Infrared spectroscopic study of stereo-controlled poly(N-isopropylacrylamide) with an extended chain conformation induced by adsorption on a gold surface

Shimoaka, Takafumi; Rikiyama, Kazuaki; Katsumoto, Yukiteru; Hasegawa, Takeshi
November 2013
Analytical & Bioanalytical Chemistry;Nov2013, Vol. 405 Issue 27, p9411
Academic Journal
Poly( N-isopropylacrylamide) (PNiPAM) compounds with various diad tacticities were prepared, and the molecular interaction properties in a thin film deposited on a gold surface were analyzed using infrared spectroscopy. The intramolecular and intermolecular interactions were found to depend on the tacticity, and only atactic (diad ratio 46 %) PNiPAM exhibits poor molecular interaction even in the bulk sample. On the other hand, the same series of compounds dissolved in an acetone solution were spread on a gold surface to form a thin film. In the dissolution process, the polymer molecules are relaxed via solvation, and they are bound to the gold surface by a molecular interaction to form a submonolayer thin film. In the thin film, the molecular interaction with the gold surface via the N–H group was monitored in the infrared spectra only for a nearly isotactic ( m = 90) PNiPAM by an apparent shift of the N–H stretching vibration band. This shift was confirmed by changing the degree of hydrophilicity of the gold surface: a larger shift is found on a gold surface with stronger hydrophilicity. As a result, the conformation of a nearly isotactic molecule is found to be extended by the interaction with the gold surface, which works to immobilize the molecule.


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