Bimodal Rates for Cavitation-Induced Chain Exchange Between Micelles

Taylor Larison; Eric Williams; Coby S. Collins; Sai Venkatesh Pingali; Morgan Stefik

doi:10.1021/acs.macromol.3c01040

Bimodal Rates for Cavitation-Induced Chain Exchange Between Micelles

Taylor Larison, Eric Williams, Coby S. Collins, Sai Venkatesh Pingali, Morgan Stefik

Biological Labeling and Scattering

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

Ultrasonic cavitation temporarily activates chain exchange for otherwise kinetically trapped block polymer micelles. Initial studies of cavitation-induced exchange (CIE) examined dilute polymer concentrations (0.1-1.0 wt %) with low extents of mixing (R(t) of ∼0.9 or ∼10% mixed). This study examines CIE kinetics with in situ SANS measurements during continuous ultrasonication for extended timescales that reach deeper extents of mixing (R(t) of ∼0.6 or ∼40% mixed) with semidilute polymer concentrations (1.0-5.0 wt %). All these time-dependent measurements revealed two distinct mixing rates: a fast initial rate for ∼15 min followed by transition to a 10.8x slower steady rate corresponding to the transition from gas-bubbles to vapor-bubbles. The faster rate of chain exchange for gas-bubble cavitation further connects the CIE to surface area turnover as the rate-limiting step. Both regimes had exchange rates that were directly proportional to the polymer concentration without apparent steric hindrances, suggesting that neither gas-bubble nor vapor-bubble cavitation heat was rate-limiting.

Original language	English
Pages (from-to)	7818-7826
Number of pages	9
Journal	Macromolecules
Volume	56
Issue number	19
DOIs	https://doi.org/10.1021/acs.macromol.3c01040
State	Published - Oct 10 2023

Funding

T.L., E.W., C.C., and M.S. acknowledge support by the National Science Foundation under NSF Award No. DMR-1752615. We thank the University of Minnesota Chemical Engineering and Materials Science department for GPC data. This work made use of the resources at the High Flux Isotope Reactor, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory (IPTS-21752.1 and IPTS 25337.1). The research at Oak Ridge National Laboratory’s Center for Structural Molecular Biology (CSMB), which operates the Bio-SANS instrument, was supported by the U.S. Department of Energy, Office of Science, through the Office of Biological and Environmental Research under Contract FWP ERKP291, using facilities supported by the Office of Basic Energy Research, U.S. Department of Energy. This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan). We thank Dr. Ting Ge for helpful discussions. T.L., E.W., C.C., and M.S. acknowledge support by the National Science Foundation under NSF Award No. DMR-1752615. We thank the University of Minnesota Chemical Engineering and Materials Science department for GPC data. This work made use of the resources at the High Flux Isotope Reactor, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory (IPTS-21752.1 and IPTS 25337.1). The research at Oak Ridge National Laboratory’s Center for Structural Molecular Biology (CSMB), which operates the Bio-SANS instrument, was supported by the U.S. Department of Energy, Office of Science, through the Office of Biological and Environmental Research under Contract FWP ERKP291, using facilities supported by the Office of Basic Energy Research, U.S. Department of Energy. This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). We thank Dr. Ting Ge for helpful discussions.

Funders	Funder number
DOE Public Access Plan
Oak Ridge National Laboratory
Office of Basic Energy Research	DE-AC05-00OR22725
United States Government
University of Minnesota Chemical Engineering and Materials Science department
National Science Foundation	DMR-1752615
U.S. Department of Energy
Office of Science
Biological and Environmental Research	FWP ERKP291
Oak Ridge National Laboratory	IPTS 25337.1, IPTS-21752.1
Canadian Society for Molecular Biosciences

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10.1021/acs.macromol.3c01040

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abstract = "Ultrasonic cavitation temporarily activates chain exchange for otherwise kinetically trapped block polymer micelles. Initial studies of cavitation-induced exchange (CIE) examined dilute polymer concentrations (0.1-1.0 wt %) with low extents of mixing (R(t) of ∼0.9 or ∼10% mixed). This study examines CIE kinetics with in situ SANS measurements during continuous ultrasonication for extended timescales that reach deeper extents of mixing (R(t) of ∼0.6 or ∼40% mixed) with semidilute polymer concentrations (1.0-5.0 wt %). All these time-dependent measurements revealed two distinct mixing rates: a fast initial rate for ∼15 min followed by transition to a 10.8x slower steady rate corresponding to the transition from gas-bubbles to vapor-bubbles. The faster rate of chain exchange for gas-bubble cavitation further connects the CIE to surface area turnover as the rate-limiting step. Both regimes had exchange rates that were directly proportional to the polymer concentration without apparent steric hindrances, suggesting that neither gas-bubble nor vapor-bubble cavitation heat was rate-limiting.",

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PY - 2023/10/10

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Bimodal Rates for Cavitation-Induced Chain Exchange Between Micelles

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