Amphiphilic miktoarm star copolymers have a unique internal structure and many attractive properties with respect to solution self-assembly, such as a high density of internal and peripheral functionalities, low CMC values, and high loading efficiency. However, compared to their linear analogs, the complex architecture demands asymmetric polymer arms emanating from a single core, which poses a significant synthetic challenge. Herein, we demonstrate an approach for the synthesis of polypept(o)ide-based AB3- and A3B-type miktoarm PeptoStars consisting of polypeptidic poly(γ-benzyl-l-glutamate (pGlu(OBn)) as the hydrophobic A arm and polypeptoidic polysarcosine (pSar) as the hydrophilic B arm. These structures, which are completely derived from endogenous amino acids, were realized by the core-first method using a tetrafunctional initiator and the corresponding N-carboxyanhydrides (NCAs) via a controlled, living nucleophilic ring-opening polymerization (ROP). The asymmetric architecture was achieved through an orthogonal protecting group strategy with multiple protection/deprotection steps. Characterization via 1H NMR-, 1H DOSY-spectroscopy, and size-exclusion chromatography (SEC) indicate the presence of well-formed miktoarm PeptoStars with low dispersities (Đ = 1.09–1.14), the precise control over the degree of polymerization and Poisson-like molecular weight distributions.Schwiertz et al. report on the synthesis of miktoarm star polymers based on polypept(o)ides by nucleophilic ring opening polymerization of N-carboxyanhydrides. The reported procedures allow for precise control over chain length, number of arms and end group functionality.

中文翻译：

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轻松合成两亲性 AB3 和 A3B miktoarm PeptoMiktoStars

两亲性 miktoarm 星形共聚物具有独特的内部结构和在溶液自组装方面的许多吸引人的特性，例如高密度的内部和外围功能、低 CMC 值和高负载效率。然而，与其线性类似物相比，复杂的结构需要从单个核心发出的不对称聚合物臂，这构成了重大的合成挑战。在此，我们展示了一种合成基于多肽（异）物的 AB3 和 A3B 型 miktoarm PeptoStars 的方法，该 PeptoStars 由多肽聚（γ-苄基-l-谷氨酸（pGlu（OBn））作为疏水性 A 臂和多肽聚肌氨酸 (pSar) 作为亲水性 B 臂。这些结构完全来源于内源性氨基酸，使用四官能引发剂和相应的 N-羧酸酐 (NCA) 通过受控的活性亲核开环聚合 (ROP) 通过核优先方法实现。不对称架构是通过具有多个保护/去保护步骤的正交保护组策略实现的。通过 1H NMR-、1H DOSY 光谱和尺寸排阻色谱 (SEC) 表征表明存在具有低分散性 (Đ = 1.09–1.14) 的结构良好的 miktoarm PeptoStars，精确控制聚合度和泊松-像分子量分布。Schwiertz 等。关于通过 N-羧酸酐的亲核开环聚合合成基于多肽（o）化物的 miktoarm 星形聚合物的报告。报告的程序允许精确控制链长，