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Cooperative Weak Dispersive Interactions Actuate Catalysis in a Shape-Selective Abiological Racemase


Wang, Yujia; Rickhaus, Michel; Blacque, Olivier; Baldridge, Kim K; Juricek, Michal; Siegel, Jay S (2022). Cooperative Weak Dispersive Interactions Actuate Catalysis in a Shape-Selective Abiological Racemase. Journal of the American Chemical Society, 144(6):2679-2684.

Abstract

A simple abiological host–guest system demonstrates racemase activity with catalytic rate enhancements of 104 without employing traditional functional groups. Cooperative weak interactions enhanced through shape-complementarity between the catalyst active site and the reaction transition state drive this activity, as proposed by Pauling for enzymes. In analogy to the Jencks’ concept of catalytic antibodies, it is shown that a hapten resembling the planar transition state of the bowl inversion acts as a potent inhibitor of this catalytic process. In contrast, no substrate/product inhibition is detected, and a relatively weak binding of the substrate is observed (Ka ≈ 102 M–1 at 293 K). This simple box-and-bowl system demonstrates that shape selectivity arising from cooperative dispersive forces suffices for the emergence of a catalytic system with an enzyme-like thermodynamic profile.

Abstract

A simple abiological host–guest system demonstrates racemase activity with catalytic rate enhancements of 104 without employing traditional functional groups. Cooperative weak interactions enhanced through shape-complementarity between the catalyst active site and the reaction transition state drive this activity, as proposed by Pauling for enzymes. In analogy to the Jencks’ concept of catalytic antibodies, it is shown that a hapten resembling the planar transition state of the bowl inversion acts as a potent inhibitor of this catalytic process. In contrast, no substrate/product inhibition is detected, and a relatively weak binding of the substrate is observed (Ka ≈ 102 M–1 at 293 K). This simple box-and-bowl system demonstrates that shape selectivity arising from cooperative dispersive forces suffices for the emergence of a catalytic system with an enzyme-like thermodynamic profile.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Catalysis
Physical Sciences > General Chemistry
Life Sciences > Biochemistry
Physical Sciences > Colloid and Surface Chemistry
Uncontrolled Keywords:Colloid and Surface Chemistry, Biochemistry, General Chemistry, Catalysis
Language:English
Date:16 February 2022
Deposited On:28 Feb 2022 08:01
Last Modified:28 Jan 2024 02:45
Publisher:American Chemical Society (ACS)
ISSN:0002-7863
OA Status:Hybrid
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1021/jacs.1c11032
Project Information:
  • : FunderSNSF
  • : Grant IDPP00P2_170534
  • : Project TitleControl of Spin Interactions in Helical Systems
  • : FunderSNSF
  • : Grant IDPP00P2_198900
  • : Project TitleA â��Closer Lookâ�� at Open-Shell Nanographenes Through Bond and Space
  • : FunderH2020
  • : Grant ID716139
  • : Project TitleINSPIRAL - Spin-Delocalization with a Twist: Chiral Open-Shell Helices
  • Content: Published Version
  • Licence: Creative Commons: Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0)