NMR in single crystal metallic ferromagnets: GdAl2

Necessary conditions to observe NMR in wall-free metallic single crystal ferromagnets are formulated. ²⁷Al NMR study in a magnetized single crystal GdAl₂ confirms the validity of the preconditions. Improved resolution and control over orientation, both inherent to single crystal study, enable for the first time an angular dependent NMR measurement of hyperfine interaction in metallic ferromagnetic system. The significance of the measured hyperfine tensor $\text{A}\text{?}\text{(A}{}_{\mathrm{\chi \chi }}\text{/λ}\text{h}\text{?}\text{= A}{}_{\mathrm{yy}}\text{/λ}\text{h}\text{?}\text{= - 14.825}\text{kG}$; $\text{A}{}_{\mathrm{zz}}\text{/gl}\text{h}\text{?}\text{= - 15.313}\text{kG}$) is briefly discussed.     

Rearrangement of Aryl Geranyl Ethers

This article describes the thermal rearrangement reactions of aryl geranyl ethers. These reactions depend on the structure of the aryl moiety of the substrate and the reaction conditions used. The naphthyl ethers underwent a [1,3]-alkyl shift, followed by acid-catalyzed intramolecular cyclization. The microwave-assisted rearrangement of isoquinolinyl ether showed a pattern of an abnormal Claisen rearrangement. The multi step rearrangement of the quinolyl ether afforded a spiro compound. These new reactions were used to synthesize novel heterocyclic compounds.     

Über gewisse Verallgemeinerungen des Landauschen und des Schottkyschen Satzes

Ohne Zusammenfassung     

Comparison of the efficiency and the specificity of DNA-bound and free cationic porphyrin in photodynamic virus inactivation

The risk of transmitting infections by blood transfusion has been substantially reduced. However, alternative methods for inactivation of pathogens in blood and its components are needed. Application of photoactivated cationic porphyrins can offer an approach to remove non-enveloped viruses from aqueous media. Here we tested the virus inactivation capability of meso-Tetrakis(4-N-methylpyridyl)porphyrin (TMPyP) and meso-Tri-(4-N-methylpyridyl)monophenylporphyrin (TMPyMPP) in the dark and upon irradiation. T7 bacteriophage, as a surrogate on non-enveloped viruses was selected as a test system. TMPyP and TMPyMPP reduce the viability of T7 phage already in the dark, which can be explained by their selective binding to nucleic acid. Both compounds proved to be efficient photosensitizers of virus inactivation. The binding of porphyrin to phage DNA was not a prerequisite of phage photosensitization, moreover, photoinactivation was more efficiently induced by free than by DNA bound porphyrin. As optical melting studies and agarose gel electrophoresis of T7 nucleoprotein revealed, photoreactions of TMPyP and TMPyMPP affect the structural integrity of DNA and also of viral proteins, despite their selective DNA binding.     

Palladium-catalyzed amination of quinaldine-5-triflate

Palladium-catalyzed amination reactions of quinoline triflate and the effect of a Pd catalyst, its ligands, solvents, bases, and temperature were studied. This method facilitated an easier pathway for the preparation of aminoquinoline derivatives as potential precursors of new serotoninerg agents.      

Minimizing the Stabbing Number of Matchings, Trees, and Triangulations

The (axis-parallel) stabbing number of a given set of line segments is the maximum number of segments that can be intersected by any one (axis-parallel) line. This paper deals with finding perfect matchings, spanning trees, or triangulations of minimum stabbing number for a given set of vertices. The complexity of finding a spanning tree of minimum stabbing number is one of the original 30 questions on “The Open Problems Project” list of outstanding problems in computational geometry by Demaine, Mitchell, and O’Rourke. We show -hardness of stabbing problems by means of a general proof technique. For matchings, this also implies a nontrivial lower bound on the approximability. On the positive side, we propose a cut-based integer programming formulation for minimizing the stabbing number of matchings and spanning trees. From the corresponding linear programming relaxation we obtain polynomial-time lower bounds and show that there always is an optimal fractional solution that contains an edge of at least constant weight. We conjecture that the resulting iterated rounding scheme constitutes a constant-factor approximation algorithm. An extended abstract appeared in the Proceedings of the 15th ACM-SIAM Symposium on Discrete Algorithms [11]. M.E. Lübbecke visits to Kingston and Stony Brook were supported by a DFG travel grant. H. Meijer partially supported by NSERC while visiting Braunschweig in 2002.     

