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Title: 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];  [1];  [1];  [1]; ORCiD logo [1]
  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 Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & 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. doi: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. doi: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 = {2017},
month = {6}
}

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Cited by: 22 works
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Works referencing / citing this record:

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journal, May 2019

  • Zeng, Heng; Xie, Mo; Huang, Yong-Liang
  • Angewandte Chemie International Edition, Vol. 58, Issue 25
  • DOI: 10.1002/anie.201904160

A Discrete Self-Assembled Pd 12 Triangular Orthobicupola Cage and its Use for Intramolecular Cycloaddition
journal, August 2018

  • Bhat, Imtiyaz Ahmad; Devaraj, Anthonisamy; Zangrando, Ennio
  • Chemistry - A European Journal, Vol. 24, Issue 52
  • DOI: 10.1002/chem.201803039

Coordination‐Assembled Lanthanide‐Organic Ln 3 L 3 Sandwiches or Ln 4 L 4 Tetrahedron: Structural Transformation and Luminescence Modulation
journal, May 2019

  • Hu, Shao‐Jun; Guo, Xiao‐Qing; Zhou, Li‐Peng
  • Chinese Journal of Chemistry, Vol. 37, Issue 7
  • DOI: 10.1002/cjoc.201900101

Quantified structural speciation in self-sorted CoII6L 4 cage systems
journal, January 2018

  • Rizzuto, Felix J.; Kieffer, Marion; Nitschke, Jonathan R.
  • Chemical Science, Vol. 9, Issue 7
  • DOI: 10.1039/c7sc04927g

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  • Kieffer, Marion; Bilbeisi, Rana A.; Thoburn, John D.
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