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81.
The rate of electron transfer from organic sulfides to [CrV(ehba)2]− (ehba-2-ethyl-2-hydroxy butyric acid) decreases with a decrease in the polarity of the medium. The anionic surfactant, SDS and the cationic surfactant, CTAB have different effects on the kinetics of this reaction. The micellar inhibition observed in the presence of SDS is probably due to the decrease in the polarity and the electrostatic repulsion faced by the anionic oxidant from the anionic micelle and the partition of the hydrophobic substrate between the aqueous and micellar phases. The micellar catalysis in the presence of CTAB is attributed to the increase in the concentration of both reactants in the micellar phase. This micellar catalysis is observed to offset the retarding effects of the less polar micellar medium and the unfavorable charge-charge interaction between the + charge developed on S center in the transition state and the cationic micelle. This catalysis is contrary to the enormous micellar inhibition observed with IO4−, HSO5− and HCO4− oxidation of organic sulfides. 相似文献
82.
1INTRODUCTIONRecentlyorganicnonlinearoptical(NLO)materialsarebeingdevelopedforfre-quencyconversionoflaserinopto-electrics-Especiallybluelightisrequiredforopti-calmemoryofhighdensityrecording.Becauseadiodelaserisusedasalightsource,thenonlinearmaterialswhichhaveextremelyhighvalueofNLOcoefficientsandthetransmissionofblueregionarenecessary.Sincethesecond-orderNLOpropertyoforganiccompoundisderivedfromconjugateddelocalizedrrelectrons,thecompoundswhichhavebeenreportedhavefocusedonthenitroanil… 相似文献
83.
Paul Ruelle Michel Buchmann Hô Nam-Tran Ulrich W. Kesselring 《Journal of computer-aided molecular design》1992,6(5):431-448
Summary The thermodynamics of mobile order is applied to predict the aqueous solubility of liquid and solid aliphatic and polycyclic aromatic hydrocarbons. The solubility values are mainly determined by the magnitude of the hydrophobic effect. However, contrary to the solubilities of the alkanes, the solubilities of polycyclic aromatic hydrocarbons in water predicted in absence of solute-solvent hydrogen (H) bonds are systematically too low. This shows the contribution of weak specific interactions between the OH groups and the electrons of the aromatic substances. According to the theory, these interactions are characterized by a stability bility constant Ko which can be derived from solubility data. At 25°C, this constant amounts to 80 cm3/mol, the order of magnitude of which can be explained by the competition of these intermolecular bonds with the rather weak self-association bonds in the secondary chains of water. 相似文献
84.
K. Benmansour 《European Polymer Journal》2003,39(7):1443-1449
In order to determine the counter-anion effect on conductivity of poly[N-(3,6,9-trioxadecyl)-4-vinylpyridinium)] backbone in aqueous solutions, a set of three polyelectrolytes with three different counter-ions: poly[N-(3,6,9-trioxadecyl)-4-vinylpyridinium]bromide P4VP164Br and its chlorate and tosylate derivatives P4VP164ClO4 and P4VP164Ts respectively, were prepared by spontaneous polymerization of 4-vinylpyridine. This method gives a grafted polyelectrolyte having a positive charge on each pyridinic moiety on the backbone. The conductivities of cationic polyelectrolyte aqueous solution were determined in the concentration range from 10−4 to 10−2 M at 25 °C. The variation of the conductivity versus concentration of the investigated system exhibits a typical polyelectrolyte behavior. The polycation mobility was found to be dependent on the counter-anion nature. Thus, the polyelectrolyte conductivity increases with the ion size. This shows that big ions are weakly or not associated to the backbone.In order to confirm this steric hindrance, we have considered the conductivities of these three anions Br−, ClO4− and Ts− in their sodium salts, both alone and in the presence of 3,6,9-trioxadecanol (PEO164) free chains. In the two cases, the conductivities decrease in the order ΛBr>ΛClO4>ΛTs.These results suggest that counter-ion mobility is mainly influenced by steric effect PEO164 grafted chains.Values of the conductivity predicted from Manning rod-like polyelectrolyte model were compared with our experimental results. 相似文献
85.
The anomeric effect has been studied for a variety of compounds using the MM4 force field, and also using MP2/6-311++G(2d,2p) ab initio calculations and experimental data for reference purposes. Geometries and energies, including conformational, rotational barriers, and heats of formation were examined. Overall, the agreement of MM4 with the experimental and ab initio data is good, and significantly better than the agreement obtained with the MM3 force field. The anomeric effect is represented in MM4 by various explicit terms in the force constant matrix. The bond length changes are accounted for with torsion-stretch elements. The angle changes are accounted for with torsion-bend elements. The energies are taken into account with a number of torsional terms in the usual way. A torsion-torsion interaction is also of some importance. With all of these elements included in the calculation, the MM4 results now appear to be adequately accurate. The heats of formation were examined for a total of 12 anomeric compounds, and the experimental values were fit by MM4 with an RMS error of 0.42 kcal/mol. 相似文献
86.
