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991.
The structure and stability of classical and bridged C2H
3
+
is reinvestigated. The SCF and CEPA-PNO computations performed with flexibles andp basis sets including twod-sets on carbon confirm our previous results. We find the protonated acetylene structure to be more stable than the vinyl
cation by 3.5–4 kcal/mol. The energy barrier for the interconversion of these two structures is at most a few tenths of a
kcal/mol. The equilibrium SCF geometries of Weberet al. [15] are affected insignificantly by further optimization at the CEPA-PNO level.
Several structures for the interaction of C2H
3
+
with HF have been investigated at the SCF level. With our largest basis set which includes a complete set of polarization
functions we find a remarkable levelling of the stabilities of most of the structures. In these cases the stabilization energy
ΔE ranges from −10 to −13 kcal/mol. 相似文献
992.
Ginting Suka IrwanShin-ichi Kuroda Hitoshi Kubota Takashi Kondo 《European Polymer Journal》2002,38(6):1145-1150
The effect of monomer concentration on photografting of methacrylic acid (MAA) onto linear low-density polyethylene (PE) film (thickness=30 μm) was investigated at 60 °C in water solvent together with the location of MAA-grafted chains. Xanthone was used as a photoinitiator which was coated on the film sample earlier. The higher percentage of grafting and graft efficiency were afforded for the system with the higher monomer concentration. The resultant MAA-grafted films were subjected to measurements of pH-responsive character and ability to adsorb cupric ion in order to understand the characteristics of function introduced. The grafted samples exhibited the pH-responsive character, where they shrank and swelled in acidic and alkaline media, respectively. The pH-responsive character of the grafted films was higher for the samples prepared in the system with a higher monomer concentration. Moreover, the grafted samples exhibited the ability to adsorb cupric ion, and the ability was reduced when the sample was prepared in the system with a higher monomer concentration. The different extents of the pH-responsive character and ability to adsorb cupric ion of the resulting grafted PE films were discussed in terms of location of grafted chains in the film substrate, which was determined by a scanning electron microscope and an attenuated total reflection infrared spectroscopy. 相似文献
993.
W/O型微乳液活化能和导电机理研究 总被引:15,自引:0,他引:15
电导行为是微乳液的重要性质之一。自Lagourette和Lagues发现了W/O型微乳液电导渗透(Percolation)现象后,人们开始了微乳液导电机理的研究。较流行的观点认为,界面层中表面活性剂分子的阴离子在微乳颗粒碰撞时发生跃迁而使W/O型微乳液具有导电性。 相似文献
994.
使用双沸点仪测定了丙酮、乙酸乙酯、对二氧六环、乙腈或三乙胺与甲醇或1,2→二氯乙烷以及二者混合物等十一组二元体系在99.3 kPa下的汽液平衡数据(T,x,p), 计算了有关体系的过量吉布斯自由能。结果表明, 六种非质子溶剂与甲醇组成的二元系GE>0; 乙腈或三乙胺与1,2-二氯乙烷组成的二元系GE>0, 而丙酮、乙酸乙酯或对二氧六环与1,2-二氯乙烷的二元混合物GE<0。从同种分子间或不同种分子间的缔合作用对上述结果进行了讨论。本文还在固定极性非质子溶剂(第三组分)物质的量浓度的条件下, 测定了非质子溶剂+1,2-二氯乙烷+甲醇三元混合物的汽液平衡数据, 考察了非质子溶剂的加入对甲醇+1,2-二氯乙烷二元系GE的影响。 相似文献
995.
