Trinuclear nickel complexes with triplesalen ligands: simultaneous occurrence of mixed valence and valence tautomerism in the oxidized species

The coordination chemistries of the triple tetradentate triplesalen ligands H(6)talen, H(6)talen(t)(-)(Bu)(2), and H(6)talen(NO)(2) have been investigated with nickel(II). These triplesalen ligands provide three salen-like coordination environments bridged in a meta-phenylene arrangement by a phloroglucinol backbone. The structures of the complexes [(talen)Ni(II)(3)], [(talen(t)(-)(Bu)(2)Ni(II)(3)], and [(talen(NO)(2)Ni(II)(3)] have been determined by single-crystal X-ray diffraction. All three compounds are composed of neutral trinuclear complexes with square-planar coordinated Ni(II) ions in a salen-like coordination environment. Whereas the overall molecular structure of [(talen(NO)(2)Ni(II)(3)] is nearly planar, the structures of [(talen)Ni(II)(3)] and [(talen(t)(-)(Bu)(2)Ni(II)(3)] are bowl-shaped as a result of ligand folding. The strongest ligand folding occurs at the central nickel-phenolate bond of [(talen(t)(-)(Bu)(2)Ni(II)(3)], resulting in the formation of a chiral hemispherical pocket. The dependence of the physical properties by the substituents on the terminal phenolates has been studied by FTIR, resonance Raman, UV-vis-NIR absorption, and electrochemistry. The three nickel-salen subunits are electronically interacting via the pi system of the bridging phloroglucinol backbone. The strength of this interaction is mediated by two opposing effects: the electron density at the terminal phenolates and the folding of the ligand at the central phenolates. The parent complex [(talen)Ni(II)(3)] is irreversibly oxidized at 0.32 V versus ferrocenium/ferrocene (Fc(+)/Fc), whereas [(talen(t)(-)(Bu)2)Ni(II)(3)] and [(talen(NO)(2)Ni(II)(3)] exhibit reversible oxidations at 0.22 V versus Fc(+)/Fc and 0.52 V versus Fc(+)/Fc, respectively. The oxidized species [(talen(t)(-)(Bu)(2)Ni(3)](+) and [(talen(NO)(2)Ni(3)](+) undergo a valence-tautomeric transformation involving a Ni(III) and a phenoxyl radical species, as observed by EPR spectroscopy. Thus, these oxidized forms exhibit the phenomena of valence tautomerism and mixed valence simultaneously. The extent of delocalization of the radical species and of the Ni(III) species is discussed.     

Electrochemical and spectroscopic investigations of immobilized de novo designed heme proteins on metal electrodes.

On the basis of rational design principles, template-assisted four-helix-bundle proteins that include two histidines for coordinative binding of a heme were synthesized. Spectroscopic and thermodynamic characterization of the proteins in solution reveals the expected bis-histidine coordinated heme configuration. The proteins possess different binding domains on the top surfaces of the bundles to allow for electrostatic, covalent, and hydrophobic binding to metal electrodes. Electrostatic immobilization was achieved for proteins with lysine-rich binding domains (MOP-P) that adsorb to electrodes covered by self-assembled monolayers of mercaptopropionic acid, whereas cysteamine-based monolayers were employed for covalent attachment of proteins with cysteine residues in the binding domain (MOP-C). Immobilized proteins were studied by surface-enhanced resonance Raman (SERR) spectroscopy and electrochemical methods. For all proteins, immobilization causes a decrease in protein stability and a loosening of the helix packing, as reflected by a partial dissociation of a histidine ligand in the ferrous state and very low redox potentials. For the covalently attached MOP-C, the overall interfacial redox process involves the coupling of electron transfer and heme ligand dissociation, which was analyzed by time-resolved SERR spectroscopy. Electron transfer was found to be significantly slower for the mono-histidine-coordinated than for the bis-histidine-coordinated heme. For the latter, the formal heterogeneous electron-transfer rate constant of 13 s(-1) is similar to those reported for natural heme proteins with comparable electron-transfer distances, which indicates that covalently bound synthetic heme proteins provide efficient electronic communication with a metal electrode as a prerequisite for potential biotechnological applications.     

Competition between photobleaching and fluorescence increase of photosensitizing porphyrins and tetrasulphonated chloroaluminiumphthalocyanine

The time-dependent fluorescence changes of photosensitizing porphyrins and tetrasulphonated chloroaluminiumphthalocyanine (A1C1SPc) were measured at different intracellular sites using video-enhanced microscopy and image processing. To obtain variations in intracellular fluorescence intensity, different radiant exposures of a Kr+ laser-pumped dye laser were delivered via a 600 microns plastic-clad silica fibre connected to the microscope. During irradiation, competition between photobleaching and fluorescence increase of the different dyes was observed. The porphyrins normally showed photobleaching, which was dependent on the sensitizer and its specific accumulation within the cell. Photobleaching was less pronounced for hydrophilic uroporphyrin than for more hydrophobic dyes. In contrast with an almost exponential decrease in porphyrin fluorescence with increasing light dose, the fluorescence intensity of A1C1SPc significantly increased at the beginning of irradiation, and could be correlated with intracellular deaggregation.     

Optimal boundary regularity for minimal surfaces with a free boundary

Let x(w), w=u+iv B, be a minimal surface in ³ which is bounded by a configuration , S consisting of an arc and of a surface S with boundary. Suppose also that x(w) is area minimizing with respect to , S. Under appropriate regularity assumptions on and S, we can prove that the first derivatives of x(u, v) are Hölder continuous with the exponent =1/2 up to the free part of B which is mapped by x(w) into S. An example shows that this regularity result is optimal.     

Synthesis,spectral characterization and electrochemical properties of 1H-3-(o-, m- and p-ferrocenylphenyl)-1-phenylpyrazole-4-carboxaldehydes

New ferrocene derivatives – 1H-1-phenylpyrazole-4-carboxaldehydes containing o-, m- and p-ferrocenylphenyl group at position 3 – were synthesized and characterized. The electrochemical investigation showed that the position of the ferrocenyl group does not affect the redox potential of these compounds. The X-ray crystal structure of the ortho-derivative is also presented. The screening for the in vitro antimicrobial activity against eleven bacterial and three fungal/yeast strains exhibited complete inactivity of these aldehydes, but n-butyl imines of ortho and meta derivatives showed moderate activity compared to those of the used standards.