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121.
应用分子动力学模拟了25 ℃和50 ℃时新型室温熔盐二(三氟甲基磺酸酰)亚胺锂[LiN(SO2CF3)2, LiTFSI]与尿素(摩尔比为1:3.6)体系的结构与动力学性质. 在两个温度下体系的微观结构基本相同, Li+的配位数约为5, 且都是与溶剂和阴离子中的氧原子发生配位. 对TFSI-的研究表明, 每个TFSI-只提供四个氧中的一个与Li+配位; 而且在Li+的配位层中, TFSI-具有顺、反和gauche 等不同的构象, 并且不同构象出现的几率会随着温度的改变而改变. 相似文献
122.
The equilibrium constants, K
2, have been determined for the proton-transfer reactions of 1-phenacylquinolinium ion, PHQ+, with several amines {triethylamine (TEA), N,N,N′,N′-tetramethylethylenediamine (ED), N,N,N′, N′-tetramethylpropanediamine (PD), N,N,N′,N′-tetramethylbutanediamine (BD), and 1,8-bis(dimethylamino-naphthalene (DMAN)} in acetonitrile (AN), AN-tetrahydrofuran (THF)
and AN-ethanol (EtOH) mixtures. The reaction was followed spectrophotometrically using a stopped-flow technique. The K
2 value decreased for DMAN and increased for TEA with increasing vol-% of THF in AN-THF mixtures. The changes in the K
2 value for ED, PD and BD changed in the order: ED, PD and BD from a pattern similar to TEA to a pattern similar to DMAN. The
change in the K
2 value for DMAN with increasing vol-% of THF in AN-THF mixtures was explained by the effect of polarity on the stability of
P−Q+ (the deprotonated product of PHQ+). The effect of THF on the K
2 value is consistent with that of the peak wavelength of the absorption spectrum of P−Q+. The change in the K
2 value for TEA, ED, PD and BD depended on the structures of the protonated bases, one of the products for this reaction. The
effect of EtOH on the K
2 value for DMAN was examined in ternary EtOH-THF-AN mixtures that contain different amounts of EtOH and whose relative permittivities
were adjusted to that of EtOH. The K
2 value increased with increasing vol-% of EtOH because of the stabilization of P−Q+ upon the formation of the hydrogen-bonded complex with EtOH. The absorption spectrum of P−Q+ demonstrated a blue shift as the vol-% of EtOH increased. 相似文献
123.
四苯硼钠-甲苯胺蓝缔合物纳米微粒体系减色效应研究 总被引:2,自引:2,他引:2
在PH4.0醋酸-醋酸钠介质中,甲苯胺蓝在600nm处有一个吸收峰,随着四苯硼钠浓度的增大甲苯胺蓝在600nm处吸收峰降低,颜色减弱,这是由于甲苯胺蓝-四苯硼钠缔合物分子间存在较强的疏水作用及分子间作用力,聚集形成纳米微粒所致,甲苯胺蓝-四苯硼钠纳米微粒体系亦在600mm处有1个吸收峰,在400mm、470mm和580mm处产生3共振散射峰,其中400mm和580mm为甲苯胺蓝-四苯硼钠复合纳米微粒产生的特征共振散射峰,这也表明有纳米微粒存在,丙酮浓度的影响实验结果等表明,纳米微粒的形成是产生其减色效应的原因。 相似文献
124.
Summary. Phenoxyacetic acid distribution in two-phase systems n-aliphatic hydrocarbon (C5–C8) – water and its dimerization in organic phase were investigated. The values of distribution coefficient (D
HR), distribution constant (K
D), and dimerization constant (K
dim) of acid were obtained. The empirical correlations of these quantities with Hildebrand solubility parameter of organic solvents were established. The influence of pH of the aqueous phase as well as the polarity of the applied organic solvents on phenoxyacetic acid physical chemistry in
the two-phase systems was described. 相似文献
125.
