Elucidating the Feature of Intermediate Water in Hydrated Poly(ω-methoxyalkyl acrylate)s by Molecular Dynamics Simulation and Differential Scanning
Elucidating the Feature of Intermediate Water in Hydrated Poly(ω-methoxyalkyl acrylate)s by Molecular Dynamics Simulation and Differential Scanning
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通过分子动力学模拟和差示扫描阐明水合聚（丙烯酸ω-甲氧基烷基酯）中中间水的特征
DOI：
10.1021/acsapm.0c00776
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发表时间：
2020
影响因子：
5
通讯作者：
Masaru Tanaka
中科院分区：
文献类型：
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作者：
Shin-nosuke Nishimura;Tomoya Ueda;Shingo Kobayashi;Masaru Tanaka
抗血栓涂层材料是生产血液接触医疗器械不可缺少的材料。廉价的合成聚合物的物理涂层对于降低医疗费用和为患者提供接受医疗护理的机会是理想的。聚（丙烯酸2-甲氧基乙酯）（PMEA）均聚物是广泛分布的涂层材料，几乎满足这些要求。然而，PMEA均聚物涂层具有改进的空间，因为其差的涂层性能导致去湿，从而限制了可用的基材。本文中，我们使用倍半硅氧烷（SQ）和聚（丙烯酸2-甲氧基乙酯）（PMEA）制造了一种无机/有机杂化材料，称为SQ/PMEA杂化物，以克服现有PMEA均聚物涂层的局限性。以含巯基的无规型倍半硅氧烷（SQ-SH）为单体，偶氮二异丁腈为热引发剂，通过巯基引发丙烯酸2-甲氧基乙酯（MEA）自由基聚合，成功地合成了SQ/PMEA杂化材料。该聚合策略仅通过改变单体和SQ-SH的进料组成而不需要复杂的步骤就可以容易地提供具有各种Si含量的所需杂化物。SQ/PMEA混合物显示出在任何聚合物组合物中形成对于生物相容性至关重要的中间水。通过优化Si含量，即使在潮湿条件下，与PMEA均聚物相比，该混合物在聚合物、陶瓷和金属的表面上形成光滑且稳定的涂层，并显著抑制人血小板粘附。此外，杂化涂层不仅表现出抗血栓形成的特性，但也显着促进粘附和人脐静脉内皮细胞（HUVECs）的延伸。混合材料的这些特性对于长期使用的血液接触装置的表面处理是有吸引力的，包括体外膜氧合（ECMO）装置、血管和支架。这一策略在生物医学领域如组织工程、再生医学和微创医学的发展中具有潜力。
Antithrombotic coating material is indispensable for the production of blood-contacting medical devices. Physical coatings of inexpensive synthetic polymers are desirable to reduce medical expenses and provide patients with an opportunity to receive medical care. Poly(2-methoxyethyl acrylate) (PMEA) homopolymers are widely diffused coating materials that almost meet these requirements. However, the PMEA homopolymer coating has room for improvement because its poor coating properties cause dewetting, thus limiting the available substrates. Herein, we fabricated an inorganic/organic hybrid material using silsesquioxane (SQ) and poly(2-methoxyethyl acrylate) (PMEA) called the SQ/PMEA hybrid to overcome the limitations of existing PMEA homopolymer coatings. The SQ/PMEA hybrid was successfully synthesized by thiol-initiated radical polymerization of 2-methoxyethyl acrylate (MEA) from thiol group-containing random-type silsesquioxane (SQ-SH) utilizing 2,2′-azobis(isobutyronitrile) as a thermal initiator. This polymerization strategy readily afforded the required hybrid with various Si contents by merely changing the feed composition of the monomer and SQ-SH without a complicated procedure. The SQ/PMEA hybrid showed the formation of intermediate water essential for biocompatibility in any polymer composition. By optimizing the Si content, the hybrid formed a smooth and stable coating layer on surfaces of polymers, ceramics, and metals compared with the PMEA homopolymer even under wet conditions and significantly suppressed human platelet adhesion. In addition, the hybrid coating not only exhibited antithrombotic properties but also drastically promoted the adhesion and extension of human umbilical vein endothelial cells (HUVECs). These characteristics of the hybrid material are attractive for the surface treatment of blood-contacting devices used for a long time, including extracorporeal membrane oxygenation (ECMO) devices, blood vessels, and stents. This strategy has potential in the advancement of the biomedical fields such as tissue engineering, regenerative medicine, and minimally invasive medicine.