Chemistry in nanoconfined water

Muñoz‐Santiburcio, Daniel; Marx, Dominik

doi:10.1039/c6sc04989c

Cited by 119 publications

(172 citation statements)

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“…The significant acceleration of reactions in confined environments has recently been reported in the literature (1)(2)(3)(4)(5)(6)(7). The reaction environments investigated span a diverse range, including charged microdroplets (1-3), microdiameter emulsions (5), inverted micelles (8), and the surfaces of aerosol particles (9).…”

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confidence: 94%

Prebiotic phosphorylation enabled by microdroplets

Vaida

2017

Proc. Natl. Acad. Sci. U.S.A.

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confidence: 94%

Prebiotic phosphorylation enabled by microdroplets

Vaida

2017

Proc. Natl. Acad. Sci. U.S.A.

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“…[8][9][10] For example, a study focused on prebiotic peptide chemistry in water nanoconfined by mineral surfaces found that not only the energetics of the reactions, but also the reaction mechanisms, can be affected by nanoconfinement. 11 Recently, Zare et al and Cooks and co-workers have shown that many reactions can be accelerated in microdroplets, such as the spontaneous phosphorylation of sugars, production of ribonucleosides, and Diels-Alder chemistry. 6,[12][13][14][15] However, the underlying origin of the acceleration of the microdroplet remains unclear.…”

Section: Introductionmentioning

confidence: 99%

Diels–Alder Reactions in Water Are Determined by Microsolvation

2019

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Nanoconfined aqueous environments and the recent advent of accelerated chemistry in microdroplets are increasingly being investigated for catalysis. The mechanisms underlying the enhanced reactivity in alternate solvent environments, and whether the enhanced reactivity due to nanoconfinement is a universal phenomenon, are not fully understood. Here, we use ab initio molecular dynamics simulations to characterize the free energy of a retro-Diels-Alder reaction in bulk water at very different densities and in water nanoconfined by parallel graphene sheets. We find that the broadly different global solvation environments accelerate the reactions to a similar degree with respect to the gas phase reaction, with activation free energies that do not differ by more than kbT from each other.The reason for the same acceleration factor in the extremely different solvation environments is that it is the microsolvation of the dienophile's carbonyl group that governs the transition state stabilization and mechanism, which is not significantly disrupted by either the lower density in bulk water or the strong nanoconfinement conditions used here. Our results also suggest that significant acceleration of Diels Alder reactions in microdroplets or on-water conditions can't arise from local microsolvation when water is present, but instead must come from highly altered reaction environments that drastically change the reaction mechanisms.

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“…Arrhenius (2003) considered the mineral as exhibiting "primitive cellular metabolic function." In this regard, it has been recently suggested that green rust and mackinawite, the objet trouvé at the ancient alkaline mounds, could have acted as the multitask protoenzymes, condensers, or nanoengines-the prebiological machinery-to enable the emergence of life (Russell and Nitschke, 2017;Muñoz-Santiburcio and Marx, 2017). Russell and Nitschke (2017) described a model whereby nitrate in the Hadean Ocean is reduced to nitric oxide, ammonia, and aminogen in the hydrated interlayers of green rust, fed with electrons from hydrothermal hydrogen.…”

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confidence: 99%