Force-activated reactivity switch in a bimolecular chemical reaction at the single molecule level

ORAL

Abstract

Mechanical force is a distinct and usually less explored way to activate chemical reaction because it can deform the reacting molecules along a well-defined direction of the reaction coordinate. However, the effect of mechanical force on the free- energy surface that governs a chemical reaction is still largely unknown. The combination of protein engineering with single-molecule force-clamp spectroscopy allows us to study the influence of mechanical force on the rate at which a protein disulfide bond is reduced by some reducing agents in a bimolecular substitution reaction (so-called SN2). We found that cleavage of a protein disulfide bond by hydroxide anions exhibits an abrupt reactivity ``switch'' at 500 pN, after which the accelerating effect of force on the rate of an SN2 chemical reaction greatly diminishes. We propose that an abrupt force- induced conformational change of the protein disulfide bond shifts its ground state, drastically changing its reactivity in SN2 chemical reactions. Our experiments directly demonstrate the action of a force-activated switch in the chemical reactivity of a single molecule. References: S. Garcia-Manyes, J. Liang, R. Szoszkiewicz, T-L. Kuo and J. M. Fernandez, Nature Chemistry, 1, 236-242, 2009.

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Authors

  • Robert Szoszkiewicz

    Kansas State University

  • John Poate

    Brigham Young University, Los Alamos National Laboratory, Department of Physics and Astronomy, University of Utah, USA, MV Systems, Inc., USA, Helmholtz-Zentrum Berlin fuer Materialien und Energie, Abteilung Silizium-Photovoltaik, Germany, Colorado School of Mines, Department of Physics, USA, Georgia Institute of Technology, Arizona State University, Physics Department of Babolsar University, Iran, Physics Department, New Mexico State University, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, 85287-1604, USA, Department of Electrical Engineering, University of Arkansas, Fayetteville, AR 72701, USA, Department of Physics, Arizona State University, Tempe, AZ, 85287-1504, USA, Colorado State University, University of Wisconsin, NSF ERC for Extreme Ultraviolet Science and Technology, Colorado State University, BYU-Provo, Michigan Technical University and Pierre Auger Collaboration, University of Colorado, Colorado School of Mines, Department of Physics, Colorado State University, Department of Physics, Cornell University, NASA, University of Massachusetts at Amherst, University of Massachusetss at Amherst, APS President, Harvard University, Society of Physics Students, Duke University, Computer Science, Brigham Young University, Chemistry \& Biochemistry, Brigham Young University, University of Arizona, University of Utah, Kansas State Univ., Bethel University, University of New Mexico, Stanford University, JILA, University of Colorado at Boulder, NIST, JILA, University of Colorado at Boulder, National Renewable Energy Laboratory, University of Denver, University of Colorado, Boulder, NREL, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, 85287- 1604, USA, DU, ERI, Eleanor Roosevelt Institute (ERI), Cerro Tololo Interamerican Observatory, Utah State University, Center for Atmospheric and Space Sciences, Sciprint.org, University of Colorado at Boulder, JILA and University of Colorado, Kirchhoff Institute for Physics, University of Heidelberg, Utah Valley University, University of New South Wales, San Francisco State University, Weber State University, Cambridge University, Department of Physics and Astronomy, University of Utah, Kansas State University, Columbia University, NY, University of Colorado/JILA, Vice-President for Research and Technology Transfer, Colorado School of Mines

  • John Poate

    Brigham Young University, Los Alamos National Laboratory, Department of Physics and Astronomy, University of Utah, USA, MV Systems, Inc., USA, Helmholtz-Zentrum Berlin fuer Materialien und Energie, Abteilung Silizium-Photovoltaik, Germany, Colorado School of Mines, Department of Physics, USA, Georgia Institute of Technology, Arizona State University, Physics Department of Babolsar University, Iran, Physics Department, New Mexico State University, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, 85287-1604, USA, Department of Electrical Engineering, University of Arkansas, Fayetteville, AR 72701, USA, Department of Physics, Arizona State University, Tempe, AZ, 85287-1504, USA, Colorado State University, University of Wisconsin, NSF ERC for Extreme Ultraviolet Science and Technology, Colorado State University, BYU-Provo, Michigan Technical University and Pierre Auger Collaboration, University of Colorado, Colorado School of Mines, Department of Physics, Colorado State University, Department of Physics, Cornell University, NASA, University of Massachusetts at Amherst, University of Massachusetss at Amherst, APS President, Harvard University, Society of Physics Students, Duke University, Computer Science, Brigham Young University, Chemistry \& Biochemistry, Brigham Young University, University of Arizona, University of Utah, Kansas State Univ., Bethel University, University of New Mexico, Stanford University, JILA, University of Colorado at Boulder, NIST, JILA, University of Colorado at Boulder, National Renewable Energy Laboratory, University of Denver, University of Colorado, Boulder, NREL, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, 85287- 1604, USA, DU, ERI, Eleanor Roosevelt Institute (ERI), Cerro Tololo Interamerican Observatory, Utah State University, Center for Atmospheric and Space Sciences, Sciprint.org, University of Colorado at Boulder, JILA and University of Colorado, Kirchhoff Institute for Physics, University of Heidelberg, Utah Valley University, University of New South Wales, San Francisco State University, Weber State University, Cambridge University, Department of Physics and Astronomy, University of Utah, Kansas State University, Columbia University, NY, University of Colorado/JILA, Vice-President for Research and Technology Transfer, Colorado School of Mines

