Kim Young Ha, Han Dong Keun, Park Ki Dong, Kim Soo Hyun
Biomaterials Research Center, Korea Institute of Science and Technology, Seoul 130-650, Republic of Korea.
Biomaterials. 2003 Jun;24(13):2213-23. doi: 10.1016/s0142-9612(03)00023-1.
In our laboratory sulfonated PEO (PEO-SO(3)) was designed as a "negative cilia model" to investigate a synergistic effect of PEO and negatively charged SO(3) groups. PEO-SO(3) itself exhibited a heparin-like anticoagulant activity of 14% of free heparin. Polyurethane grafted with PEO-SO(3) (PU-PEO-SO(3)) increased the albumin adsorption to a great extent but suppressed other proteins, while PU-PEO decreased the adsorption of all the proteins. The platelet adhesion was decreased on PU-PEO but least on PU-PEO-SO(3) to demonstrate an additional effect of SO(3) groups. The enhanced blood compatibility of PU-PEO-SO(3) in the ex vivo rabbit and in vivo canine implanting tests was confirmed. Furthermore, PU-PEO-SO(3) exhibited an improved biostability and suppressed calcification in addition to the enhanced antithrombogenicity. The in vivo antithrombogenicity and biostability were improved in the order of PU<PU-PEO<PU-PEO-SO(3). The calcium amounts deposited was decreased in the order of PU>PU-PEO>PU-PEO-SO(3) in spite of the possible attraction between negative SO(3) groups and positive calcium ions. The bioprosthetic tissue (BT) was grafted with H(2)N-PEO-SO(3) via glutaraldehyde (GA) residues after conventional GA fixation. BT-PEO-SO(3) also displayed the decreased calcification by in vivo animal models. The application of PEO-SO(3) was extended by designing amphiphilic copolymers containing PEO-SO(3) moiety and hydrophobic long alkyl groups as anchors. The superior effect of PEO-SO(3) groups on thromboresistance compared to PEO was confirmed also in the case of copolymers coated or blended with other polymers and the systems coupled by UV irradiation, photoreaction or gold/sulfur or silane coupling technology, and therefore it might be very useful for the medical devices.
在我们实验室中，磺化聚环氧乙烷（PEO-SO(3)）被设计为一种“负性纤毛模型”，以研究聚环氧乙烷（PEO）与带负电荷的SO(3)基团的协同效应。PEO-SO(3)本身表现出相当于游离肝素14%的类肝素抗凝活性。接枝了PEO-SO(3)的聚氨酯（PU-PEO-SO(3)）极大地增加了白蛋白的吸附，但抑制了其他蛋白质的吸附，而PU-PEO则降低了所有蛋白质的吸附。血小板在PU-PEO上的黏附减少，但在PU-PEO-SO(3)上最少，这证明了SO(3)基团的额外作用。PU-PEO-SO(3)在体外兔和体内犬植入试验中增强的血液相容性得到了证实。此外，PU-PEO-SO(3)除了增强抗血栓形成性外，还表现出改善生物稳定性和抑制钙化的特性。体内抗血栓形成性和生物稳定性按PU＜PU-PEO＜PU-PEO-SO(3)的顺序得到改善。尽管负性SO(3)基团与正性钙离子之间可能存在吸引力，但沉积的钙量按PU＞PU-PEO＞PU-PEO-SO(3)的顺序减少。生物假体组织（BT）在常规戊二醛（GA）固定后，通过GA残基接枝了H(2)N-PEO-SO(3)。BT-PEO-SO(3)在体内动物模型中也显示出钙化减少。通过设计含有PEO-SO(3)部分和疏水性长烷基作为锚定基团的两亲共聚物，扩展了PEO-SO(3)的应用。在与其他聚合物涂层或共混以及通过紫外线照射、光反应或金/硫或硅烷偶联技术耦合的体系中，与PEO相比，PEO-SO(3)基团在抗血栓性方面的优越效果也得到了证实，因此它可能对医疗器械非常有用。
