Polymer microstructures rely on tacticity, yet exploration in polyamines has focused predominantly on atactic polymers. We introduce a method to synthesize a diverse library of ortho and para-cyanobenzenesulfonyl-activated-methyl aziridines using R, S, and racemic alaninol. Living anionic ring-opening polymerization of racemic sulfonyl aziridines yields soluble polymers, while enantiomerically-pure sulfonyl aziridines follow a dispersion polymerization with complete monomer conversion giving access to stereoblock copolymers. Removal of activation groups is achieved using dodecanethiol and tert-butylimino-tri(pyrrolidino)phosphorane to obtain isotactic or atactic linear polypropylene imines (LPPIs). High-purity L-PPIs are obtained in salt and neutral forms with high yields. Stereoblock copolymers of poly-R-block-S-polysulfonamides and respective polypropylene imine stereoblocks are synthesized, revealing helical structures in water influenced by the monomer type and sequence in CD spectroscopy. Molecular dynamics simulations confirm the helical nature of isotactic LPPIs in water. Bulk characterization demonstrates the first crystalline isotactic polyamines via spherulite growth in polarized light, atomic force microscopy and XRD analyses. In cell-transfection studies, the synthesized isotactic LPPIs exhibit lower toxicity and transfection efficiency than commercial hyperbranched polyethylene imine, with longer chains showing increased transfection efficiency. These isotactic polymers open avenues for complex macromolecular architectures with optically active polyamines akin to poly(amino acid)s but lacking hydrolytically cleavable amide links.

中文翻译：

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 螺旋多胺


聚合物微观结构依赖于策略性，但对多胺的探索主要集中在无规聚合物上。我们介绍了一种使用 R、S 和外消旋丙氨酸合成邻位和对氰基苯磺酰激活甲基氮丙啶的多样化文库的方法。外消旋磺酰氮杂啶的活阴离子开环聚合产生可溶性聚合物，而对映体纯磺酰氮杂氮杂糖胺在分散聚合后完全单体转化，从而获得立体嵌段共聚物。使用十二烷硫醇和叔丁基亚氨基-三（吡咯烷基）磷烷去除活化基团，以获得等规或无规线性聚丙烯亚胺 （LPPIs）。高纯度 L-PPI 以盐和中性形式获得，产量高。合成了聚-R-嵌段-S-聚磺酰胺和相应的聚丙烯亚胺立体嵌段的立体嵌段共聚物，揭示了水中受 CD 光谱中单体类型和序列影响的螺旋结构。分子动力学模拟证实了水中等规 LPPI 的螺旋性质。本体表征证明了通过在偏振光、原子力显微镜和 XRD 分析中的球晶生长首次形成结晶等规多胺。在细胞转染研究中，合成的等规 LPPI 表现出比市售超支化聚乙烯亚胺更低的毒性和转染效率，较长的链显示出更高的转染效率。这些等规聚合物为复杂的大分子结构开辟了道路，其具有类似于聚（氨基酸）但缺乏可水解可裂解酰胺键的光学活性多胺。