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TU Dresden » Fakultät Mathematik und Naturwissenschaften » Fachrichtung Chemie und Lebensmittelchemie » Metal-Organic Frameworks
Overview of granted projects - Part II

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

 

        Consortium:

        Dr. Marko Bertmer, Leipzig
        University of Leipzig
        Department of Physics and Geosciences
        Chair of Experimental Physics

        Professor Dr. Michael Fröba, Hamburg
        University of Hamburg
        Department of Chemistry
        Institute of Inorganic and Applied Chemistry

        Professor Dr. Martin Hartmann, Erlangen
        Erlangen Catalysis Resource Center

        Professor Dr. Andreas Pöppl, Leipzig
        University of Leipzig
        Department of Physics and Geosciences
        Chair of Experimental Physics

        Project:

        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

        Abstract:

        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.

        Results:

         

        Publications:

        M. Mendt, B. Jee, D. Himsl, L. Moschkowitz, T. Ahnfeldt, N. Stock, M. Hartmann, A. Pöppl
        "A Continuous-Wave Electron Paramagnetic Resonance Study of Carbon Dioxide Adsorption in the Metal–Organic Frame-Work MIL-53"
        Appl. Magn. Reson. 45 (2014) 269–285.
         

         

        O. Kozachuk, M. Meilikhov, K. Yusenko, A. Schneemann, B. Jee, A. V. Kuttatheyil, M. Bertmer, C. Sternemann, A. Pöppl, R. A. Fischer
        "A Solid-Solution Approach to Mixed-Metal Metal–Organic Frameworks – Detailed Characterization of Local Structures, Defects and Breathing Behaviour of Al/V Frameworks"
        Eur. J. Inorg. Chem. (2013), 4546–4557.
         

         

        B. Jee, M. Hartmann, A. Pöppl
        "H2 , D2 and HD adsorption upon the metal-organic framework [Cu2.97 Zn0.03 (btc)2]n studied by pulsed ENDOR and HYSCORE spectroscopy"
        Mol. Phys. 111 (2013), 2950-2966.
         

         

        Bettina Jee, Petko St. Petkov, Georgi N. Vayssilov, Thomas Heine, Martin Hartmann, Andreas Pöppl
        "A Combined Pulsed Electron Paramagnetic Resonance Spectroscopic and DFT Analysis of the 13CO2 and 13CO Adsorption on the Metal-Organic Framework Cu2.97Zn0.03(btc)2"
        J. Phys. Chem. C 2013, 117, 8231-8240.
         

         

        F. Gul-E-Noor, M. Mendt, D. Michel, A. Pöppl, H. Krautscheid, J. Haase, M. Bertmer
        "Adsorption of Small Molecules on Cu3(btc)2 and Cu3-xZnx(btc)2 Metal-Organic Frameworks (MOF) As Studied by Solid-State NMR"
        J. Phys. Chem. C 2013, 117, 7703-7712.
         

         

        A.V. Kuttatheyil, D. Lässig, J. Lincke, M. Kobalz, M. Baias, K. König, J. Hofmann, H. Krautscheid, C.J. Pickard, J. Haase, M. Bertmer
        "Synthesis, Crystal Structure, and Solid-State NMR Investigations of Heteronuclear Zn/Co Coordination Networks — A Comparative Study"
        Inorg. Chem. 2013, 52, 4431-4442.
         

         

        Katharina Peikert, Frank Hoffmann and Michael Fröba
        "Amino Substituted Cu3(btc)2: A New Metal-Organic Framework with a Versatile Functionality"
        Chem. Commun. 2012, 48, 11196 - 11198.
         

         

        O. Kozachuk, K. Khaletskaya, M. Halbherr, A. Bétard, M. Meilikhov, R. S. Seidel, B. Jee, A. Pöppl, R. A. Fischer
        "Microporous Mixed-Metal Layer-Pillared [Zn1–xCux(bdc)(dabco)0.5] MOFs: Preparation and Characterization"
        Eur. J. Inorg. Chem. 2012, 1688-1695.
         

         

        J. Lincke, D. Lässig, K. Stein, J. Moellmer, A. V. Kuttatheyil, C. Reichenbach, A. Moeller, R. Staudt, G. Kalies, M. Bertmer, H. Krautscheid
        "A novel Zn4O-based triazolyl benzoate MOF: synthesis, crystal structure, adsorption properties and solid state 13C NMR investigations"
        Dalton Trans. 2012, 41, 817-824.
         

         

        F. Gul-E-Noor, B. Jee, M. Mendt, D. Himsl, A. Pöppl, M. Hartmann, J. Haase, H. Krautscheid, M. Bertmer
        "Formation of Mixed Metal Cu3-xZnx(btc)2 Frameworks with Different Zinc Contents: Incorporation of Zn2+ into the Metal-Organic Framework Structure as Studied by Sold-State NMR"
        J. Phys. Chem. C 2012, 116, 20866-20873.
         

         

        F. Gul-E-Noor, B. Jee, A. Pöppl, M. Hartmann, D. Himsl, M. Bertmer
        "Effects of varying water adsorption on a Cu3(BTC)2 metal–organic framework (MOF) as studied by 1H and 13C solid-state NMR spectroscopy"
        Phys. Chem. Chem. Phys. 2011, 13, 7783 - 7788.
         

         

        B. Jee, K. Koch, L. Moschkowitz, D. Himsl, M. Hartman, A. Pöppl
        "Electron Spin Resonance Study of Nitroxide Radical Adsorption at Cupric Ions in the Metal-Organic Framework Compound Cu3(btc)2"
        J. Phys. Chem. Lett. 2011, 2, 357 – 361.
         

         

        M. Meilikhov, K. Yusenko, A. Torrisi, B. Jee, C. Mellot-Draznieks, A. Pöppl, R. A. Fischer
        "Reduction of a Metal–Organic Framework by an Organometallic Complex: Magnetic Properties and Structure of the Inclusion Compound [5-C5H5)2Co]0.5@MIL-47(V)"
        Angew. Chem. Int. 2010, Ed. 49, 6212-6215.
         

         

        B. Jee, K. Eisinger, F. Gul-E-Noor, M. Bertmer, M. Hartmann, D. Himsl, A. Pöppl
        "Continuous Wave and Pulsed Electron Spin Resonance Spectroscopy of Paramagnetic Framework Cupric Ions in the Zn(II) Doped Porous Coordination Polymer Cu3-xZnx(btc)2"
        J. Phys. Chem. C 2010, 114,16630-16639.
         

         

        M. Mendt, B. Jee, N. Stock, T. Ahnfeldt, M. Hartmann, D. Himsl, A. Pöppl
        "Structural Phase Transitions and Thermal Hysteresis in the Metal-Organic Framework Compound MIL-53 As Studied by Electron Spin Resonance Spectroscopy"
        J. Phys. Chem. C 2010, 114, 19443–19451.
         

         

        B. Jee, D. Himsl, M. Icker, M. Hartmann, A. Pöppl
        "Untersuchungen zur chemischen Stabilität von Cu3(btc)2 (HKUST-1) durch N2-Adsorption, Röntgenpulverdiffraktometrie und EPR-Spektroskopie"
        Chemie Ingenieur Technik 2010, 82, No. 7.
         
 
 

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