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

Research output: Contribution to journalArticle

30 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

Fingerprint

Magic angle spinning
Nuclear magnetic resonance
PHEMA
Polyhydroxyethyl Methacrylate
Polarization
Gels
Temperature
Water
acrylic acid
Coagulation
Biocompatibility
Chemical activation
Association reactions
Polymers

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry

Cite this

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. / Miwa, Yuko; Ishida, Hiroyuki; Saitô, Hazime; Tanaka, Masaru; Mochizuki, Akira.

In: Polymer, Vol. 50, No. 25, 27.11.2009, p. 6091-6099.

Research output: Contribution to journalArticle

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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.",
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T1 - 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

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AU - Saitô, Hazime

AU - Tanaka, Masaru

AU - Mochizuki, Akira

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N2 - 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.

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