Stereocomplex Organized by Chiral Recognition between L- and D-Enantiomers of Poly(gamma-alkyl glutamate) with Short Alkyl Side Chain
Stereocomplex Organized by Chiral Recognition between L- and D-Enantiomers of Poly(gamma-alkyl glutamate) with Short Alkyl Side Chain
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具有短烷基侧链的聚（γ-烷基谷氨酸）的L-和D-对映体之间通过手性识别形成的立体络合物
DOI：
10.1016/j.polymer.2012.11.080
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发表时间：
2013
期刊：
影响因子：
4.6
通讯作者：
坂尻浩一・中楯順一・顔竹君・渡辺順次
中科院分区：
文献类型：
--
作者：
西堀麻衣子;松原一郎;伊藤敏雄;申ウソク;坂尻浩一・中楯順一・顔竹君・渡辺順次
研究了α-螺旋聚谷氨酸-γ-烷基酯（PnLG）和聚谷氨酸-γ-烷基酯（PnDG）的外消旋混合物（PnG）中基于手性识别的立体复合物的形成。当具有n = 1-3的相对短侧链的PnG的对映体溶液在DMF中混合时，沉淀以具有等摩尔含量的PnLG和PnDG的细纤维形式发生，表明形成了l和d分子的立体复合物。沉淀物中含有10- 12vol%的DMF溶剂，并具有α-螺旋的四方堆积结构。在α-螺旋多肽系统中不常见的四螺旋堆积对称性，被认为是由在晶格中规则排列的l和d螺旋之间的侧链的“钮入孔”堆积产生的。
Stereocomplex formation based on chiral recognition was examined in racemic mixtures (PnG) of α-helical poly(γ-alkyl l-glutamate) (PnLG) and poly(γ-alkyl d-glutamate) (PnDG), where n, the carbon number of the side-chain alkyl groups, was varied from 1 to 6. When enantiomorphic solutions of PnG with relatively short side chains of n = 1–3 were mixed in DMF, precipitation occurred as fine fibrils with an equimolar content of PnLG and PnDG, demonstrating the formation of a stereocomplex of l and d molecules. The precipitates included 10–12 vol% of DMF solvent and possessed tetragonal packing structure of α-helices. The tetragonal packing symmetry, which is unusual in the α-helical polypeptide system, was considered to be produced by “knobs-into-holes” packing of side chains between l and d helices regularly arrayed in a lattice.