Chiral recognition by novel host-guest complexation based on a combination of hydrophobic and electrostatic interactions in aqueous media

基于水介质中疏水性和静电相互作用的新型主客体络合的手性识别

基本信息

批准号：
07672291
负责人：
DOBASHI Akira
金额：
$ 1.22万
依托单位：
Tokyo University of Pharmacy and Life Science
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

Our aim is to develop novel chiral host-guest complexation made up by hydrophobic and electrostatic interactions to discriminate enantiomers of aromatic amino acids. A chiral host comprised of two L-tyrosine residues and Diederich's bisphenol (4,4-bis (4-hydroxyphenyl) piperidine) can make a cyclic struucture with complementary electrostatic interactions between ammonium (NH_3^+) and carboxylate (COO^-) groups of the terminal tyrosine residues. This was found by conformational analysis of the host with molecular mechanics and molecular dynamics calculations. This cyclic host formed a dimer interlinked via their electrostatic forces in water and the dimerization equilibrirum constant estimated by NMR measurement was 170 (M^<-1>) at 25ﾟC.Fluorescence study using pyrene, dansylic acid (DNS) and 8-anilino-1-naphthalenesulfonic acid (ANS) showed that the dimeric host had a hydrophobic cavity to entrap these probes. Enantiomers of aromatic amino acids such as phenylalanine, tyrosine and tryptophan were discriminated with reversed phase chromatography using ODS packing coated by the chiral host. The L enantiomers were retained in greater extent than the D enantiomers in all amino acids resolved. The amino acid enantiomes should be bound to the dimeric host by inclusion of its aromatic side chains into the hydrophobic cavity and rearrangement of electrostatic networks between the four sets of NH_3^+ and COO^- groups.

我们的目的是开发由疏水和静电相互作用组成的新型手性宿主络合物，以区分芳族氨基酸的对映异构体。手性宿主完成了两种L-酪氨酸残留物和Diederich的双酚（4,4-双基（4-羟基苯基）哌啶）可以通过氨（NH_3^+）和羧酸盐（COO^ - ）（COO^ - ）组的静电相互作用而形成环状结构。通过通过分子力学和分子动力学计算对宿主进行构象分析发现了这一点。这款环状宿主在25°C.使用Pyrene，使用pyrene，Dansylic Acid（DNS）和8-尼古兰1-萘甲硫酸含量的杂化剂（Aneptity to to to to to to to to to to to a ventity to a vertity to a vertity to hote a ventity to a ryptity to a ryptitient and Onderient Aneptient（An）中，通过NMR测量估计的二聚体和二聚体等效的符号相互链接的二聚体相互链接，并显示了液压剂（An）。问题。芳族氨基酸的对映异构体，例如苯丙氨酸，酪氨酸和色氨酸，用手性宿主涂有覆盖的OD堆积相反的相色谱法进行了歧视。在所有分析的氨基酸中，L比D对映异构体的保留程度更大。氨基酸对映异构体应通过将其芳香的侧链纳入疏水腔中，并在四组NH_3^+组之间的静电网络和静电网络的重排结合到二聚体。