双敏感性环糊精超分子聚集体的制备及其性能研究
收稿日期: 2013-07-15
网络出版日期: 2013-08-30
基金资助
项目受国家自然科学基金(No. 21004029)和江苏省先进功能高分子材料设计及应用重点实验室(苏州大学)开放研究基金(No. KJS1141)资助.
Preparation and Properties of Supramolecular Aggregation of Dual-Sensitive Cyclodextrins
Received date: 2013-07-15
Online published: 2013-08-30
Supported by
Project supported by the National Natural Science Foundation of China (No. 21004029) and Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application (Soochow University, No. KJS1141).
利用光敏感性环糊精衍生物与温度敏感性聚合物主客体间的包结络合作用制备了具有光/温度双敏感性的环糊精超分子聚集体. 首先制备了主体分子光敏感性4-羟基肉桂酸-β-环糊精(4HCA-CD); 再以末端带金刚烷基团(AD)的三硫酯作为链转移剂, 用可逆加成-断裂链转移自由基聚合(RAFT)法制备温度敏感性双臂聚合物AD-PNIPAM-AD; 用傅里叶变换红外光谱(FT-IR)、核磁共振氢谱(1H NMR)证明了化合物的结构. 利用β-CD的疏水空腔和AD之间的络合性能, 制备了4HCA-CD/AD-PNIPAM-AD双敏感性超分子复合物, 通过二维核磁(2D NMR)对其包结性能进行了探究, 结果证实金刚烷包结于环糊精的空腔中. 所得4HCA-CD/AD-PNIPAM-AD复合物具有光敏感性, 用紫外光照射后, 复合物的分子量增大近一倍. 而且, 4HCA-CD/AD-PNIPAM-AD复合物可以自组装形成超分子聚集体, 其粒径随温度的升降发生可逆的减小或增大.
孔蕊 , 施冬健 , 刘蓉瑾 , 吴超 , 倪沛红 , 陈明清 . 双敏感性环糊精超分子聚集体的制备及其性能研究[J]. 化学学报, 2013 , 71(11) : 1540 -1546 . DOI: 10.6023/A13070742
Polymer inclusion complexes with supramolecular structures formed between various polymers and cyclodextrins (CDs) have been attracted increasing attention. The stimuli-responsive supramolecules including pH, temperature, light, and magnetic fields as "smart" soft materials have been found promising in bioapplications, because they could respond environmental changes and self-induce structural transformations. Thus, to design and achieve responsive supramolecule is of significance not only to scientific research but also to potential applications. In this report, light and temperature dual-sensitive supramolecules were prepared by host-guest interaction between light-sensitive cyclodextrin derivatives and temperature-sensitive polymers. Light-sensitive 4-hydroxycinnamic acid modified β-cyclodextrin (4HCA-CD) was prepared firstly as host compound. Then, two adamantanes (ADs) terminated temperature-sensitive AD-poly(N-isopropyl-acrylamide)-AD polymer (AD-PNIPAM-AD) was prepared by reversible addition fragmentation chain transfer polymerization (RAFT) using two ADs terminated compound as chain transfer agent. The structures of 4HCA-CD and AD-PNIPAM-AD were confirmed by FT-IR and 1H NMR spectra. Molecular weight and its distribution of AD-PNIPAM-AD were determined by GPC. The 4HCA-CD/AD-PNIPAM-AD complex was prepared by mixing 4HCA-CD and AD-PNIPAM-AD, and was confirmed by 2D NMR spectrum and GPC. With UV irradiation, the absorbance of cinnamate group at 290 nm by ultraviolet visible spectrophotometer (UV-vis) spectra reduced, and the molecular weight of the complex increased about twice. These results suggested that the 4HCA-CD/AD-PNIPAM-AD complex had light-sensitivity. Moreover, the complex showed thermo-sensitivity, and the lower critical solution temperature (LCST) of the obtained host-guest inclusion complexation was 34 ℃. Up to LCST, the complex solution produced floccules. Below to LCST, the floccules disappeared and homogeneous solution recovered. The 4HCA-CD/AD-PNIPAM-AD complex could self-assemble into supramolecular aggregation by adding additional water into the complex solution in DMF. Interestingly, the size of the formed aggregation reduced after increasing the temperature up to LCST, possibly due to hydrophilic and hydrophobic transformation and re-assembly of the aggregations. Furthermore, the size could be recycled to the original size by decreasing temperature lower than LCST.
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