手性温敏凝胶 P(NIPAM-co-NALL)的制备及识别性能

doi:10.7503/cjcu20130743

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (3): 645.doi: 10.7503/cjcu20130743

手性温敏凝胶 P(NIPAM-co-NALL)的制备及识别性能

陈娇娇¹(), 侯蔺桐², 蒋奕¹, 张霞³

1. 天津工业大学环境与化学工程学院, 中空纤维膜材料与膜过程省部共建国家重点实验室培育基地
2. 材料科学与工程学院, 天津 300387
3. 江南大学生态纺织教育部重点实验室, 无锡 214122

收稿日期:2013-07-31 出版日期:2014-03-10 发布日期:2014-01-20
作者简介:联系人简介: 陈娇娇, 女, 博士, 副教授, 主要从事手性分离材料研究. E-mail: chenjiaojiao@tjpu.edu.cn
基金资助:
国家自然科学基金(批准号: 20904039和51003075)、天津市应用基础及前沿技术研究计划(批准号: 10JCYBJC02900)和江南大学生态纺织教育部重点实验室基金(批准号: KLET1212)资助

Preparation and Recognization Property of Chiral Thermo-sensitive P(NIPAM-co-NALL) Hydrogels^†

CHEN Jiaojiao^1,^*(), HOU Lintong², JIANG Yi¹, ZHANG Xia³

1. School of Environmental and Chemical Engineering, State Key Laboratory of Hollow Fiber Membrane Materials and Membrane Processes Department of Materials Science
2. School of Material and Chemical Engineering, Tianjin Polytechnic University, Tianjin 300387, China
3. Key Laboratory of Eco-textiles, Ministry of Education, Jiangnan University, Wuxi 214122, China

Received:2013-07-31 Online:2014-03-10 Published:2014-01-20
Contact: CHEN Jiaojiao E-mail:chenjiaojiao@tjpu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.20904039, 51003075), the Tianjin Research Program of Application Foundation and Advanced Technology, China(No.10JCYBJC02900) and the Open Project Program of Key Laboratory of Eco-textiles, Ministry of Education, Jiangnan University, China(No.KLET1212)

摘要/Abstract

摘要：

以L-亮氨酸(L-Leu)为手性源, 经酯化和缩合等步骤制备手性单体(NALL), 以该单体为手性识别基团, 在交联剂N,N'-亚甲基双丙烯酰胺和引发剂偶氮二异丁腈的作用下, 与N-异丙基丙烯酰胺(NIPAM)以不同的质量比发生自由基共聚, 制备了一系列新型手性温敏水凝胶P(NIPAM-co-NALL), 其结构经红外光谱确证. 相比于PNIPAM水凝胶, 疏水性单体NALL的引入使 P(NIPAM-co-NALL)凝胶的温敏性下降. 以D, L-苯丙氨酸为模型药物对P(NIPAM-co-NALL)凝胶的手性识别和拆分性能进行研究, 结果表明, 手性温敏凝胶对D型对映体具有选择吸附性, 且吸附量随着手性单体含量的增加而增加; 提高温度(40 ℃)有利于手性温敏凝胶对D, L-苯丙氨酸的手性识别和拆分. P(NIPAM-co-NALL)凝胶在重复使用后依然具有手性识别性能, 但其吸附量随着使用次数的增加而下降, 3次重复使用后吸附量下降到原来的27.6%.

关键词: 温敏凝胶, N-异丙基丙烯酰胺, L-亮氨酸, 手性识别

Abstract:

