Hydrogen bonds driven conformation autoregulation and sol-gel transition of poly(3,5-disubstituted phenylacetylene)s
Hydrogen bonds driven conformation autoregulation and sol-gel transition of poly(3,5-disubstituted phenylacetylene)s
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氢键驱动的聚（3,5-二取代苯乙炔）构象自动调节和溶胶-凝胶转变
DOI：
10.1016/j.eurpolymj.2019.05.060
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发表时间：
2019-09
影响因子：
6
通讯作者：
Wan Xinhua
中科院分区：
文献类型：
--
作者：
Wang Sheng;Tan Junyan;Guan Xiaoyan;Chen Junxian;Zhang Jie;Wan Xinhua
在[Rh（nbd）Cl]2催化下，合成了两种新型的顺式3，5-二取代聚苯乙炔，它们分别带有一个非手性甲氧羰基和一个手性（S）-/（R）-[1-（2-萘基）乙基]氨甲酰基侧基，即sP-Me-Nap 2/rP-Me-Nap 2。用~ 1H NMR、X-射线衍射、CD、DSC、拉曼、FTIR、WAXD和计算机计算等技术对单体和聚合物的结构进行了表征，发现sP-Me-Nap 2和rP-Me-Nap 2在CHCl_3中随时间的推移，自发地从伸展的顺-反式螺旋转变为收缩的顺-顺式螺旋。这种构象自动调节不仅引起稀溶液中颜色从黄色到无色的变化，而且在浓度大于1.0mg/mL（0.1%w/v）时诱导溶胶-凝胶转变。透射电子显微镜（TEM）揭示了一个三维互联网络结构的有机凝胶。计算结果表明，从弱2/1氢键模式到强3/1氢键模式的转变降低了螺旋构象的总能量，有利于螺旋构象的自动调节和溶胶-凝胶转变。
Two novelcis3,5-disubstituted polyphenylacetylenes bearing an achiral methoxycarbonyl and a chiral (S)-/(R)-[1-(naphthalen-2-yl)ethyl]carbamoyl pendant groups,sP-Me-Nap2/rP-Me-Nap2, were synthesized under catalysis of [Rh(nbd)Cl]2. Various techniques including1H NMR, X-ray crystallographic analysis, CD, DSC, Raman, FTIR, WAXD, and computer calculations were applied to characterize the structures of monomers and polymers in both solution and solid states.sP-Me-Nap2andrP-Me-Nap2spontaneously transferred from a stretchedcis-transoidhelix to a contractedcis-cisoidhelix in CHCl3with time. This conformation autoregulation not only caused the color change between yellow and colorless in dilute solution, but also induced the sol-gel transition at the concentration of above 1.0 mg/mL (0.1% w/v). Transmission electron microscopy (TEM) revealed a three-dimensional interconnected network structure of the organogel. According to computer calculations, it was proposed that transition from weak 2/1 hydrogen bonding model to strong 3/1 hydrogen bonding model decreased the total energy of helical conformation, which facilitated this conformation autoregulation and sol-gel transition.
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影响因子：
8.4
作者：
Fan J;Zou J;He X;Zhang F;Zhang S;Raymond JE;Wooley KL
通讯作者：
Wooley KL
影响因子：
8.4
作者：
Leiras S;Freire F;Quiñoá E;Riguera R
通讯作者：
Riguera R
通过分子内 n -> pi 相互作用稳定聚（3,5-二取代苯乙炔）的顺-顺螺旋结构
影响因子：
5.5
作者：
Wang Sheng;Shi Ge;Guan Xiaoyan;Zhang Jie;Wan Xinhua
通讯作者：
Wan Xinhua
影响因子：
5.5
作者：
Katsuhiro Maeda;Hiroaki Mochizuki;K. Osato;E. Yashima
通讯作者：
Katsuhiro Maeda;Hiroaki Mochizuki;K. Osato;E. Yashima
影响因子：
15
作者：
Goto, H;Zhang, HQ;Yashima, E
通讯作者：
Yashima, E