Network structures and dynamics of dry and swollen poly(acrylate)s. Characterization of high- and low-frequency motions as revealed by suppressed or recovered intensities (SRI) analysis of 13C NMR

Yuko Miwa, Hiroyuki Ishida, Hazime Saitô, Masaru Tanaka, Akira Mochizuki

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32 Citations (Scopus)

Abstract

We recorded temperature-dependent high-resolution 13C NMR spectra of dry and swollen poly(acrylate)s [poly(2-methoxyethyl acrylate) (PMEA), poly(2-hydroxyethyl methacrylate) (PHEMA), and poly(tetrahydrofurfuryl acrylate) (PTHFA)] by dipolar decoupled-magic angle spinning (DD-MAS) and cross-polarization-magic angle spinning (CP-MAS) methods, to gain insight into their network structures and dynamics. Suppressed or recovered intensities (SRI) analysis of 13C CP-MAS and DD-MAS NMR was successfully utilized, to reveal portions of dry and swollen polymers which undergo fast and slow motions with fluctuation frequencies in the order of 108 Hz and 104-105 Hz, respectively. Fast isotropic motions with frequency higher than 108 Hz at ambient temperature were located to the portions in which 13C CP-MAS NMR signals of swollen PMEA were selectively suppressed. In contrast, low-frequency motion was identified to the portions in which 13C DD-MAS (and CP-MAS) signals are most suppressed at the characteristic suppression temperature(s) Ts. Network of PMEA gels (containing 7 wt% of water) turns out to be formed by partial association of backbones only, as manifested from their Ts gradient at lowered temperature, whereas networks of PHEMA (containing 40 wt% of water) and PTHFA (9 wt% of water) gels are tightly formed through mutual inter-chain associations of both backbones and side-chains, as viewed from the raised Ts values for both near at ambient temperature. It is also interesting to note that flexibility of gel network (PMEA > PTHFA > PHEMA) characterized by the suppression temperature Ts (PMEA < PTHFA < PHEMA) is well related with a characteristic parameter for biocompatibility such as the production of TAT (thrombin-antithrombin III complex) as a marker of activation of the coagulation system.

Original languageEnglish
Pages (from-to)6091-6099
Number of pages9
Journalpolymer
Volume50
Issue number25
DOIs
Publication statusPublished - Nov 27 2009
Externally publishedYes

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All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry

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