Synthesis and characterization of a new family of electroactive alkali metal doped mesoporous Nb, Ta, and Ti oxides and evidence for an Anderson transition in reduced mesoporous titanium oxide

Recently we reported that mesoporous niobium oxide can be chemically reduced by Na-naphthalene while fully retaining its mesostructure. This was the first report of a molecular sieve acting as a stoichiometric electron acceptor. Herein we expand on the initial work by presenting a detailed study on Li-, Na-, K-, Rb-, and Cs-reduced samples of mesoporous Nb oxide, as well as Li-reduced mesoporous Ta and Ti oxides. While the Nb- and Ta-based materials fully retained their structure on reduction as determined by X-ray diffraction (XRD) and nitrogen adsorption, the Li-reduced Ti material retained high surface area and narrow pore size distribution, but lost its diffraction pattern, indicating an increased level of disorder in this material. X-ray photoelectron spectroscopy (XPS) and UV-visible reflectance spectroscopy revealed that all reduced mesoporous oxides studied have a similar electronic structure, corresponding to the presence of a disordered impurity band in the material lying between the valence band and the conduction band. Electron paramagnetic resonance (EPR) studies suggest that the electron in this impurity level is unpaired and best described as a free electron, only loosely bound to the alkali or transition metal. SQUID magnetometry showed that all reduced materials are paramagnetic, further confirming the presence of unpaired electrons in the structure. All materials in this study were insulating with the exception of the Li-reduced mesoporous Ti material, which was highly conducting, possibly due to an Anderson transition. Electrochemical studies on the unreduced mesoporous oxides demonstrated that while the Ta and Nb materials are capacitors with only a small degree of reversible electrochemical behavior in the bulk sample, the Ti material was an electrical conductor with fully reversible redox behavior.     

Orotic acid: a milk constituent Enzymatic determination by means of a new microcalorimetric method

The presence of orotic acid (a precursor of nucleic acid) in milk is very important in order to ensure its nutritional value and good conservation. In the literature, chromatographic, spectrophotometric and polarographic methods are reviewed. The reported values have a very wide interval range (19-664 mg l(-1)) and a low precision. The new method proposed in this article employs an enzymatic reaction. It has been improved on standards and then tested on milk samples. The same samples were also tested by means of a known spectrophotometric method. The new analytical method for orotic acid determination is reliable; the results are more accurate and more precise if compared with the usual methods, and it shows the same sensibility. The calorimetric analysis is faster and easier, owing to the fact that no sample treatments are required.     

Electromagnetic corrections to neutrino processes in the leading logarithmic approximation,the value of sin θ and the W and Z masses

The parameters of the Weinberg-Salam model can be defined by amplitudes at a momentum scale M = O(M_W, M_Z). We derive the leading logarithmic e.m. correction to the relations giving the neutrino amplitudes at a momentum scale μ ? M in terms of sin²θ(M), α(M), M_W and M_Z. For leptonic processes, the Fermi constant is not corrected, but a running, universal, sin²θ(μ) > sin²θ(M) should be used. The Fermi constant for semileptonic processes is renormalized by a factor $\text{?(μ) > 1}$, for charged currents, and is not renormalized, for neutral current processes. The latter are described by the same sin²θ(μ) as the leptonic ones. We estimate that sin²θ(M) is about 0.013 smaller than the value of sin²θ obtained from semileptonic data with no correction, thereby improving the agreement with grand unified theories. The prediction for W (Z) masses and widths in terms of the low energy parameters are discussed. Using previous calculations at order α, we obtain predictions for the masses which are accurate up to and including terms of order (αlnM²)².     

H2 storage materials (22 KJ/mol) using organometallic Ti fragments as sigma-H2 binding sites

Low-coordinate Ti (III) fragments with controlled geometries designed specifically for sigma-H2 binding were grafted onto mesoporous silica using tri- and tetrabenzyl Ti precursors. The hydrogen storage capacity was tested as a function of precursor and precursor loading level. At an optimal loading level of 0.2 mol equiv tetrabenzyl Ti the total storage capacity at -196 degrees C was 21.45 wt % and 34.10 kg/m(3) at 100 atm, and 3.15 wt % and 54.49 kg/m(3) for a compressed pellet under the same conditions. The adsorption value of this material was 1.66 wt %, which equates to an average of 2.7 H2 per Ti center. The adsorption isotherms did not reach saturation at 60 atm, suggesting that the theoretical maximum of 5 H2 per Ti in this system may be reached at higher pressures. The binding enthalpies rose with surface coverage to a maximum of 22.15 kJ/mol, which is more than double that of the highest recorded previously and within the range predicted for room temperature performance. The adsorption values of 0.99 at -78 degrees C and 0.69 at 25 degrees C demonstrate retention of 2.4 H2 and 1.1 H2 per Ti at these temperatures, respectively. These findings suggest that Kubas binding of H2 may be exploited at ambient temperature to enhance the storage capacities of high-pressure cylinders currently used in hydrogen test vehicles.     

