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

Content Provider	Royal Society of Chemistry (RSC)
Author	Kai, Naoki Tateishi, Yohei Noguchi, Hidenori Tanaka, Keiji Nagamura, Toshihiko Uosaki, Kohei
Copyright Year	2010
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 N2 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.
Starting Page	303
Ending Page	311
Page Count	9
File Format	HTM / HTML PDF
ISSN	17599954
Volume Number	1
Issue Number	3
Journal	Polymer Chemistry
DOI	10.1039/b9py00227h
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Glass transition Spectroscopy Ester SFG Methyl group Poly(methyl methacrylate) Hydrophobe Carbonyl group Hydrophile Nitrogen Methylene group Hydrogen bond
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Biochemistry Bioengineering Biomedical Engineering Polymers and Plastics

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