Complex formation processes of terminally protected peptides containing two or three histidyl residues. Characterization of the mixed metal complexes of peptides

Copper(ii), nickel(ii) and zinc(ii) complexes of the peptides Ac-HVVH-NH(2) and Ac-HAAHVVH-NH(2) have been studied by potentiometric, UV-vis, CD, EPR and NMR spectroscopic measurements. Both tetra and heptapeptides can form relatively stable macrochelates with copper(ii), nickel(ii) and zinc(ii) ions, in which the ligands are coordinated via the side-chain imidazole functions. Formation of the macrochelates slightly suppresses, but cannot prevent the copper(ii) and nickel(ii) ion promoted deprotonation and coordination of the amide functionalities. The overall stoichiometry of the major species is [MH(-3)L](-) with a 4N (= N(-),N(-),N(-),N(im)) coordination mode. In the case of Ac-HAAHVVH-NH(2), coordination isomers of this species can exist with a preference for copper(ii) or nickel(ii) binding at the internal histidyl residue. In the copper(ii)-Ac-HAAHVVH-NH(2) system, the presence of the two anchoring sites results in the formation of dinuclear complexes. The existence of these species requires the involvement of amide functions in metal binding. Both equilibrium and spectroscopic data support the fact that the copper(ii) ions of the dinuclear species are independent from each other providing a good chance for the formation of various mixed metal complexes. It was found that zinc(ii) is not able to significantly alter the copper(ii) binding of the heptapeptide, but it can occupy the uncoordinated histidyl sites. The formation of the copper(ii)-nickel(ii) mixed species was obtained in alkaline solutions and CD spectra suggest the statistical distribution of the two metal ions among the histidyl residues. The binding of HAAHVVH to palladium(ii) is exclusive below pH 8 and the mixed metal species of palladium(ii) and copper(ii) ions are formed only in slightly basic solutions.     

Interaction of Cu(II) and Ni(II) with the 63-93 fragment of histone H2B

Chromatin proteins are believed to represent reactive sites for metal ion binding. We have synthesized the 31 amino acid peptide Ac-NSFVNDIFERIAGEASRLAHYNKRSTITSRE-NH2, corresponding to the 63-93 fragment of the histone H2B and studied its interaction with Cu(II) and Ni(II). Potentiometric and spectroscopic studies (UV-vis, CD, NMR and EPR) showed that histidine 21 acts as an anchoring binding site for the metal ion. Complexation of the studied peptide with Cu(II) starts at pH 4 with the formation of the monodentate species CuH2L. At physiological pH values, the 3N complex (N(Im), 2N(-)), CuL is favoured while at basic pH values the 4N (N(Im), 3N(-)) coordination mode is preferred. Ni(II) forms several complexes with the peptide starting from the distorted octahedral NiH2L at about neutral pH, to a square planar complex where the peptide is bound through a (N(Im), 3N(-)) mode in an equatorial plane at basic pH values. These results could be important in revealing more information about the mechanism of metal induced toxicity and carcinogenesis.     

Tailoring GaN semiconductor surfaces with biomolecules

Functionalization of semiconductors constitutes a crucial step in using these materials for various electronic, photonic, biomedical, and sensing applications. Within the various possible approaches, selection of material-binding biomolecules from a random biological library, based on the natural recognition of proteins or peptides toward specific material, offers many advantages, most notably biocompatibility. Here we report on the selective functionalization of GaN, an important semiconductor that has found broad uses in the past decade due to its efficient electroluminescence and pronounced chemical stability. A 12-mer peptide ("GaN_probe") with specific recognition for GaN has evolved. The subtle interplay of mostly nonpolar hydrophobic and some polar amino acidic residues defines the high affinity adhesion properties of the peptide. The interaction forces between the peptide and GaN are quantified, and the hydrophobic domain of the GaN_probe is identified as primordial for the binding specificity. These nanosized binding blocks are further used for controlled placement of biotin-streptavidin complexes on the GaN surface. Thus, the controlled grow of a new, patterned inorganic-organic hybrid material is achieved. Tailoring of GaN by biological molecules can lead to a new class of nanostructured semiconductor-based devices.