  • John Poate

    Brigham Young University, Los Alamos National Laboratory, Department of Physics and Astronomy, University of Utah, USA, MV Systems, Inc., USA, Helmholtz-Zentrum Berlin fuer Materialien und Energie, Abteilung Silizium-Photovoltaik, Germany, Colorado School of Mines, Department of Physics, USA, Georgia Institute of Technology, Arizona State University, Physics Department of Babolsar University, Iran, Physics Department, New Mexico State University, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, 85287-1604, USA, Department of Electrical Engineering, University of Arkansas, Fayetteville, AR 72701, USA, Department of Physics, Arizona State University, Tempe, AZ, 85287-1504, USA, Colorado State University, University of Wisconsin, NSF ERC for Extreme Ultraviolet Science and Technology, Colorado State University, BYU-Provo, Michigan Technical University and Pierre Auger Collaboration, University of Colorado, Colorado School of Mines, Department of Physics, Colorado State University, Department of Physics, Cornell University, NASA, University of Massachusetts at Amherst, University of Massachusetss at Amherst, APS President, Harvard University, Society of Physics Students, Duke University, Computer Science, Brigham Young University, Chemistry \& Biochemistry, Brigham Young University, University of Arizona, University of Utah, Kansas State Univ., Bethel University, University of New Mexico, Stanford University, JILA, University of Colorado at Boulder, NIST, JILA, University of Colorado at Boulder, National Renewable Energy Laboratory, University of Denver, University of Colorado, Boulder, NREL, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, 85287- 1604, USA, DU, ERI, Eleanor Roosevelt Institute (ERI), Cerro Tololo Interamerican Observatory, Utah State University, Center for Atmospheric and Space Sciences, Sciprint.org, University of Colorado at Boulder, JILA and University of Colorado, Kirchhoff Institute for Physics, University of Heidelberg, Utah Valley University, University of New South Wales, San Francisco State University, Weber State University, Cambridge University, Department of Physics and Astronomy, University of Utah, Kansas State University, Columbia University, NY, University of Colorado/JILA, Vice-President for Research and Technology Transfer, Colorado School of Mines

  • John Poate

    Brigham Young University, Los Alamos National Laboratory, Department of Physics and Astronomy, University of Utah, USA, MV Systems, Inc., USA, Helmholtz-Zentrum Berlin fuer Materialien und Energie, Abteilung Silizium-Photovoltaik, Germany, Colorado School of Mines, Department of Physics, USA, Georgia Institute of Technology, Arizona State University, Physics Department of Babolsar University, Iran, Physics Department, New Mexico State University, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, 85287-1604, USA, Department of Electrical Engineering, University of Arkansas, Fayetteville, AR 72701, USA, Department of Physics, Arizona State University, Tempe, AZ, 85287-1504, USA, Colorado State University, University of Wisconsin, NSF ERC for Extreme Ultraviolet Science and Technology, Colorado State University, BYU-Provo, Michigan Technical University and Pierre Auger Collaboration, University of Colorado, Colorado School of Mines, Department of Physics, Colorado State University, Department of Physics, Cornell University, NASA, University of Massachusetts at Amherst, University of Massachusetss at Amherst, APS President, Harvard University, Society of Physics Students, Duke University, Computer Science, Brigham Young University, Chemistry \& Biochemistry, Brigham Young University, University of Arizona, University of Utah, Kansas State Univ., Bethel University, University of New Mexico, Stanford University, JILA, University of Colorado at Boulder, NIST, JILA, University of Colorado at Boulder, National Renewable Energy Laboratory, University of Denver, University of Colorado, Boulder, NREL, Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, 85287- 1604, USA, DU, ERI, Eleanor Roosevelt Institute (ERI), Cerro Tololo Interamerican Observatory, Utah State University, Center for Atmospheric and Space Sciences, Sciprint.org, University of Colorado at Boulder, JILA and University of Colorado, Kirchhoff Institute for Physics, University of Heidelberg, Utah Valley University, University of New South Wales, San Francisco State University, Weber State University, Cambridge University, Department of Physics and Astronomy, University of Utah, Kansas State University, Columbia University, NY, University of Colorado/JILA, Vice-President for Research and Technology Transfer, Colorado School of Mines