Investigating Fundamental Principles of Nonequilibrium Assembly Using Temperature-Sensitive Copolymers

Chittari, Supraja S.; Obermeyer, Allie C.; Knight, Abigail S.

doi:10.1021/jacs.3c00883

Title: Investigating Fundamental Principles of Nonequilibrium Assembly Using Temperature-Sensitive Copolymers

Journal Article · 13 March 2023 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c00883 · OSTI ID:1995729

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University of North Carolina at Chapel Hill, NC (United States)
Columbia University, New York, NY (United States)

Both natural biomaterials and synthetic materials benefit from complex energy landscapes that provide the foundation for structure–function relationships and environmental sensitivity. Understanding these nonequilibrium dynamics is important for the development of design principles to harness this behavior. Using a model system of poly(ethylene glycol) methacrylate-based thermoresponsive lower critical solution temperature (LCST) copolymers, we explored the impact of composition and stimulus path on nonequilibrium thermal hysteretic behavior. Through turbidimetry analysis of nonsuperimposable heat–cool cycles, we observe that LCST copolymers show clear hysteresis that varies as a function of pendent side chain length and hydrophobicity. Hysteresis is further impacted by the temperature ramp rate, as insoluble states can be kinetically trapped under optimized temperature protocols. As a result, this systematic study brings to light fundamental principles that can enable the harnessing of out-of-equilibrium effects in synthetic soft materials.

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Research Organization:: University of North Carolina at Chapel Hill, NC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0021295; DGE-2040435; CHE-1828183

OSTI ID:: 1995729

Journal Information:: Journal of the American Chemical Society, Vol. 145, Issue 11; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Absorption
Copolymers
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Title: Investigating Fundamental Principles of Nonequilibrium Assembly Using Temperature-Sensitive Copolymers

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