Journal
JOURNAL OF PHYSICAL CHEMISTRY B
Volume 123, Issue 40, Pages 8492-8498Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcb.9b07088
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Funding
- U.S. Army Research Laboratory
- Army Research Office [W911NF-15-0143]
- Duke University Department of Chemistry
- National Science Foundation (PREM Center for Interfaces) [DMR-1205670]
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The cis-to-trans isomerization of azobenzene is accelerated in a bulk PDMS elastomer under uniaxial tension. The kinetics are cleanly described by a single-exponential first-order process (k = 2.7 X 10(-5) s(-1)) in the absence of tension but become multiexponential under constant strains of 40-90%. The complex kinetics can be reasonably modeled as a two-component process. The majority (similar to 92%) process is slower and occurs with a rate constant that is similar to that of the unstrained system (k = 2.3-2.7 x 10(-5)s(-1)) whereas the rate constant of the minority (similar to 8%) process increases from k = 10.1 X 10(-5) s(-1) at 40% strain to k = 21.3 X 10(-5) s(-1) at 90% strain. Simple models of expected force-rate relationships suggest that the average force of tension per strand in the minority component ranges from 28 to 44 pN across strains of 40-90%.
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