Encapsulating Subsite analogues of the [FeFe]-hydrogenases in micelles enables direct water interactions

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Fritzsch, Robby and Brady, Owen and Adair, Elaine and Wright, Joseph A. and Pickett, Christopher J. and Hunt, Neil (2016) Encapsulating Subsite analogues of the [FeFe]-hydrogenases in micelles enables direct water interactions. Journal of Physical Chemistry Letters, 7. pp. 2838-2843. ISSN 1948-7185 (https://doi.org/10.1021/acs.jpclett.6b01338)

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Abstract

Encapsulation of sub-site analogues of the [FeFe]-hydrogenase enzymes in supramolecular structures has been shown to dramatically increase their catalytic ability, but the molecular basis for this enhancement remains unclear. We report the results of experiments employing infrared absorption, ultrafast infrared pump-probe and 2D-IR spectroscopy to investigate the molecular environment of Fe2(pdt)(CO)6 (pdt: propanedithiolate) [1] encapsulated in the dispersed alkane phase of a heptane-dodecyltrimethylammonium bromide-water microemulsion. It is demonstrated that 1 is partitioned between two molecular environments, one that closely resembles bulk heptane solution and a second that features direct hydrogen-bonding interactions with water molecules that penetrate the surfactant shell. Our results demonstrate that the extent of water access to the normally water-insoluble sub-site analogue 1 can be tuned with micelle size, while IR spectroscopy provides a straightforward tool that can be used to measure and finetune the chemical environment of catalyst species in self-assembled structures.

ORCID iDs

Fritzsch, Robby ORCID logoORCID: https://orcid.org/0000-0003-0198-1691, Brady, Owen, Adair, Elaine, Wright, Joseph A., Pickett, Christopher J. and Hunt, Neil ORCID logoORCID: https://orcid.org/0000-0001-7400-5152;
  • Item type:Article
    ID code:57012
    Dates:
    Date
    Event
    21 July 2016
    Published
    10 July 2016
    Published Online
    9 July 2016
    Accepted
    Notes:“This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://dx.doi.org10.1021/acs.jpclett.6b01338
    Subjects:Science > Chemistry > Physical and theoretical chemistry
    Department:Faculty of Science > Physics
    Technology and Innovation Centre > Bionanotechnology
    Depositing user: Pure Administrator
    Date deposited:21 Jul 2016 09:01
    Last modified:12 Dec 2024 04:35
    URI:https://strathprints.strath.ac.uk/id/eprint/57012
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