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971.
Hui‐Xian Yeong Dr. Hong‐Wei Xi Dr. Yongxin Li Prof. Dr. Kok Hwa Lim Dr. Cheuk‐Wai So 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(35):11786-11790
The synthesis and reactivity of a silyliumylidene cation stabilized by an amidinate ligand and 4‐dimethylaminopyridine (DMAP) are described. The reaction of the amidinate silicon(I) dimer [ L Si:]2 ( 1 ; L =PhC(NtBu)2) with one equivalent of N‐trimethylsilyl‐4‐dimethylaminopyridinium triflate [4‐NMe2C5H4NSiMe3]OTf and two equivalents of DMAP in THF afforded [ L Si(DMAP)]OTf ( 2 ). The ambiphilic character of 2 is demonstrated from its reactivity. Treatment of 2 with 1 in THF afforded the disilylenylsilylium triflate [ L′ 2( L )Si]OTf ( 3 ; L′ = L Si:) with the displacement of DMAP. The reaction of 2 with [K{HB(iBu)3}] and elemental sulfur in THF afforded the silylsilylene [ L SiSi(H){(NtBu)2C(H)Ph}] ( 4 ) and the base‐stabilized silanethionium triflate [ L Si(S)DMAP]OTf ( 5 ), respectively. Compounds 2 , 3 , and 5 have been characterized by X‐ray crystallography. 相似文献
972.
973.
A Rapid and Efficient Way to Dynamic Creation of Cross‐Reactive Sensor Arrays Based on Ionic Liquids
Wei Zhu Weina Li Haowei Yang Yin Jiang Chen Wang Prof. Dr. Yu Chen Prof. Dr. Guangtao Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(35):11603-11612
Based on the simple counterion exchange of ionic liquids, a rapid, facile, and efficient strategy to create a cross‐reactive sensor array with a dynamic tunable feature was developed, and exemplified by the construction of a sensor array for the identification and classification of nitroaromatics and explosives mimics. To achieve a good sensing system with fast response, good sensitivity, and low detection limit, the synthesized ionic liquid receptors were tethered onto a silica matrix with a macro‐mesoporous hierarchical structure. Through the facile anion exchange approach, abundant ionic‐liquid‐based individual receptors with diversiform properties, such as different micro‐environments, diverse molecular interactions, and distinctive physico‐chemical properties, were easily and quickly synthesized to generate a distinct fingerprint of explosives for pattern recognition. The reversible anion exchange ability further endowed the sensor array with a dynamic tunable feature as well as good controllability and practicality for real‐world application. With the assistance of statistical analysis, such as principal component analysis (PCA) and linear discrimination analysis (LDA), an optimized‐size array with a good resolution was rationally established from a large number of IL‐based receptors. The performed experiments suggested that the ionic‐liquid‐based sensing protocol is a general and powerful strategy for creating a cross‐reactive sensor array that could find a wide range of applications for sensing various analytes or complex mixtures. 相似文献
974.
Changwei Wang Dr. Zhenhua Chen Prof. Dr. Wei Wu Prof. Dr. Yirong Mo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1436-1444
The generalized anomeric effect refers to the conformational preference of a gauche structure over an anti structure for molecules with a R‐X‐C‐Y moiety. Whereas there are conflicting reports regarding the origin of this ubiquitous effect, a general consensus is that both the steric (more specifically electrostatic) and hyperconjugative interactions contribute. Here we employed the block‐localized wavefunction (BLW) method, which is the simplest variant of ab initio valence bond (VB) theory and can define reference electron‐localized states self‐consistently, to evaluate the magnitude of the hyperconjugation effect in a number of acyclic molecules exhibiting the generalized anomeric effect. The BLW‐based energy decomposition analysis revealed that both the steric and hyperconjugation effects contribute to the conformational preferences of methoxymethyl fluoride and methoxymethyl chlorides. But for the other systems under investigation, including methanediol, methanediamine, aminomethanol and dimethoxymethane, the hyperconjugative interactions play a negative role in the conformational preferences and the steric effect is solely responsible for the generalized anomeric effect. 相似文献
975.
