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Open AccessFeature PaperArticle

Tacticity-Dependent Interchain Interactions of Poly(N-Isopropylacrylamide) in Water: Toward the Molecular Dynamics Simulation of a Thermoresponsive Microgel

Department of Chemical Sciences and Technologies, University of Rome Tor Vergata, Via della Ricerca Scientifica I, 00133 Roma, Italy
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Author to whom correspondence should be addressed.
Academic Editor: David Díaz Díaz
Received: 2 March 2017 / Revised: 11 April 2017 / Accepted: 14 April 2017 / Published: 19 April 2017
(This article belongs to the Special Issue Micro- and Nanogels)
The discovery that the lower critical solution temperature (LCST) of poly(N-Isopropylacrylamide) (PNIPAM) in water is affected by the tacticity opens the perspective to tune the volume phase transition temperature of PNIPAM microgels by changing the content of meso dyads in the polymer network. The increased hydrophobicity of isotactic-rich PNIPAM originates from self-assembly processes in aqueous solutions also below the LCST. The present work aims to detect the characteristics of the pair interaction between polymer chains, occurring in a concentration regime close to the chain overlap concentration, by comparing atactic and isotactic-rich PNIPAM solutions. Using atomistic molecular dynamics simulations, we successfully modelled the increased association ability of the meso-dyad-rich polymer in water below the LCST, and gain information on the features of the interchain junctions as a function of tacticity. Simulations carried out above the LCST display the PNIPAM transition to the insoluble state and do not detect a relevant influence of stereochemistry on the structure of the polymer ensemble. The results obtained at 323 K provide an estimate of the swelling ratio of non-stereocontrolled PNIPAM microgels which is in agreement with experimental findings for microgels prepared with low cross-linker/monomer feed ratios. This study represents the first step toward the atomistic modelling of PNIPAM microgels with a controlled tacticity. View Full-Text
Keywords: PNIPAM; tacticity; LCST; volume phase transition temperature (VPTT); hydrogels; polymer network PNIPAM; tacticity; LCST; volume phase transition temperature (VPTT); hydrogels; polymer network
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MDPI and ACS Style

Paradossi, G.; Chiessi, E. Tacticity-Dependent Interchain Interactions of Poly(N-Isopropylacrylamide) in Water: Toward the Molecular Dynamics Simulation of a Thermoresponsive Microgel. Gels 2017, 3, 13.

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