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

作　　者：陈娇娇[1] 侯蔺桐[2] 蒋奕[1] 张霞[3] 

机构地区：[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,天津300387 [2]天津工业大学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

出　　处：《高等学校化学学报》2014年第3期645-651,共7页Chemical Journal of Chinese Universities

基　　金：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);江南大学生态纺织教育部重点实验室基金(批准号:KLET1212)资助~~

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%.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 car-boxyl 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 （ 1 H NMR） . Then the subsequent co-polymerization 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-phenyl-alanine（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 con-tents of chiral monomer or the controlling temperature would improve the chiral recognizable capacity and effi-ciency 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.

关 键 词：温敏凝胶 N-异丙基丙烯酰胺 L-亮氨酸 手性识别 

分 类 号：O632[理学—高分子化学] O647[理学—化学]