Web Release Date: March 8,
"Fatal Adsorption" of Brushlike Macromolecules: High Sensitivity of C-C Bond Cleavage Rates to Substrate Surface Energy
and
Caudill Laboratories, Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599-3290, and Center for Macromolecular Engineering, Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania,15213
Received December 17, 2007
Abstract:
Adsorption-induced degradation of brushlike macromolecules was monitored through molecular imaging by atomic force microscopy. The rate constant for C-C bond cleavage was shown to be extremely sensitive to the substrate surface energy. A few percent increase in the surface energy from 69.2 to 71.2 mN/m led to an order of magnitude increase of the scission rate. The absolute values of the rupture forces ranging from 2.57 to 2.47 nN are in agreement with previously calculated and measured values for stretching surface-tethered molecules.
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