Zheng Wang Shuai Luo Dr. Shoude Zhang Wu‐Lin Yang Yang‐Zi Liu Prof. Dr. Honglin Li Prof. Dr. Xiaoyan Luo Prof. Dr. Wei‐Ping Deng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(21):6739-6745
The first catalytic enantioselective 1,3‐dipolar cycloaddition of azomethine ylides to α‐aminoacrylate catalyzed by a AgOAc/ferrocenyl oxazolinylphosphine (FOXAP) system was developed, which exhibits excellent exo‐ and enantioselectivity (92–99 % ee). This process provides efficient access to useful 4‐aminopyrrolidine‐2,4‐dicarboxylic acid (APDC)‐like compounds containing a unique quaternary α‐amino acid unit. 相似文献
976.
Dr. Matthias Lein Dr. Linbin Jiang Dr. Wanxing Wei Prof. Dr. Jianyi Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(42):14126-14142
The mechanism of CuI‐catalyzed allylic alkylation and the influence of the leaving groups (OPiv, SPiv, Cl, SPO(OiPr)2; Piv: pivavloyl) on the regioselectivity of the reaction have been explored by using density functional theory (DFT). A comprehensive comparison of many possible reaction pathways shows that [(iPr)2Cu]? prefers to bind first oxidatively to the double bond of the allylic substrate at the anti position with respect to the leaving group, and this is followed by dissociation of the leaving group. If the leaving group is not taken into account, the reaction then undergoes an isomerization and a reductive elimination process to give the α‐ or γ‐selective product. If OPiv, SPiv, Cl, or SPO(OiPr)2 groups are present, the optimal route for the formation of both α‐ and γ‐substituted products changes from the stepwise elimination to the direct process, in which the leaving group plays a stabilizing role for the reactant and destabilizes the transition state. The differences to the energy barrier for the α‐ and γ‐substituted products are 2.75 kcal mol?1 with SPO(OiPr)2, 2.44 kcal mol?1 with SPiv, 2.33 kcal mol?1 with OPiv, and 1.98 kcal mol?1 with Cl, respectively; these values show that α regioselectivity in the allylic alkylation follows a SPO(OiPr)2>SPiv>OPiv>Cl trend, which is in satisfactory agreement with the experimental findings. This trend mainly originates in the differences between the attractive electrostatic forces and the repelling steric interactions of the SPO(OiPr)2, SPiv, OPiv, and Cl groups on the Cu group. 相似文献
977.
Hui Chen Chun-lin Fan Zhi-bin Wang Qiao-ying Chang Wei Wang Xiao-ying Li Guo-fang Pang 《Accreditation and quality assurance》2013,18(4):351-358
In this study, the method for determining the stable carbon isotope ratio value was validated. Measurement uncertainty of stable carbon isotope ratio value of whole honey and its extracted protein derived from repeatability, reference gas, reference standards and calibration curve was calculated by applying the “bottom-up” approach according to Eurachem/CITAC guide. The expanded uncertainties for all results ranged from 0.14 to 0.19 ‰, with most of them between 0.15 and 0.16 ‰ (the coverage factor k = 2, the level of confidence p is approximately 95 %). The percentage contribution of each source to the relative combined uncertainty was calculated. The data indicated that calibration curves have more contribution to the relative combined uncertainty than repeatability and reference standards. On the other hand, the measurement uncertainty of C-4 sugar content in honey was estimated. Based on these results, 58 honey samples, such as acacia, chaste, Northeast China black bee, flowers and jujube honey, have been gathered to determine the C-4 plant sugar content adulteration in honey by elemental analyzer with an isotope ratio mass spectrometer. It can be found that all honey samples were not adulterated by C-4 plant sugar. 相似文献
978.
979.
气相色谱-串联质谱法测定饮用水、酱油和食醋中四种杀鼠剂 总被引:1,自引:0,他引:1
采用气相色谱串联质谱法测定饮用水、酱油和食醋中4种鼠药氟乙酰胺、鼠立死、毒鼠强和杀鼠酮的含量。饮用水样品用固相萃取(苯乙烯二乙烯苯和甲基丙稀酸甲脂聚合物固相萃取柱)富集净化;食醋和酱油样品用乙腈为提取溶剂,加入少量石墨化炭黑去除色素的快速萃取法提取净化,采用INNOWAX弹性的石英毛细管柱分析。结果表明本方法测定选定样品基质的回收率和相对标准偏差分别在57.2%~102.2%,1.9%~9.5%之间;饮用水中除去杀鼠酮的最低检测浓度为2.0μg/L外,其他均小于0.5μg/L;食醋和酱油中杀鼠酮的最低检测浓度为0.10 mg/kg,其他均小于0.025 mg/kg。本方法适用于突发中毒事件中几种食品样品中4种鼠药的同时快速定性和准确定量。 相似文献
980.