The introduction of chirality into aqueous self-assemblies by employing isotactic block copolymers (BCPs) is an emerging field of interest as it promises special membrane properties of polymersomes not accessible by atactic BCPs. However, isotactic BCPs typically exhibit crystalline behaviour, inducing high membrane stiffness and limiting their applicability in systems involving membrane proteins or sensitive cargo. In this study, an isotactic yet fully amorphous BCP is introduced which overcomes these limitations. Three BCPs composed of poly(butylene oxide)-block-poly(glycidol) (PBO-b-PG), differing solely in their tacticities (R/S, R and S), were synthesised and characterised regarding their structural, optical and thermal properties. Their self-assembly into homogenous phases of nanoscopic polymersomes (referred to as small unilamellar vesicles, SUVs) was analysed, revealing stability differences between SUVs composed of the different BCPs. Additionally, microscopic giant unilamellar vesicles (GUVs) were prepared by double emulsion microfluidics. Only the atactic BCP formed GUVs which were stable over several hours, whereas GUVs composed of isotactic BCPs ruptured within several minutes after formation. The ability of atactic PBO-b-PG to form microreactors was elucidated by reconstituting the membrane protein OmpF in the GUV membrane by microfluidics and performing an enzyme reaction inside its lumen. The system presented here serves as platform to design versatile vesicles with flexible membranes composed of atactic or isotactic BCPs. Hence, they allow for the introduction of chirality into nano- or microreactors which is a yet unstudied field and could enable special biotechonological applications.

中文翻译：

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完全无定形和全同立构嵌段共聚物及其自组装成纳米和微观囊泡

通过使用等规嵌段共聚物 (BCP) 将手性引入水性自组装体是一个新兴的兴趣领域，因为它承诺无规 BCP 无法获得的聚合物囊泡的特殊膜特性。然而，全同立构 BCP 通常表现出结晶行为，导致高膜刚度并限制其在涉及膜蛋白或敏感货物的系统中的适用性。在这项研究中，引入了一种等规但完全无定形的 BCP，它克服了这些限制。三个聚（环氧丁烷）构成的过境点-嵌段-聚（缩水甘油）（PBO- b -PG），仅在其立构规整度（不同ř /小号，- [R和小号)，对其结构、光学和热特性进行了合成和表征。分析了它们自组装成纳米级聚合物囊泡（称为小单层囊泡，SUV）的均质相，揭示了由不同 BCP 组成的 SUV 之间的稳定性差异。此外，通过双乳液微流体制备了微观巨型单层囊泡（GUVs）。只有无规 BCP 形成的 GUVs 在几个小时内保持稳定，而由等规 BCPs 组成的 GUVs 在形成后几分钟内破裂。无规立构 PBO- b的能力通过微流体技术在 GUV 膜中重建膜蛋白 OmpF 并在其管腔内进行酶反应，阐明了形成微反应器的 -PG。此处介绍的系统用作设计具有由无规或全同立构 BCP 组成的柔性膜的多功能囊泡的平台。因此，它们允许将手性引入纳米或微反应器，这是一个尚未研究的领域，可以实现特殊的生物技术应用。