Supramolecular chiral emergence in water even after compensating for helix chirality in vesicular helix-peptide-aromatic frameworks
Supramolecular chiral emergence in water even after compensating for helix chirality in vesicular helix-peptide-aromatic frameworks
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DOI：
10.1038/s41428-023-00781-w
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发表时间：
2023-04
期刊：
影响因子：
2.8
通讯作者：
Y. Yoshimoto;Yuya Suzuki;T. Imai;S. Kimura;Hirotaka Uji
中科院分区：
文献类型：
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作者：
Y. Yoshimoto;Yuya Suzuki;T. Imai;S. Kimura;Hirotaka Uji
利用两亲性多肽在水中形成纳米片和囊泡的分子组装体来研究非手性分子的超分子手性出现。新设计的两亲性多肽包含一个亲水性聚（Sar）嵌段、两个疏水性螺旋嵌段和一个π-共轭嵌段（SL-π-D）。这两个螺旋块分别是右旋和左旋螺旋的(L-Leu-Aib)4和(D-Leu-Aib)4，以补偿导致SL-π-D非手性分子的螺旋手性。 SL-π-D 在三氟乙醇 (TFE)/水溶液中自组装成均匀的纳米片和囊泡，具体取决于溶液中的 TFE 含量。在自组装成纳米片和囊泡时，由于激子耦合而引起的棉花效应出现在非手性 π-共轭块中。与纳米片相比，这种超分子手性出现在囊泡中得到增强。手性的起源本质上源自(螺旋嵌段)-(π-共轭嵌段)-(螺旋嵌段)的结构，并进一步源自囊泡形态。
Supramolecular chiral emergence from achiral molecules is studied with amphiphilic polypeptides upon forming molecular assemblies of nanosheets and vesicles in water. A newly designed amphiphilic polypeptide contains a hydrophilic poly(Sar) block, two hydrophobic helical blocks, and a π-conjugate block (SL-π-D). The two helical blocks are (L-Leu-Aib)4and (D-Leu-Aib)4of right- and left-handed helices, respectively, to compensate for the helical chirality resulting in the achiral molecule of SL-π-D. SL-π-D self-assembled in trifluoroethanol (TFE)/water solutions into uniform nanosheets and vesicles depending on the TFE content in the solutions. The induced Cotton effect due to exciton coupling appears in the achiral π-conjugate block upon self-assembling into nanosheets and vesicles. This supramolecular chiral emergence is enhanced in vesicles compared to nanosheets. The origin of the chirality intrinsically arises from the structure of (helix block)-(π-conjugate block)-(helix block) and further from vesicular morphology.