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Development of chiral stationary phases consisting of low-molecular-weight cellulose covalently bonded to silica gel

开发由共价键合到硅胶上的低分子量纤维素组成的手性固定相

基本信息

批准号：
14360196
负责人：
HABU Naoto
金额：
$ 8.58万
依托单位：
Utsunomiya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2003
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14360196/
关键词：
cellulose chiral chiral resolution covalent bond HPLC

项目摘要

We prepared chiral supports whose chiral stationary phase (CSP), consisting of a low-molecular-weight cellulose derivative (degree of polymerization : 15), is covalently bonded to silica gel. The cellulose used as the base material of the CSP was pre-hydrolysed with phosphoric acid before the coupling reaction to unite a reducing terminal in the cellulose and anaminopropyl group on the surface of silanized silica. After substituting hydroxyl groups in cellulose by using 3,5-dichlorophenyl isocyanate or phenylisocyanate, we tested the CSP thus obtained for its performance in chiral recognition and found a wide range of chiral discrimination ability. We also confirmed that an elution using ‘strong' solvents as a mobile phase could be achieved, which is difficult for the coated-type CSPs because the mobile phase may dissolve the CSP. However, more enantiomeric mixtures showed larger selectivity factors (α) when eluted on the coated-type CSPs than on the covalently bonded CSPs. A coated-type CSP consisting of the low-molecular-weight cellulose phenylcarbamate, prepared as a control CSP sample, showed comparable performance with the commercial coated-type column (CHIRALCEL【○!R】 OC), so the slightly poorer performance of the chemically bonded CSPs may be explained by the difficulty of the polymer consisting of the CSPs in taking an optimal supermolecular structure required for chiral recognition due to the fixation to the silica gel. The low degree of polymerization may have an additional effect.

我们制备了手性载体，其手性固定相(CSP)由低分子量的纤维素衍生物(聚合度：15)组成，与硅胶共价键合。作为CSP基料的纤维素在偶联反应前用磷酸预水解，使纤维素中的还原末端与硅烷化二氧化硅表面的氨基丙基结合在一起。用3，5-二氯苯基异氰酸酯或苯基异氰酸酯取代纤维素中的羟基后，我们测试了所得到的CSP的手性识别性能，发现了广泛的手性识别能力。我们还证实了可以实现用强溶剂作为流动相的洗脱，这对于包覆型CSP来说是困难的，因为流动相可能会溶解CSP。然而，更多的对映体混合物在包覆型CSP上洗脱时显示出比共价键合CSP上更大的选择性因子(α)。由低相对分子质量的苯氨基甲酸纤维素酯组成的包覆型CSP的性能与商业包覆型色谱柱(CHIRALCEL[0！R]OC)的性能相当，因此化学键合的CSP的性能略差的原因可能是由CSP组成的聚合物由于固定在硅胶上而难以获得手性识别所需的最佳超分子结构。低聚合度可能还有一个额外的影响。