Three new metabolites, kunzeanones A (1), B (2), and C (3), along with three known compounds, cryptostrobin (4), (+)-spathulenol (5), and (−)-globulol (6), were isolated from the non-polar fraction of the dried leaves of Kunzea ambigua (Myrtaceae), which shows ichthyotoxicity toward a small fish, medaka. The structures of these new compounds were elucidated as condensates of alkylated phloroglucinol with methylflavanone and germacrane-type sesquiterpene, respectively, on the basis of spectral analyses including 1-D and 2-D NMR spectra. The stereochemistries of kunzeanones A and B were determined by X-ray crystallographic analysis. A sesquiterpene, (+)-spathulenol (5), among the isolates was characterized as the ichthyotoxic principle of the extract. 相似文献
87.
Tarek M. El-Gogary Mostafa A. Diab Shreen F. El-Tantawy 《Monatshefte für Chemie / Chemical Monthly》2006,137(8):1027-1042
Summary. Equilibrium constants and molar extinction coefficients for 1:1 charge-transfer complexes between 2-hydroxyaniline (HA), 5-chloro-2-hydroxyaniline (CHA), and 4-bromo-2,6-dimethylaniline (BMA) as donors and iodine, as a typical σ-acceptor were determined spectrophotometrically in chloroform, dichloromethane, and
carbontetrachloride solutions. Spectral characteristics and formation constants are discussed in terms of donor molecular
structure and solvent polarity. The stoichiometry of the complexes was established to be 1:1. For this purpose, optical data
were subjected to the form of the Rose-Drago equation for 1:1 equilibria. Electronic absorption spectra of the studied anilines were measured in different solvents. Spectral
data were reported and band maxima were assigned to the appropriate molecular orbital transitions (π–π* and n–π* electronic transition). Solvent effects on the electronic transitions were discussed. Optimized geometry of the studied anilines
was obtained at B3LYP/6-31 + G(d). The effect of the electronic factors of the substituents on the geometrical parameters
of the ring has been explored. Geometrical values of the ring deviate from the regular hexagonal ring. Intramolecular H-bonds
in HA and CHA have been computed at B3LYP/6-31 + G(d) and MP2/6-31 + G(d) levels. The H-bonding distance was calculated to be 2.105 ? in
HA and 2.127 ? in CHA.
Abstracted from her M.Sc. thesis 相似文献
88.
库拉索芦荟抑菌效果研究 总被引:4,自引:0,他引:4
研究了库拉索芦荟提取液对食品中常见的污染菌:大肠杆菌、青霉、根霉、曲霉、毛霉的抑制作用.研究结果表明:用不同的方法对大肠杆菌做抑菌实验,抑菌效果差别较大.滤纸片法的效果最不明显,而管碟法和实验中的新方法效果很明显;用滤纸片法和管碟法对霉菌做抑菌实验效果不明显,而用平板对峙培养法对霉菌进行抑菌实验效果明显.库拉索芦荟提取液对曲霉、毛霉、青霉都有一定的抑制作用,而对根霉的抑制作用不明显,且芦荟叶皮汁比凝胶汁的抑菌作用强,经高温处理的芦荟汁的抑菌能力无明显变化. 相似文献
89.
富钾硅复合物对水稻土中有效K,Si,Ca,Mg的影响 总被引:1,自引:0,他引:1
郭碧花 《西华师范大学学报(哲学社会科学版)》2005,26(1):52-54
富钾硅复合物为绿豆岩煅烧产物,本文通过盆栽对比实验研究它对水稻土中有效K,Si,Ca,Mg的影响,结果表明:水稻土中施入K,Si,Ca,Mg后,被水稻带走部分养分,土壤养分仍有变化;尽管富钾硅复合物中的K,Si,Ca,Mg多为枸溶性养分,但均能供给水稻生长发育需要,并具有一定后效. 相似文献
90.
信息共享被看作是供应链管理的一个重要因素,信息共享所产生的价值对供应链的高效运作贡献很大;该文就两阶段供应链中库存信息共享所产生的价值进行讨论,并将其与不共享库存信息时的状况做了比较,然后用Excel软件进行模拟分析。 相似文献