Journal
ACS CATALYSIS
Volume 12, Issue 5, Pages 2821-2830Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.1c05635
Keywords
silica; glycine dimerization; aqueous interface; molecular dynamics; metadynamics; umbrella sampling; interface chemistry; prebiotic chemistry
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Funding
- Vrije Universiteit Brussel in Belgium
- PL-Grid Infrastructure
- Vrije Universiteit Brussel
- Flemish Supercomputer Center (VSC)
- FWO
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This study investigates the mechanism of peptide bond formation over a silica surface in an aqueous environment, revealing a strong catalytic effect of the interface on the reaction.
The amino acid condensation reaction on a heterogeneous mineral surface has been regarded as one of the important pathways for peptide bond formation. In this work, the mechanism of peptide bond formation over a silica surface in an aqueous environment is studied using ab initio molecular dynamics calculations coupled with enhanced sampling methods such as metadynamics and umbrella sampling. The model includes a periodically repeated slab of amorphous SiO2 forming an interface with explicit liquid water. The adopted simulation method allowed reconstruction of a prejudice-free reaction mechanism of glycine dimerization and quantification of the corresponding free energy profile, with a detailed characterization of transition states and of the role of water. The resulting three-step mechanism features an overall free energy barrier of 155 kJ/mol at 300 K In comparison to the bulk liquid phase, our results indicate that the interface has a strong catalytic effect on the condensation reaction, which we trace back to the capability of the silica-water interface in promoting an addition reaction by a transition state stabilization. The silica- water interface is found to behave as a less-polar reaction medium with respect to bulk water, promoting addition reactions and disfavoring elimination reactions.
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