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dc.contributor.authorWelborn, Valerie Vaissieren
dc.contributor.authorLi, Wan-Luen
dc.contributor.authorHead-Gordon, Teresaen
dc.date.accessioned2020-05-22T13:55:40Z
dc.date.available2020-05-22T13:55:40Z
dc.date.issued2020-01-21en
dc.identifier.issn2041-1723en
dc.identifier.other415en
dc.identifier.urihttp://hdl.handle.net/10919/98529
dc.description.abstractSupramolecular assemblies have gained tremendous attention due to their ability to catalyze reactions with the efficiencies of natural enzymes. Using ab initio molecular dynamics, we identify the origin of the catalysis by the supramolecular capsule Ga4L612- on the reductive elimination reaction from gold complexes and assess their similarity to natural enzymes. By comparing the free energies of the reactants and transition states for the catalyzed and uncatalyzed reactions, we determine that an encapsulated water molecule generates electric fields that contributes the most to the reduction in the activation free energy. Although this is unlike the biomimetic scenario of catalysis through direct host-guest interactions, the electric fields from the nanocage also supports the transition state to complete the reductive elimination reaction with greater catalytic efficiency. However it is also shown that the nanocage poorly organizes the interfacial water, which in turn creates electric fields that misalign with the breaking bonds of the substrate, thus identifying new opportunities for catalytic design improvements in nanocage assemblies.en
dc.description.sponsorshipOffice of Science, Office of Basic Energy Sciences CPIMS program, Chemical Sciences Division of the U.S. Department of EnergyUnited States Department of Energy (DOE) [DE-10AC02-05CH11231]; Office of Science of the U.S. Department of Energy under an ASCR Leadership Computing Challenge (ALCC) award [DE-AC02-05CH11231]en
dc.format.mimetypeapplication/pdfen
dc.language.isoenen
dc.rightsCreative Commons Attribution 4.0 Internationalen
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.titleInterplay of water and a supramolecular capsule for catalysis of reductive elimination reaction from golden
dc.typeArticle - Refereeden
dc.description.notesThis work was supported by the Director, Office of Science, Office of Basic Energy Sciences CPIMS program, Chemical Sciences Division of the U.S. Department of Energy under Contract No. DE-10AC02-05CH11231. This research used computational resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, under an ASCR Leadership Computing Challenge (ALCC) award.en
dc.title.serialNature Communicationsen
dc.identifier.doihttps://doi.org/10.1038/s41467-019-14251-6en
dc.identifier.volume11en
dc.identifier.issue1en
dc.type.dcmitypeTexten
dc.type.dcmitypeStillImageen
dc.identifier.pmid31964874en


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Creative Commons Attribution 4.0 International
License: Creative Commons Attribution 4.0 International