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    顾缘缘, 王曜东, 王研, 刘立佳. 含联苯侧链聚苯乙炔手性诱导体系中的溶剂致螺旋翻转[J]. 功能高分子学报, 2019, 32(6): 747-754. doi: 10.14133/j.cnki.1008-9357.20190529001
    引用本文: 顾缘缘, 王曜东, 王研, 刘立佳. 含联苯侧链聚苯乙炔手性诱导体系中的溶剂致螺旋翻转[J]. 功能高分子学报, 2019, 32(6): 747-754. doi: 10.14133/j.cnki.1008-9357.20190529001
    GU Yuanyuan, WANG Yaodong, WANG Yan, LIU Lijia. Solvent-Depended Helicity Inversion of Polyphenylacetylene in Chiral Induction of Polyphenylacetylene Bearing Diphenyl Pendants[J]. Journal of Functional Polymers, 2019, 32(6): 747-754. doi: 10.14133/j.cnki.1008-9357.20190529001
    Citation: GU Yuanyuan, WANG Yaodong, WANG Yan, LIU Lijia. Solvent-Depended Helicity Inversion of Polyphenylacetylene in Chiral Induction of Polyphenylacetylene Bearing Diphenyl Pendants[J]. Journal of Functional Polymers, 2019, 32(6): 747-754. doi: 10.14133/j.cnki.1008-9357.20190529001

    含联苯侧链聚苯乙炔手性诱导体系中的溶剂致螺旋翻转

    Solvent-Depended Helicity Inversion of Polyphenylacetylene in Chiral Induction of Polyphenylacetylene Bearing Diphenyl Pendants

    • 摘要: 合成了非光学活性的带有双羟基联苯结构的苯乙炔单体(PhDHPA),并通过非手性铑催化剂引发其配位聚合得到了非光学活性的聚苯乙炔(Poly(PhDHPA))。通过核磁共振等对所合成化合物进行了结构表征,利用凝胶渗透色谱仪测定了所得聚合物分子量和分子量分布。 在Poly(PhDHPA)的良性溶剂中分别添加手性醇及手性胺等小分子后,通过圆二色/紫外-可见光谱(CD/UV-Vis)对溶液中的聚合物螺旋结构进行了表征分析,系统考察了手性小分子、 溶剂及温度对聚合物螺旋结构诱导行为的影响。结果表明:原本非光学活性的Poly(PhDHPA),在其溶液中加入手性小分子后,其在紫外-可见光区域内表现出明显的 CD 信号,该聚合物主链被手性小分子成功诱导为单向螺旋结构。薄荷醇所诱导得到的螺旋结构具有良好的热稳定性,且在使用同一手性小分子时,聚合物在不同溶剂中可呈螺旋方向相反的诱导螺旋结构。

       

      Abstract: Achiral (4-(dodecyloxy)-4'-ethynyl-1,1'-biphenyl-3,5-diyl) dimethanol (PhDHPA) was synthesized, and then was polymerized under the cataysis of an achiral rhodium catalyst, the chemical structures of intermediate compounds and PhDHPA monomer were characterized by nuclear magnetic resonance spectroscopy (1H-NMR), and the molecular weight and dispersion coefficient of the Poly(PhDHPA) were determined by gel permeation chromatography (GPC). The resulting Poly(PhDHPA) was achiral, however, when chiral bias such as R-(+)-1-phenylethanol, S-(-)-dimethyl-1-butanal, L-menthol, and R-phenylethylamine, was added in the solution of Poly(PhDHPA), it showed clear circular dichroism (CD) signals in the absorption regions of the polyphenylacetylenes backbones. The sign and pattern of the induced CD signals showed the dependence on the type of chiral bias and the solvent in the system. These indicate that one-handed helix structure could be successfully induced on the main chain of Poly(PhDHPA) by the chiral bias. The chiral induction might be due to the inter-molecular hydrogen bonds or π-π stacking interactions between the polymer with the chiral bias. It is interesting that merely change the solvent caused the helix inversion of the polymer even under the same chiral bias, and the influences of solvent and chiral bias on the induced helical structure of Poly(PhDHPA) in the solution were systematically investigated. The CD-UV/Vis spectra of Poly(PhDHPA)/L-menthol in different solvents was performed at the temperature region from −10 ℃ to 50 ℃, indicating that the helical structure induced by L-menthol showed good thermostability.

       

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