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

一氧化碳（CO）是一种重要的生物信号分子，具有有益的药用特性。然而，气态CO的施用由于其毒性而具有挑战性，因此需要CO释放分子（CORM）以在预定的位置和时间施用CO。低氧化态的铁、锰和铁的羰基络合物允许在照射时施用CO（photoCORM）。将合成具有新功能的CORM，例如可切换的溶解度，发光和拉曼报告分子。我们扩大我们的调查对金属络合物，显示CO释放后的金属络合物（redoxCORM）或通过配体取代反应的氧化。此外，将生成非活性CORM（iCORM）用于比较反应性和毒性研究，以分离CO、金属离子和共配体的作用模式。因此，将研究CO释放的机制，以确定副产物和终产物。将阐明CO释放的基本物理化学过程，以设计具有改进的靶向和CO释放特性的CORM，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回路调整释放特性。为了最大限度地减少金属基相互作用，将不溶性CORM嵌入非织造布中，产生CO释放材料（CORMA）。在共价固定化策略之后，可聚合的Yanus头配体将用于第二代CORMA。它们含有金属结合单元以及可聚合侧链。在均聚和金属羰基络合物的插入后，可以获得新型的光可降解的CORMA作为不溶性粉末，用于高效的CO释放，金属离子保持被捕获在聚合物基质中。传感系统的基础上，通过荧光和表面增强拉曼光谱（Sers）的小信号分子CO的选择性检测将被开发，以定量地确定在水介质中的CO浓度。

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.