Porous Capsules' Interactions with Corks and Simultaneously Smaller Entering Cations: Sphere Surface Supramolecular Chemistry and Modeling Biological Cation Transport - Novel Synthetic and NMR Studies
Final Report Abstract
Polyoxometalates (POM) have been well known for many years; they are usually characterized in great detail as solids by X-Ray spectrometry, yielding chemically (and esthetically) interesting compounds. In previous studies we had learned that the well defined situation in the solid state is not necessarily reflected in solution. Escpecially small cations like Li+, Na+ etc. are permanently in slow exchange conditions in solutions of various solvents. The project was designed to obtain more profound insight into these processes, to establish methods for the reliable determination of ingredients inside and outside of the capsule, and to find out about the spectrum of molecules and external parameters which are responsible for the various processes with respect to possible applications. The main target were unique molybdenum oxide-based porous capsules, ball type molecules abbreviated Mo132 (ingredients). Because the interior of these capsules can be designed synthetically by applying a broad selection of linkers, e.g., various organic moieties, these compounds open up a playground for numerous studies under largely varied conditions. NMR has turned out to be the method of choice to get access to a surprising number of various exchange reactions, leading to the conclusion, that, commonly in solution, there are always dynamical processes, including some flexibility in the pore size, meanings that – unlike in the solid state – there are no well-defined conditions (atom positions). Surprising results could be obtained when the capsules were investigated in a medium containing small organic molecules, such as hexanol up to decanol or various carbon chain aldehydes. Depending on the size and nature of the organic molecule, different situations could be pictured. Finally, we have been able to demonstrate that, using the correct conditions, the capsules can extract CO2 from the environment, easily fixing ca. 30 molecules of CO2 per one capsule.
Publications
- Mimicking Biological Cation-Transport Based on Sphere-Surface Supramolecular Chemistry: Simultaneous Interaction of
Porous Capsules with Molecular Plugs and Passing Cations.
Chemistry - A European Journal, Vol. 13. 2007, Issue 27, pp. 7650–7658.
A. Merca, E.T.K. Haupt, T. Mitra, H. Bögge, D. Rehder, A. Müller
(See online at https://dx.doi.org/10.1002/chem.200700294) - Cation behavior at an artificial cell interface: binding distinguished by ion hydration energetics and size.
J.C.S. Chemical Communications, Issue 8. 2008, pp. 948-950.
A. Merca, H. Bögge, M. Schmidtmann, Y. Zhou, E.T.K. Haupt, M. K. Sarker, C.L. Hill, A. Müller
(See online at https://dx.doi.org/10.1039/B718260K) - Cellular cation transport by porous nano-capsules based on polyoxomolybdates, modelled by 6/7Li and 23Na NMR.
Magnetic Resonance in Chemistry, Vol. 46. 2008, Issue S1, pp. S24–S29.
D. Rehder, E.T.K. Haupt, A. Müller
(See online at https://dx.doi.org/10.1002/mrc.2343) - Confinement and Step-Wise Reopening of Channels in an Artificial Cell/Inorganic Capsule: A 7Li NMR Study.
Chemistry - A European Journal, Vol. 14. 2008, Issue 29, pp. 8808–8811.
E.T.K. Haupt, C. Wontorra, D. Rehder, A. Merca, A. Müller
(See online at https://dx.doi.org/10.1002/chem.200801122) - A Spherical Butyrate 24 Aggregate with a Hydrophobic Cavity in a Capsule with Flexible Pores: Confinement Effects and
Uptake-Release Equilibria at Elevated Temperature.
Angewandte Chemie, Vol.121. 2009, Issue 43, pp. 8195–8200.
Angewandte Chemie International Edition, Volume 48. 2009, Issue 43, pp. 8051–8056.
Ch. Schäffer, H. Bögge, A. Merca, I.A. Weinstock, D. Rehder, E.T.K. Haupt, A. Müller
(See online at https://dx.doi.org/10.1002/ange.200903910) - Guests on Different Internal Capsule Sites Exchange with Each Other and with the Outside. Angewandte Chemie, Vol. 123. 2011, Issue 2, pp. 430–434. Angewandte Chemie International Edition, Vol. 50. 2011, Issue 2, pp. 410–414.
O. Petina, D. Rehder, E.T.K. Haupt, A. Grego, I.A. Weinstock, A. Merca, H. Bögge, J. Szakacs, A. Müller
(See online at https://dx.doi.org/10.1002/ange.201005596) - Hydrophobic Interactions and Clustering in a Porous Capsule: Option To Remove Hydrophobic Materials from Water.
Chemistry - A European Journal, Vol. 17. 2011, Issue 35, pp. 9634–9639.
Ch. Schäffer; A. M. Todea; H. Bögge; O. A. Petina; D. Rehder; E.T.K. Haupt; A. Müller
(See online at https://dx.doi.org/10.1002/chem.201101454) - Picking up 30 CO2 Molecules by a Porous Metal Oxide Capsule Based on the Same Number of Receptors.
Angewandte Chemie, Vol. 124. 2012, Issue 42, pp. 10680–10683.
Angewandte Chemie International Edition, Vol. 51. 2012, Issue 42, pp. 10528–10531.
S. Garai, E.T.K. Haupt, H. Bögge, A. Merca, A. Müller
(See online at https://dx.doi.org/10.1002/ange.201204089)
