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二苯基芘基胺功能化多肽：二级结构、聚集诱导发光及碳纳米管分散性

Diphenylpyrenylamine-functionalized polypeptides: secondary structures, aggregation-induced emission, and carbon nanotube dispersibility.

作者信息

El-Mahdy Ahmed F M, Kuo Shiao-Wei

机构信息

Department of Materials and Optoelectronic Science, National Sun Yat-Sen University Kaohsiung 80424 Taiwan

Chemistry Department, Faculty of Science, Assiut University Assiut 71516 Egypt.

出版信息

RSC Adv. 2018 Apr 23;8(28):15266-15281. doi: 10.1039/c8ra02369g.

DOI:10.1039/c8ra02369g
PMID:35539482
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9080069/
Abstract

In this study we prepared-through ring-opening polymerization of γ-benzyl-l-glutamate -carboxyanhydride (BLG-NCA) initiated by ,di(4-aminophenyl)-1-aminopyrene (pyrene-DPA-2NH)-poly(γ-benzyl-l-glutamate) (PBLG) polymers with various degrees of polymerization (DP), each featuring a di(4-aminophenyl)pyrenylamine (DPA) luminophore on the main backbone. The secondary structures of these pyrene-DPA-PBLG polypeptides were investigated using Fourier transform infrared spectroscopy and wide-angle X-ray diffraction, revealing that the polypeptides with DPs of less than 19 were mixtures of α-helical and β-sheet conformations, whereas the α-helical structures were preferred for longer chains. Interestingly, pyrene-DPA-2NH exhibited weak photoluminescence (PL), yet the emission of the pyrene-DPA-PBLG polypeptides was 16-fold stronger, suggesting that attaching PBLG chains to pyrene-DPA-2NH turned on a radiative pathway for the non-fluorescent molecule. Furthermore, pyrene-DPA-2NH exhibited aggregation-caused quenching; in contrast, after incorporation into the PBLG segments with rigid-rod conformations, the resulting pyrene-DPA-PBLG polypeptides displayed aggregation-induced emission. Transmission electron microscopy revealed that mixing these polypeptides with multiwalled carbon nanotubes (MWCNTs) in DMF led to the formation of extremely dispersible pyrene-DPA-PBLG/MWCNT composites. The fabrication of MWCNT composites with such biocompatible polymers should lead to bio-inspired carbon nanostructures with useful biomedical applications.

摘要

在本研究中，我们通过γ-苄基-L-谷氨酸羧基酸酐（BLG-NCA）的开环聚合反应制备了聚（γ-苄基-L-谷氨酸）（PBLG）聚合物，该反应由二（4-氨基苯基）-1-氨基芘（芘-DPA-2NH）引发，所得聚合物具有不同的聚合度（DP），每条主链上均带有二（4-氨基苯基）芘基胺（DPA）发光团。使用傅里叶变换红外光谱和广角X射线衍射对这些芘-DPA-PBLG多肽的二级结构进行了研究，结果表明，聚合度小于19的多肽是α-螺旋和β-折叠构象的混合物，而较长链则更倾向于形成α-螺旋结构。有趣的是，芘-DPA-2NH表现出较弱的光致发光（PL），而芘-DPA-PBLG多肽的发射强度则强16倍，这表明将PBLG链连接到芘-DPA-2NH上为这种非荧光分子开启了一条辐射途径。此外，芘-DPA-2NH表现出聚集导致的猝灭；相反，在掺入具有刚性棒状构象的PBLG链段后，所得的芘-DPA-PBLG多肽表现出聚集诱导发光。透射电子显微镜显示，在N，N-二甲基甲酰胺（DMF）中将这些多肽与多壁碳纳米管（MWCNT）混合会导致形成极易分散的芘-DPA-PBLG/MWCNT复合材料。用这种生物相容性聚合物制备MWCNT复合材料应能产生具有有用生物医学应用的仿生碳纳米结构。

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