean values were < 7%. With the proposed procedure, 22 proteropterous catfish-eggs oil samples from the northwestern coast of Venezuela were measured; while the organic mercury lay in the range 2.0 and 3.3 micrograms l-1, inorganic mercury was not detected.  相似文献   
65.
Micellization in water-ethylene glycol (EG) N-dodecyl, N-tetradecyl, and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (SB3-12, SB3-14, and SB3-16, respectively) micellar solutions, with the weight percent of EG changing within the range 0-40, was studied by means of surface tension measurements. Information about the influence of the added EG on the aggregation number of the sulfobetaine micelles and on the polarity of the interfacial region of micelles was obtained through fluorescence and spectroscopic measurements. Surface tension measurements also provide information about the dependence of the surface excess concentration, the minimum area per surfactant molecule, the surface pressure at the cmc, and the standard Gibbs energy of adsorption on the added weight percent of the organic solvent. The Gordon parameter of the water-EG mixtures was also estimated by means of surface tension measurements. The thermodynamic and structural changes originated by the presence of EG control the micellar kinetic effects observed in the reaction methyl 4-nitrobenzenesulfonate + Br(-) occurring in the water-EG sulfobetaine micellar solutions. Information about the distribution of bromide ions between the bulk and micellar pseudophases was obtained through conductivity measurements. The kinetic micellar effects were quantitatively explained by using the pseudophase kinetic model.  相似文献   
66.
67.
Integral cross sections and thermal rate constants have been calculated for the N((2)D)+H(2) reaction and its isotopic variants N((2)D)+D(2) and the two-channel N((2)D)+HD by means of quasiclassical trajectory and statistical quantum-mechanical model methods on the latest ab initio potential-energy surface [T.-S. Ho et al., J. Chem. Phys. 119, 3063 (2003)]. The effect of rotational excitation of the diatom on the dynamics of these reactions has been investigated and interesting discrepancies between the classical and statistical model calculations have been found. Whereas a net effect of reagent rotation on reactivity is always observed in the classical calculations, only a very slight effect is observed in the case of the asymmetric N((2)D)+HD reaction for the statistical quantum-mechanical method. The thermal rate constants calculated on this Potential-Energy Surface using quasiclassical trajectory and statistical model methods are in good agreement with the experimental determinations, although the latter are somewhat larger. A reevaluation of the collinear barrier of the potential surface used in the present study seems timely. Further theoretical and experimental studies are needed for a full understanding of the dynamics of the title reaction.  相似文献   
68.
The diamagnetic square planar d(8) complexes [meso-arylcorrolato]copper(III) become paramagnetic upon warming, indicative of the equilibrium between the [corrolato]copper(III) and the [corrolato](+)* copper(II) forms of the complex. [meso-Triphenylcorrolato]copper(III) was structurally characterized and found to be saddled.  相似文献   
69.
A modified poly(ethylene glycol) (PEG) has been developed as the soluble polymeric supports for liquid phase synthesis of novel thiourea derivatives.In each step of the sequence,the PEG-bound products were precipitated in cold Et2O and the unreacted materials and by-products were removed by simple filtration.The progress of reaction,purity of the isolation and the structure of the PEG-bound products were easily monitored by TLC,IR and ^1H NMR spectra.Representative thiourea derivatives were obtained in moderate yields with excellent purity from this modified PEG-bound product by the cleavage with 50% TFA/H2O.  相似文献   
70.
Using a coaxial cylindric electron spectrometer and an electrostatic ion energy analyzer in tandem, a direct measurement of the difference of the energy of convoy peak electron and the electron equivalent ion energy of protons emerging from the downstream surface of C, Au and Al foils is performed in the proton energy range from 60 to 250 keV. This measurement is made possible using the accepted evidence that for a gas target these energies are equal. It is found that also for the beam foil convoy peak electrons, within an experimental average uncertainty of about ±0.1 eV, there is no difference between these energies. If one accepts that the origin of convoy electrons is from inside the solid, the conclusion is that no retardation by the solid surface potential barrier, which is of the order of a few eV, is observed. This is attributed to the strong electron-ion Coulomb interaction which almost completely overshadows the force exerted on the electron by the field of the surface barrier.  相似文献   
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