A series of novel thermo-sensitive hydrogels based on N-isopropylacrylamide(NIPAM) containing L-leucine groups was designed and synthesized for chiral recognition. L-Leucine used as chiral pool, the chiral monomer N-acryloyl-L-leucine methyl ester(NALL) was obtained by sterifization with methanol to protect carboxyl group and then condensation with acryloyl chloride in the presence of trirthylamine in N,N-dimethylfo-mamid(DMF)and gave the chiral monomers N-acryloyl-L-leucine methyl ester(NALL), whose structure was characterized by infrared(IR) and proton nuclear magnetic resonance(¹H NMR). Then the subsequent copolymerization was carried on between NALL as chiral recognition units, NIPAM and N,N'-methylenebisacry-lamide(MBAA) as linkage agent in the presence of azobisisobutyronitrile(AIBN) in ethanol with different mass ratios. The P(NIPAM-co-NALL) hydrogels were identified by IR. The swelling behavior, deswelling and reswelling kinetics of the chiral hydrogels were studied, and the results showed that all the P(NIPAM-co-NALL) hydrogels exhibited evident temperature-sensitivity. Due to the hydrophobicity of NALL incorporated into the structure of the chiral gels, the thermo-sensitivity of the chiral gels was lower than that of PNIPAM gel. The chiral selective adsorption and chiral recognition performance were also investigated by D, L-phenylalanine(D, L-Phe) as model drugs. The results indicated that compared with PNIPAM gel, the chiral gels performed higher adsorption rate and larger adsorption quantities for D-Phe enantiomers. Increasing the contents of chiral monomer or the controlling temperature would improve the chiral recognizable capacity and efficiency of resolution. Furthermore, P(NIPAM-co-NALL) hydrogels could be reused, which remained the chiral recognition property after three-times reuse although the absorption capacity decreased to 27.6% of the original.

Key words: Thermo-sensitive hydrogel, N-Isopropylacrylamide, L-Leucine, Chiral recognization

中图分类号:

O632
O647

TrendMD:

陈娇娇, 侯蔺桐, 蒋奕, 张霞. 手性温敏凝胶 P(NIPAM-co-NALL)的制备及识别性能. 高等学校化学学报, 2014, 35(3): 645.

CHEN Jiaojiao, HOU Lintong, JIANG Yi, ZHANG Xia. Preparation and Recognization Property of Chiral Thermo-sensitive P(NIPAM-co-NALL) Hydrogels^†. Chem. J. Chinese Universities, 2014, 35(3): 645.

图/表 12

Scheme 1 Synthetic routes of P(NIPAM-co-NALL) hydrogels

Table 1 Feed composition of P(NIPAM-co-NALL) hydrogels

r	m(NIPAM)/mg	m(NALL)/mg	m(MBAA)/mg	m(AIBN)/mg
0	339.5	0	23.1	5
0.05	326.7	16.3	23.1	5
0.1	314.9	31.5	23.1	5

Fig.1 FTIR spectra of PNIPAM and P(NIPAM-co-NALL) hydrogels with various NALL contents r: a. 0; b. 0.05; c. 0.1.

Fig.2 Relationship between SR and temperature(A) and DSC curves(B) of PNIPAM and P(NIPAM-co-NALL) hydrogels r: a. 0; b. 0.05; c. 0.1.

Fig.3 Deswelling kinetics of PNIPAM and P(NIPAM- co-NALL) hydrogels at 45 ℃ r: a. 0; b. 0.05; c. 0.1.

Fig.4 Reswelling kinetics of PNIPAM and P(NIPAM- co-NALL) hydrogels at 25 ℃ r: a. 0; b. 0.05; c. 0.1.

Fig.5 Equilibrium absorption capacity of PNIPAM and P(NIPAM-co-NALL) hydrogels(r=0.1) at 40 ℃

Fig.6 Absorption kinetics of P(NIPAM-co-NALL) hydrogels(r=0.1) at 25 ℃(a) and 40 ℃(b)

Fig.7 Variation of absorption kinetics of PNIPAM and P(NIPAM-co-NALL) hydrogels with various NALL contents at 40 ℃ r: a. 0; b. 0.05; c. 0.1.

Fig.8 Equilibrium absorption capacity of P(NIPAM-co-NALL) hydrogels(r=0.1) at 40 ℃ in multiple absorption-release test

Fig.9 Optical rotation([α]) with adsorbing time of PNIPAM and P(NIPAM-co-NALL) hydrogelsInitial total concentration of rac-phenlyalanine solution, 50 mmol/L. r: a. 0; b. 0.05; c. 0.1.

Fig.10 Optical rotation([α]) with adsorbing time of P(NIPAM-co-NALL) hydrogels(r=0.1) at 25 ℃(a) and 40 ℃(b)

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手性温敏凝胶 P(NIPAM-co-NALL)的制备及识别性能

Preparation and Recognization Property of Chiral Thermo-sensitive P(NIPAM-co-NALL) Hydrogels^†

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手性温敏凝胶 P(NIPAM-co-NALL)的制备及识别性能

Preparation and Recognization Property of Chiral Thermo-sensitive P(NIPAM-co-NALL) Hydrogels†

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Preparation and Recognization Property of Chiral Thermo-sensitive P(NIPAM-co-NALL) Hydrogels^†