Controlling the aqueous solubility of PNIPAM with hydrophobic molecular units
[Display omitted] •PNIPAM and PS oligomers and their co-polymers are simulated in water below and above the PNIPAM LCST.•LCST of pure PNIPAM is strongly associated with structural changes in the proximal water molecules.•Coil-to-globule transition in PNIPAM present in co-polymers promotes faster deh...
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Veröffentlicht in: | Computational materials science 2017-01, Vol.126 (C), p.191-203 |
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Sprache: | eng |
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•PNIPAM and PS oligomers and their co-polymers are simulated in water below and above the PNIPAM LCST.•LCST of pure PNIPAM is strongly associated with structural changes in the proximal water molecules.•Coil-to-globule transition in PNIPAM present in co-polymers promotes faster dehydration above LCST.•Increase in PS units in PNIPAM-co-PS co-polymers accelerates the coil-to-globule transition.
The effect of co-polymerization of thermo-sensitive polymers with hydrophilic or hydrophobic co-monomers on the LCST and the structure of proximal water remains a fundamental and challenging problem. Here, we employ all-atom molecular dynamics simulations to investigate the aqueous solubility of a thermo-sensitive polymer, poly(N-isopropylacrylamide) (PNIPAM), a hydrophobic polymer polystyrene (PS) and block co-polymers of PNIPAM-co-PS. The simulations of pure oligomers of PNIPAM and PS and their co-polymers are conducted below and above the LCST of PNIPAM to elucidate the effect of increase in number of PS units in PNIPAM-co-PS co-polymers on the coil-to-globule transition of PNIPAM and structure of proximal water. Our simulations suggest that while the LCST of pure PNIPAM oligomers is strongly associated with the structural changes in the proximal water molecules present near PNIPAM, inclusion of PS units disrupts the interactions between PNIPAM and water and promotes the faster dehydration of PNIPAM chains above its LCST. This phenomenon is manifested by a coil-to-globule transition in PNIPAM chains present in PNIPAM-co-PS co-polymers at much shorter times as compared to the pure PNIPAM oligomers. Our results also reveal that with increase in the number of PS units in PNIPAM-co-PS co-polymers the coil-to-globule transition is accelerated. |
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ISSN: | 0927-0256 1879-0801 |
DOI: | 10.1016/j.commatsci.2016.09.030 |