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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.
The photoinduced cyclodextrin supramolecular aggregates with dual sensitivity to light / temperature were prepared by inclusion complexation between the photo-sensitive cyclodextrin derivatives and the temperature-sensitive polymer host and guest.At first, the host molecule photosensitivity (4-hydroxycinnamic acid-β-cyclodextrin (4HCA-CD)) was synthesized by reversible addition-fragmentation chain transfer radical polymerization (RAFT) using trithioester with terminal adamantyl group (AD) as chain transfer agent ) Method was used to prepare temperature-sensitive double-arm polymer AD-PNIPAM-AD. The structure of the compound was confirmed by Fourier transform infrared spectroscopy (FT-IR) and 1H nuclear magnetic resonance (1H NMR) Cavity and AD, the 4HCA-CD / AD-PNIPAM-AD dual-sensitive supramolecular complex was prepared and its entrapment performance was investigated by two-dimensional nuclear magnetic resonance (2D NMR). As a result, it was confirmed that adamantane Encapsulated in the cyclodextrin cavity.The resulting 4HCA-CD / AD-PNIPAM-AD complex was photosensitized and the molecular weight of the complex was almost doubled after UV irradiation.Moreover, 4HCA-CD / AD-PNIPAM-AD complexes can self-assemble to form supramolecular aggregates, and their particle size reversibly decreases or increases with increasing or decreasing temperature.