Synthesis and characterization of nanocapsules with shells made up of Al13 tridecamers

The synthesis of samples by the sol-gel method with aluminum tri-sec-butoxide as cation precursor, 2-propanol as solvent, and sulfuric acid as hydrolysis catalyst gave rise to nanocapsules with an average diameter of 20 nm and a shell thickness of 3.5 nm. The analysis of the X-ray diffraction patterns and the 27Al MAS NMR spectra showed that the shell of the nanocapsules was made up of Al13 tridecamers ordered in a noncrystalline symmetry. The interaction between the capsule's shells opened the capsule structure, producing curved fibers, but maintaining the atomic local order. This opening of the capsules favored the reordering of the atomic local order of Al13 tridecamers into the one of crystalline boehmite, when the sample was aged at room temperature for several days; it also increased the pore volume and the specific surface area of the sample. The crystallization transformed the curved fibers into rods made of small crystalline boehmite bars. The capsule morphology was preserved after calcining the nonaged sample at 700 degrees C, indicating that the transformation of the phase made up of ordered Al13 tridecamers into a noncrystalline alumina was pseudomorphic. We describe and partially explain one of the possible atomic ordering evolutions from the one of an isolated Al13 tridecamer, to the phase forming the nanocapsules shell, until eventually coming to the ordering corresponding to boehmite crystalline rods.     

Ideals of operators and the metric approximation property

We prove that a Banach space X has the metric approximation property if and only if , the space of all finite rank operators, is an ideal in , the space of all bounded operators, for every Banach space Y. Moreover, X has the shrinking metric approximation property if and only if is an ideal in for every Banach space Y.Similar results are obtained for u-ideals and the corresponding unconditional metric approximation properties.     

Preparation and characterization of Co80Nb20-xBx amorphous metallic ribbons

Co₈₀Nb₁₄B₆, Co₈₀Nb₁₂B₈ and Co₈₀Nb₁₀B₁₀ amorphous alloys were obtained through the melt-spinning process. The ribbons structure was investigated by X-ray diffractometry and the crystallization process and the thermal stability were studied by means of differential thermal analysis and thermomechanical technique. It was observed that the crystallization temperature depends on the alloy composition and occurs in a temperature range between 420 and 730°C. The coercive field of all alloys was determined by magnetic susceptibility measurements, the values of which range from 2.78 to 5.95 A m^-1. This revised version was published online in August 2006 with corrections to the Cover Date.     

FTIR study of the ethanol electrooxidation on Pt(100) modified by osmium nanodeposits

In the present work, ethanol electrooxidation on a Pt(100) electrode modified by different coverage degrees of osmium nanoislands obtained by spontaneous depositions, was extensively studied employing in situ FTIR spectroscopy. A collection of spectra of the ethanol adsorption and oxidation processes was acquired during the first series of a positive potential step, to determine the intermediate species, as well as the main products formed. The spectroscopic results obtained were correlated with conventional electrochemical results obtained by cyclic voltammetry. It was shown that the catalytic activity of Pt(100) for ethanol oxidation increases significantly after osmium deposition and that the mechanistic pathway for this reaction depends directly on the osmium coverage degree. Thus, for low osmium coverage (theta;( Os) up to 0.15) the formation of CO as an intermediate was favored and hence the full oxidation of adsorbed ethanol to CO(2) was increased. For higher osmium coverages (theta;(Os) up to 0.33), the higher the coverage is, the more the direct ethanol oxidation to acetaldehyde and acetic acid is favored. For osmium coverage degree of 0.40, the catalytic activity of the electrode for ethanol oxidation decreased. On an almost complete osmium layer (theta;(Os) = 0.92) obtained by electrodeposition at 50 mV vs reversible hydrogen electrode, the catalytic activity for ethanol oxidation shows a much lower value.     

Monotonicity inequalities for ther-area and a degeneracy theorem forr-minimal graphs

We establish monotonicity inequalities for the r-area of a complete oriented properly immersed r-minimal hypersurface in Euclidean space under appropriate quasi-positivity assumptions on certain invariants of the immersion. The proofs are based on the corresponding first variational formula. As an application, we derive a degeneracy theorem for an entire r-minimal graph whose defining function ƒ has first and second derivatives decaying fast enough at infinity: Its Hessian operator D² ƒ has at least n − r null eigenvalues everywhere.     

