The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, Japan.
J Biomater Sci Polym Ed. 2010;21(14):1831-48. doi: 10.1163/092050610X488269. Epub 2010 Jun 23.
The excellent biocompatibility of PMEA was ascribed by Tanaka to the predominant population of intermediate water in the hydrated polymer matrix. The intermediate water concept was examined using the 'nano-plate model' on the basis of new results (by Morita) of a time-resolved IR study on the water sorption process into PMEA. The examination showed that the image picture proposed by Tanaka concerning the role of intermediate water was in consistent with experimental results so far obtained. Morita showed that the intermediate water exhibited a strong peak at 3400 cm(-1) in its IR spectrum. Water sorption profiles of MMA, PEG and PMVE were found to be similar to that of PMEA. It was shown that the biocompatibility of these polymers could be explained by the intermediate water concept. It was also pointed out that PVP and PDMAA have a considerable amount of intermediate water under appropriate circumstances. The PHEMA-water system showed neither clear peak for cold crystallization in DSC chart, nor the strong peak at 3400 cm(-1) in its IR spectrum, because the PHEMA system did not contain enough intermediate water to show similar behavior to PMEA. The hydrated PHEMA matrix contains a stable network structure of water molecules including the nodes of OH groups of its side-chains. In the stable network system, most water molecules should be hydrogen bonded strongly to form non-freezing water, but not intermediate water. The inferior biocompatibility of PHEMA was ascribed to the stable network structure of water molecules. Some of the PHEMA co-polymers, on the other hand, were found to have highly improved biocompatibility. Mechanism for the improvement was discussed in terms of loosening the network structure, which could be brought about by introducing ionic groups or branching to the polymer chains through co-polymerization with appropriate 'key monomers'. The mobility of polymer chains, as well as the population of three kinds of water in polysaccharide molecules in aqueous medium could change in response to their chemical structure such as nature of ionic groups, the degree of branching, etc. Polysaccharides located at the utmost-outer layer of blood cells probably possess a loosened network structure to form soft biological surface where intermediate water predominates. Cellulose, on the other hand, has a common feature with PHEMA in the sense of predominance of the non-freezing water in its hydrated system. Note: The word 'biocompatibility' is used in general as the term evaluating properties of materials which do not cause adverse effect when the materials come into contact with living organisms, such as proteins, biological cells and tissues. This review paper primarily deals with 'biocompatibility' of polymer materials against various biological elements in blood flow system.
聚甲基丙烯酸乙酯(PMEA)具有优异的生物相容性,这一特性归因于其水合聚合物基质中占主导地位的中间水。中间水的概念是基于 Morita 在对 PMEA 水吸附过程的时间分辨红外研究的新结果(Morita)的“纳米板模型”进行检验的。检验表明,Tanaka 提出的关于中间水作用的图像与迄今为止获得的实验结果是一致的。Morita 表明,中间水在其红外光谱中显示出 3400cm(-1)处的强峰。发现 MMA、PEG 和 PMVE 的水吸附曲线与 PMEA 的相似。研究表明,这些聚合物的生物相容性可以用中间水的概念来解释。研究还指出,在适当的条件下,PVP 和 PDMA 也含有相当数量的中间水。PHEMA-水体系在 DSC 图谱中既没有冷结晶的明显峰,也没有 3400cm(-1)处的强峰,因为 PHEMA 体系中没有足够的中间水来表现出与 PMEA 类似的行为。水合 PHEMA 基质包含水分子的稳定网络结构,包括其侧链上 OH 基团的节点。在稳定的网络系统中,大多数水分子应该通过氢键强烈结合形成非冻结水,而不是中间水。PHEMA 的低生物相容性归因于水分子的稳定网络结构。另一方面,一些 PHEMA 共聚物的生物相容性得到了显著提高。通过共聚引入适当的“关键单体”,形成离子基团或支链,从而改变聚合物链的网络结构,讨论了提高生物相容性的机制。聚合物链的流动性以及多糖分子在水介质中的三种水的含量可能会根据其化学结构(如离子基团的性质、支化程度等)发生变化。位于血细胞最外层的多糖可能具有松散的网络结构,形成以中间水为主的柔软生物表面。另一方面,纤维素在其水合体系中以非冻结水为主,这与 PHEMA 有共同的特点。注意:“生物相容性”一词通常是指当材料与生物体(如蛋白质、生物细胞和组织)接触时不会产生不良反应的材料的性能评估术语。本文综述主要涉及聚合物材料对血流系统中各种生物元素的“生物相容性”。