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Studies on the behavior of nanoconfined homopolymers with cyclic chain architecture

J. Chem. Phys. 123, 054903 (2005); doi:10.1063/1.1992474

Published 9 August 2005

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Johnny R. Maury-Evertsz and Gustavo E. López
Theoretical and Computational Chemistry Group, Department of Chemistry, University of Puerto Rico, University of Puerto Rico at Mayagüez P.O. Box 9019, Mayagüez, Puerto Rico 00681-9019
We have performed Monte Carlo simulations to study the effect of cyclic architecture on the behavior of homopolymer chains under several conditions of confinement. The collapse of the rings in two stages, a coil-to-globule and a liquidlike-to-solidlike transition, was observed even at extreme confinement. Both transitions were observed at lower temperatures than for linear chains of the same length, 2%–5% lower for unconfined systems, and 10%–15% lower for wall separations below three bond lengths due to the effect of confinement. When the plates separation approached the two-dimensional regime, the coil-to-globule transition shifted to lower temperatures. The inverse trend was observed when the chain length was increased. In the collapsed state, the average size and conformations of linear and cyclic molecules of same length were similar independently of confinement. At temperatures near the coil-to-globule transition, the radius of gyration of unconfined linear chains, <R<sub>g</sub><sup>2</sup>>linear, became larger than for the cyclic chains, <R<sub>g</sub><sup>2</sup>>cyclic, and this difference increased considerably with confinement. The radius of gyration ratio <R<sub>g</sub><sup>2</sup>>linear/<R<sub>g</sub><sup>2</sup>>cyclic in this region decreased rapidly. The decrease was more pronounced and occurred at lower temperatures for slit width confinements. At higher temperatures, in the coil state, the radius of gyration ratio became nearly constant for a given separation, and varied from 0.56 for unconfined systems to 0.47 when the chain was completely confined between the walls. This reduction was attributed to the higher increase in the average size of linear chains with confinement when compared with cyclic chains, due to architectural restrictions. ©2005 American Institute of Physics
History: Received 22 December 2004; accepted 13 June 2005; published 9 August 2005
Permalink: http://link.aip.org/link/?JCPSA6/123/054903/1
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KEYWORDS and PACS

Keywords
PACS
  • 61.25.Hq
    Structure of macromolecular and polymer solutions, and polymer melts; swelling
  • 61.20.Ja
    Computer simulation of liquid structure
  • 36.20.Fz
    Macromolecular constitution (chains and sequences)
  • 36.20.Hb
    Macromolecular configuration (bonds, dimensions)
  • 64.70.Dv
    Solid–liquid transitions
  • YEAR: 2005

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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