<p>Blood-compatible polymers are widely used in biomedical applications, yet the relationships between the effect of their fundamental properties under hydrated conditions on biological properties remain poorly understood. Here, we synthesized a series of poly(2-methoxyethyl acrylate)s (PMEAs) with controlled molecular weights and dispersities. The critical entanglement molecular weight (<i>M</i><sub>c</sub>) of PMEA in the dry condition revealed by rheological analysis was approximately 24&#xa0;kDa, which is comparable to that of poly(methyl methacrylate). In contrast, PMEA exposed to water, i.e., under water-saturated conditions showed a <i>M</i><sub>c</sub> of 36&#xa0;kDa. Similar to the established understanding, DSC analysis validated the presence of three types of hydration water, i.e., non-freezing, intermediate, and free waters. However, among these, the amount of non-freezing and free waters increased markedly along with the increase in molecular weight above <i>M</i><sub>c</sub>. Importantly, ELISA tests revealed the significant suppression of fibronectin denaturation by employing PMEAs with molecular weights exceeding the <i>M</i><sub>c</sub>. Our findings reveal how precision polymer design especially for molecular weight or polymer chain entanglement affects hydration and biological performance, thus providing molecular insight into the design of next-generation blood-compatible materials.</p>

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Hydration and Entanglement Contrasts Between Dry and Wet States in Blood-Compatible Poly(2-methoxyethyl acrylate)

  • Yi Zhang,
  • Yukiko Tanaka,
  • Satoshi Honda,
  • Masaru Tanaka

摘要

Blood-compatible polymers are widely used in biomedical applications, yet the relationships between the effect of their fundamental properties under hydrated conditions on biological properties remain poorly understood. Here, we synthesized a series of poly(2-methoxyethyl acrylate)s (PMEAs) with controlled molecular weights and dispersities. The critical entanglement molecular weight (Mc) of PMEA in the dry condition revealed by rheological analysis was approximately 24 kDa, which is comparable to that of poly(methyl methacrylate). In contrast, PMEA exposed to water, i.e., under water-saturated conditions showed a Mc of 36 kDa. Similar to the established understanding, DSC analysis validated the presence of three types of hydration water, i.e., non-freezing, intermediate, and free waters. However, among these, the amount of non-freezing and free waters increased markedly along with the increase in molecular weight above Mc. Importantly, ELISA tests revealed the significant suppression of fibronectin denaturation by employing PMEAs with molecular weights exceeding the Mc. Our findings reveal how precision polymer design especially for molecular weight or polymer chain entanglement affects hydration and biological performance, thus providing molecular insight into the design of next-generation blood-compatible materials.