Effect of monomeric sequence on mechanical properties of P(VP-co-HEMA) hydrogels at low hydration

Seung Geol Lee, Giuseppe F. Brunello, Seung Soon Jang, J. Hannah Lee, David G. Bucknall

Research output: Contribution to journalArticle

24 Citations (Scopus)

Abstract

We have used molecular modeling of both random and blocky hydrogel networks of poly (N-vinyl-2-pyrrolidone-co-2-hydroxyethyl methacrylate) with VP:HEMA = 37:13 composition to investigate the effect of the monomeric sequence on the mechanical properties. The degrees of monomer sequence randomness for the random and the blocky copolymers were 1.170 and 0.104, respectively, and the degree of polymerization was set as 50. The equilibrated density of the dry gel network was 0.968 +/- 0.007 and 0.911 +/- 0.007 g/cm(3) for the random and the blocky sequences, respectively. In the partially hydrated state with 10 wt % water content, the effect of the monomeric sequence causes more distinct differences in density of 1.004 +/- 0.007 and 0.916 +/- 0.009 g/cm(3) for the random and the blocky copolymer network, respectively. We observed that in such networks, the water molecules are associated more closely with the N-vinyl-2-pyrrolidone than with the hydroxyethyl methacrylate moieties, which is consistent with results from quantum mechanical solvation free energy calculations. By simulating a compressive deformation of the dry gels up to 80% strain, we found that the random sequence network develops higher stress levels than the blocky network. We also found that stress reduction occurs in the random sequence network due to the hydration, which is not evident in the blocky sequence network. This difference in stress reduction between the random and the blocky sequence networks is due to the difference in the structural rearrangement of monomers in the presence of water during deformation. The random sequence network is able to undergo much more efficient rearrangement of HEMA units than in the. blocky sequence network.

Original languageEnglish
Pages (from-to)6604-6612
Number of pages9
JournalJournal of Physical Chemistry B
Volume113
Issue number19
DOIs
Publication statusPublished - 14 May 2009

Keywords

  • MOLECULAR-DYNAMICS SIMULATIONS
  • POLYMER-WATER INTERACTION
  • AQUEOUS CH3CN SOLUTION
  • CROSS-LINKED PAA
  • 2-HYDROXYETHYL METHACRYLATE
  • CONTROLLED-RELEASE
  • SWELLING BEHAVIOR
  • IN-VITRO
  • NANOPHASE-SEGREGATION
  • COPOLYMERIC HYDROGELS

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