Allopurinol and its interactions with Cu<Superscript>2+</Superscript> ions: radical reactions and complex structure

Allopurinol (ALP), an inhibitor of the xanthine oxidase enzime, is reported to provide protection against free-radical mediated damage by various mechanisms, including free-radical scavenging and metal chelation (i.e. Cu(II)). To obtain a wider insight into the molecular aspects of the beneficial action of ALP, free ALP and the Cu(II)- ALP system were investigated by radiation chemical and spectroscopic studies. Pulse radiolysis experiments show that ALP is a good · OH scavenger (1.8 × 10⁹ and 5.4 × 10⁹ M^-1 s^-1 at pH 6.0 and 11.0, respectively), leading to · OH-adducts and transient semi-oxidized species, such as phenoxyl radicals. The latter are also formed by the reaction of ALP with some specific one-electron oxidizing radicals (i.e. N₃ and SO₄ ^-). The semi-oxidized species are stabilized by their resonance properties and scarcely react with oxygen. In addition, the chelation of Cu(II) by ALP does not significantly affect the reactivity of the drug towards ·OH (2.5×0⁹ M^-1 s^-1). Raman and the IR spectra support the good chelating ability of ALP, indicating the formation of two Cu(II)- ALP complexes with a slightly different structure. Depending on the metal/ligand ratio, pyrimidine nitrogens may take part to the Cu(II) co-ordination in addition to the N pyrazolic atoms and the C O groups of some ALP molecules. These results suggest that ALP may inhibit oxidative damage both through the direct radical scavenging and the copper-chelation mechanism. In fact, both the conversion of a harmful radical, such as ·OH, into a less reactive transient species, and the capture of copper ions, which play a relevant role in metal-catalysed generation of reactive oxygen species, will prove beneficial for the cell protection.     

On the direct calculation of the time evolution of excited molecular states in the presence of nonadiabatic interactions

The possibility is explored of calculating the time evolution of a given initial molecular state, in the presence of sufficiently strong nonadiabatic interactions, with a fully quantum-mechanical approach. Two methods are presented. The first one is based on the determination of the molecular eigenstates, with expansion of the nuclear wavefunctions on a Hermite basis. The second method is based on the Padé 1,1 approximation of the time evolution operator and on a finite difference representation of the time-dependent nuclear wavefunctions. Both methods are applied to simple models of a diatomic molecule.     

XPS, ICP and DPASV analysis of medieval pottery — Statistical multivariate treatment of data

Medieval ceramic sherds have been studied by inductively coupled plasma (ICP) emission spectroscopy and X-ray photoelectron spectroscopy (XPS) in order to acquire knowledge about technological achievements in pottery production in Apulia during the Middle Ages. The XPS results allow to characterize the surface glazes, which are transparent owing to the presence of PbO or opaque-white in case of Sn addition. The study of coloured glossy surfaces, after an optimized chemical etching, has also shed light on the pigment nature of the painted decorations, whose red colour is to be attributed to the presence of Pb₃O₄ and not of Fe oxides. Quantitative determinations were performed by ICP measurements on samples of differently coloured glazes, clayey slips and ceramic bulks. Pb and Cu, present in one green glaze, were also determined by differential pulsed anodic stripping voltammetry (DPASV). The analytical results were treated by different statistical techniques of multivariate analysis.     

Standard pH values for potassium hydrogenphthalate reference buffer solutions in 10, 30 and 50% (w/w) 1,4-dioxane/water mixed solvents at temperatures from 288.15 to 318.15 K

Standard pH(S) values for 0.05 mol kg^?1 potassium hydrogenphthalate (KHpH) reference buffer solutions in 10, 30 and 50% (w/w) 1,4-dioxane/water solvent mixtures within the temperature range 288.15–318.15 K are determined from e.m.f. measurements of the cell without transference Pt|H₂|KHPh + KCl|AgCl|Ag|Pt. The consistency of the results is analysed by a recently described method of multilinear regression of the quantity p(a_Hγ_Cl) as a function of both solution composition and temperature. The standard pH(S) determined can be reproduced to within ±0.01 by the equation pH(S) - 4.004 + 3.309w + 0.408z + 1.037w³ - 14.95zw² + 27.1zw³, where w is the weight fraction of dioxane in the solvent mixture,z = (T –θ)/θ, and θ - 298.15 K. Values of the first ionization constant of phthalic acid (H₂Ph; benzene-1,2-dicarboxylic acid) in the above solvent mixtures are also determined from e.m.f. measurements of the cell without transference Pt|H₂|H₂Ph + KHPh + KCl|AgCl|Ag|Pt.     

