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Title: Structure of rigid polymers confined to nanoparticles: Molecular dynamics simulations insight

Abstract

Nanoparticles (NPs) grafted with organic layers form hybrids able to retain their unique properties through integration into the mesoscopic scale. The organic layer structure and response often determine the functionality of the hybrids on the mesoscopic length scale. Using molecular dynamics (MD) simulations, we probe the conformation of luminescent rigid polymers, dialkyl poly(p-phenylene ethynylene)s (PPE), end-grafted onto a silica nanoparticle in different solvents as the molecular weights and polymer coverages are varied. We find that, in contrast to NP-grafted flexible polymers, the chains are fully extended independent of the solvent. In toluene and decane, which are good solvents, the grafted PPEs chains assume a similar conformation to that observed in dilute solutions. In water, which is a poor solvent for the PPEs, the polymer chains form one large cluster but remain extended. The radial distribution of the chains around the core of the nanoparticle is homogeneous in good solvents, whereas in poor solvents clusters are formed independent of molecular weights and coverages. As a result, the clustering is distinctively different from the response of grafted flexible and semiflexible polymers.

Authors:
 [1];  [2];  [1];  [2]
  1. Clemson Univ., Clemson, SC (United States)
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1241371
Report Number(s):
SAND-2016-1842J
Journal ID: ISSN 0743-7463; 619626
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 32; Journal Issue: 8; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Maskey, Sabina, Lane, J. Matthew D., Perahia, Dvora, and Grest, Gary S. Structure of rigid polymers confined to nanoparticles: Molecular dynamics simulations insight. United States: N. p., 2016. Web. doi:10.1021/acs.langmuir.5b04568.
Maskey, Sabina, Lane, J. Matthew D., Perahia, Dvora, & Grest, Gary S. Structure of rigid polymers confined to nanoparticles: Molecular dynamics simulations insight. United States. https://doi.org/10.1021/acs.langmuir.5b04568
Maskey, Sabina, Lane, J. Matthew D., Perahia, Dvora, and Grest, Gary S. 2016. "Structure of rigid polymers confined to nanoparticles: Molecular dynamics simulations insight". United States. https://doi.org/10.1021/acs.langmuir.5b04568. https://www.osti.gov/servlets/purl/1241371.
@article{osti_1241371,
title = {Structure of rigid polymers confined to nanoparticles: Molecular dynamics simulations insight},
author = {Maskey, Sabina and Lane, J. Matthew D. and Perahia, Dvora and Grest, Gary S.},
abstractNote = {Nanoparticles (NPs) grafted with organic layers form hybrids able to retain their unique properties through integration into the mesoscopic scale. The organic layer structure and response often determine the functionality of the hybrids on the mesoscopic length scale. Using molecular dynamics (MD) simulations, we probe the conformation of luminescent rigid polymers, dialkyl poly(p-phenylene ethynylene)s (PPE), end-grafted onto a silica nanoparticle in different solvents as the molecular weights and polymer coverages are varied. We find that, in contrast to NP-grafted flexible polymers, the chains are fully extended independent of the solvent. In toluene and decane, which are good solvents, the grafted PPEs chains assume a similar conformation to that observed in dilute solutions. In water, which is a poor solvent for the PPEs, the polymer chains form one large cluster but remain extended. The radial distribution of the chains around the core of the nanoparticle is homogeneous in good solvents, whereas in poor solvents clusters are formed independent of molecular weights and coverages. As a result, the clustering is distinctively different from the response of grafted flexible and semiflexible polymers.},
doi = {10.1021/acs.langmuir.5b04568},
url = {https://www.osti.gov/biblio/1241371}, journal = {Langmuir},
issn = {0743-7463},
number = 8,
volume = 32,
place = {United States},
year = {Thu Feb 04 00:00:00 EST 2016},
month = {Thu Feb 04 00:00:00 EST 2016}
}

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Cited by: 8 works
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Works referencing / citing this record:

Environmentally responsive surface-modified silica nanoparticles for enhanced oil recovery
journal, September 2016


Free-energy predictions and absorption spectra calculations for supramolecular nanocarriers and their photoactive cargo
journal, January 2017