Synthesis and functional evaluation of carbon monoxide releasing molecules (CORMs) and materials (CORMAs)

一氧化碳释放分子（CORM）和材料（CORMA）的合成和功能评价

• 批准号: 214879100
• 负责人: Professor Dr. Matthias Westerhausen, since 4/2018
• 金额: --
• 依托单位: Institut für Anorganische und Analytische Chemie
• 依托单位国家: 德国
• 项目类别: Research Units
• 财政年份: 2012
• 资助国家: 德国
• 起止时间: 2011-12-31 至 2018-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/214879100?language=en
• 关键词: Synthesis; functional; evaluation; carbon; monoxide

Carbon monoxide (CO) is a biologically important signaling molecule with beneficial medicinal properties. However, administration of gaseous CO is challenging due to its toxicity and, therefore, CO-releasing molecules (CORMs) are needed to administer CO at a predetermined location and time. Carbonyl complexes of iron, manganese and rhenium in low oxidation states allow administration of CO upon irradiation (photoCORMs). Such CORMs with novel functionalities, such as switchable solubility, luminescence and Raman reporters, will be synthesized. We expand our investigations towards metal complexes that show CO release also after oxidation of the metal complexes (redoxCORMs) or via ligand substitution reactions. In addition, inactive CORMs (iCORMs) will be generated for comparative reactivity and toxicity studies in order to separate the mode of action of CO, metal ions and coligands. Therefore, the mechanism of CO release will be investigated to identify side and end products. The underlying physico-chemical processes of CO release will be elucidated to design CORMs with improved properties with respect to targeting and CO release in order to use them in biological systems within FOR 1738. Close cooperation between members of the research unit ensures tuning of release properties via feedback loops. To minimize metal-based interactions, insoluble CORMs will be embedded in nonwovens yielding CO-releasing materials (CORMAs). Following a covalent immobilization strategy, polymerizable Yanus-head ligands will be used in 2nd generation CORMAs. They contain a metal binding unit as well as polymerizable side chains. After homopolymerization and insertion of metal carbonyl complexes novel light-triggerable CORMAs can be obtained as insoluble powders for highly efficient CO release with the metal ions remaining trapped in the polymer matrix. Sensing systems based on selective detection of the small signaling molecule CO via fluorescence and surface enhanced Raman spectroscopy (SERS) will be developed to quantitatively determine CO concentrations in aqueous media.

一氧化碳(CO)是一种重要的生物信号分子，具有良好的药用价值。然而，由于气态CO的毒性，给药是具有挑战性的，因此，需要CO释放分子(球茎)在预定的位置和时间给药。铁、锰和Re的低氧化态的羰基络合物允许在照射时给一氧化碳(光CORM)。这种具有新功能的球体将被合成，如可切换的溶解性、发光和拉曼报告。我们将我们的研究扩展到在金属络合物(RedoxCORM)氧化后或通过配体取代反应也显示出CO释放的金属络合物。此外，还将产生非活性球茎(ICORM)，用于比较反应性和毒性研究，以分离CO、金属离子和配基的作用模式。因此，将对CO的释放机理进行研究，以确定副产物和最终产物。将阐明CO释放的基本物理化学过程，以设计具有更好的靶向和CO释放性能的球茎，以便在FOR 1738内的生物系统中使用它们。研究单位成员之间的密切合作确保通过反馈循环调整释放特性。为了最大限度地减少与金属的相互作用，不溶性球茎将被嵌入产生CO释放材料(CORMA)的非织造布中。遵循共价固定化策略，可聚合的Yanus-Head配体将用于第二代CORMA。它们含有金属结合单元和可聚合的侧链。通过均聚和插入金属羰基络合物后，可以得到新型的光触发CORMA粉末，用于高效地释放CO，金属离子被困在聚合物基质中。基于通过荧光和表面增强拉曼光谱(SERS)选择性检测小信号分子CO的传感系统将被开发用于定量测定水介质中的CO浓度。