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

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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.