Dynamics of Uncrystallized Water, Ice, and Hydrated Polymer in Partially Crystallized Poly(vinylpyrrolidone)-Water Mixtures.

In this study, we investigated the cooperative molecular dynamics of poly(vinylpyrrolidone) (PVP), ice, and uncrystallized water (UCW) in partially crystallized PVP-water mixtures by means of broadband dielectric spectroscopy. Three relaxation processes, denoted I, II, and III, were observed at temperatures ranging from immediately below the crystallization temperature (Tc) to approximately 200 K. At temperatures of 173-193 K, processes I and II cannot be distinguished. Below 168 K, process II separates into two processes: process IV at higher frequencies and process V at lower frequencies. Process I contributes to process V. In partially crystallized mixtures, process I originates from UCW in an uncrystallized phase with PVP. Process II is attributed to ice in the mixture, with a relaxation time that is 2 orders of magnitude smaller than that of pure ice. The concentration dependence of the strength of process II and the relaxation time relative to that of ice in bovine serum albumin (BSA)-water and gelatin-water mixtures strongly support this conclusion. Observation of processes IV and V indicates the presence of multiple ice relaxation processes. Process III is attributed to the α process of PVP in the uncrystallized phase in 40 and 50 wt % PVP mixtures. For mixtures with 30 wt % PVP or less, process III is attributed not only to the α process of PVP but also to interfacial polarization.