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化学驱动的超分子材料

Chemically Fueled Supramolecular Materials.

作者信息

Chen Xiaoyao, Würbser Michaela A, Boekhoven Job

机构信息

Department of Chemistry, School of Natural Sciences, Technical University of Munich, Lichtenbergstrasse 4, 85748 Garching bei München, Germany.

出版信息

Acc Mater Res. 2023 Apr 14;4(5):416-426. doi: 10.1021/accountsmr.2c00244. eCollection 2023 May 26.

Abstract

In biology, the function of many molecules is regulated through nonequilibrium chemical reaction cycles. The prototypical example is the phosphorylation of an amino acid in an enzyme which induces a functional change, e.g., it folds or unfolds, assembles or disassembles, or binds a substrate. Such phosphorylation does not occur spontaneously but requires a phosphorylating agent with high chemical potential (for example, adenosine triphosphate (ATP)) to be converted into a molecule with lower chemical potential (adenosine diphosphate (ADP)). When this energy is used to regulate an assembly, we speak of chemically fueled assemblies; i.e., the molecule with high potential, the fuel, is used to regulate a self-assembly process. For example, the binding of guanosine triphosphate (GTP) to tubulin induces self-assembly. The bound GTP is hydrolyzed to guanosine diphosphate (GDP) upon assembly, which induces tubulin disassembly. The result is a dynamic assembly endowed with unique characteristics, such as time-dependent behavior and the ability to self-heal. These intriguing, unique properties have inspired supramolecular chemists to create similar chemically fueled molecular assemblies from the bottom up. While examples have been designed, they remain scarce partly because chemically fueled reaction cycles are rare and often complex. Thus, we recently developed a carbodiimide-driven reaction cycle that is versatile and easy to use, quantitatively understood, and does not suffer from side reactions. In the reaction cycle, a carboxylate precursor reacts with a carbodiimide to form an activated species like an anhydride or ester. The activated state reacts with water and thereby reverts to its precursor state; i.e., the activated state is deactivated. Effectively, the precursor catalyzes carbodiimides' conversion into waste and forms a transient activated state. We designed building blocks to regulate a range of assemblies and supramolecular materials at the expense of carbodiimide fuel. The simplicity and versatility of the reaction cycles have democratized and popularized the field of chemically fueled assemblies. In this Account, we describe what we have "learned" on our way. We introduce the field exemplified by biological nonequilibrium self-assembly. We describe the design of the carbodiimide-driven reaction cycle. Using examples from our group and others, we offer design rules for the building block's structure and strategies to create the desired morphology or supramolecular materials. The discussed morphologies include fibers, colloids, crystals, and oil- and coacervate-based droplets. We then demonstrate how these assemblies form supramolecular materials with unique material properties like the ability to self-heal. Besides, we discuss the concept of reciprocal coupling in which the assembly exerts feedback on its reaction cycle and we also offer examples of such feedback mechanisms. Finally, we close the Account with a discussion and an outlook on this field. This Account aims to provide our fundamental understanding and facilitate further progress toward conceptually new supramolecular materials.

摘要

在生物学中,许多分子的功能是通过非平衡化学反应循环来调节的。典型的例子是酶中氨基酸的磷酸化,它会引发功能变化,例如,酶折叠或展开、组装或拆卸,或者结合底物。这种磷酸化不会自发发生,而是需要具有高化学势的磷酸化剂(例如三磷酸腺苷(ATP))转化为化学势较低的分子(二磷酸腺苷(ADP))。当这种能量用于调节组装时,我们称之为化学驱动组装;也就是说,具有高势能的分子,即燃料,被用于调节自组装过程。例如,鸟苷三磷酸(GTP)与微管蛋白的结合会诱导自组装。组装时,结合的GTP会水解为鸟苷二磷酸(GDP),这会诱导微管蛋白拆卸。结果是形成了一种具有独特特性的动态组装体,如随时间变化的行为和自我修复能力。这些引人入胜的独特性质激发了超分子化学家自下而上地创造类似的化学驱动分子组装体。虽然已经设计出了一些例子,但它们仍然很少,部分原因是化学驱动反应循环很少见且往往很复杂。因此,我们最近开发了一种由碳二亚胺驱动的反应循环,它用途广泛、易于使用、能定量理解,且没有副反应。在这个反应循环中,羧酸盐前体与碳二亚胺反应形成一种活性物种,如酸酐或酯。活性状态与水反应,从而恢复到其前体状态;即活性状态被失活。实际上,前体催化碳二亚胺转化为废物,并形成一个短暂的活性状态。我们设计了一些构建模块,以碳二亚胺燃料为代价来调节一系列的组装体和超分子材料。反应循环的简单性和通用性使化学驱动组装体领域得以普及。在本综述中,我们描述了我们在这个过程中学到的东西。我们介绍了以生物非平衡自组装为代表的领域。我们描述了碳二亚胺驱动反应循环的设计。通过我们小组和其他小组的例子,我们提供了构建模块结构的设计规则以及创造所需形态或超分子材料的策略。所讨论的形态包括纤维、胶体、晶体以及基于油和凝聚层的液滴。然后,我们展示了这些组装体如何形成具有独特材料特性(如自我修复能力)的超分子材料。此外,我们讨论了相互耦合的概念,即组装体对其反应循环施加反馈,并且我们还提供了这种反馈机制的例子。最后,我们以对该领域的讨论和展望来结束本综述。本综述旨在提供我们的基本理解,并促进在概念上新型超分子材料方面取得进一步进展。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e84c/10226104/0d095ccec3e0/mr2c00244_0001.jpg

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