Roy & Diana Vagelos Laboratories, Department of Chemistry , University of Pennsylvania , Philadelphia , Pennsylvania 19104-6323 , United States.
DWI-Leibniz Institute for Interactive Materials , RWTH Aachen University , 52074 Aachen , Germany.
Biomacromolecules. 2019 Feb 11;20(2):712-727. doi: 10.1021/acs.biomac.8b01405. Epub 2018 Nov 7.
Natural, including plant, and synthetic phenolic acids are employed as building blocks for the synthesis of constitutional isomeric libraries of self-assembling dendrons and dendrimers that are the simplest examples of programmed synthetic macromolecules. Amphiphilic Janus dendrimers are synthesized from a diversity of building blocks including natural phenolic acids. They self-assemble in water or buffer into vesicular dendrimersomes employed as biological membrane mimics, hybrid and synthetic cells. These dendrimersomes are predominantly uni- or multilamellar vesicles with size and polydispersity that is predicted by their primary structure. However, in numerous cases, unilamellar dendrimersomes completely free of multilamellar assemblies are desirable. Here, we report the synthesis and structural analysis of a library containing 13 amphiphilic Janus dendrimers containing linear and branched alkyl chains on their hydrophobic part. They were prepared by an optimized iterative modular synthesis starting from natural phenolic acids. Monodisperse dendrimersomes were prepared by injection and giant polydisperse by hydration. Both were structurally characterized to select the molecular design principles that provide unilamellar dendrimersomes in higher yields and shorter reaction times than under previously used reaction conditions. These dendrimersomes are expected to provide important tools for synthetic cell biology, encapsulation, and delivery.
天然的、包括植物的和合成的酚酸被用作构建自组装树枝状大分子和树枝状聚合物的结构异构体库的构建块，这些都是可编程合成大分子的最简单例子。两亲性 Janus 树枝状聚合物可以从多种构建块合成，包括天然酚酸。它们在水中或缓冲液中自组装成具有生物膜模拟物、杂交和合成细胞功能的囊泡状树枝状聚合物体。这些树枝状聚合物体主要是具有预测其一级结构的大小和多分散性的单或多层囊泡。然而，在许多情况下，人们希望完全没有多层组装的单层囊泡。在这里，我们报告了包含 13 种两亲性 Janus 树枝状聚合物的文库的合成和结构分析，这些树枝状聚合物的疏水部分含有线性和支化的烷基链。它们是通过从天然酚酸开始的优化迭代模块化合成制备的。单分散的树枝状聚合物体通过注射制备，而巨大的多分散体则通过水合作用制备。对两者都进行了结构表征，以选择提供单层树枝状聚合物体的分子设计原则，这些原则比以前使用的反应条件下提供更高的产率和更短的反应时间。这些树枝状聚合物体有望为合成细胞生物学、封装和输送提供重要工具。
