Issue 13, 2011
From the journal:

Physical Chemistry Chemical Physics

Mechanically activated rupture of single covalent bonds: evidence of force induced bond hydrolysis†

Sebastian W. Schmidt,abc   Alfred Kersch,a   Martin K. Beyer*b  and  Hauke Clausen-Schaumann*ac  

* Corresponding authors

a Munich University of Applied Sciences, Department of Precision- and Micro-Engineering, Engineering Physics, Lothstr. 34, 80335 Munich, Germany
E-mail: clausen-schaumann@hm.edu
Fax: +49 (0)89-1265-1480
Tel: +49 (0)89-1265-1671

b Institut für Physikalische Chemie, Christian-Albrechts-Universität zu Kiel, Olshausenstr. 40, 24098 Kiel, Germany
E-mail: beyer@phc.uni-kiel.de
Fax: +49 (0)431-880-2830
Tel: +49 (0)431-880-2831

c Center for Nanoscience (CeNS), Geschwister-Scholl-Platz 1, 80539 Munich, Germany

Abstract

We have used temperature-dependent single molecule force spectroscopy to stretch covalently anchored carboxymethylated amylose (CMA) polymers attached to an amino-functionalized AFM cantilever. Using an Arrhenius kinetics model based on a Morse potential as a one-dimensional representation of covalent bonds, we have extracted kinetic and structural parameters of the bond rupture process. With 35.5 kJ mol−1, we found a significantly smaller dissociation energy and with 9.0 × 102 s−1 to 3.6 × 103 s−1 also smaller Arrhenius pre-factors than expected for homolytic bond scission. One possible explanation for the severely reduced dissociation energy and Arrhenius pre-factors is the mechanically activated hydrolysis of covalent bonds. Both the carboxylic acid amide and the siloxane bond in the amino-silane surface linker are in principle prone to bond hydrolysis. Scattering, slope and curvature of the scattered data plots indicate that in fact two competing rupture mechanisms are observed.

Graphical abstract: Mechanically activated rupture of single covalent bonds: evidence of force induced bond hydrolysis

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Article information

DOI
https://doi.org/10.1039/C0CP02827D
Article type
Paper
Submitted
23 Nov 2010
Accepted
27 Jan 2011
First published
21 Feb 2011

Phys. Chem. Chem. Phys., 2011,13, 5994-5999

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Mechanically activated rupture of single covalent bonds: evidence of force induced bond hydrolysis

S. W. Schmidt, A. Kersch, M. K. Beyer and H. Clausen-Schaumann, Phys. Chem. Chem. Phys., 2011, 13, 5994 DOI: 10.1039/C0CP02827D

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