Studies on Molecular Recognition and Precise Separation Using Cyclodextrin Derivatives

环糊精衍生物的分子识别与精密分离研究

• 批准号: 04650682
• 负责人: TANAKA Minoru
• 金额: $ 1.28万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04650682/
• 关键词: Cyclodextrins; Selective modifications; Molecular recognition; Optical resolution; NMR; Capollary electrophoresis; キャピラリーゾーン電気泳動

1. Three kinds of hydroxyl groups of alpha-, beta- or gamma-cyclodextrun (CD) were selectively methylated to produce mono-, di-, or trimethylated CDs. Heptakis (3- or 6-monoacetyl, 2,3- or 3,6-diacetyl and 2,3,6-triacetyl)-beta-CDs were synthesized. The hydtoxyl groups of alpha- and gamma-CDs at their 2,3-positions were also diacetylated.2. The chiral separation ability of these CD diribatives as chiral slectors in capillary zone electrophoresis (CZE) was investigated using twelve dansylamino acids. Unmodified and 6-jmonomethylaed beta-CEs exhibite similar high enantioselectiveties. In these cases, the D-enantiomers invariably migrated faster than the crresponding L-enantioers. Methlation of the 2-hydroxyl groups in beta-CD resulted in the complete disappearance of enantioselectivity except for dansyl-DL-alpha-aminobutyric acid. On the other hand, beta-CD still exhibited chiralseparation ability after 3-methylation. Contrary to the cases of unmodified and 6-monmethylated beta-CDs, the L enantiomers migrated faster in the presence of 3-monomethylated beta-CD, Unmodified gamma-CD also exhibited high enantioselectivity, and 2,3,6-trimethylated alpha-CD and 2,6-dimethylated gamma-CD could resolve six dansylamino acid. The acetylated beta-CD derivatives could scarcely resolve them but gave camplate baseline sepatations of DL-alanyl beta-naphthylamide sterically saller than dansylamino acids.3. The chiral recognition ability of some of the CD derivatives were also studied by 600 MHz NMR.2,6-Dimethylated beta-CD and unmodified gamma-(duplication of their proton signals after addition of the CDs), and 2,3-diacetylated and unmodified beta-CDs for DL-alanyl beta-naphthylamide.

1.α-、β-或γ-环糊精（CD）的三种羟基被选择性甲基化以产生单-、二-或三甲基化的CD。合成了七（3-或6-单乙酰基、2，3-或3，6-二乙酰基和2，3，6-三乙酰基）-β-CD。α-和γ-CD的2，3-位的羟基也被二乙酰化。以十二种丹磺酰氨基酸为手性选择剂，考察了这些CD双功能化合物在毛细管区带电泳中的手性分离能力。未修饰的和6-甲基化的β-CE具有相似的高对映选择性。在这些情况下，D-对映体总是比相应的L-对映体迁移得更快。β-CD中2-羟基的甲基化导致对映体选择性完全消失，除了丹磺酰基-DL-α-氨基丁酸。另一方面，β-CD在3-甲基化后仍具有手性分离能力。与未修饰和6-单甲基化β-CD的情况相反，在3-单甲基化β-CD存在下，L对映体迁移更快，未修饰的γ-CD也表现出高的对映体选择性，并且2，3，6-三甲基化α-CD和2，6-二甲基化γ-CD可以拆分6个丹磺酰氨基酸。乙酰化的β-CD衍生物几乎不能分离它们，但DL-丙氨酰β-萘胺的基线分离空间位阻小于丹磺酰氨基酸.还通过600 MHz NMR研究了一些CD衍生物的手性识别能力。2，6-二甲基化的β-CD和未修饰的γ-（添加CD后其质子信号的复制）以及2，3-二乙酰化和未修饰的β-CD用于DL-丙氨酰β-萘酰胺。

项目成果

YAMASHOJI,Yuko: "Chiral Recognition and Enantiomeric Separation of Alanine β-Naphthylamide by Cyclodextrins" Analytica Chimica Acta. 268. 39-47 (1992)

YAMASHOJI, Yuko：“环糊精对丙氨酸 β-萘酰胺的手性识别和对映体分离”《分析化学学报》268. 39-47 (1992)。

Yamashoji,Yuko: "Chiral Recognition and Enantiomeric Separation of Alanine β-Naphthylamide by Cyclodextrins" Anal.Chim.Acta. 268. 39-47 (1992)

Yamashoji, Yuko：“环糊精对丙氨酸 β-萘酰胺的手性识别和对映体分离”Anal.Chim.Acta 268. 39-47 (1992)

Yoshinaga,Masanobu: "Use of Selectively Methylated β-Cyclodextrin Derivatives in Chiral Separation of Dansylamino Acids by Capillary Zone Electrophoresis" J.Chromatogr.(in contribution).

Yoshinaga, Masanobu：“使用选择性甲基化 β-环糊精衍生物通过毛细管区带电泳手性分离丹酰氨基酸”J.Chromatogr.（贡献中）。

YAMASHOJI, Yuko: "Chiral Recoghition and Enantiomeric Separation of Alanine beta-Naphthylamide by Cyclodextrins" Anal. Chim. Acta268. 268. 39-47 (1992)

YAMASHOJI、Yuko：“环糊精对丙氨酸 β-萘酰胺的手性识别和对映体分离”分析。

TANAKA, Minoru: "Enantiomeric Separation of Dansylamino Acids by Capillary Zone Elextrophoresis Based on Complexation with Cyclodextrins" Fresenius J, Anal, Chem.343. 896-900 (1992)

TANAKA, Minoru：“基于环糊精络合的毛细管区电泳对丹酰氨基酸的对映体分离”Fresenius J，Anal，Chem.343。