Probing the water coordination of protein-targeted MRI contrast agents by pulsed ENDOR spectroscopy.

A novel methodology based on electron-nuclear double resonance (ENDOR) spectroscopy is used for the direct determination of the water coordination number (q) of gadolinium-based magnetic resonance imaging (MRI) contrast agents. Proton ENDOR spectra can be obtained at approximately physiological concentrations for metal complexes in frozen aqueous solutions either in the presence or absence of protein targets. It is shown that, depending on the structure of the co-ligand, the water hydration number of a complex in aqueous solution can be significantly different to when the complex is noncovalently bound to a protein. From the ENDOR spectra of the exchangeable protons, precise information on the metal-proton distance can be derived as well. These essential parameters directly correlate with the efficacy of MRI contrast agents and should therefore aid the development of novel, highly efficient compounds targeted to various proteins.     

Substituent control of hydrogen bonding in palladium(II)-pyrazole complexes

Inter- and intramolecular hydrogen bonding of an N-H group in pyrazole complexes was studied using ligands with two different groups at pyrazole C-3 and C-5. At C-5, groups such as methyl, i-propyl, phenyl, or tert-butyl were present. At C-3, side chains L-CH(2)- and L-CH(2)CH(2)- (L = thioether or phosphine) ensured formation of chelates to a cis-dichloropalladium(II) fragment through side-chain atom L and the pyrazole nitrogen closest to the side chain. The significance of the ligands is that by placing a ligating side chain on a ring carbon (C-3), rather than on a ring nitrogen, the ring nitrogen not bound to the metal and its attached proton are available for hydrogen bonding. As desired, seven chelate complexes examined by X-ray diffraction all showed intramolecular hydrogen bonding between the pyrazole N-H and a chloride ligand in the cis position. In addition, however, intermolecular hydrogen bonding could be controlled by the substituent at C-5: complexes with either a methyl at C-5 or no substituent there showed significant intermolecular hydrogen bonding interactions, which were completely avoided by placing a tert-butyl group at C-5. The acidity of two complexes in acetonitrile solutions was estimated to be closer to that of pyridinium ion than those of imidazolium or triethylammonium ions.     

Fixed points and matching points in partitions

The Ramanujan Journal - We study fixed points in integer partitions viewed, respectively, as weakly increasing or weakly decreasing structures. A fixed point is a point with value i in position i....     

Der Systembegriff der Kontrolltheorie und Regel-Relative

To characterize E. D. Sontag’s system of axioms for control-systems in a more operative manner we consider an equivalent algebraic structure, which we name Regel- Relative.     

Spectroscopy of excited state positronium

Electric dipole transitions in the microwave range have been induced between the fine-structure levels of positronium in the excited staten=2. As an indication of the transitions, we used the increase in Lyman- radiation when the metastable 2³S₁-level is depopulated. The results for the transitions 2³S₁2³P_0,1,2 are ₀=18499.65±1.20±4.00 MHz, ₁=13012.42 ±0.65±1.54 MHz and ₂=8624.38±0.54±1.40 MHz. The first error is statistical and the second systematic. The precision of the present measurement has improved by a factor of 3, compared to previous data. Recent bound state QED-calculations have been extended to the orderR _t8 ⁴ln ^–1. The not yet completely calculated orderR _t8 ⁴ is estimated to contribute less than 1 MHz. Our experimental results are in good agreement with theory. By applying a weak magnetic field, we were able to observe the transition 2³S₁2¹P₁ which is strictly forbidden byC-invariance in zero field. Our result, corrected for Zeeman- and motional Starkeffect, is ₃=11180.0±5.0±4.0 MHz. An upper limit for theC-violating matrix element of MHz could be deduced. Our experiment used moderated slow positrons from the bremsstrahlung and pair production of a pulsed electron linear accelerator (TEPOS facility at the university of Giessen).