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2-
N -邻苯二甲酰亚胺壳聚糖基手性固定相的制备及手性识别能力研究Studies on Preparation and Chiral Recognition of 2-
N -phthaloyl Chitosan-based Chiral Stationary Phases- 高分子学报 2016年第11期 页码：1555-1562
- 作者机构：
1.哈尔滨工程大学材料科学与化学工程学院 超轻材料与表面技术教育部重点实验室 哈尔滨 150001
2.Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
- 作者简介：
张丽丽,E-mail:zhanglili1984@hrbeu.edu.cn Li-li Zhang,E-mail:zhanglili1984@hrbeu.edu.cn
沈军,E-mail:shenjun@hrbeu.edu.cn Jun Shen,E-mail:shenjun@hrbeu.edu.cn
- 基金信息：国家自然科学基金(21474024);国家自然科学基金(51603054);国家自然科学基金(51673052);黑龙江省自然科学基金(E201419);黑龙江省自然科学基金(B2015022);黑龙江省博士后基金(LHB-Z15050);中央高校基本科研业务费专项基金(HEUCF20161011);国家大学生创新创业训练计划(201610217067)
DOI：10.11777/j.issn1000-3304.2016.16072
中图分类号：纸质出版日期：2016-11，
收稿日期：2016-3-15，
修回日期：2016-4-28，
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张丽丽, 沈军, 岡本佳男, 李玉龙. 2-
N -邻苯二甲酰亚胺壳聚糖基手性固定相的制备及手性识别能力研究[J]. 高分子学报, 2016,(11):1555-1562.Li-li Zhang, Jun Shen, Yoshio Okamoto, Yu-long Li. Studies on Preparation and Chiral Recognition of 2-
N -phthaloyl Chitosan-based Chiral Stationary Phases[J]. Acta Polymerica Sinica, 2016,(11):1555-1562.张丽丽, 沈军, 岡本佳男, 李玉龙. 2-
N -邻苯二甲酰亚胺壳聚糖基手性固定相的制备及手性识别能力研究[J]. 高分子学报, 2016,(11):1555-1562. DOI： 10.11777/j.issn1000-3304.2016.16072.Li-li Zhang, Jun Shen, Yoshio Okamoto, Yu-long Li. Studies on Preparation and Chiral Recognition of 2-
N -phthaloyl Chitosan-based Chiral Stationary Phases[J]. Acta Polymerica Sinica, 2016,(11):1555-1562. DOI： 10.11777/j.issn1000-3304.2016.16072.
摘要
为了开发具有高效手性识别能力的新型多糖类手性固定相，合成了5种糖单元2-位具有邻苯二甲酰亚胺，而3，6-位同时具有4种不同苯基氨基甲酸酯基团(2-氯、3-氯、4-氯和3，5二氯取代的苯基氨基甲酸酯)和一种无取代的苯基氨基甲酸酯基团的壳聚糖类衍生物，并将其涂覆在氨丙基硅胶表面制备成HPLC手性固定相.利用红外光谱和核磁氢谱对所合成的衍生物进行结构表征与分析，并应用HPLC法评价其对10种对映体的手性识别能力.研究结果表明：这些新型壳聚糖类手性固定相的手性识别能力受苯基氨基甲酸酯取代基中芳环上侧基的引入位置、数量和空间位阻的影响较大.同时色谱测试中所使用流动相的成分对该类手性固定相的识别能力也具有较大影响.进一步探讨了这些衍生物的氨基甲酸酯残基核磁氢谱中N—H质子的化学位移和红外光谱中N—H波数与手性识别能力之间的关系.
Abstract
To develop novel polysaccharide-based chiral stationary phases with high chiral recognition
five novel chitosan derivatives
bearing
N
-phthaloyl at 2-position of a glucose ring and four different phenylcarbamate substituents including 2-chloro
3-chloro
4-chloro and 3
5-dichloro
and one chitosan derivative bearing unsubstituted phenylcarbamate at 3- and 6-positions were synthesized by combination of a procedure on the regioselective acylation of 2-position.The structures of the obtained chitosan derivatives were characterized by FTIR and
1
H-NMR.They were then coated on the macroporous silica gel to be used as chiral stationary phases for high-performance liquid chromatography (HPLC).Their chiral recognition abilities were evaluated using ten racemates by HPLC.The results indicated that these coated-type chitosan CSPs exhibited characteristic chiral recognition ability
mainly depending on the position
number and steric hindrance of the substituents introduced on the aromatic moieties of the chitosan derivatives.Meanwhile
the eluent content in chromatographic tests had a great influence on the chiral recognition abilities of the chitosan-based CSPs.The racemates
1
3
6
7
8
10
were better resolved using a hexane/2-propanol (99/1) mixture as the eluent in comparison with the results obtained using hexane/2-propanol (90/10) mixture as the eluent on chitosan 2-phthaloyl-3
6-di(3
5-dichlorophenylcarbamate derivative (CSP-
3e
).The correlations between the chiral recognition abilities and the chemical shifts of the N-H protons in the
1
H-NMR spectra and the N-H frequencies in the IR spectra of the carbamate moieties of these derivatives were also discussed further.Among the CSPs based on the chitosan derivatives bearing different substituents at 2 and 3
6-postions of the glucose unit
those based on the chitosan derivatives (CSP-
3e
) bearing 3
5-dichlorophenylcarbamates at 3
6-positions showed higher chiral recognition abilities while those based on the derivatives bearing 2-chlorophenylcarbamates at 3
6-positions showed relatively lower recognition ability.Compared to chitosan 2-(3
5-dichlophenylurea)-3
6-di(3
5-dichlorophenylcarbamate) (CSP-ref) and chitosan 2-phthaloyl-3
6-(3
5-dichlorophenylcarbamate) (CSP-
3e
-ref)
the chitosan derivative (CSP-
3e
) showed complementary and similar chiral recognition abilities for some racemates.
关键词
壳聚糖2-N-邻苯二甲酰亚胺苯基氨基甲酸酯手性固定相手性识别能力
Keywords
ChitosanRegioselective substituentsPhenylcarbamateChiral stationary phasesChiral recognition
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