MOFs as carrier for nitric oxide delivery in biological systems - microscopic fundamentals of adsorption and controlled release studied by infrared and electron and nuclear spin resonance spectroscopy

用于物理吸附的配位不饱和骨架金属离子位点与用于在多孔MOF材料中化学吸附一氧化氮（NO）的胺官能化连接体组合的存在为它们在生物应用中用作递送剂提供了有希望的前景。但在实际医疗中利用MOFs作为NO载体需要进一步优化多孔材料和在微观尺度上对NO吸附和释放过程的深入理解。因此，本计画致力于利用电子自旋共振（ESR）、核磁共振（NMR）、红外（IR）等光谱技术，研究一氧化氮在多功能材料中的吸附、储存与控制释放。我们的光谱方法结合了不同技术的优势，相对于抗磁性和顺磁性物种，并将提供详细的知识NO在金属离子位点的吸附和结合强度，所形成的NO吸附复合物的几何和电子结构，以及它们在各种条件下的热稳定性和化学稳定性。光谱方法将通过宏观NO吸附和释放实验来完成。除了在已知的MOF结构上研究NO吸附之外，还将开发和研究新型的MOF材料，该材料将联合收割机的物理和化学吸附位点结合在孔结构内用于NO储存和递送应用。

The presence of coordinatively unsaturated framework metal ion sites for physisorption in combination with amine-functionalized linkers for chemisorption of nitric oxide (NO) in porous MOF materials offer promising perspectives for their use as delivery agents in biological applications. But utilization of MOFs as NO carrier in actual medical treatments requires further optimization of the porous materials and a solid understanding of the NO adsorption and release processes on a microscopic scale. Therefore, this project is devoted to the study of the adsorption, storage, and controlled release of NO in MOF materials by electron spin resonance (ESR), nuclear magnetic resonance (NMR), and infrared (IR) spectroscopy. Our spectroscopic approach combines the advantages of the different techniques with respect to diamagnetic and paramagnetic species and will provide detailed knowledge about the adsorption and bonding strengths of NO at the metal ion sites, the geometrical and electronic structure of the formed NO adsorption complexes, and their thermal and chemical stability under various conditions. The spectroscopic methods will be completed by macroscopic NO adsorption and release experiments. Besides the study of NO adsorption over already known MOF structures, novel MOF materials which combine physi- and chemisorption sites for NO storage and delivery applications within the pore structure will be developed and investigated.