Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, Israel.
Nat Nanotechnol. 2020 Apr;15(4):256-271. doi: 10.1038/s41565-020-0652-2. Epub 2020 Apr 17.
Confining molecules can fundamentally change their chemical and physical properties. Confinement effects are considered instrumental at various stages of the origins of life, and life continues to rely on layers of compartmentalization to maintain an out-of-equilibrium state and efficiently synthesize complex biomolecules under mild conditions. As interest in synthetic confined systems grows, we are realizing that the principles governing reactivity under confinement are the same in abiological systems as they are in nature. In this Review, we categorize the ways in which nanoconfinement effects impact chemical reactivity in synthetic systems. Under nanoconfinement, chemical properties can be modulated to increase reaction rates, enhance selectivity and stabilize reactive species. Confinement effects also lead to changes in physical properties. The fluorescence of light emitters, the colours of dyes and electronic communication between electroactive species can all be tuned under confinement. Within each of these categories, we elucidate design principles and strategies that are widely applicable across a range of confined systems, specifically highlighting examples of different nanocompartments that influence reactivity in similar ways.
限制分子可以从根本上改变它们的化学和物理性质。在生命起源的各个阶段，限制效应被认为是至关重要的，而生命仍然依赖于多层次的分隔，以在温和条件下维持非平衡状态并有效地合成复杂的生物分子。随着对合成受限系统的兴趣不断增加，我们意识到，在非生物系统和自然界中，限制条件下的反应性原则是相同的。在这篇综述中，我们对纳米限制效应对合成系统中化学反应性的影响进行了分类。在纳米限制下，可以调节化学性质以提高反应速率、增强选择性和稳定反应性物质。限制效应还会导致物理性质的变化。在限制下，光发射器的荧光、染料的颜色以及电活性物质之间的电子通讯都可以进行调节。在这些类别中的每一个类别中，我们都阐明了广泛适用于各种受限系统的设计原则和策略，特别强调了以类似方式影响反应性的不同纳米隔室的例子。
