Chiral teletransmission in the cis-cisoidal sequence of copoly(substituted acetylene)s by multiple stage solvent exchange of the copolymer solution through a membrane
Chiral teletransmission in the cis-cisoidal sequence of copoly(substituted acetylene)s by multiple stage solvent exchange of the copolymer solution through a membrane
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DOI：
10.1016/j.polymer.2018.09.023
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发表时间：
2018-10
期刊：
影响因子：
4.6
通讯作者：
Lijia Liu;Yuanyuan Gu;Yudan Wang;T. Aoki;Guan Wang;Takeshi Kaneko;M. Teraguchi
中科院分区：
文献类型：
--
作者：
Lijia Liu;Yuanyuan Gu;Yudan Wang;T. Aoki;Guan Wang;Takeshi Kaneko;M. Teraguchi
共聚（4-十二烷氧基-3，5-二羟甲基苯乙炔/对-蒎烷基二甲基硅基苯乙炔）（copoly（1/2））由非手性的4-十二烷氧基-3，5-二羟甲基苯乙炔的顺-顺式序列（1）和手性的对-蒎烷基二甲基硅基苯乙炔的顺-反式序列（2）组成。计算得到1和2的竞聚率分别为r1= 1.49和r2= 0.50。通过用甲醇（不良溶剂）代替共聚（1/2）溶液中的THF（良好溶剂），通过浓度驱动渗透膜多次，观察到顺-顺式主链在308 nm处的CD强度逐步增加。手性2单元中的局部手性被成功地传递到非手性1的顺-顺序列中。即使当1/2摩尔比达到50时，这种多级溶剂交换方法仍然有效地将2中的局部手性传递到共聚物中的顺-顺式序列1中。在copoly（1/2）的溶液中直接加入甲醇和copoly（1/2）在THF/甲醇中退火不能实现这种手性遥传。因此，这种通过膜在共聚物溶液中进行多级溶剂交换的新方法适用于实现顺式聚乙炔的高效手性传递和放大。
Copoly(4-dodecyloxyl-3,5-dihydroxymethyl-phenylacetylene/p-pinanyldimethylsilylphenylacetylene) (copoly(1/2)) consist of both thecis-cisoidalsequence of achiral 4-dodecyloxyl-3,5-dihydroxymethyl-phenylacetylene (1) andcis-transoidalsequence of chiralp-pinanyldimethylsilylphenylacetylene (2). The reactivity ratios of1and2in the copolymerization were estimited as r1= 1.49 and r2= 0.50, respectively. By replacing THF (a good solvent) of copoly(1/2) solution with methanol (a poor solvent) gradually by concentration-driven permeation through a membrane for several times, stepwise increase in the CD intensity at 308 nm arisen from thecis-cisoidalmain-chain was observed. The local chirality in chiral2units was successfully transmitted to thecis-cisoidalsequence of achiral1. Even when the molar ratio of1/2reaches 50, this method of the multiple-stage-solvent-exchange is still effective for transmitting the local chirality in2to thecis-cisoidalsequence1in the copolymer. Directly adding methanol to the copoly(1/2)'s solution and annealing of copoly(1/2) in THF/methanol could not realize this chiral teletransmission. Hence, this new method of the multiple stage solvent exchange in the copolymer solution through a membrane is suitable and efficient to realize the efficient chirality transmission and amplification in thecis-cisoidalpolyacetylene.