Reynolds Melissa M, Saavedra Joseph E, Showalter Brett M, Valdez Carlos A, Shanklin Anna P, Oh Bong K, Keefer Larry K, Meyerhoff Mark E
Department of Chemistry, The University of Michigan, Ann Arbor, MI 48109, Basic Science Program, SAIC Frederick, National Cancer Institute at Frederick, Frederick, Maryland 21702, and Chemistry Section, Laboratory of Comparative Carcinogenesis, National Cancer Institute at Frederick, Frederick, Maryland 21702.
J Mater Chem. 2010 Jan 1;20(15):3107-2114. doi: 10.1039/c000152j.
Nitric oxide (NO) has been shown to exhibit significant anti-platelet activity and its release from polymer matrices has been already utilized to increase the biocompatibility of various blood-contacting devices. Herein, details of a new synthetic approach for preparing NO-releasing diazeniumdiolated polyurethanes (PU) are described. The method's utility is demonstrated by the incorporation of methoxymethyl- or sugar-protected pre-formed diazeniumdiolate moieties directly into chain extender diols which are then incorporated into the polyurethane backbone. This approach provides the ability to control the number of diazeniumdiolate groups incorporated into the polymer backbone, and hence the surface flux of NO that can ultimately be liberated from polymeric films prepared from the new PU materials. The method provides a means of covalently attaching diazeniumdiolate groups to polyurethanes in a form that resists dissociation of NO during processing but can be activated for spontaneous NO release via hydrolysis of the carbohydrate or methoxymethyl moieties under basic and acidic conditions, respectively.
一氧化氮（NO）已被证明具有显著的抗血小板活性，并且其从聚合物基质中的释放已被用于提高各种血液接触装置的生物相容性。在此，描述了一种制备释放NO的重氮二醇化聚氨酯（PU）的新合成方法的细节。该方法的实用性通过将甲氧基甲基或糖保护的预制重氮二醇部分直接掺入扩链二醇中得到证明，然后将扩链二醇掺入聚氨酯主链中。这种方法能够控制掺入聚合物主链中的重氮二醇基团的数量，从而控制最终可从由新型PU材料制备的聚合物膜中释放的NO的表面通量。该方法提供了一种将重氮二醇基团以共价方式连接到聚氨酯上的手段，其形式在加工过程中能抵抗NO的解离，但分别在碱性和酸性条件下可通过碳水化合物或甲氧基甲基部分的水解而被激活以实现NO的自发释放。
