论文标题

自限制组装的平衡机制

Equilibrium mechanisms of self-limiting assembly

论文作者

Hagan, Michael F., Grason, Gregory M.

论文摘要

自组装是合成和生物系统中无处不在的过程,广泛地定义为自发组织多个亚基(例如大分子,颗粒)中有序的多单元结构。绝大多数平衡组装过程产生了两种状态:一种由分散的分离亚基组成,另一个由无限尺寸的散装状态组成。这篇综述着重于更专业的{\ it自限制组装}的类别,该类别描述了导致有限尺寸结构的平衡组装过程。这些系统提出了一个通用和基本的问题,如何在相同亚基之间涉及非共价相互作用的热力学过程``测量''并选择组装结构的大小?在这篇综述中,我们首先介绍了组装热力学的基本统计机械框架,并使用它来强调确保平衡组装的关键物理成分,以在有限的尺寸下终止。然后,我们介绍了自限制组装系统的示例,并根据两个广泛的类别在此框架中对它们进行分类:{\ it自闭合汇编}和{\ IT开放式填充汇编}。这些包括生物学和合成软物质的众所周知的病例 - 两亲物的胶束化以及锥形亚基的壳/小管形成 - 以及鲜为人知的组装类别,例如较短的有吸引力的有吸引力/远程排斥系统和几何型组件。对于这些自限制机制,我们描述了选择平衡组装大小的物理机制,以及有限尺寸选择的潜在局限性。最后,我们讨论了有限尺寸组件的替代机制,并与它们相对于平衡,单物种组件中的自我界定而实现的尺寸对照形成对比。

Self-assembly is a ubiquitous process in synthetic and biological systems, broadly defined as the spontaneous organization of multiple subunits (e.g. macromolecules, particles) into ordered multi-unit structures. The vast majority of equilibrium assembly processes give rise to two states: one consisting of dispersed disassociated subunits, and the other, a bulk-condensed state of unlimited size. This review focuses on the more specialized class of {\it self-limiting assembly}, which describes equilibrium assembly processes resulting in finite-size structures. These systems pose a generic and basic question, how do thermodynamic processes involving non-covalent interactions between identical subunits ``measure'' and select the size of assembled structures? In this review, we begin with an introduction to the basic statistical mechanical framework for assembly thermodynamics, and use this to highlight the key physical ingredients that ensure equilibrium assembly will terminate at finite dimensions. Then, we introduce examples of self-limiting assembly systems, and classify them within this framework based on two broad categories: {\it self-closing assemblies} and {\it open-boundary assemblies}. These include well-known cases in biology and synthetic soft matter -- micellization of amphiphiles and shell/tubule formation of tapered subunits -- as well as less widely known classes of assemblies, such as short-range attractive/long-range repulsive systems and geometrically-frustrated assemblies. For each of these self-limiting mechanisms, we describe the physical mechanisms that select equilibrium assembly size, as well as potential limitations of finite-size selection. Finally, we discuss alternative mechanisms for finite-size assemblies, and draw contrasts with the size-control that these can achieve relative to self-limitation in equilibrium, single-species assemblies.

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