Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 133, Issue 43, Pages 17479-17484Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja207491r
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Funding
- National Science Foundation [DMR 0906985, DMR 0969301, CBET-0609087]
- Direct For Mathematical & Physical Scien
- Division Of Materials Research [969301] Funding Source: National Science Foundation
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Significant tension on the order of 1 nN is self-generated along the backbone of bottlebrush macromolecules due to steric repulsion between densely grafted side chains. The intrinsic tension is amplified upon adsorption of bottlebrush molecules onto a substrate and increases with grafting density, side chain length, and strength of adhesion to the substrate. These molecules were employed as miniature tensile machines to study the effect of mechanical force on the kinetics of disulfide reduction by dithiothreitol (DTT). For this purpose, bottlebrush macromolecules containing a disulfide linker in the middle of the backbone were synthesized by atom transfer radical polymerization (ATRP). The scission reaction was monitored through molecular imaging by atomic force microscopy (AFM). The scission rate constant increases linearly with the concentration of DTT and exponentially with mechanical tension along the disulfide bond. Moreover, the rate constant at zero force is found to be significantly lower than the reduction rate constant in bulk solution, which suggests an acidic composition of the water surface with pH = 3.7. This work demonstrates the ability of branched macromolecules to accelerate chemical reactions at specific covalent bonds without applying an external force.
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