David M. Rogers Claire Wells Melanie Joseph Vanessa J. Boddington Joseph J.W. McDouall 《Journal of Molecular Structure》1998,434(1-3):239-245
We describe a procedure which may be used to aid selection of the active space in multiconfigurational self-consistent field (MCSCF) calculations for general chemical systems. Starting from a restricted Hartree-Fock calculation, we define a hierarchy of interacting virtual orbitals for every occupied orbital. The most strongly interacting orbitals are then taken to constitute the active space in a configuration interaction (CI) calculation. The natural orbital occupation numbers obtained from the CI calculation are then used to choose the active space to be used in a subsequent MCSCF calculation. We illustrate our method on a number of systems (Li2, B2, C2, carbonyl oxide and the transition state for oxidation of H2S by dioxirane). In all these cases, ‘intuitive’ active spaces are inadequate, as are active spaces derived from the natural orbitals of unrestricted Hartree-Fock calculations. 相似文献
996.
Enzymatic determination of phenols using peanut peroxidase 总被引:4,自引:0,他引:4
The influence of phenol and its derivatives on the kinetics of oxidation of aryldiamines (indicator-substrates) catalyzed by novel plant peroxidase—cationic peanut peroxidase—was studied. The character of influence of phenols on the kinetics of enzymatic oxidation of benzidine, o-dianisidine, and 3,3′,5,5′-tetramethylbenzidine (TMB) with hydrogen peroxide was found to depend on a correlation between redox properties of phenols and the indicator-substrate of peroxidase. Thus, the catalytic activity of peanut peroxidase is inhibited by phenols with redox potentials higher than that of aryldiamines mentioned above, whereas phenols with potentials below those of aryldiamines, play the role of second substrates of the enzyme. The enzymatic procedures for the determination of numerous phenols on the level of their concentrations 0.05–80 μM were developed using the reactions of benzidine, o-dianisidine, and TMB oxidation. Different analytical signals—the indicator reaction rate and the induction period duration—were used for the determination of phenols, belonging to various groups—the inhibitors and second substrates of the enzyme, respectively. 相似文献
997.
Conformations of 2-methoxytetrahydropyran as a model for the six-membered ring in aldopyranosides have been calculated by the PCILO method using the algorithm of the conjugated gradient to optimize the geometry. The calculated geometry of the fourteen basic forms of 2-methoxytetrahydropyran was found to be in agreement with the available data obtained by X-ray diffraction of pyranosides. The results indicate differences in the geometry of 2-methoxytetrahydropyran resulting from the change of the axial vs. equatorial position of the methoxyl group. These changes are particularly meaningful in the values of bond angles and they are in agreement with the anomeric and exoanomeric effects. The experimentally found differences in the energies of an axial (4
C
1) and equatorial (1
C
4) conformer, G = 2.9–3.7 kJ/mol, and the dipole moment, = 1.20 ± 0.05 D (1D = 3.33 10–30mAs) agree well with the calculated values E = 3.18 kJ/mol and <> = 1.18 D which, in turn, suggest that the axial conformer is preferred over the equatorial one by a ratio a:e = 78:22. 相似文献
998.
The crystal structure of a second high-pressure copper vanadate phase, CuVO3(II), has been determined and refined by full-matrix least-squares procedures using automatic diffractometer data to a residual R = 0.042 (Rw = 0.051). The space group is rhombohedral, , with hexagonal unit cell a = 4.966(2) and c = 14.084(5) Å [aR = 5.501(2) Å and α = 53.66(3)°]. The structure is the fully ordered ilmenite-type and, on the basis of published magnetic data and the interatomic distances, the valence distribution Cu+V5+O3 is proposed. This represents a unique example of Cu+ in an octahedral environment. 相似文献
999.
Impedance biosensors are a class of electrical biosensors that show promise for point-of-care and other applications due to low cost, ease of miniaturization, and label-free operation. Unlabeled DNA and protein targets can be detected by monitoring changes in surface impedance when a target molecule binds to an immobilized probe. The affinity capture step leads to challenges shared by all label-free affinity biosensors; these challenges are discussed along with others unique to impedance readout. Various possible mechanisms for impedance change upon target binding are discussed. We critically summarize accomplishments of past label-free impedance biosensors and identify areas for future research. 相似文献
1000.
本文用数学期望方法研究了非线型共缩聚物的重均分子量,并推导出重均分子量表达式,将3种特例的理论曲线与实验结果相比较,两者基本相符。 相似文献