Nanoscale organization of a phthalocyanine-fullerene system: remarkable stabilization of charges in photoactive 1-D nanotubules

Induction of self-organization between zinc phthalocyanine (ZnPc) and C60 moieties in a novel amphiphilic ZnPc-C60 salt results in uniformly nanostructured 1-D nanotubules. Their photoreactivity, in terms of ultrafast charge separation (i.e., approximately 1012 s-1) and ultraslow charge recombination (i.e., approximately 103 s-1), is remarkable. In addition, the observed ZnPc*+-C60*- lifetime of 1.4 ms implies, relative to that of the monomeric ZnPc-C60 ( approximately 3 ns), an impressive stabilization of 6 orders of magnitude.     

Reaction of singlet oxygen with some benzylic sulfides

Product distribution, total quenching rate (k_T), and rate of chemical reaction (k_r) with singlet oxygen have been determined for some alkyl, benzyl, α-methylbenzyl, and cumyl sulfides. Their contributions depend on the steric hindering around the sulfur atom. In protic solvents, the sulfoxide is the main product via a hydrogen-bonded persulfoxide. In apolar solvents, intramolecular α-H abstraction leads to oxidative C-S bond cleavage, with varying efficiency. The behavior of sulfides is compared to that of alkenes and amines.     

Optical Nanocomposite Planar Waveguides Doped with Rare-Earth and Noble Metal Elements

The present paper is focused on multilayer Er³⁺-doped silica-titania planar waveguides, co-doped with silver, which were prepared by spin-coating on silica glass, or buffered single crystal silicon substrates. The single layer thickness (0.4 m) and refractive index (1.60–1.63) were measured by spectroscopic ellipsometry at 715 nm. The thickness of the waveguides (measured by mechanical profilometry) was 1 m and their optical propagation losses were measured at different laser wavelengths (488 nm, 514 nm and 633 nm), exhibiting an approximately Rayleigh-like behavior. The thermal precipitation of silver nanocrystallites was achieved, both in air and under a controlled atmosphere (dry nitrogen) and these were characterized by visible absorption spectroscopy, which clearly showed the development of a plasmon absorption band near 415 nm, by X-ray diffraction (XRD) and Transmission Electron Microscopy (TEM). The Er³⁺ metastable level lifetimes for the emission at ca. 1.54 m were found to be ca. 4–6 ms, for Er³⁺ concentrations varying between 0.2–2.0 mol% (or (0.4–4.4) × 10²⁰ ions/cm³), but no significant variation was observed with the Ag concentration added (up to 2.5 mol%).     

Collection and analytical characterisation of the atmospheric particulate in the city of Bari

In this paper an application of new procedures for atmospheric particulate analysis is illustrated. PM10, PAHs (benzo[a]anthracene (BaA), benzo[b]fluoranthene (BbF), benzo[j]fluoranthene (BjF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), indeno[1, 2, 3-cd]pyrene (Ip), dibenzo[a, h]anthracene (DbA)) and heavy metals (Cu, Ni, Zn, Co, Mn, Cd, Fe and Pb) were investigated. PM10 determination was performed by gravimetric method, PAHs were measured by GC-MS, and heavy metals by HPIC. An air quality monitoring campaign on the territory of Bari municipality has been organised, and its results are shown.     

(±)‐6‐tert‐Butyl‐8‐hydroxymethyl‐2‐­phenyl‐4H‐1,3‐benzodioxin and 2,2,2′,2′,6,6′‐hexamethyl‐8,8′‐methylenebis(4H‐1,3‐benzodioxin)

Two compounds containing 1,3‐benzodioxin groups are reported, namely (±)‐6‐tert‐butyl‐8‐hydroxy­methyl‐2‐phenyl‐4H‐1,3‐benzodioxin, C₁₉H₂₂O₃, (I), and 2,2,2′,2′,6,6′‐hexamethyl‐8,8′‐methyl­enebis(4H‐1,3‐benzodioxin), C₂₃H₂₈O₄, (II).The hydroxy groups of neighbouring mol­ecules in (I) are hydrogen bonded to each other, giving rise to double‐row chains. The mol­ecule in (II) adopts a `butterfly' conformation, with the O atoms in distal positions. In both compounds, the dioxin rings are in distorted half‐chair conformations.     

Systems-based design of bi-ligand inhibitors of oxidoreductases: filling the chemical proteomic toolbox

Genomics-driven growth in the number of enzymes of unknown function has created a need for better strategies to characterize them. Since enzyme inhibitors have traditionally served this purpose, we present here an efficient systems-based inhibitor design strategy, enabled by bioinformatic and NMR structural developments. First, we parse the oxidoreductase gene family into structural subfamilies termed pharmacofamilies, which share pharmacophore features in their cofactor binding sites. Then we identify a ligand for this site and use NMR-based binding site mapping (NMR SOLVE) to determine where to extend a combinatorial library, such that diversity elements are directed into the adjacent substrate site. The cofactor mimic is reused in the library in a manner that parallels the reuse of cofactor domains in the oxidoreductase gene family. A library designed in this manner yielded specific inhibitors for multiple oxidoreductases.