Chiral HPLC separation with self-assembled organic stationary phase

使用自组装有机固定相进行手性 HPLC 分离

• 批准号: 13555234
• 负责人: IHARA Hirotaka
• 金额: $ 7.04万
• 依托单位: Kyushu University (2003)Kumamoto University (2001-2002)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13555234/
• 关键词: Self-assembling systems; Chirality; Enantiomer; Diastereomer; Ordered structure; Liquid chromatography; Polymer grafting; 塩基性ポリマー; グラフトポリマー; 逆相分配; 液体クロマトグラフィー; 光学活性; トリプトファン; ダンシル基; クシ型ポリマー; シリカゲル; 有機-無機ハイブリッド; グルタミン酸; 分子認識; 円二色スペクトル

Chiral separation is still significant target in analytical chemistry and separation technology because each enantiomer provides absolutely different action in biosystems. HPLC with chiral stationary phase has been recognized as a facile method to perform it. However, there are few examples those were accomplished with a reversed phase-HPLC mode as the most convenient HPLC. This is due to no hydrophobicity difference in each enantiomer. Therefore, we focused on self-assembled systems to enhance microenvironmental effect in molecular recognition and applied these systems for functional organic stationary phases. Our research project clarified that (1)poly(octadecyl acrylate)-grafted silica showed distinct enhanced selectivity to recognize small difference in the molecular shape of polyaromatic hydrocarbons through disordered-to-ordered stale phase transition of the long-chain alkyl moieties, (2)the enhanced selectivity was brought about from multiple carbonyl-π interaction between the stationary phase and solutes, and (3)combination of this HPLC with diastereomerizing agents showed enhanced selectivity for the resultant diastereomers.

手性分离仍然是分析化学和分离技术的重要目标，因为每种对映体在生物系统中提供绝对不同的作用。使用手性固定相的 HPLC 已被认为是一种简便的方法。然而，很少有例子是使用反相 HPLC 模式作为最方便的 HPLC 来完成的。这是由于每种对映体没有疏水性差异。因此，我们专注于自组装系统来增强分子识别中的微环境效应，并将这些系统应用于功能有机固定相。我们的研究项目阐明：（1）聚（丙烯酸十八烷基酯）接枝二氧化硅表现出明显增强的选择性，通过长链烷基部分的无序到有序的陈相转变来识别多芳烃分子形状的微小差异，（2）增强的选择性是由固定相和溶质之间的多个羰基-π相互作用带来的，以及（3）该HPLC与 非对映异构化剂对所得非对映异构体表现出增强的选择性。

项目成果

T.Sagawa, S.Fukugawa, T.Yamada, H.Ihara: "Self-Assembled Fibrillar Networks through Highly Oriented Aggregates of Porphyrin, Pyrene, and N, N-Dimethylaniline Hydrophobized by Dialkyl L-Glutamine in Organic Media"Langmuir. 18. 7223-7228 (2002)

T.Sakawa、S.Fukukawa、T.Yamada、H.Ihara：“通过有机介质中二烷基 L-谷氨酰胺疏水化的卟啉、芘和 N,N-二甲基苯胺的高度定向聚集体形成自组装纤维网络”Langmuir。

H.Ihara, T.Sakurai, T.Yamada, T.Hashimoto, M.Takafuji, T.Sagawa, H.Hachisako: "Chirality Control of Self-Assembling Organogels from Lipophilic L-Glutamide Derivative with Metal Chlorides"Langmuir. Vol.18. 7120-7123 (2002)

H.Ihara、T.Sakurai、T.Yamada、T.Hashimoto、M.Takafuji、T.Sakawa、H.Hachisako：“亲脂性 L-谷酰胺衍生物与金属氯化物的自组装有机凝胶的手性控制”Langmuir。

M.Takafuji, T.Sakurai, T.Hashimoto, N.Kido, T.Yamada, T.Sagawa, H.Hachisako, H.Ihara: "Metal ion-induced chirality and morphology control of self-assembling organogels from L-glutamic acid-derived lipids"Chemistry Letters. 548-549 (2002)

M.Takafuji、T.Sakurai、T.Hashimoto、N.Kido、T.Yamada、T.Sakawa、H.Hachisako、H.Ihara：“金属离子诱导的手性和 L-谷氨酸自组装有机凝胶的形态控制

H.Ihara, W.Dong, T.Mimaki, M.Nishihara, T.Sakurai, M.Takafuji, S.Nagaoka: "Poly(4-vinylpyridine) as novel organic phase for RP-HPLC. Unique selectivity for polycyclic aromatic hydrocarbons"Journal of Liquid Chromatography. Vol.26. 2473-2485 (2003)

H.Ihara、W.Dong、T.Mimaki、M.Nishihara、T.Sakurai、M.Takafuji、S.Nagaoka：“聚（4-乙烯基吡啶）作为 RP-HPLC 的新型有机相。对多环芳烃具有独特的选择性

H.Ihara, M.Takafuji, T.Sakurai, M.Katsumoto, N.Ushijima, Tomohiro Shirosaki, H.Hachisako: "Novel self-assembling organogelators by combination of double chain-alkylated L-glutamide and polymeric head group"Organic & Biomolecular Chemistry(J.Chem.Soc., Per

H.Ihara、M.Takafuji、T.Sakurai、M.Katsumoto、N.Ushijima、Tomohiro Shirosaki、H.Hachisako：“通过双链烷基化 L-谷酰胺和聚合头基组合的新型自组装有机凝胶剂”有机