Molecular Recognition in Organic Crystals

1.用核磁共振波谱法研究了高效液相色谱手性固定相纤维素氨基甲酸三苯酯的手性识别机理。苯氨基甲酸酯类衍生物可溶于氯仿，在NMR和HPLC中对几种对映体表现出手性识别，基于自旋-晶格弛豫时间、~ 1H NMR滴定和分子间NOE研究了它们与对映体之间的结合几何构型和动力学<1H>.在此基础上，结合分子模拟，对手性识别机理进行了合理的解释。2.聚（（4-羧基苯基）乙炔）和聚（（4-二羟基硼苯基）乙炔）分别与手性胺和手性糖络合后，表现出基于螺旋结构的诱导圆二色性（ICD）。多炔类化合物可以作为一种新的探针用于确定胺或糖的手性。3.用X射线衍射法测定了蒽或蒽醌的双间苯二酚和双吡啶衍生物的加合物的晶体结构。蒽-双（间苯二酚）化合物形成由氢键链组成的分子片。所有的加合物都表现出强烈的形成柱的倾向，这些柱是通过氢键的一维或二维网络的自组装而形成的。4.对聚集体、外消旋体以及手性伯胺与非手性酸的对映体纯盐进行了X射线晶体学研究。结果表明，聚集盐与外消旋复合盐之间2_1-柱的形成和组装受2_1-柱之间的货车范德华相互作用控制。

1.Chiral recognition mechanism of trisphenylcarbamates of cellulose which are effective chiral stationary phases for HPLC was investigated using NMR spectroscopy. The phenylcarbamate derivatives are soluble in chloroform and exhibited chiral discrimination for several enantiomers in NMR as well as in HPLC.The binding geometry and dynamics between the derivatives and enantiomers were investigated on the basis of spin-lattice relaxation time, ^<1H> NMR titrations, and intermolecular NOEs. On the basis of these results, combined with molecular modeling, the chiral discrimination mechanism was reasonably explained.2.Poly ((4-carboxyphenyl) acetylene) and poly ((4-dihydroxyborophenyl) acetylene) were found to exhibit the induced circular dichroism (ICD) based on the helical structures by the complexation with chiral molecules for instance, chiral amines and sugars, respectively. The polyacetylenes can be used as a novel probe for determining the chirality of amines or sugars.3.The crystal structures of several adducts of the bis (resorcinol) and bis (pyridine) derivatives of anthracene or anthraquinone were determined by X-ray analysis. Anthracene-bis (resorcinol) compound forms molecular sheets consisting of hydrogen-bonded chains. All the adducts show a strong tendency to form columns, which are constructed via self-assembly of hydrogen-bonded one-dimensional or two-dimensional networks.4.X-ray crystallographic studies were carried out for conglomerates and racemic compounds, and enantiomerically pure salts of chiral primary amines with achiral acids. The results suggest that the formation and the assembly of 2_1-columns between conglomerate salts and racemic compound salts are governed by van der Waals interaction between the 2_1 columns.