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Single-Event Spectroscopy and Unravelling Kinetics of Covalent Domains Based on Cyclobutane Mechanophores.

Publication ,  Journal Article
Bowser, BH; Wang, S; Kouznetsova, TB; Beech, HK; Olsen, BD; Rubinstein, M; Craig, SL
Published in: Journal of the American Chemical Society
April 2021

Mechanochemical reactions that lead to an increase in polymer contour length have the potential to serve as covalent synthetic mimics of the mechanical unfolding of noncovalent "stored length" domains in structural proteins. Here we report the force-dependent kinetics of stored length release in a family of covalent domain polymers based on cis-1,2-substituted cyclobutane mechanophores. The stored length is determined by the size (n) of a fused ring in an [n.2.0] bicyclic architecture, and it can be made sufficiently large (>3 nm per event) that individual unravelling events are resolved in both constant-velocity and constant-force single-molecule force spectroscopy (SMFS) experiments. Replacing a methylene in the pulling attachment with a phenyl group drops the force necessary to achieve rate constants of 1 s-1 from ca. 1970 pN (dialkyl handles) to 630 pN (diaryl handles), and the substituent effect is attributed to a combination of electronic stabilization and mechanical leverage effects. In contrast, the kinetics are negligibly perturbed by changes in the amount of stored length. The independent control of unravelling force and extension holds promise as a probe of molecular behavior in polymer networks and for optimizing the behaviors of materials made from covalent domain polymers.

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Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

April 2021

Volume

143

Issue

13

Start / End Page

5269 / 5276

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences
 

Citation

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ICMJE
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Bowser, B. H., Wang, S., Kouznetsova, T. B., Beech, H. K., Olsen, B. D., Rubinstein, M., & Craig, S. L. (2021). Single-Event Spectroscopy and Unravelling Kinetics of Covalent Domains Based on Cyclobutane Mechanophores. Journal of the American Chemical Society, 143(13), 5269–5276. https://doi.org/10.1021/jacs.1c02149
Bowser, Brandon H., Shu Wang, Tatiana B. Kouznetsova, Haley K. Beech, Bradley D. Olsen, Michael Rubinstein, and Stephen L. Craig. “Single-Event Spectroscopy and Unravelling Kinetics of Covalent Domains Based on Cyclobutane Mechanophores.Journal of the American Chemical Society 143, no. 13 (April 2021): 5269–76. https://doi.org/10.1021/jacs.1c02149.
Bowser BH, Wang S, Kouznetsova TB, Beech HK, Olsen BD, Rubinstein M, et al. Single-Event Spectroscopy and Unravelling Kinetics of Covalent Domains Based on Cyclobutane Mechanophores. Journal of the American Chemical Society. 2021 Apr;143(13):5269–76.
Bowser, Brandon H., et al. “Single-Event Spectroscopy and Unravelling Kinetics of Covalent Domains Based on Cyclobutane Mechanophores.Journal of the American Chemical Society, vol. 143, no. 13, Apr. 2021, pp. 5269–76. Epmc, doi:10.1021/jacs.1c02149.
Bowser BH, Wang S, Kouznetsova TB, Beech HK, Olsen BD, Rubinstein M, Craig SL. Single-Event Spectroscopy and Unravelling Kinetics of Covalent Domains Based on Cyclobutane Mechanophores. Journal of the American Chemical Society. 2021 Apr;143(13):5269–5276.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

April 2021

Volume

143

Issue

13

Start / End Page

5269 / 5276

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences