DNA interaction of platinum(II) complexes with 1,10-phenanthroline and extended phenanthrolines

The interaction with DNA of the platinum(II) square planar complexes [Pt(N-N)(py)(2)](2+) (N-N = 1,10-phenanthroline (phen), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq), dipyrido[3,2-a:2',3'-c]phenazine (dppz), benzodipyrido[b:3,2-h:2'3'-f]phenazine (bdppz)) has been investigated by means of absorption, circular and linear dichroism spectroscopy, DNA melting, and viscosity. In the presence of excess [DNA] all the complexes intercalate to the double helix. For those with the most extended phenanthrolines the binding mode depends on the [DNA]/[complex] ratio (q); at low q values the substances bind externally to DNA probably self-aggregating along the double helix. When the DNA concentration is large enough, the aggregate breaks up and the complex intercalates within the nucleobases. The complexes self-aggregate, without added DNA, in the presence of a large salt concentration.     

Myoglobin modification by enzyme-generated dopamine reactive species

The generation of reactive quinone species (DAQ) from oxidation of dopamine (DA) is involved in neurodegenerative pathologies like Parkinson's disease (A. Borta, G. U. H?glinger, J. Neurochem. 2007, 100, 587-595). The oxidation of DA to DAQ can occur either in a single two-electron process or in two consecutive one-electron steps, through semiquinone radicals, giving rise to different patterns of reactions. The former type of reaction can be promoted by tyrosinase, the latter by peroxidases in the presence of H(2)O(2), which can be formed under oxidative stress conditions. Both enzymes were employed for the characterization of the thiol-catechol adducts formed by reaction of DA and cysteine or glutathione, and for the identification of specific amino acid residues modified by DAQs in two representative target proteins, human and horse heart myoglobin. Our results indicate that the cysteinyl-DA adducts are formed from the same quinone intermediate independently of the mechanism of DA oxidation, and that the hallmark of a radical mechanism is the formation of the cystine dimer. The reactivity of quinone species also controls the DA-promoted derivatization of histidine residues in proteins. However, for the modification of the cysteine residue in human myoglobin, a radical intramolecular mechanism has been proposed, in which the protein acts both as the catalyst and target of the reaction. Most importantly, the modification of myoglobins through DAQ linkages, and in particular by DA oligomers, has dramatic effects on their stability, as it induces protein unfolding and incorporation into insoluble melanic precipitates.     

Enhanced downconversion of UV light by resonant scattering of aluminum nanoparticles

Metallic nanoparticles are known to enhance nonlinear optical processes due to a local enhancement of the optical field. This strategy has been proposed to enhance downconversion in thin film solar cells, but has various disadvantages, among which is the fact that the enhancement occurs only in a tiny volume close to the particles. We report on a very different physical mechanism that can lead to significant downconversion enhancement, namely, that of resonant light scattering, and which is a large volume effect. We show that only a tiny amount of resonantly scattering metallic (aluminum) nanoparticles is enough to create a significant enhancement of the fluorescence of dye molecules in the visible wavelength range. The strategy can be applied in general to increase the emission of UV-absorbing constituents, and is of particular use for solar energy.     

Modeling of waveguide UV-induced Bragg gratings with arbitrary apodization function: Tools for designing high-performance related devices

We present a semi-analytical modeling suitable for the investigation of the spectral characteristics of UV-waveguide Bragg gratings (UV-WBGs) having arbitrary apodization function and extending both in the film layer and in the overlayer. The modeling is based on a proper combination of coupled mode theory and transfer matrix formalism and provides a powerful tool for designing and simulation of complex UV-grating based structures. The results of a detailed investigation of UV-WBGs in doped silica based channel optical waveguides are presented and critical issues for upgrading the performances of related device are discussed. Validation of the modeling is provided by means of an extensive comparison between theoretical and experimental results relevant to UV-WBGs realized in phosphorous (P)- and boron (B)-doped silica based waveguides.     

Liquid-liquid phase separation of a surfactant-solubilized membrane protein

Solubilization of membrane proteins requires surfactants, whose structural properties play a crucial role in determining the protein phase behavior. We show that ionization of a pH-sensitive surfactant, lauryldymethylamino-N-oxide, bound to the bacterial photosynthetic Reaction Center, induces protein phase segregation in micrometric "droplets." Liquid-liquid phase separation takes place in a narrow pH range, is promoted by increasing temperature, and vanishes by adding salt. After a fast initial droplet growth, the nearly arrested kinetics at a later stage leaves the system in a finely divided, long-lasting emulsified state.