Decorating Conjugated Polymer Chains with Naturally Occurring Molecules: Synthesis, Solvatochromism, Chain Helicity, and Biological Activity of Sugar-Containing Poly(phenylacetylene)s
Decorating Conjugated Polymer Chains with Naturally Occurring Molecules: Synthesis, Solvatochromism, Chain Helicity, and Biological Activity of Sugar-Containing Poly(phenylacetylene)s
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DOI：
10.1021/ma062629d
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发表时间：
2007-03
期刊：
影响因子：
5.5
通讯作者：
K. Cheuk;J. Lam;B. Li;Yong Xie;B. Tang
中科院分区：
文献类型：
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作者：
K. Cheuk;J. Lam;B. Li;Yong Xie;B. Tang
合成了含有不同糖部分和功能性桥（1 - 5）的苯乙炔衍生物。它们的聚合受到有机铑络合物的影响，以高产率（高达99%）产生相应的聚合物P1-P5，具有高分子量（Mw高达1.2 × 106）和立体异构性（Z含量高达100%）。多烯主链在160 - 230 °C下发生不可逆的Z-到-E异构化。该聚合物的溶液表现出溶剂化变色性：它们的主链取向随周围介质的变化而变化。聚合物在其多烯主链吸收的长波长区域中显示出棉花效应，揭示了手性糖侧基诱导聚合物链采取单手性过量的螺旋构象。在手性侧基和多烯主链之间插入柔性亚甲基间隔基阻碍了螺旋诱导过程并降低了主链圆二色性。大多数聚合物中的丙酮化合物保护基团可以被...
Phenylacetylene derivatives containing different sugar moieties and functional bridges (1−5) are synthesized. Their polymerizations are affected by organorhodium complexes, producing corresponding polymers P1−P5 with high molecular weights (Mw up to 1.2 × 106) and stereoregularities (Z content up to 100%) in high yields (up to 99%). The polyene backbones undergo irreversible Z-to-E isomerization at ∼160−230 °C. The solutions of the polymers exhibit solvatochromism: their backbone absorptions change with variations in the surrounding media. The polymers show Cotton effects in the long wavelength region where their polyene backbones absorb, revealing that the chiral sugar pendants have induced the polymer chain to take a helical conformation with an excess in one-handedness. Inserting a flexible methylene spacer between the chiral pendant and the polyene backbone hampers the helicity induction process and lowers the backbone circular dichroism. The acetonide protection groups in most of the polymers can be...