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Title: Topological Effects in Isolated Poly[n]catenanes: Molecular Dynamics Simulations and Rouse Mode Analysis

Abstract

Poly[n]catenanes are mechanically interlocked polymers consisting of interlocking ring molecules. We report that over the years, researchers have speculated that the permanent topological interactions within the poly[n]catenane backbone could lead to unique dynamical behaviors. To investigate these unusual polymers, molecular dynamics simulations of isolated poly[n]catenanes have been conducted, along with a Rouse mode analysis. Owing to the mechanical bonds within the molecule, the dynamics of poly[n]catenanes at short length scales are significantly slowed and the distribution of relaxation times is broadened; these same behaviors have been observed in melts of linear polymers and are associated with entanglement. Lastly, despite these entanglement-like effects, at large length scales poly[n]catenanes do not relax much slower than isolated linear polymers and are less strongly impacted by increased segmental stiffness.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2]
+ Show Author Affiliations
  1. Univ. of Chicago, IL (United States)
  2. Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE: National Science Foundation (NSF); University of Chicago - Materials Research Science & Engineering Center (MRSEC)
OSTI Identifier:
1498496
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Macro Letters
Additional Journal Information:
Journal Volume: 7; Journal Issue: 8; Journal ID: ISSN 2161-1653
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Rauscher, Phillip M., Rowan, Stuart J., and de Pablo, Juan J. Topological Effects in Isolated Poly[n]catenanes: Molecular Dynamics Simulations and Rouse Mode Analysis. United States: N. p., 2018. Web. doi:10.1021/acsmacrolett.8b00393.
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Rauscher, Phillip M., Rowan, Stuart J., & de Pablo, Juan J. Topological Effects in Isolated Poly[n]catenanes: Molecular Dynamics Simulations and Rouse Mode Analysis. United States. https://doi.org/10.1021/acsmacrolett.8b00393
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Rauscher, Phillip M., Rowan, Stuart J., and de Pablo, Juan J. Wed . "Topological Effects in Isolated Poly[n]catenanes: Molecular Dynamics Simulations and Rouse Mode Analysis". United States. https://doi.org/10.1021/acsmacrolett.8b00393. https://www.osti.gov/servlets/purl/1498496.
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@article{osti_1498496,
title = {Topological Effects in Isolated Poly[n]catenanes: Molecular Dynamics Simulations and Rouse Mode Analysis},
author = {Rauscher, Phillip M. and Rowan, Stuart J. and de Pablo, Juan J.},
abstractNote = {Poly[n]catenanes are mechanically interlocked polymers consisting of interlocking ring molecules. We report that over the years, researchers have speculated that the permanent topological interactions within the poly[n]catenane backbone could lead to unique dynamical behaviors. To investigate these unusual polymers, molecular dynamics simulations of isolated poly[n]catenanes have been conducted, along with a Rouse mode analysis. Owing to the mechanical bonds within the molecule, the dynamics of poly[n]catenanes at short length scales are significantly slowed and the distribution of relaxation times is broadened; these same behaviors have been observed in melts of linear polymers and are associated with entanglement. Lastly, despite these entanglement-like effects, at large length scales poly[n]catenanes do not relax much slower than isolated linear polymers and are less strongly impacted by increased segmental stiffness.},
doi = {10.1021/acsmacrolett.8b00393},
journal = {ACS Macro Letters},
number = 8,
volume = 7,
place = {United States},
year = {Wed Jul 18 00:00:00 EDT 2018},
month = {Wed Jul 18 00:00:00 EDT 2018}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acsmacrolett.8b00393
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Cited by: 42 works
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Figures / Tables:

Fig. 1 Fig. 1: Some of the polymers studied. (a) poly[n]catenane with number of rings n = 25, macrocycle size m = 30, total size N = 750 (b) poly[n]catenane, n = 5, m = 100, N = 500 (c) linear polymer, N = m = 225 (d) Ring polymer, N =more » m = 100. Macrocycles are indexed by position along the chain (i).« less
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    Works referencing / citing this record:

    Human bloodsucking parasite in service of materials science
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    Combining Chemistry, Materials Science, Inspiration from Nature, and Serendipity to Develop Stimuli‐Responsive Polymeric Materials
    journal, January 2020

    • Rowan, Stuart J.; Weder, Christoph
    • Israel Journal of Chemistry, Vol. 60, Issue 1-2
    • DOI: 10.1002/ijch.201900098
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