Muñoz-Santiburcio Daniel, Marx Dominik
Lehrstuhl für Theoretische Chemie , Ruhr - Universität Bochum , 44780 Bochum , Germany . Email:
Chem Sci. 2017 May 1;8(5):3444-3452. doi: 10.1039/c6sc04989c. Epub 2017 Mar 20.
Nanoconfined liquids have extremely different properties from the bulk, which profoundly affects chemical reactions taking place in nanosolvation. Here, we present extensive simulations of a vast set of chemical reactions within a water lamella that is nanoconfined by mineral surfaces, which might be relevant to prebiotic peptide formation in aqueous environments. Our results disclose a rich interplay of distinct effects, from steric factors typical of reactions occurring in small spaces to a charge-stabilization effect in nanoconfined water at extreme conditions similar to that observed in bulk water when changing from extreme to ambient conditions. These effects are found to modify significantly not only the energetics but also the mechanisms of reactions happening in nanoconfined water in comparison to the corresponding bulk regime.
纳米受限液体具有与本体液体截然不同的性质，这深刻影响了纳米溶剂化过程中发生的化学反应。在此，我们对由矿物表面纳米受限的水层内的大量化学反应进行了广泛模拟，这些反应可能与水环境中的益生元肽形成有关。我们的结果揭示了不同效应之间丰富的相互作用，从小空间中典型反应的空间位阻因素到在极端条件下纳米受限水中的电荷稳定效应，这种效应类似于在从极端条件转变到环境条件时本体水中观察到的情况。与相应的本体体系相比，发现这些效应不仅显著改变了纳米受限水中反应的能量学，还改变了反应机理。
