Crooks Fluctuation Theorem for Single Polymer Dynamics in Time-Dependent Flows: Understanding Viscoelastic Hysteresis
Nonequilibrium work relations have fundamentally advanced our understanding of molecular processes. In recent years, fluctuation theorems have been extensively applied to understand transitions between equilibrium steady-states, commonly described by simple control parameters such as molecular exten...
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| Format: | Article |
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MDPI AG
2021-12-01
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| Series: | Entropy |
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| Online Access: | https://www.mdpi.com/1099-4300/24/1/27 |
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| author | Yuecheng Zhou Folarin Latinwo Charles M. Schroeder |
| author_facet | Yuecheng Zhou Folarin Latinwo Charles M. Schroeder |
| author_sort | Yuecheng Zhou |
| collection | DOAJ |
| description | Nonequilibrium work relations have fundamentally advanced our understanding of molecular processes. In recent years, fluctuation theorems have been extensively applied to understand transitions between equilibrium steady-states, commonly described by simple control parameters such as molecular extension of a protein or polymer chain stretched by an external force in a quiescent fluid. Despite recent progress, far less is understood regarding the application of fluctuation theorems to processes involving <i>nonequilibrium</i> steady-states such as those described by polymer stretching dynamics in nonequilibrium fluid flows. In this work, we apply the Crooks fluctuation theorem to understand the nonequilibrium thermodynamics of dilute polymer solutions in flow. We directly determine the nonequilibrium free energy for single polymer molecules in flow using a combination of single molecule experiments and Brownian dynamics simulations. We further develop a time-dependent extensional flow protocol that allows for probing viscoelastic hysteresis over a wide range of flow strengths. Using this framework, we define quantities that uniquely characterize the coil-stretch transition for polymer chains in flow. Overall, generalized fluctuation theorems provide a powerful framework to understand polymer dynamics under far-from-equilibrium conditions. |
| first_indexed | 2024-03-10T01:31:26Z |
| format | Article |
| id | doaj.art-334481b99ee0460da29cf5c879e7ee54 |
| institution | Directory Open Access Journal |
| issn | 1099-4300 |
| language | English |
| last_indexed | 2024-03-10T01:31:26Z |
| publishDate | 2021-12-01 |
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| series | Entropy |
| spelling | doaj.art-334481b99ee0460da29cf5c879e7ee542023-11-23T13:40:42ZengMDPI AGEntropy1099-43002021-12-012412710.3390/e24010027Crooks Fluctuation Theorem for Single Polymer Dynamics in Time-Dependent Flows: Understanding Viscoelastic HysteresisYuecheng Zhou0Folarin Latinwo1Charles M. Schroeder2Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801, USADepartment of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801, USADepartment of Materials Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801, USANonequilibrium work relations have fundamentally advanced our understanding of molecular processes. In recent years, fluctuation theorems have been extensively applied to understand transitions between equilibrium steady-states, commonly described by simple control parameters such as molecular extension of a protein or polymer chain stretched by an external force in a quiescent fluid. Despite recent progress, far less is understood regarding the application of fluctuation theorems to processes involving <i>nonequilibrium</i> steady-states such as those described by polymer stretching dynamics in nonequilibrium fluid flows. In this work, we apply the Crooks fluctuation theorem to understand the nonequilibrium thermodynamics of dilute polymer solutions in flow. We directly determine the nonequilibrium free energy for single polymer molecules in flow using a combination of single molecule experiments and Brownian dynamics simulations. We further develop a time-dependent extensional flow protocol that allows for probing viscoelastic hysteresis over a wide range of flow strengths. Using this framework, we define quantities that uniquely characterize the coil-stretch transition for polymer chains in flow. Overall, generalized fluctuation theorems provide a powerful framework to understand polymer dynamics under far-from-equilibrium conditions.https://www.mdpi.com/1099-4300/24/1/27fluctuation theoremsnonequilibrium thermodynamicspolymer dynamicsconformation hysteresisviscoelasticity |
| spellingShingle | Yuecheng Zhou Folarin Latinwo Charles M. Schroeder Crooks Fluctuation Theorem for Single Polymer Dynamics in Time-Dependent Flows: Understanding Viscoelastic Hysteresis Entropy fluctuation theorems nonequilibrium thermodynamics polymer dynamics conformation hysteresis viscoelasticity |
| title | Crooks Fluctuation Theorem for Single Polymer Dynamics in Time-Dependent Flows: Understanding Viscoelastic Hysteresis |
| title_full | Crooks Fluctuation Theorem for Single Polymer Dynamics in Time-Dependent Flows: Understanding Viscoelastic Hysteresis |
| title_fullStr | Crooks Fluctuation Theorem for Single Polymer Dynamics in Time-Dependent Flows: Understanding Viscoelastic Hysteresis |
| title_full_unstemmed | Crooks Fluctuation Theorem for Single Polymer Dynamics in Time-Dependent Flows: Understanding Viscoelastic Hysteresis |
| title_short | Crooks Fluctuation Theorem for Single Polymer Dynamics in Time-Dependent Flows: Understanding Viscoelastic Hysteresis |
| title_sort | crooks fluctuation theorem for single polymer dynamics in time dependent flows understanding viscoelastic hysteresis |
| topic | fluctuation theorems nonequilibrium thermodynamics polymer dynamics conformation hysteresis viscoelasticity |
| url | https://www.mdpi.com/1099-4300/24/1/27 |
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