Photoinduced NO release by visible light irradiation from pyrazine-bridged nitrosyl ruthenium complexes

The binuclear complex [RuII(NH3)5(pz)RuII(bpy)2(NO)](PF6)5 was prepared and characterized by elemental analysis, UV-vis, and IR spectroscopy. The complex UV-vis spectrum has presented bands at 242, 286, and 530 nm in acetate buffer solution at pH 4.5. The photochemical study by laser flash-photolysis at 532 nm showed the NO release account from the NO measured by a NO sensor. The quantum yield for NO release (0.025 +/- 0.004 mol einsten-1) was determined with a laser flash-photolysis apparatus (Continuum Q-switched Nd:YAG laser). The major irradiation product of the [RuII(NH3)5(pz)RuII(bpy)2(NO)]5+ complex besides nitric oxide is [RuIII(NH3)5(pz)RuII(bpy)2(H2O)]5+.     

Nonextensive thermostatistics and the H theorem

The kinetic foundations of Tsallis' nonextensive thermostatistics are investigated through Boltzmann's transport equation approach. Our analysis follows from a nonextensive generalization of the "molecular chaos hypothesis." For q>0, the q-transport equation satisfies an H theorem based on Tsallis entropy. It is also proved that the collisional equilibrium is given by Tsallis' q-nonextensive velocity distribution.     

Shifted identical bands: A new phenomenon

The levels in ¹⁶²Gd were identified in spontaneous fission studies. Its transition energies are remarkably similar to those in ¹⁶⁰Gd. From that work, an analysis of yrast bands in even-even proton to neutron-rich Ba to Pb nuclei led to the discovery of a new phenomenon, shifted identical bands (SIB). SIBs are yrast bands in neighboring nuclei (a, b) with moments of inertia which are identical when shifted by a constant amount κ, so J _1a (1+κ)=J _1b , from 2⁺ to 8⁺ and higher to 16⁺. Out of over 700 comparisons, 55 SIBs were found from stable to the most neutron-rich Ce-W nuclei with $\left| {\bar k} \right|$ between 1.5% and 13%, where the spread in κ is less than ±1%, and only four identical bands ( $\bar k \cong 0$ ). As examples, we found for ¹⁵⁸Sm-¹⁶⁰Gd, $\bar k = \left( { - 3.2_{ - 0.2}^{ + 0.1} } \right)\%$ (where the ± is the total spread in κ from ?3.1 to ?3.4); ¹⁵⁶Nd-¹⁶⁰Gd, (?10.6 _?0.2 ^+0.4 )%; ¹⁵⁸Sm-¹⁶⁰Sm, (3.4 _?0.3 ^+0.5 )%. The J ₁ values were fitted to a variable moment of inertia model with parameters J ₀ and C whose values correlate with the SIB J ₁ values. The SIBs are not correlated either with deformation or with the N _p N _n product of the IBA model.     

Age-induced phase transitions on mechanically alloyed amorphous GaSe

After aging it for four years at room temperature, a mechanically alloyed amorphous GaSe powder was transformed to a multi-phase crystalline alloy, where major phase is the trigonal Se one. The structural, thermal and optical properties of this aged amorphous GaSe were investigated through systematic X-ray diffraction, differential scanning calorimetry and Raman scattering measurements. The X-ray diffraction results on the aged GaSe powder suggest the presence of oxides, and X-ray absorption spectroscopy was employed to further investigate it.     

Complete assignment of NMR data of 22 phenyl‐1H‐pyrazoles' derivatives

Complete assignment of ¹H and ¹³C NMR chemical shifts and J(¹H/¹H and ¹H/¹⁹F) coupling constants for 22 1‐phenyl‐1H‐pyrazoles' derivates were performed using the concerted application of ¹H 1D and ¹H, ¹³C 2D gs‐HSQC and gs‐HMBC experiments. All 1‐phenyl‐1H‐pyrazoles' derivatives were synthesized as described by Finar and co‐workers. The formylated 1‐phenyl‐1H‐pyrazoles' derivatives were performed under Duff's conditions. Copyright © 2011 John Wiley & Sons, Ltd.