Brunstedt M R, Ziats N P, Robertson S P, Hiltner A, Anderson J M, Lodoen G A, Payet C R
Department of Macromolecular Science, Case Western Reserve University, Cleveland, Ohio 44106.
J Biomed Mater Res. 1993 Mar;27(3):367-77. doi: 10.1002/jbm.820270310.
To understand better blood interactions with poly(ether urethane urea) (PEUU) materials, a radioimmunoassay and whole or diluted human plasma were used to characterize the presence of fibrinogen, immunoglobulin G, factor VIII/von Willebrand factor, Hageman factor (factor XII), and albumin on a PEUU formulation and on PEUU formulations modified with the amphiphilic additive Methacrol 2138F (co[diisopropylaminoethyl methacrylate (DIPAM)/decyl methacrylate] [3/1]), or with hydrophobic acrylate or methacrylate polymer or copolymer additives. The protein adsorption assay showed that PEUU films loaded or coated with Methacrol 2138F (Methacrol) or homopoly-DIPAM (h-DIPAM) adsorbed significantly lower amounts of the studied proteins than did either the base PEUU formulations or the PEUUs loaded with the more hydrophobic acrylate or methacrylate polymer additives. Experiments with Methacrol-loaded PEUUs, where the loading of Methacrol was varied from 0.25 wt% to 20.0 wt%, showed that the adsorption of each of the characterized proteins did not vary significantly throughout the Methacrol loading range, and that all Methacrol-loaded PEUU formulations adsorbed significantly lower amounts of the studied proteins than did the unloaded PEUU. Phase separation within the additive loaded PEUUs was characterized by scanning electron microscopy (SEM). The solubility parameters of the additives, as well as of the base PEUU, were calculated and used to interpret differences in phase separation of the additive modified PEUUs. The analysis showed that additives of lower solubility parameter phase-separated into fewer large microdroplets within the PEUU matrix. SEM analysis also showed that additive microdroplets were not present on the air side surface of loaded PEUUs. To explain the differences in protein adsorption to the air side of additive loaded PEUUs when compared to the base PEUU, it was assumed that the additives near this region of the solvent swollen PEUU matrix may have migrated to, at, or near the PEUU-air interface during film formation, creating an additive enriched PEUU surface region. Once at this surface region, it was suggested that dynamic surface reorientation in response to an aqueous medium ensured that the additives were able significantly to influence protein adsorption behavior only if they interacted with aqueous media more favorably than the PEUU.
为了更好地理解血液与聚(醚聚氨酯脲)(PEUU)材料的相互作用,采用放射免疫分析法以及全血或稀释的人血浆来表征纤维蛋白原、免疫球蛋白G、凝血因子VIII/血管性血友病因子、哈格曼因子(凝血因子XII)和白蛋白在一种PEUU制剂以及用两亲性添加剂甲基丙烯酸2138F(共[甲基丙烯酸二异丙基氨基乙酯(DIPAM)/甲基丙烯酸癸酯][3/1])、疏水性丙烯酸酯或甲基丙烯酸酯聚合物或共聚物添加剂改性的PEUU制剂上的存在情况。蛋白质吸附试验表明,负载或涂覆有甲基丙烯酸2138F(Methacrol)或均聚-DIPAM(h-DIPAM)的PEUU薄膜吸附的所研究蛋白质的量明显低于基础PEUU制剂或负载有更疏水的丙烯酸酯或甲基丙烯酸酯聚合物添加剂的PEUU。对负载不同含量甲基丙烯酸酯(含量从0.25 wt%到20.0 wt%不等)的PEUU进行的实验表明,在所研究的甲基丙烯酸酯负载范围内,每种表征蛋白质的吸附量没有显著变化,并且所有负载甲基丙烯酸酯的PEUU制剂吸附的所研究蛋白质的量都明显低于未负载的PEUU。通过扫描电子显微镜(SEM)对负载添加剂的PEUU内部的相分离进行了表征。计算了添加剂以及基础PEUU的溶解度参数,并用于解释添加剂改性PEUU相分离的差异。分析表明,溶解度参数较低的添加剂在PEUU基质内相分离成较少的大微滴。SEM分析还表明,负载的PEUU的空气侧表面不存在添加剂微滴。为了解释与基础PEUU相比,负载添加剂的PEUU的空气侧蛋白质吸附的差异,假定在溶剂溶胀的PEUU基质的该区域附近的添加剂在成膜过程中可能迁移到PEUU-空气界面处、界面上或界面附近,形成一个添加剂富集的PEUU表面区域。一旦到达该表面区域,有人提出,响应水性介质的动态表面重排确保只有当添加剂与水性介质的相互作用比PEUU更有利时,它们才能显著影响蛋白质吸附行为。