Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology , Changzhou University , Changzhou 213164 , P. R. China.
College of Biological, Chemical Sciences and Engineering , Jiaxing University , Jiaxing 314001 , P. R. China.
Langmuir. 2019 Dec 24;35(51):16761-16769. doi: 10.1021/acs.langmuir.9b03255. Epub 2019 Dec 11.
π-Conjugated porphyrins have aroused particular attention for nanofabrication and biomimics; however, little attention has been paid to porphyrins-based chiral analysis owing to the achiral feature of porphyrins. Here, we demonstrated a chiral self-assembly of achiral porphyrin induced by l- and d-lysine (l- and d-Lys), and the resultant porphyrin self-assembly exhibited alterable morphologies depending on the inducer used (l- or d-Lys). The supramolecular chirality of the self-assembly was characterized by circular dichroism (CD) spectra, confirming successful transfer of molecular chirality from l- and d-Lys to the self-assembly. The enantioselective property of the chiral self-assembly was also investigated by using tryptophan (Trp) isomers as the model, and the results indicated that the developed chiral self-assembly showed significantly higher affinity toward l-Trp than d-Trp. Also in this work, the l-/d-Lys-induced chiral self-assembly of porphyrin and the supramolecular interaction between the self-assembly and l-/d-Trp were also studied by density functional theory (DFT).
π 共轭卟啉因其在纳米制造和仿生学方面的应用而引起了特别关注；然而，由于卟啉的手性特征，基于卟啉的手性分析很少受到关注。在这里，我们展示了手性赖氨酸（l- 和 d-赖氨酸）诱导的非手性卟啉的手性自组装，所得卟啉自组装的形态可以根据所使用的诱导剂（l-或 d-赖氨酸）而改变。通过圆二色性（CD）光谱对自组装的超分子手性进行了表征，证实了分子手性从 l-和 d-赖氨酸成功转移到自组装中。通过色氨酸（Trp）异构体作为模型也研究了手性自组装的对映选择性，结果表明，所开发的手性自组装对 l-Trp 的亲和力明显高于 d-Trp。此外，在这项工作中，还通过密度泛函理论（DFT）研究了 l-/d-赖氨酸诱导的卟啉手性自组装以及自组装与 l-/d-Trp 之间的超分子相互作用。
