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在下缘带有酰胺和酰肼基团、呈锥形、部分锥形和1,3-交替构象的对叔丁基硫杂杯[4]芳烃是用于在有机相中与s、p和d族元素的金属阳离子构建纳米结构的“智能”构建单元。

p-tert-Butyl thiacalix[4]arenes functionalized with amide and hydrazide groups at the lower rim in cone, partial cone, and 1,3-alternate conformations are "smart" building blocks for constructing nanosized structures with metal cations of s-, p-, and d-elements in the organic phase.

作者信息

Yushkova Elena A, Stoikov Ivan I

机构信息

Department of Chemistry, Kazan State University, A.M. Butlerov Chemical Institute, 420008, Kazan, Kremlevskaya, 18, Russian Federation.

出版信息

Langmuir. 2009 May 5;25(9):4919-28. doi: 10.1021/la8040902.

Abstract

The ability of p-tert-butyl thiacalix[4]arenes functionalized with tertiary and secondary amide and hydrazide groups at the lower rim in cone, partial cone, and 1,3-alternate conformations to self-assemble and recognize metal ions of s- (Li(+), Na(+), K(+), Cs(+)), p- (Al(3+), Pb(2+)) and d- (Fe(3+), Co(3+), Ni(2+), Cu(2+), Ag(+), Cd(2+), Hg(2+)) elements was investigated by picrate extraction method and dynamic light scattering (DLS). DLS was used for determination of the hydrodynamic diameter, polydispersity index, and molecular weight of nanoscale aggregate systems consisting of p-tert-butyl thiacalix[4]arene molecules and metal nitrates. Also for quantitative determination of the dimer shape from the values of molecular weight and the particles size, the Perrin factor (F) was established. It was shown that in most cases the dimers of stereoisomers of p-tert-butyl thiacalix[4]arenes tetra-substituted at the lower rim by secondary amide groups represent the prolate spheroid.

摘要

研究了在下缘以叔酰胺、仲酰胺和酰肼基团功能化的对叔丁基硫杂杯[4]芳烃在锥式、部分锥式和1,3-交替构象下自组装并识别s-(Li⁺、Na⁺、K⁺、Cs⁺)、p-(Al³⁺、Pb²⁺)和d-(Fe³⁺、Co³⁺、Ni²⁺、Cu²⁺、Ag⁺、Cd²⁺、Hg²⁺)元素金属离子的能力,采用苦味酸盐萃取法和动态光散射(DLS)进行研究。DLS用于测定由对叔丁基硫杂杯[4]芳烃分子和金属硝酸盐组成的纳米级聚集体系统的流体动力学直径、多分散指数和分子量。还从分子量和颗粒尺寸值定量测定二聚体形状,建立了佩兰因子(F)。结果表明,在大多数情况下,在下缘被仲酰胺基团四取代的对叔丁基硫杂杯[4]芳烃立体异构体的二聚体呈长椭球体。

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