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“Fatal Adsorption” of Brushlike Macromolecules: High Sensitivity of C−C Bond Cleavage Rates to Substrate Surface Energy

2008; American Chemical Society; Volume: 130; Issue: 13 Linguagem: Inglês

10.1021/ja7111806

1943-2984

N. Sh. Lebedevа, Frank Sun, Hyung‐il Lee, Krzysztof Matyjaszewski, Sergei S. Sheiko,

Ion-surface interactions and analysis

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.