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Published on: June 10, 2018
Water structure of poly(2-methoxyethyl acrylate) observed by nuclear magnetic resonance spectroscopy
Akira Mochizuki1, Yuko Miwa2, Chie Yahata1
1Department of Bio-Medical Engineering, School of Engineering, Tokai University, Isehara, Kanagawa, Japan.
Abstract:
Poly(2-methoxyethyl acrylate) (PMEA) is known to show excellent blood compatibility. The performance of PMEA has been attributed to the existence of cold-crystallizable water in it, as observed using differential scanning calorimetry (DSC). However, little is known on the property of the water in PMEA above 0 °C, especially at ambient temperature including the body temperature, because blood compatibility is observed at 37 °C. The present study was performed to clarify the state of water in PMEA in the temperature range 15-45 °C using solution nuclear magnetic resonance spectroscopy (NMR). In addition, water in poly(butyl acrylate) (PBA), which exhibited poor blood compatibility, was used as a control. In the NMR spectra of water in PMEA, two peaks appeared at 4.87 ppm and 3.71 ppm at 30 °C, showing the existence of two types of water structures. The peak intensity of the upfield water was considerably higher than that of the downfield water. On the other hand, the hydrated PBA showed only one peak at 4.98 ppm at 30 °C. The dynamic property of water in these polymers was estimated from the deuterium solution NMR spin-lattice relaxation time, T12H. The T12H values of peaks observed at 4-5 ppm were relatively high, denoting rapid motion, while those of water at 3.7 ppm in PMEA were small, denoting slow mobility. Thus, the states of water molecules in PMEA in terms of chemical shift and mobility were considered different from those in PBA at ambient temperature.
Insights
Poly(2-methoxyethyl acrylate) (PMEA) exhibits superior blood compatibility due to unique water structures. Solution NMR reveals distinct water states and mobilities in PMEA compared to poly(butyl acrylate) (PBA) at body temperatures.
Area of Science:
- Polymer Science
- Biomaterials Science
- Physical Chemistry
Background:
- Poly(2-methoxyethyl acrylate) (PMEA) demonstrates excellent blood compatibility, often attributed to cold-crystallizable water.
- Understanding water properties in PMEA above 0°C, particularly at body temperature (37°C), is crucial for its biomedical applications.
- Previous studies primarily focused on sub-zero water states, leaving a knowledge gap at physiological temperatures.
Purpose of the Study:
- To investigate the state and dynamics of water within PMEA at temperatures ranging from 15°C to 45°C.
- To compare the water properties in PMEA with those in poly(butyl acrylate) (PBA), a polymer with poor blood compatibility.
- To elucidate the relationship between water structure/mobility and polymer blood compatibility.
Main Methods:
- Solution Nuclear Magnetic Resonance (NMR) spectroscopy was employed to analyze water in PMEA and PBA.
- Proton NMR chemical shifts were measured to identify different water environments.
- Deuterium NMR spin-lattice relaxation times (T1^2H) were used to assess water molecule dynamics.
Main Results:
- At 30°C, PMEA exhibited two distinct water peaks in NMR spectra (4.87 ppm and 3.71 ppm), indicating two types of water structures with differing intensities.
- Hydrated poly(butyl acrylate) (PBA) showed only a single water peak at 4.98 ppm at 30°C.
- NMR relaxation data revealed that water at 3.71 ppm in PMEA had significantly lower mobility (smaller T1^2H values) compared to more mobile water (higher T1^2H values) observed in both polymers at higher chemical shifts.
Conclusions:
- The study demonstrates that PMEA contains at least two distinct water populations with different chemical shifts and dynamic properties at ambient and body temperatures.
- The observed differences in water states and mobility between PMEA and PBA suggest a link between polymer hydration and blood compatibility.
- These findings provide new insights into the molecular basis of PMEA's excellent hemocompatibility.
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