Conformational Selection as the Mechanism of Guest Binding in a Flexible Supramolecular Host
Abstract
This work offers a detailed mechanistic investigation of host-guest encapsulation behavior in a new enzyme-mimetic metal-ligand host and provides the first observation of a conformational selection mechanism (as opposed to induced fit) in a supramolecular system. The Ga4L4 host described features a C3-symmetric ligand motif with meta-substituted phenyl spacers, which enables the host to initially self-assemble into an S4-symmetric structure and then subsequently isomerize to a T-symmetric tetrahedron for better accommodation of a sufficiently large guest. Selective inversion recovery 1H NMR studies provide structural insights into the self-exchange behaviors of the host and the guest individually in this dynamic system. Kinetic analysis of the encapsulation-isomerization event revealed that increasing the concentration of guest inhibits the rate of host-guest relaxation, a key distinguishing feature of conformational selection. A comprehensive study of this simple enzyme mimic provides insight into analogous behavior in biophysics and enzymology and aims to inform the design of efficient self-assembled microenvironment catalysts.
- Authors:
-
[1]
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF)
- OSTI Identifier:
- 1464149
- Grant/Contract Number:
- AC02-05CH11231; DGE 1106400
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 139; Journal Issue: 23; Related Information: © 2017 American Chemical Society.; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Hong, Cynthia M., Kaphan, David M., Bergman, Robert G., Raymond, Kenneth N., and Toste, F. Dean. Conformational Selection as the Mechanism of Guest Binding in a Flexible Supramolecular Host. United States: N. p., 2017.
Web. doi:10.1021/jacs.7b03812.
Hong, Cynthia M., Kaphan, David M., Bergman, Robert G., Raymond, Kenneth N., & Toste, F. Dean. Conformational Selection as the Mechanism of Guest Binding in a Flexible Supramolecular Host. United States. https://doi.org/10.1021/jacs.7b03812
Hong, Cynthia M., Kaphan, David M., Bergman, Robert G., Raymond, Kenneth N., and Toste, F. Dean. Mon .
"Conformational Selection as the Mechanism of Guest Binding in a Flexible Supramolecular Host". United States. https://doi.org/10.1021/jacs.7b03812. https://www.osti.gov/servlets/purl/1464149.
@article{osti_1464149,
title = {Conformational Selection as the Mechanism of Guest Binding in a Flexible Supramolecular Host},
author = {Hong, Cynthia M. and Kaphan, David M. and Bergman, Robert G. and Raymond, Kenneth N. and Toste, F. Dean},
abstractNote = {This work offers a detailed mechanistic investigation of host-guest encapsulation behavior in a new enzyme-mimetic metal-ligand host and provides the first observation of a conformational selection mechanism (as opposed to induced fit) in a supramolecular system. The Ga4L4 host described features a C3-symmetric ligand motif with meta-substituted phenyl spacers, which enables the host to initially self-assemble into an S4-symmetric structure and then subsequently isomerize to a T-symmetric tetrahedron for better accommodation of a sufficiently large guest. Selective inversion recovery 1H NMR studies provide structural insights into the self-exchange behaviors of the host and the guest individually in this dynamic system. Kinetic analysis of the encapsulation-isomerization event revealed that increasing the concentration of guest inhibits the rate of host-guest relaxation, a key distinguishing feature of conformational selection. A comprehensive study of this simple enzyme mimic provides insight into analogous behavior in biophysics and enzymology and aims to inform the design of efficient self-assembled microenvironment catalysts.},
doi = {10.1021/jacs.7b03812},
journal = {Journal of the American Chemical Society},
number = 23,
volume = 139,
place = {United States},
year = {Mon Jun 05 00:00:00 EDT 2017},
month = {Mon Jun 05 00:00:00 EDT 2017}
}
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