Tadatomi Nishikubo Atsushi Kameyama Jun Yamashita Masao Tomoi Wakichi Fukuda 《Journal of polymer science. Part A, Polymer chemistry》1993,31(4):939-947
The addition reaction of oxiranes ( 26a—e ) with carbon dioxide (CO2) was performed using insoluble polystyrene beads containing pendant quaternary ammonium or phosphonium salts as catalysts under atmospheric pressure. The reaction of 26a—e with CO2 proceeded smoothly catalyzed by 1–2 mol % of the polymer-supported quaternary onium salts to give the corresponding cyclic carbonates ( 27a—e ) in high yields at 80–90°C. In this reaction system, the catalytic activity of the polymer-supported quaternary onium salts was strongly affected by the following factors: degree of ring substitution (DRS) of the onium salt residues to the polymer, degree of crosslinking (DC) of the polystyrene beads, chain length of the alkylene spacer between the polymer back-bone and the onium salt, hydrophobicity of the alkyl group on the onium salts, and kind of onium salts. That is, the polymer-supported quaternary phosphonium salts with low DRS and DC and with long alkylene spacer chain were found to have higher catalytic activity than low molecualr weight quaternary onium salts. The above polymer-supported catalysts can easily be separated at the end of a reaction by filtration and can be reused for at least seven runs. It was also found that the rate of reaction was proportional to the products of catalyst concentration and oxirane concentration. © 1993 John Wiley & Sons, Inc. 相似文献
126.
《Electroanalysis》2006,18(6):533-550
We review recent advances in biosensors based on one‐dimensional (1‐D) nanostructure field‐effect transistors (FET). Specifically, we address the fabrication, functionalization, assembly/alignment and sensing applications of FET based on carbon nanotubes, silicon nanowires and conducting polymer nanowires. The advantages and disadvantages of various fabrication, functionalization, and assembling procedures of these nanosensors are reviewed and discussed. We evaluate how they have been used for detection of various biological molecules and how such devices have enabled the achievement of high sensitivity and selectivity with low detection limits. Finally, we conclude by highlighting some of the challenges researchers face in the 1‐D nanostructures research arena and also predict the direction toward which future research in this area might be directed. 相似文献
127.
A new technique of searching the conformational space of transition states was used to explore the cause of the rate acceleration in the gem-dialkyl effect in intramolecular cyclization reactions. Several previous hypotheses were discarded and a new hypothesis was advanced based on this new data. This hypothesis, the “Facilitated Transition” hypothesis, states that increased steric hindrance reduces the overall activation energy by facilitating rotation through the transition state. The older “Reactive Rotamer” hypothesis was eliminated by generating all conformations of the starting materials using the
and
computer programs and demonstrating that no relationship is found between rate increase and a change in the concentration of “reactive rotamers”. 相似文献
128.
129.
考察了茂环上不同取代基及钛上阴离子配体对茂基钛配合物/正丁基锂催化体系加氢活性和稳定性的影响。在充分发挥该体系催化活性的条件下,由配合物Cp2TiCl2、Cp2TiF2和Cp2Ti[OC6H3(CH3-2)Cl-4]2组成的催化体系对辛烯-1加氢的最高活性(或初活性)达到46 ̄58s^-1。 相似文献
130.
Summary Complexation equilibria of the Tl(I) ion with 18-crown-6 and dibenzo-18-crown-6 were studied polarographically in 10 nonaqueous solvents. The stability of the complexes is strongly influenced by the nature of solvents and varies with their Lewis basicities. It has been found that the logK
s value (K
s is the stability constant of the complex) can be well described by empirical relation logK
s=a DN+b, whereDN stands for the Gutmann donor number anda andb mark the regression coefficient. Addition of the second explanatory parameter, the acceptor number, is not statistically significant. This result is in agreement with the predominant role of Tl(I) ion solvation.
Elektrochemische Untersuchungen von Tl(I)-Kronenetherkomplexen in nichtwäßrigen Medien
Zusammenfassung Es wurden die Komplexierungsgleichgewichte des Tl(I)-Ions mit 18-Krone-6 und Dibenzo-18-krone-6 polarographisch in 10 nichtwäßrigen Lösungsmitteln untersucht. Die Stabilität der Komplexe wird sehr stark vom Solvens beeinflußt, wobei eine starke Abhängigkeit von der Lewis-Basizität beobachtet wird. Es wurde festgestellt, daß die logK s-Werte (K s ist die Komplexstabilitätskonstante) gut mit der empirischen Beziehung logK s=a DN+b beschrieben werden können, wobeiDN die Gutmann'sche Donorzahl unda undb die Regressionskonstanten bedeuten. Hinzunahme der Akzeptorzahl als zweiten Parameter bleibt statistisch insignifikant. Dieses Ergebnis stimmt mit dem dominierenden Einfluß der Tl(I)-Ionensolvatation überein.相似文献