Local conformation of poly(methyl methacrylate) at nitrogen and water interfaces

Yohei Tateishi, Naoki Kai, Hidenori Noguchi, Kohei Uosaki, Toshihiko Nagamura, Keiji Tanaka

Research output: Contribution to journalArticle

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Abstract

The local conformation of poly(methyl methacrylate) (PMMA) chains at the nitrogen (N2) and water interfaces was studied by infrared-visible sum-frequency generation (SFG) spectroscopy. Although SFG spectra in the C-H region for PMMA at the N2 interface have been hitherto reported, the peak assignments are not in accord with one another. Thus, we first made accurate assignments of SFG peaks using films, which had been well annealed at a temperature above the glass transition temperature for a long time, of three different deuterated PMMAs as well as normal protonated PMMA. At the N 2 interface, hydrophobic functional groups such as α methyl, ester methyl and methylene groups were present. While the α methyl group was oriented along the direction parallel to the interface, ester methyl and methylene groups were oriented normal to the interface. Quantitative discussion concerning the orientation of the functional groups of PMMA at the N2 interface was aided by a model calculation. Once the PMMA film contacted water, the carbonyl groups of the PMMA side chains were oriented to the water phase to form hydrogen bonds with water molecules, resulting in the migration of ester methyl into the internal region of the film. Concurrently, the methylene groups became randomly oriented at the water interface and/or in part migrated into the internal region. Interestingly, the α methyl groups still existed at the water interface oriented along the parallel direction. The outermost region of PMMA in water can consist of hydrophilic and hydrophobic domains with sub-nanometre scale. Water molecules H-bond to themselves near the hydrophobic domains, leading to the formation of an ice-like structure of water molecules. However, water molecules adjacent to the hydrophilic domains H-bond with carbonyl groups.

Original languageEnglish
Pages (from-to)303-311
Number of pages9
JournalPolymer Chemistry
Volume1
Issue number3
DOIs
Publication statusPublished - May 1 2010

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Polymethyl Methacrylate
Polymethyl methacrylates
Conformations
Nitrogen
Water
Esters
Molecules
Functional groups
Hydrogen
Transition Temperature
Ice
Glass
Spectrum Analysis
Hydrogen bonds
Spectroscopy
Infrared radiation
Temperature

All Science Journal Classification (ASJC) codes

  • Bioengineering
  • Biochemistry
  • Polymers and Plastics
  • Organic Chemistry

Cite this

Local conformation of poly(methyl methacrylate) at nitrogen and water interfaces. / Tateishi, Yohei; Kai, Naoki; Noguchi, Hidenori; Uosaki, Kohei; Nagamura, Toshihiko; Tanaka, Keiji.

In: Polymer Chemistry, Vol. 1, No. 3, 01.05.2010, p. 303-311.

Research output: Contribution to journalArticle

Tateishi, Y, Kai, N, Noguchi, H, Uosaki, K, Nagamura, T & Tanaka, K 2010, 'Local conformation of poly(methyl methacrylate) at nitrogen and water interfaces', Polymer Chemistry, vol. 1, no. 3, pp. 303-311. https://doi.org/10.1039/b9py00227h
Tateishi, Yohei ; Kai, Naoki ; Noguchi, Hidenori ; Uosaki, Kohei ; Nagamura, Toshihiko ; Tanaka, Keiji. / Local conformation of poly(methyl methacrylate) at nitrogen and water interfaces. In: Polymer Chemistry. 2010 ; Vol. 1, No. 3. pp. 303-311.
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