Surface-Induced Chain Alignment of Semiflexible Polymers

Semiflexible polymers tend to spontaneously align parallel to an impenetrable surface, creating a mean aligning field. The backbone segments interact with the aligning field, further enhancing the chain alignment. Using molecular dynamics (MD) simulations of bead–spring chains, we demonstrate that t...

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Published inMacromolecules Vol. 49; no. 3; pp. 963 - 971
Main Authors Zhang, Wenlin, Gomez, Enrique D, Milner, Scott T
Format Journal Article
LanguageEnglish
Published American Chemical Society 09.02.2016
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ISSN0024-9297
1520-5835
1520-5835
DOI10.1021/acs.macromol.5b02173

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Abstract Semiflexible polymers tend to spontaneously align parallel to an impenetrable surface, creating a mean aligning field. The backbone segments interact with the aligning field, further enhancing the chain alignment. Using molecular dynamics (MD) simulations of bead–spring chains, we demonstrate that the thickness of the aligned layer is about a persistence length L p for semiflexible polymers in the isotropic phase. To investigate the effect of nematic coupling on the surface-induced alignment, we develop a lattice version of self-consistent field theory (SCFT) for semiflexible chains. We predict that the strength and range of the alignment increase with increasing nematic coupling, quantified by the nematic coupling constant α. The impenetrable surface acts as a perturbation on the chain alignment, and the nematic coupling α amplifies the perturbation. By comparing the SCFT predicted order parameter profile for chains near an impenetrable surface to MD simulations, we can estimate α for semiflexible polymers.
AbstractList Semiflexible polymers tend to spontaneously align parallel to an impenetrable surface, creating a mean aligning field. The backbone segments interact with the aligning field, further enhancing the chain alignment. Using molecular dynamics (MD) simulations of bead–spring chains, we demonstrate that the thickness of the aligned layer is about a persistence length Lₚ for semiflexible polymers in the isotropic phase. To investigate the effect of nematic coupling on the surface-induced alignment, we develop a lattice version of self-consistent field theory (SCFT) for semiflexible chains. We predict that the strength and range of the alignment increase with increasing nematic coupling, quantified by the nematic coupling constant α. The impenetrable surface acts as a perturbation on the chain alignment, and the nematic coupling α amplifies the perturbation. By comparing the SCFT predicted order parameter profile for chains near an impenetrable surface to MD simulations, we can estimate α for semiflexible polymers.
Semiflexible polymers tend to spontaneously align parallel to an impenetrable surface, creating a mean aligning field. The backbone segments interact with the aligning field, further enhancing the chain alignment. Using molecular dynamics (MD) simulations of bead–spring chains, we demonstrate that the thickness of the aligned layer is about a persistence length L p for semiflexible polymers in the isotropic phase. To investigate the effect of nematic coupling on the surface-induced alignment, we develop a lattice version of self-consistent field theory (SCFT) for semiflexible chains. We predict that the strength and range of the alignment increase with increasing nematic coupling, quantified by the nematic coupling constant α. The impenetrable surface acts as a perturbation on the chain alignment, and the nematic coupling α amplifies the perturbation. By comparing the SCFT predicted order parameter profile for chains near an impenetrable surface to MD simulations, we can estimate α for semiflexible polymers.
Author Gomez, Enrique D
Milner, Scott T
Zhang, Wenlin
AuthorAffiliation The Pennsylvania State University
Department of Chemical Engineering
Materials Research Institute
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  surname: Milner
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  email: stm9@psu.edu
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SubjectTerms isotropy
mathematical theory
molecular dynamics
polymers
Title Surface-Induced Chain Alignment of Semiflexible Polymers
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