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生物手性的传播:天冬氨酸在水中的交叉和非经典结晶动力学。

Propagation of biochirality: crossovers and nonclassical crystallization kinetics of aspartic acid in water.

机构信息

Department of Chemical and Materials Engineering, National Central University, Jhong-Li City, Taiwan, R.O.C.

出版信息

Chirality. 2013 Nov;25(11):768-79. doi: 10.1002/chir.22212. Epub 2013 Jul 19.

Abstract

All experimental procedures discussed could be treated as a screening tool for probing the existence of molecular association among the chiral molecules and the solvent system. The molecular association phases of a racemic conglomerate solution (CS) and a racemic compound solution (RCS), and the templating effect of aspartic acid solid surface were observed to minimize the chance of redissolving racemic conglomerate and racemic compound aspartic acid in water and reforming an RCS in crossovers experiments. Only 1 %wt% of l-aspartic acid was adequate enough to induce a transformation from a racemic compound aspartic acid to a racemic conglomerate aspartic acid. This would make the propagation of biochirality more feasible and sound. However, tetrapeptide, (l-aspartic acid)4 , failed to induce enantioseparation as templates purely by crystallization. Nonclassical crystallization theory was needed to take into account the existence of a CS. Fundamental parameters of the crystallization kinetics such as the induction time, interfacial energy, Gibbs energetic barrier, nucleation rate, and critical size of stable nuclei of: (i) racemic compound aspartic acid, (ii) racemic compound aspartic acid seeded with 1 %wt% l-aspartic acid, (iii) racemic conglomerate aspartic acid, and (iv) l-aspartic acid were evaluated and compared with different initial supersaturation ratios. Morphological studies of crystals grown from the crystallization kinetics were also carried out.

摘要

所有讨论的实验步骤都可以作为一种筛选工具,用于探测手性分子与溶剂体系之间的分子相互作用是否存在。我们观察到外消旋聚集体溶液 (CS) 和外消旋化合物溶液 (RCS) 的分子缔合相,以及天冬氨酸固体表面的模板效应,可以最大限度地减少水相中外消旋聚集体和外消旋化合物天冬氨酸重新溶解并在交叉实验中重新形成 RCS 的机会。只有 1%wt%的 l-天冬氨酸足以诱导外消旋化合物天冬氨酸向外消旋聚集体天冬氨酸的转变。这将使生物手性的传播更加可行和合理。然而,四肽(l-天冬氨酸)4 纯粹通过结晶作为模板未能诱导对映体分离。需要考虑 CS 的存在,采用非经典结晶理论。评估并比较了结晶动力学的基本参数,如诱导时间、界面能、吉布斯能垒、成核速率和稳定核的临界尺寸:(i) 外消旋化合物天冬氨酸、(ii) 用 1%wt% l-天冬氨酸接种的外消旋化合物天冬氨酸、(iii) 外消旋聚集体天冬氨酸和 (iv) l-天冬氨酸,与不同的初始过饱和度比。还对从结晶动力学中生长的晶体的形态学研究进行了研究。

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