Light-activated transfer of nitric oxide from a porous material.
Light-activated transfer of nitric oxide from a porous material.
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DOI：
10.1002/anie.200352881
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发表时间：
2004-05
影响因子：
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通讯作者：
Jeremy T. Mitchell-Koch;T. Reed;A. Borovik
中科院分区：
文献类型：
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作者：
Jeremy T. Mitchell-Koch;T. Reed;A. Borovik
一氧化氮（NO）是哺乳动物生物学中的重要生物分子，具有一系列作用，包括心血管、呼吸和神经系统的调节功能。[1]异常NO水平与许多疾病的联系[1，2]以及NO作为体内医疗装置的抗生物污染剂的潜在用途[3]进一步强调了对新的储存-释放系统的需求。有充分的证据表明，一组不同的系统将是必要的，以满足治疗需求。[4]一个持续的挑战是制备可控地释放NO而不浸出有毒副产物的材料。[3，5]用于这种材料的有希望的方法利用多孔聚合物主体内的共价固定的金属亚硝酰基（MSNNO）络合物。[6]这些材料联合收割机结合了MSNNO单元的性质，如可逆NO结合，以及多孔主体的性质。我们在此报告的高度交联的，网络聚合物含有固定RuO 2 NO网站的合成和性能。光触发NO的控制释放，如NO在溶液中转移到金属卟啉和myoglobin.We先前已经描述了一种材料，该材料包含共价固定的钴（ii）双[2-羟基-4-（4-乙烯基苄氧基）苯甲醛]亚乙基二亚胺络合物（[CoII（1）]，参见H2-1的方案1），其在多孔宿主内用于NO的储存和释放。[6]该材料P-1 [CoII]在环境条件下快速且选择性地结合NO并缓慢释放（在14天内去除约40%的NO）。它是通过模板共聚方法制备的，类似于用于制备分子印迹聚合物的方法。[7]分子前体用于聚合，因为这允许对固定化位点进行结构操纵。在我们的设计中，[6，8]含有可聚合基团的取代惰性金属络合物用作模板以形成固定化位点：金属-NO模板络合物与聚合物主体的多个共价连接使浸出最小化。RuO 2-NO配合物与12位配体在溶液中光解NO。[9]因此，我们合成了模板配合物[Ru（1）（NO）（Cl）]，并将其用于制备相应的多孔甲基丙烯酸酯聚合物P-1 [Ru（NO）（Cl）]，这是一种利用光实现NO可控转移的材料。
Nitric oxide (NO) is an important biomolecule in mammalian biology, with a range of effects that include regulatory functions in the cardiovascular, respiratory, and nervous systems.[1] The linkage of abnormal NO levels to numerous diseases [1, 2] and the potential use of NO as an anti-biofouling agent for in vivo medical devices [3] further underscores the need for new storage–release systems. There is ample evidence that a diverse group of systems will be necessary to meet therapeutic demands.[4] One continuing challenge is the preparation of materials that controllably release NO without leaching toxic by-products.[3, 5] A promising approach for such materials utilizes covalently immobilized metal nitrosyl (MÀNO) complexes within porous polymeric hosts.[6] These materials combine the properties of the MÀ NO units, such as reversible NO binding, with those of the porous hosts. We report herein the synthesis and properties of a highly cross-linked, network polymer containing immobilized RuÀNO sites. Light triggers the controlled release of NO, as demonstrated by the transfer of NO in solution to a metalloporphyrin and myoglobin.We have previously described a material containing covalently immobilized cobalt (ii) bis [2-hydroxo-4-(4-vinylbenzyloxy) benzaldehyde] ethylenediiminate complexes ([CoII (1)], see Scheme 1 for H2-1) within porous hosts for the storage and release of NO.[6] This material, P-1 [CoII], bound NO rapidly and selectively with slow release under ambient conditions (about 40% removal of NO over 14 days). It was prepared by a template copolymerization method, similar to that used to make molecularly imprinted polymers.[7] Molecular precursors are used in polymerization, since this allows for structural manipulation of the immobilized sites. In our design,[6, 8] substitutionally inert metal complexes containing polymerizable groups are used as templates to form the immobilized sites: Multiple covalent connections of the metal–NO template complex to the polymeric hosts minimizes leaching. Monomeric RuÀNO complexes with ligands related to 12À photolytically transfer NO in solution.[9] We reasoned that the RuÀNO complex with 12À could be prepared and utilized as a template to make a new material containing NO. Therefore, the template complex [Ru (1)(NO)(Cl)] was synthesized and used to produce the corresponding porous methacrylate polymer P-1 [Ru (NO)(Cl)], a material with which controllable transfer of NO is achieved with light.