Photochirogenic nanosponges: phase-controlled enantiodifferentiating photoisomerization of (Z)-cyclooctene sensitized by pyromellitate-crosslinked linear maltodextrin
Photochirogenic nanosponges: phase-controlled enantiodifferentiating photoisomerization of (Z)-cyclooctene sensitized by pyromellitate-crosslinked linear maltodextrin
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光致性纳米海绵：均苯四酸酯交联的线性麦芽糖糊精敏化的（Z）-环辛烯的相控对映差异化光异构化
DOI：
10.1039/c6ra28211c
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发表时间：
2017-03
期刊：
影响因子：
3.9
通讯作者：
Yang Cheng
中科院分区：
文献类型：
--
作者：
Liang Wenting;Zhao Meiling;Wei Xueqin;Yan Zhiqiang;Wu Wanhua;Caldera Fabrizio;Trotta Francesco;Inoue Yoshihisa;Su Dan;Zhong Zhihui;Yang Cheng
将线性麦芽糖糊精（LM）与焦二酸酐交联，得到不同交联度的线性麦芽糖糊精聚合物。当浸泡在水中时，这些交联的LM聚合物（纳米海绵（NSs））演变成几个阶段，从溶胶到悬浮液，然后到流动凝胶，最后到刚性凝胶，其含量增加。(Z)-环烯(1Z) -手性(E)-异构体（1E）的对映分化光异构反应，作为定量评估环境-分子手性转移过程的基准反应，在含有这些pyromellit_交联LM-NSs的不同相的水介质中进行。所获得的1E的对映体过量（ee）至少在流动凝胶相之前对相相对不敏感，但在刚性凝胶相中变得高度敏感，在刚性凝胶相早期突然下降，然后在刚性凝胶相后期迅速恢复。与先前报道的类似的pyromellitate-交联cyclodextrin (CD)-和cyclic nigerosylnigerose (CNN)-NSs相依赖的ee谱进行比较发现，在NS中pyromellitate-交联环糊精(CD)-和环状黑糖(CNN)-NSs中产生的手性空隙空间是硬凝胶相ee发生剧烈变化的原因，而CD/CNN中固有的宿主空腔在敏化剂-交联NSs介导的超分子光致光作用中仅发挥有限的作用。后一种见解使我们能够通过采用更广泛的低聚糖以及底物和增敏交联剂，进一步扩大当前概念和方法的适用范围。
Linear maltodextrin (LM) was cross-linked by pyromellitic dianhydride to afford LM polymers of different cross-linking degrees. When soaked in water, these cross-linked LM polymers (nanosponges (NSs)), evolved into several phases from sol to suspension, then to flowing gel, and finally to rigid gel with an increase in their content. Enantiodifferentiating photoisomerization of (Z)-cyclooctene (1Z) to chiral (E)-isomer (1E), which was employed as a benchmark reaction to quantitatively assess the environmental-to-molecular chirality transfer process, was performed in aqueous media containing these pyromellitate-crosslinked LM-NSs in different phases. The enantiomeric excess (ee) of 1E obtained was relatively insensitive to the phases at least up to the flowing gel phase, but became highly sensitive in the rigid gel phase, exhibiting an abrupt drop in the early rigid gel phase followed by a rapid recovery in the late rigid gel phase. A comparison with the phase-dependent ee profiles previously reported for similar pyromellitate-crosslinked cyclodextrin (CD)- and cyclic nigerosylnigerose (CNN)-NSs revealed that the chiral void space created around the pyromellitate linker in NS is responsible for the dramatic changes in ee in the rigid gel phase, whereas the inherent host cavity in CD/CNN plays only limited roles in the supramolecular photochirogenesis mediated by the sensitizer-crosslinked NSs. The latter insight allows us to further expand the applicable range of the present concept and methodology by employing a much wider variety of oligosaccharides as well as substrates and sensitizing cross-linkers.
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影响因子：
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作者：
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影响因子：
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作者：
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