Ring polymers exhibit unique flow properties due to their closed chain topology. Despite recent progress, we have not yet achieved a full understanding of the nonequilibrium flow behavior of rings in nondilute solutions where intermolecular interactions greatly influence chain dynamics. In this work, we directly observe the dynamics of DNA rings in semidilute ring-linear polymer blends using single molecule techniques. We systematically investigate ring polymer relaxation dynamics from high extension and transient and steady-state stretching dynamics in a planar extensional flow for a series of ring-linear blends with varying ring fraction. Our results show multiple molecular subpopulations for ring relaxation in ring-linear blends, as well as large conformational fluctuations for rings in a steady extensional flow, even long after the initial transient stretching process has subsided. We further quantify the magnitude and characteristic time scales of ring conformational fluctuations as a function of blend composition. Interestingly, we find that the magnitude of ring conformational fluctuations follows a nonmonotonic response with increasing ring fraction, first increasing at low ring fraction and then substantially decreasing at large ring fraction in ring-linear blends. A unique set of ring polymer conformations are observed during the transient stretching process, which highlights the prevalence of molecular individualism and supports the notion of complex intermolecular interactions in ring-linear polymer blends. In particular, our results suggest that transient intermolecular structures form in ring-linear blends due to a combination of direct forces due to linear chains threading through open rings and indirect forces due to hydrodynamic interactions; these combined effects lead to large conformational fluctuations of rings over distributed time scales. Taken together, our results provide a new molecular understanding of ring polymer dynamics in ring-linear blends in the nonequilibrium flow.
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July 2021
Research Article|
July 01 2021
Dynamics and rheology of ring-linear blend semidilute solutions in extensional flow: Single molecule experiments Available to Purchase
Special Collection:
Ring Polymers
Yuecheng Zhou
;
Yuecheng Zhou
a)
1
Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign
, Urbana, Illinois 618012
Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign
, Urbana, Illinois 61801
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Charles D. Young
;
Charles D. Young
2
Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign
, Urbana, Illinois 618013
Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign
, Urbana, Illinois 61801
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Megan Lee;
Megan Lee
4
Department of Physics, University of San Diego
, San Diego, California 92110
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Sourya Banik;
Sourya Banik
5
Department of Chemical Engineering, Texas Tech University
, Lubbock, Texas 79409
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Dejie Kong;
Dejie Kong
5
Department of Chemical Engineering, Texas Tech University
, Lubbock, Texas 79409
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Gregory B. McKenna
;
Gregory B. McKenna
5
Department of Chemical Engineering, Texas Tech University
, Lubbock, Texas 79409
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Rae M. Robertson-Anderson
;
Rae M. Robertson-Anderson
4
Department of Physics, University of San Diego
, San Diego, California 92110
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Charles E. Sing
;
Charles E. Sing
2
Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign
, Urbana, Illinois 618013
Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign
, Urbana, Illinois 61801
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Charles M. Schroeder
Charles M. Schroeder
b)
1
Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign
, Urbana, Illinois 618012
Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign
, Urbana, Illinois 618013
Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign
, Urbana, Illinois 61801b)Author to whom correspondence should be addressed; electronic mail: [email protected]
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Yuecheng Zhou
1,2,a)
Charles D. Young
2,3
Megan Lee
4
Sourya Banik
5
Dejie Kong
5
Gregory B. McKenna
5
Rae M. Robertson-Anderson
4
Charles E. Sing
2,3
Charles M. Schroeder
1,2,3,b)
1
Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign
, Urbana, Illinois 61801
2
Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign
, Urbana, Illinois 61801
3
Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign
, Urbana, Illinois 61801
4
Department of Physics, University of San Diego
, San Diego, California 92110
5
Department of Chemical Engineering, Texas Tech University
, Lubbock, Texas 79409a)
Present address: Department of Chemistry, Stanford University, Stanford, CA 94305.
b)Author to whom correspondence should be addressed; electronic mail: [email protected]
Note: This paper is part of the special issue on Ring Polymers.
J. Rheol. 65, 729–744 (2021)
Article history
Received:
January 05 2021
Accepted:
April 27 2021
Citation
Yuecheng Zhou, Charles D. Young, Megan Lee, Sourya Banik, Dejie Kong, Gregory B. McKenna, Rae M. Robertson-Anderson, Charles E. Sing, Charles M. Schroeder; Dynamics and rheology of ring-linear blend semidilute solutions in extensional flow: Single molecule experiments. J. Rheol. 1 July 2021; 65 (4): 729–744. https://doi.org/10.1122/8.0000219
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