UV photolysis of catalase revisited: a spectral study of photolytic intermediates

The 365-nm irradiation of 4.6 microM (approximately equal to 1.1 mg/ml) catalase solutions in pH 7.4 phosphate buffer induces spectral modifications. Difference spectra show maxima at 434, 555, 584 nm at the beginning of the irradiation, then a final spectrum with a maximum at 568 nm and a shoulder at 530 nm is observed. These results suggest the formation of compound III (oxyferrous catalase) and compound II, respectively. In deaerated 0.1 M, pH 8.7 borate buffer, the ferrous catalase is characterized by maxima at 563 and 594 nm. Hydrogen donors such as ethyl alcohol, formate and p-cresol inhibit, but citrate ions enhance the formation of these intermediates. A mechanism involving Fe(III) reduction according to an internal electron transfer is proposed.     

Multichannel digital transmission in an optical network of communicating molecules

In present telecommunication networks, information transfer relies on the interplay of optical and electrical signals. Data are communicated optically but processed electronically. Methods to maintain the propagating signals solely at the optical level must be developed to overcome the transmission capacities and speed limits imposed by the electronic components. We have demonstrated that molecular switches can be used to gate optical signals in response to optical signals. We have realized a simple optical network consisting of three light sources, one cell containing a solution of three fluorescent molecules, one cell containing a solution of a three-state molecular switch and a detector. The light emitted by the three fluorophores is absorbed by the three states of the molecular switch. Using this simple operating principle, we have shown that multichannel digital transmission can be implemented on an ensemble of communicating molecules relying exclusively on the interplay of optical inputs and optical outputs.     

Bioaccumulation of vanadium in the epiphytic lichen Parmelia caperata from Liguria (north-west Italy)

The concentration of vanadium was measured in 35 samples of the epiphytic lichen Parmelia caperata collected along the coast of the Ligurian Sea (Italy), in order to detect the possible bioaccumulation of vanadium due to a huge crude oil burning occurred in that area in 1991. The cartographic elaboration of data shows a pattern of distribution of vanadium concentrations according to different degrees of deviation from background condition, showing that 8 years later memory of the accident is still detectable in foliose lichen thalli.     

Solid products and rate-limiting step in the thermal half decomposition of natural dolomite in a CO2 (g) atmosphere

Natural dolomite powders obtained from caves which give unusual high resistance building materials, have been decomposed in a Knudsen cell at high CO₂ pressures in the temperature range of 913-973 K. XRD traces for the final solid products, after the first half thermal decomposition, have shown, that beside the XRD patterns for the calcite and MgO, the existence of a new structure with major peaks at 2θ equal to 38.5 and 65°. This finding has been ascribed to a solid solution of MgO in calcite. The kinetic analysis of the TG curves yield a total apparent enthalpy (ΔH^∗) for the decomposition equal to 440±10 kJ mol⁻¹ for a range of fraction decomposed (α) varying between 0.2 and 0.7. This value is much closer to the theoretical expected at 950 K value ΔH=486 kJ mol⁻¹ for the dolomite decomposition in CO₂ environment, where CaO, MgO and oxides of solid solution can be the solid reaction products. The rate determining step is the transport of CO₂ across the reacting interface through an high activated thermal process due to solid state diffusion of CO₃²⁻ in the bulk and/or the grain boundaries phases of CaCO₃ and/or of the solid solution. The microstructure evolution of the solid products follows a shear-transformation mechanism. At temperatures below 943 K, porous product particles are characterized by a monomodal narrow pore size distribution around 0.05 μm. At higher temperatures, a critical level of tensions inside the particles is reached and a bimodal pore size distribution around 1 and 0.05 μm is formed.     

An approximation result for the interval coloring problem on claw-free chordal graphs

We study the problem of finding an acyclic orientation of an undirected graph, such that each (oriented) path is covered by a limited number k of maximal cliques. This is equivalent to finding a k-approximate solution for the interval coloring problem on a graph. We focus our attention on claw-free chordal graphs, and show how to find an orientation of such a graph in linear time, which guarantees that each path is covered by at most two maximal cliques. This extends previous published results on other graph classes where stronger assumptions were made.     

Positive ion chemistry of SiH4/GeF4 gaseous mixtures studied by ion trap mass spectrometry and ab initio calculations

The positive ion chemistry occurring in SiH(4)/GeF(4) gaseous mixtures was investigated by ion trap mass spectrometry and ab initio theoretical calculations. The GeF(3)(+) cation, the only fragment obtained from ionized GeF(4), was unreactive towards SiH(4). All the primary ions SiH(n)(+) (n = 0-3) react instead with GeF(4) so to form SiF(+) or SiH(2)F(+). The latter species reacts in turn with SiH(4) and GeF(4) so to form SiH(3)(+) and SiHF(2)(+), respectively. The potential energy profiles conceivably involved in these reactions were investigated by ab initio calculations performed at the MP2 and coupled cluster (CCSD(T)) level of theory.