The water structure and platelet compatibility of poly(methyl methacrylate (MMA)-block-2-hydroxyethyl methacrylate (HEMA)) were investigated. The molecular weight (Mn) of the polyHEMA segment was kept constant (average: 9600), while the Mn of the polyMMA segment was varied from 1340 to 7390. The equilibrium water content of the copolymers was found to be mainly governed by the HEMA content. The water structure in the copolymers was characterized in terms of the amounts of non-freezing and freezing water (abbreviated as Wnf and Wfz, respectively) using differential scanning calorimetry. It was found that the Wnf for the copolymers were higher than those estimated from the Wnf for the HEMA and MMA homopolymers and that the amount of excess non-freezing water depended on the polyMMA segment length. In addition, X-ray diffraction analysis revealed that some of the copolymers had cold-crystallizable water. These facts suggested that the polyMMA segments were involved in determining the water structures in the copolymers. Furthermore, the platelet compatibility of the copolymers was improved as compared to that of the HEMA homopolymer. It was therefore concluded that the platelet compatibility of the copolymer was related to the amount of excess non-freezing water.
We previously reported that the platelet compatibility of methyl methacrylate (MMA)-2-hydroxyethyl methacrylate (HEMA) diblock copolymers is related to the characteristic water structure in the copolymer, as the copolymer has an excess amount of nonfreezing water when compared with that estimated from the amounts of water in HEMA and MMA homopolymers. Thus, in this study, the relationship between water structure and polymer structure, including the heterogeneity and mobility of the copolymer, was investigated using differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR) spectroscopy. The prepared copolymers were classified into two groups: copolymers with a short, constant polyMMA segment length (Mn = ~2900) and copolymers with a constant polyHEMA segment length (Mn = ~9500), whereas the lengths of the counter segments varied. DSC analysis showed that when the polyMMA and polyHEMA segment lengths are similar, the amount of nonfreezing water increases, regardless of the total molecular weight of the copolymer. NMR analysis showed that heterogeneity of the copolymer is enhanced and the mobility of the copolymer decreases when the segment lengths are similar. These findings suggested that the excess amount of nonfreezing water is formed when the properties of water near the HEMA unit change from freezing to nonfreezing owing to interactions with the MMA unit. In addition, it is suggested that the heterogeneity of the copolymer structure or the mobility of the polymer are involved in the generation of excess nonfreezing water.
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