Calorimetric analysis of three hydroxy acids as markers for quality and safety in food

A new analytical methodology to quantify three hydroxy acids (orotic, ascorbic, L-malic acids), by isothermal solution microcalorimetry, was outlined and applied to different foods. Three specific enzymatic reactions were used to ensure the correctness of the results. The considered acids can be considered as markers in food quality for their biochemical peculiarities. The enzymatic microcalorimetric method is very reliable and linearity is satisfied in the concentration ranges useful for food analyses. The analytical results of the underlined method are very accurate, precise, sensitive and in good agreement with the values obtained with other common methods.     

Transition metal hydrazide-based hydrogen-storage materials: the first atoms-in-molecules analysis of the Kubas interaction

Molecular models of the M-H(2) binding sites of experimentally characterised amorphous vanadium hydrazide gels are studied computationally using gradient corrected density functional theory, to probe the coordination number of the vanadium in the material and the nature of the interaction between the metal and the H(2) molecules. The H(2) is found to bind to the vanadium through the Kubas interaction, and the first quantum theory of atoms-in-molecules analysis of this type of interaction is reported. Strong correlation is observed between the electron density at the H-H bond critical point and the M-H(2) interaction energy. Four coordinate models give the best reproduction of the experimental data, suggesting that the experimental sites are four coordinate. The V-H(2) interaction is shown to be greater when the non-hydrazine based ligand, THF, of the experimental system is altered to a poorer π-acceptor ligand. Upon altering the metal to Ti or Cr the M-H(2) interaction energy changes little but the number of H(2) which may be bound decreases from four (Ti) to two (Cr). It is proposed that changing the metal from V to Ti may increase the hydrogen storage capacity of the experimental system. A 9.9 wt% maximum storage capacity at the ideal binding enthalpy for room temperature performance is predicted when the Ti metal is combined with a coordination sphere containing 2 hydride ligands.     

The regression of isothermal thermogravimetric data to evaluate degradation Ea values of polymers: A comparison with literature methods and an evaluation of lifetime prediction reliability

The thermooxidative degradation of four well known polymers, polyethylene (PE), polystyrene (PS), polycarbonate (PC) and poly(methyl methacrylate) (PMMA), was carried out in a thermogravimetric (TG) analyser, at various temperatures (in the 473–533 K range), in isothermal heating conditions. The resulting set of experimental TG data was used to determine the apparent activation energy (E_a) of degradation through two isothermal literature methods, as well as through a very simple method we set up, based on the direct regression of the experimental mass loss data, in order to verify the general applicability of our method to various polymers. The results from different methods were in good agreement. Degradation experiments in dynamic heating conditions, which were also performed, gave E_a values in good agreement with those in isothermal heating conditions for PS, PC and PMMA, while for PE a large discrepancy was observed, which was discussed and interpreted. The results suggested the general applicability of our method to all polymers, independently on their structure and degradation mechanism. A long-term (about 13 months) isothermal degradation experiment was also carried out with the same polymers at relatively low temperature (423 K). Only PE and PS evidenced appreciable mass loss in the investigated period, but the experimental data were not in agreement with those from the short-term degradations at higher temperatures, thus suggesting different degradation kinetics, and a low reliability of the lifetime predictions for polymers in service based on experiments at higher temperatures.     

Proprietà di 20 ordine di un riferimento isotropo

We extend to the isotropic case, by adapted non-holonomic techniques [1], 2^° order properties of a relativistic frame of reference, generalized in the polar sense [2,3]: Riemann and gravitational tensors decomposition, Lie derivative of the Ricci rotation coefficients, commutation formulae and finally Bianchi identity. All the decomposition tensors are formally invariant (as regards the standard case), by means of the longitudinal derivative extension. Received: June 14, 2000?Published online: October 2, 2001     

Petrographic characterization and provenance determination of the white marbles used in the Roman sculptures of Forum Sempronii (Fossombrone,Marche, Italy)

The Roman municipium of Forum Sempronii (Fossombrone, Marche) was located along the ‘Via Consolare Flaminia’, in the stretch of road where it ran along the final sector of the valley of the River Metauro (Mataurus). The ancient colony of Forum Sempronii, which is cited by Strabo, Pliny, and Ptolemy, was found in the second century BC, probably on the site of an earlier community and its activity continued until the end of the fifth century AD. During ancient and more recent archaeological excavations, many fragments of coloured stones and marbles, and some white marble sculptures have been unearthed. In this paper, we report the results of the provenance identification of the white marbles used for the sculptures found in the archaeological site of Forum Sempronii and now displayed at the local archaeological museum. The determination of the source origin of the white marbles used for the sculptures has been established by mineralogical-petrographic and geochemical analyses. Microscopic study of thin sections together with carbon and oxygen stable isotope ratios indicate that more than one type of white marbles was used: Pentelikon, Lunense, and Thasian.