Ab initio calculations on large molecules using molecular fragments. Characterization of the zwitterion of glycine

The ab initio molecular fragment approach is applied to a characterization study of the ground state of the zwitterion of glycine. Included among the properties studied are the — conformational energy surface, the electronic structure, and the magnitude and direction of the dipole moment. The results of the present study are compared to the results of other theoretical and experimental studies.This work was supported in part by the National Science Foundation, the University of Kansas, and the Upjohn Company, Kalamazoo, Michigan 49001.NSF Trainee (1969-1972).Alfred P. Sloan Research Fellow (1971–1973).     

Synthesis and molecular structures of dialkylselenonium methylide complexes of indium tribromide

The reaction of bromomethyl-dibromo-indium(III), Br₂InCH₂Br with dialkylselenides, R¹SeR² (R¹ = CH₃, R² = CH₂C₆H₅; R¹ = C₂H₅, R² = CH₂C₆H₅; R¹ = R² = CH₂C₆H₅) afforded the corresponding dialkylselenonium methylide complexes of indium tribromide, Br₃InCH₂SeR¹R², which were fully characterized by NMR spectroscopy and single crystal X-ray diffraction studies.     

A novel multicomponent reaction involving isoquinoline,allenoate and activated ketone

The reaction of isoquinoline and allenoate with activated ketone resulted in a novel three component reaction, affording [1,3]oxazino[2,3-a]isoquinoline derivatives in moderate yields along with moderate diastereoselectivities via 1,4-dipolar cycloaddition. It was also found that when isatins were used as substrates, the regioselectivity of cycloadducts was different from those using ethyl trifluoropyruvate as substrate.     

Mechanism of the inverse-electron demand Diels-Alder reaction of 2-aminopyrroles with 1,3,5-triazines: detection of an intermediate and effect of added base and acid

In base, a 2-aminopyrrole reacted with a 1,3,5-triazine to give a zwitterion (Meisenheimer complex). Acid promoted its conversion to the pyrrolo[2,3-d]pyrimidine. A cascade mechanism with reversible steps is proposed to explain why both a base and an acid are needed for the cycloaddition to occur.     

单宁酸/两性离子改性油-水分离膜的制备及性能

以不锈钢网为基材, 利用单宁酸对不锈钢网进行表面预处理并功能化接枝两性离子基团, 制备了新型亲水和水下超疏油的单宁酸/两性离子改性油-水分离膜(TA-ZW-SSM). 利用X射线光电子能谱仪(XPS)、 扫描电子显微镜(SEM)及接触角测量仪等表征了其化学结构、 形态和润湿性. 研究结果表明, 两性离子基团通过化学键接枝在单宁酸预处理的不锈钢网表面. 油-水分离实验结果表明, 对于不同类型的油-水混合物, 本文制备的超亲水和水下超疏油特性的TA-ZW-SSM可实现重力驱动的高效油-水分离, 并具有较好的化学稳定性及再循环性.     

A facile and highly efficient protocol for synthesis of poly(ether sulfone)s in ionic liquid/zwitterion

A benign approach for efficient preparation of poly(ether sulfone)(PES)(η_(inh) = 0.10-0.31 dL×g~(-1)) has been presented by using ionic liquid(IL)/zwitterion(ZI) as reaction medium. It has been found that the interaction between 4,4′-dihydroxydiphenylsulfone(Bisphenol-S) and ZI at elevated temperatures results in efficient reduction of dehydration time, which is confirmed by TGA curves, melting point of the mixture and FTIR spectra. Furthermore, no agglomeration is observed at dehydration stage, which is attributed to the high solubility of Bisphenol-S dipotassium salt in IL/ZI. This also makes the polymerization temperature(150 °C) much lower than a conventional method(220-300 °C). In order to demonstrate the efficiency of IL/ZI as reaction medium, the polymerization was also performed in sulfolane under the same reaction condition as that in IL/ZI.     

