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ABSTRACT
Infrared and Raman scattering spectra of aqueous solutions of poly(ethylene glycol) with nominal weight 1000 Da have been collected and analyzed as a function of the water content both in terms of a two-state physical model and in terms of an innovative multiscale wavelet cross-correlation approach. Both the analysis procedures allow to highlight the spectral shape changes occurring when water is added to pure polymer, showing the effectiveness of the wavelet analysis. It is shown that, provided that the pure polymer spectral contribution is subtracted from the aqueous solutions spectra, the shape of the intramolecular O–H stretching band can be reproduced by a superposition of the spectrum of bulk water and of the spectrum of hydration water, i.e., the spectrum relative to the water molecules bonded to the polymer chain. The weight of the bonded-water spectrum changes with concentration furnishing a polymer hydration number value which well agrees with hydration number data, reported in literature, obtained with other techniques. On the other hand, the intramolecular infrared O–H stretching band and the low-frequency Raman spectra, for all the investigated polymeric aqueous solutions, when analyzed through a multiscale wavelet cross-correlation approach reveal that significant spectral changes are registered in the 0.00–0.46 water weight fraction range. Such complementary experimental and analytic findings suggest the picture that when the water content increases, the water molecules saturate the two lone pairs of each oxygen atom of the polymer furnishing a hydration number which agrees with previous determinations and hence supporting the validity of the wavelet approach.