Matthias J.N.Junk's Assessing the Functional Structure of Molecular Transporters PDF

By Matthias J.N.Junk

ISBN-10: 364225134X

ISBN-13: 9783642251344

ISBN-10: 3642251358

ISBN-13: 9783642251351

In his thesis, Matthias Junk takes an leading edge method of investigate the neighborhood constitution and dynamics of organic and artificial amphiphilic macromolecules able to transporting small molecules. exchanging the latter with reliable radicals, he makes use of cutting-edge electron paramagnetic resonance (EPR) spectroscopy to explain the hugely appropriate shipping functionality from the point of view of the visitor molecules. Such, he demonstrates that the practical constitution of human serum albumin in resolution considerably differs from its crystal constitution – a outcome of the protein’s adaptability to host quite a few endogenous compounds and drug molecules. extra, he exhibits that the thermal cave in of thermoresponsive hydrogels and dendronized polymers results in static and dynamic heterogeneities at the nanoscale. those heterogeneities endure outcomes for the material’s internet hosting homes and allow unexpected complicated catalytic functionalities.

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Extra info for Assessing the Functional Structure of Molecular Transporters by EPR Spectroscopy

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11 Definition of the molecular coordinate system of nitroxides and hypothetical spectra for orientations along the principal axes. Collinear g and A tensors with principal values gxx ¼ 2:0087; gyy ¼ 2:0065; gzz ¼ 2:0023 and Axx ¼ Ayy ¼ 18:2 MHz; Azz ¼ 100:9 MHz were assumed. g. due to chemical attachment), an anisotropy has to be introduced to the Brownian motion. In case of a fast rotation about one axis and a slower rotation about directions perpendicular to that axis, the rotational diffusion coefficient can be expressed in its principal axes frame by [40, 45] 0 1 D?

B A stabilization of the zwitterionic resonance structure causes an increase of the spin density at the nitrogen atom. The combined effects lead to a decrease of giso and to an increase of aiso In the rigid limit, the orientations of the paramagnetic molecules are static. In this case, the positions, intensities and widths of all resonance lines are computed for each orientation by modeling the energy level diagram [55]. 8 Time Evolution of Spin Ensembles Although a CW EPR spectrum is influenced by all magnetic interactions of the spin Hamiltonian, only few dominating interactions are sufficiently resolved for an accurate analysis.

1 g Anisotropy As stated in Sect. 3, the Electron-Zeeman interaction depends on the absolute orientation of the molecule with respect to the external magnetic field. 4 Anisotropy in EPR Spectra 21 Fig. 5 Definition of the elevation angle h and the azimuth u in a unit sphere depicting the molecular coordinate system (collinear to the principal elements of the diagonalized g tensor, gxx ; gyy ; and gzz Þ and the magnetic field vector B0 z B0 y x The orientation of the molecule can be characterized by the elevation angle h and the azimuth u of a spherical coordinate system.

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Assessing the Functional Structure of Molecular Transporters by EPR Spectroscopy by Matthias J.N.Junk

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