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
Final Report Abstract
The first project phase was devoted to the synthesis, spectroscopic characterization, and evaluation of the magnetic properties of selected molecular framework materials. Particular emphasis was placed on studying and tailoring the guest-dependent magnetic properties. It was shown that ESR and NMR spectroscopy can be employed synergetically, for the one being susceptible to paramagnetic, the other for diamagnetic systems. The different strategies proposed have successfully been employed in order to modulate the magnetic exchange interaction between the metallic connectors with the aim to tune the macroscopic collaborative magnetic properties of the materials under study. 1) Materials with similar structure but variable composition, e.g. (CuZn)3(btc)2, Al/Cr-Mil-53 and Al/V-MIL-53) have been prepared in order to achieve magnetic dilution. 2) Diamagnetic guest molecules (H2O, NH3, CH3OH and CO) were adsorbed onto the materials in order study the host/guest interaction of magnetically diluted materials in comparison to the parent sample. 3) Finally, the properties of the magnetic MOFs were modified by interaction with electron-donating (Cobaltocene, CoCp2) and paramagnetic guest such as di-tert-butyl nitroxide and nitric oxide. These studies confirmed that electron transfer from the guest molecules to the metal organic framework is indeed possible resulting in a reduction of the vanadium atoms in MIL-47 and a concomitant oxidation of cobaltocene. Adsorption studies of DTBN revealed interesting magnetic coupling phenomena between the paramagnetic adsorbate and the Cu(II) framework ion in Cu3(btc)2 which are subject to further studies in the remaining time of the project. Moreover, NO has been identified as candidate for further studies aiming at exploring the fundamental interaction with MOF framework ions as well as storage and release with respect to biomedical applications.
Publications
- Adsorptive Separation of Isobutene and Isobutane, Langmuir 2008, 24, 8634 - 8642
M. Hartmann, S. Kunz, D. Himsl, O. Tangermann
- Cw and Pulsed ESR Spectroscopy of Cupric Ions in the Metal-Organic Framework Compound Cu3(BTC)2, J. Phys. Chem. C 2008, 112, 2678 - 2684
A. Pöppl, S. Kunz, D. Himsl, M. Hartmann
- Improving the Hydrogen Adsorption Properties of a Hydroxy Modified MIL 53(Al) structural analogue by Lithium Doping, Angew. Chem. Int. Ed. 2009, 48, 4639 - 4642
D. Himsl, D. Wallacher, M. Hartmann
- Cw and Pulsed ESR Spectroscopy of Paramagnetic Framework Cupric Ions in the Zn(II) Doped Porous Coordination Polymer Cu1-xZnx(btc)2, J. Phys. Chem. C 2010, 114, 16630 - 16639
B. Jee, K. Eisinger, F. Gul-E-Noor, M. Bertmer, M. Hartmann, D. Himsl, A. Pöppl
- Reduction of a Metal-Organic Framework by an Organometallic Complex: Magnetic Properties and Structure of the Inclusion Compound [(η5-C5H5)2Co]0.5@MIL-47(V), Angew. Chem. Int. Ed. 2010, 49, 6212 - 6215
M. Meilikhov, K. Yusenko, A. Torrisi, B. Jee, C. Mellot-Draznieks, A. Pöppl, R. A. Fischer
- 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
M. Mendt, B. Jee, N. Stock, T. Ahnfeldt, M. Hartmann, D. Himsl, A. Pöppl
- Untersuchungen zur chemischen Stabilität von Cu3(btc)2 (HKUST-1) durch N2-Adsorption, Röntgenpulverdiffraktometrie und ESR-Spektroskopie, Chemie Ingenieur Technik 2010, 82, 1025 - 1029
B. Jee, D. Himsl, M. Icker, M. Hartmann, A. Pöppl