盐水溶液中离子与丙氨酸极性基团间的作用对丙氨酸缔合的影响:密度泛函理论与分子动力学模拟

采用密度泛函理论和经典分子动力学模拟研究了盐水溶液中Na⁺、Cu²⁺、Zn²⁺、Cl^-与丙氨酸分子间的相互作用对丙氨酸分子缔合的影响. 密度泛函理论的计算结果显示丙氨酸分子与Na⁺、Cu²⁺、Zn²⁺、Cl^-之间的相互作用可增强其电荷分离. 经典分子动力学模拟结果显示在水溶液中两性离子形式的丙氨酸存在三种缔合结构.盐水溶液中, 阳离子、阴离子与丙氨酸间的相互作用均能一定程度上减弱丙氨酸分子的缔合. 但是阳离子与丙氨酸间的相互作用明显受离子水合作用的影响. 由于Cu²⁺水合作用较强, 虽在气相中Cu²⁺与丙氨酸分子之间相互作用明显比Na⁺强, 但是在水溶液中则情况刚好相反. 在ZnCl₂稀溶液中, Zn²⁺与丙氨酸间的相互作用被其第一水合壳层隔开. 但这种相互作用仍能明显影响丙氨酸分子的缔合, 这与Zn²⁺的水合壳层特征有关. 另外, 离子与丙氨酸之间的相互作用, 不仅会削弱丙氨酸的缔合, 也可导致丙氨酸分子间的缔合结构发生转变. 离子浓度也会影响其与丙氨酸分子间的缔合形式以及丙氨酸的缔合结构.     

Increments to chiral recognition facilitating enantiomer separations of chiral acids, bases, and ampholytes using Cinchona-based zwitterion exchanger chiral stationary phases

The intramolecular distances of anion and cation exchanger sites of zwitterionic chiral stationary phases represent potential tuning sites for enantiomer selectivity. In this contribution, we investigate the influence of alkanesulfonic acid chain length and flexibility on enantiomer separations of chiral acids, bases, and amphoteric molecules for six Cinchona alkaloid-based chiral stationary phases in comparison with structurally related anion and cation exchangers. Employing polar-organic elution conditions, we observed an intramolecular counterion effect for acidic analytes which led to reduced retention times but did not impair enantiomer selectivities. Retention of amphoteric analytes is based on simultaneous double ion pairing of their charged functional groups with the acidic and basic sites of the zwitterionic selectors. A chiral center in the vicinity of the strong cation exchanger site is vital for chiral separations of bases. Sterically demanding side chains are beneficial for separations of free amino acids. Enantioseparations of free (un-derivatized) peptides were particularly successful in stationary phases with straight-chain alkanesulfonic acid sites, pointing to a beneficial influence of more flexible moieties. In addition, we observed pseudo-enantiomeric behavior of quinine and quinidine-derived chiral stationary phases facilitating reversal of elution orders for all analytes.     

Mechanisms of the cascade synthesis of substituted 4-amino-1,2,4-triazol-3-one from Huisgen zwitterion and aldehyde hydrazone: a DFT study

The detailed reaction mechanisms of the title reaction are shed light on by using the density functional theory (DFT). The calculated results have demonstrated that the whole reaction takes place via four processes (processes (I-IV)), among which, three possible reaction mechanisms are proposed for process (II) (channels 1-3) and two for process (IV) (channels 4-5). According to our calculated results, channel 3 and channel 5 are verified to be most energetically favorable. As interpreted in the text, in process (II), the proton transfer should be performed prior to the nucleophilic attack, and the AA-Type transfer strategy is more likely to occur. The global reactivity index (GRI) and frontier molecular orbital (FMO) analyses of the aldehyde hydrazone have further supported the AA-Type mechanism. In process (IV), however, the titled product has been demonstrated to be formed by the synergetic elimination of two protons via a six-membered ring transition state. Taking an integrated view, the highest energy barrier for the whole reaction along the most favorable pathway is 32.19 kcal/mol, which is consistent with the mild thermal experimental conditions. More interestingly, the qualified mechanisms in this work have given a perfect explanation to the optimal reactants molar ratio of highest yields (R1/R2/R3 = 2/1/1) employed in the experiment.