Post-polymerization modification of the side chain in optically active polymers by thiol-ene reaction
Post-polymerization modification of the side chain in optically active polymers by thiol-ene reaction
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DOI：
10.1039/c6py01946c
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发表时间：
2017-02-14
影响因子：
4.6
通讯作者：
Onitsuka, Kiyotaka
中科院分区：
文献类型：
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作者：
Kanbayashi, Naoya;Miyamoto, Sou;Onitsuka, Kiyotaka
在这项研究中，我们研究了通过聚合后对单一光学活性聚合物进行修饰来合成含有不同侧链的光学活性聚合物的新方法。通过不对称聚合合成的旋光性聚合物(Poly-1)中的侧链通过硫醇烯反应进行了修饰，主链不需要外消旋。这种转化能够定量地引入广泛的官能团，并且所得到的每个光学活性聚合物(聚-2)的溶解度可以根据所引入的取代基而改变。圆二色谱表明，通过270 nm附近的新的Cotton效应，聚合物形成了动态二级结构。在实验中，侧链上引入了十二硫基，限制了主链的柔韧性，并在一定程度上抑制了聚合物的构象波动。此外，当侧链上引入羟基时，Cotton效应减弱，其强度与溶剂有关。因此，引入的取代基和溶剂的极性会影响聚合物的构象波动。
In this study, we examined novel synthetic methods for optically active polymers bearing various side chains from post-polymerization modification of a single optically active polymer. The side chain in the optically active polymer (poly-1) which was synthesized by asymmetric polymerization is modified using the thiol ene reaction without racemization of the main chain. This transformation enables quantitative introduction of a wide range of functional groups, and the solubility of each resulting optically active polymer (poly-2) can be changed depending on the introduced substituent. The CD spectra of the modified polymer revealed the formation of a dynamic secondary structure through a new Cotton effect around 270 nm. In the experiments, the introduction of a dodecylthio group into the side chain restricted the flexibility of the main chain and suppressed the conformational fluctuations in the polymer to some extent. Moreover, when a hydroxyl group was introduced into the side chain, the Cotton effect was decreased, with the degree of intensity dependent on the solvent. Thus, the introduced substituents and polarity of the solvents influence the conformational fluctuations of the polymer.