Complex coacervate microdroplets are finding increased utility in synthetic cell applications due to their cytomimetic properties. However, their intrinsic membrane-free nature results in instability that limits their application in protocell research. Herein, we present the development of a new protocell model through the spontaneous interfacial self-assembly of copolymer molecules on biopolymer coacervate microdroplets. This hierarchical protocell model not only incorporates the favorable properties of coacervates (such as spontaneous assembly and macromolecular condensation) but also assimilates the essential features of a semipermeable copolymeric membrane (such as discretization and stabilization). This was accomplished by engineering an asymmetric, biodegradable triblock copolymer molecule comprising hydrophilic, hydrophobic, and polyanionic components capable of direct coacervate membranization via electrostatic surface anchoring and chain self-association. The resulting hierarchical protocell demonstrated striking integrity as a result of membrane formation, successfully stabilizing enzymatic cargo against coalescence and fusion in discrete protocellular populations. The semipermeable nature of the copolymeric membrane enabled the incorporation of a simple enzymatic cascade, demonstrating chemical communication between discrete populations of neighboring protocells. In this way, we pave the way for the development of new synthetic cell constructs.

中文翻译：

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共聚物稳定的凝聚层原型细胞的分层自组装

复杂的凝聚层微滴由于其细胞模拟特性而在合成细胞应用中发现了越来越多的效用。但是，它们固有的无膜性质导致不稳定，从而限制了它们在原代细胞研究中的应用。在本文中，我们通过生物聚合物凝聚微滴上共聚物分子的自发界面自组装，提出了一种新的原生细胞模型。这种分层的原始细胞模型不仅融合了凝聚层的良好特性（例如自发组装和大分子缩合），而且还吸收了半透共聚膜的基本特征（例如离散化和稳定化）。这是通过工程化一个不对称的，可生物降解的三嵌段共聚物分子来实现的，该分子包括亲水性，疏水性，以及能够通过静电表面锚定和链自缔合直接凝聚膜的聚阴离子组分。最终的分层原始细胞表现出惊人的完整性，这是由于形成了膜，从而成功地稳定了酶货物对离散原始细胞群中的聚结和融合。共聚物膜的半透性使得能够掺入简单的酶联级联反应，从而证明相邻原生细胞的离散群体之间的化学连通。这样，我们为新的合成细胞构建体的开发铺平了道路。成功地稳定了酶促货物，以防止离散原细胞群体中的聚结和融合。共聚物膜的半透性使得能够合并简单的酶联级联反应，从而证明相邻原生细胞的离散群体之间的化学连通。这样，我们为新的合成细胞构建体的开发铺平了道路。成功地稳定了酶促货物，以抵抗离散原细胞群体中的聚结和融合。共聚物膜的半透性使得能够合并简单的酶联级联反应，从而证明相邻原生细胞的离散群体之间的化学连通。这样，我们为新的合成细胞构建体的开发铺平了道路。