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Synthesis of Expanded Poly(l-amino acid) Containing Phenylethynyl(terpyridine)platinum(II) Moieties
Macromolecules ( IF 5.5 ) Pub Date : 2024-04-16 , DOI: 10.1021/acs.macromol.4c00297
Taka-aki Okamura 1 , Ayumi Okada 1 , Kiyotaka Onitsuka 1
Affiliation  

Elaborately designed chiral 3D structures, such as proteins, promise outstanding functions. Herein, expanded poly(l-amino acid)s containing phenylethynyl (terpyridine)platinum(II) moieties are presented. Expanded polypeptides were synthesized by stepwise elongation or unsymmetrical metallosupramolecular polycondensation through a copper-catalyzed coupling reaction between the terminal acetylene and platinum–chloride groups. Robust platinum–acetylide bonds were retained in polar solvents, and the molar mass was determined using 1H diffusion-ordered NMR spectroscopy (DOSY). The resulting expanded poly(l-leucine) and poly(l-valine) were 8-mer and 9-mer, respectively, in solution. Despite the slight differences in the side chains, that is, with or without a CH2 group, the dihedral angles (ϕ and ψ) were effectively regulated to determine the local structures. The CD spectra reflected the individual structures of the right-handed 7/2 and 4/1 helices, which were estimated by theoretical calculations. Appropriate selection of amino acid sequences results in a molecular architecture with the desired three-dimensional structure.

中文翻译:

含有苯乙炔基(三联吡啶)铂(II)部分的膨胀聚(l-氨基酸)的合成

精心设计的手性 3D 结构(例如蛋白质)有望实现出色的功能。本文中,提出了含有苯乙炔基(三联吡啶)铂(II)部分的扩展聚( 1-氨基酸)。扩展的多肽是通过末端乙炔和氯化铂基团之间的铜催化偶联反应,通过逐步延伸或不对称金属超分子缩聚来合成的。极性溶剂中保留了牢固的铂-乙炔键,并使用1 H 扩散有序核磁共振波谱 (DOSY)测定摩尔质量。所得扩展的聚( 1-亮氨酸)和聚( 1-缬氨酸)在溶液中分别为8聚体和9聚体。尽管侧链略有差异,即有或没有CH 2基团,但二面角(ψ 和ψ)可以有效调节以确定局部结构。 CD 谱反映了右旋 7/2 和 4/1 螺旋的各个结构,这是通过理论计算估计的。适当选择氨基酸序列会产生具有所需三维结构的分子结构。
更新日期:2024-04-16
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