Studies on the Development of Selectively Modified Cyclodextrin Stationary Phases for HPLC

选择性修饰环糊精HPLC固定相的研制

• 批准号: 07555568
• 负责人: TANAKA Minoru
• 金额: $ 1.6万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07555568/
• 关键词: Liquid chromatography; Chemically modified cyclodextrin stationary phases; Chiral separation; Dansylamino acid derivatives

The method to isolate selectively methylated beta-and gamma-cyclodextrin (CD) derivatives could be established. Their hydroxyl groups at 2-position (2-MM-) 3-position (3-MM-), both 2- and 3-positions (2,3-DM-) and 2-, 3-and 6-positions (2,3,6-TM-) were methylated. The mono-, di- and trimethylated CD derivatives are donared by prefixing the unmodified CD with MM-, DM- and TM-, respectively.After monoallyloxyethylation, the unmodified and methylated CDs were treated with dimethoxymethylsilane, followed by coupling on the silica gel surface. Selectively methylated CD-bonded stationary phases for HPLC without an unreacted spacer arm could be thus obtained. This preparation method of the CD stationary phases brought about a ready estimation of the precise amount of CD immobilized and easy immobilization of the gamma-CD derivatives as well as the beta-CD ones.The chiral recognition abilities of the resulting gamma-CD stationary phases were evaluated using dansylamino acids as model solutes. Unmodified gamma-CD and 3-MM-gamma-CD stationary phases could resolve most of their enantiomers, while 2-MM-gamma-CD and 2,3,6-TM-gamma-CD stationary phases could not at all. These results positively suggest an important contribution of the 2-hydroxyl group to the chiral recognition for these solutes. It is found that the selectively methylated gamma-CD stationary phases exhibit the high enantioselectivities as expected. Similar investigation is now in progress on the selectively methylated beta-CD stationary phases.

可以建立选择性分离甲基化β-和γ-环糊精(CD)衍生物的方法。它们的2-位(2-MM-)、3-位(3-MM-)、2-和3-位(2,3-DM-)以及2-、3-和6-位(2,3,6-TM-)的羟基被甲基化。单、二和三甲基化的CD衍生物是通过在未修饰的CD上分别加上MM-、DM-和TM-来提供的。单烯丙氧基乙基化后，未修饰和甲基化的CD用二甲氧基甲基硅烷处理，然后在硅胶表面上偶联。由此可以获得用于HPLC的选择性甲基化环糊精键合固定相，而没有未反应的间隔臂。这种 CD 固定相的制备方法可以方便地估计 CD 固定的精确量，并且可以轻松固定 γ-CD 衍生物以及 β-CD 衍生物。使用丹酰氨基酸作为模型溶质评估所得 γ-CD 固定相的手性识别能力。未修饰的 gamma-CD 和 3-MM-gamma-CD 固定相可以分离大部分对映体，而 2-MM-gamma-CD 和 2,3,6-TM-gamma-CD 固定相根本不能。这些结果积极表明 2-羟基对这些溶质的手性识别做出了重要贡献。结果发现，选择性甲基化的γ-CD固定相表现出预期的高对映选择性。目前正在对选择性甲基化 β-CD 固定相进行类似的研究。

项目成果

Yoshinaga,Masanobu: "Enantiomeric Separation of Dansylamino Acids by Capillary Electrophoresis with Selectively Methylated γ-Cyclodextrin Derivatives" Analytica Chimica Acta. 316. 121-127 (1995)

Yoshinaga, Masanobu：“使用选择性甲基化 γ-环糊精衍生物通过毛细管电泳分离丹酰氨基酸”，Analytica Chimica Acta 316. 121-127 (1995)。

Yoshinaga, Masanobu: "Enantiomeric Separation of Dansylamino Acids by Capillary Electrophoresis with Selectively Methylated gamma-Cyclodextrin Derivatives" Analytica Chimica Acta. 316. 121-127 (1995)

Yoshinaga, Masanobu：“使用选择性甲基化γ-环糊精衍生物通过毛细管电泳分离丹酰氨基酸的对映体”分析化学学报。

Tanaka,Minoru: "Preparation and Retention Behavior of Cyclodextrin-Bonded Stationary Phases on a Silica Support without an Unreacted Spacer Chain" Analytical Sciences. 11. 227-231 (1995)

Tanaka,Minoru：“没有未反应的间隔链的二氧化硅载体上环糊精键合固定相的制备和保留行为”分析科学。

Tanaka, Minoru: "Preparation and Retention Behavior of Cyclodextrin-Bonded Stationary Phases on a Silica Support without an Unreacted Spacer Chain" Analytical Sciences. 11. 227-231 (1995)

Tanaka, Minoru：“没有未反应的间隔链的二氧化硅载体上环糊精键合固定相的制备和保留行为”分析科学。

Yoshinaga, Masanobu: "Enantiomeric Separation of Dansylamino Acids by Capillary Electrophoresis with Selectively Methylated γ-Cyclodextrin Derivatives" Analytica Chimica Acta. 316. 121-127 (1995)

Yoshinaga, Masanobu：“使用选择性甲基化 γ-环糊精衍生物通过毛细管电泳分离丹酰氨基酸”，Analytica Chimica Acta 316. 121-127 (1995)。