Development and validation of a high-performance liquid chromatography-mass spectrometry assay for determination of amphetamine, methamphetamine, and methylenedioxy derivatives in meconium

A procedure based on liquid chromatography-mass spectrometry (LC-MS) is described for determination of amphetamine, methamphetamine, and methylendioxy derivatives in meconium, using 3,4-methylendioxypropylamphetamine as internal standard. The analytes were initially extracted from the matrix by 17 mM methanolic HCl. Subsequently, a solid-phase extraction with Bondelut Certify columns was applied. Chromatography was performed on a C(18) reversed-phase column using a linear gradient of 10 mM ammonium bicarbonate, pH 9.0-methanol as a mobile phase. Analytes were determined in LC-MS single ion monitoring mode with an atmospheric pressure ionization-electrospray interface. The method was validated in the range 0.005-1.00 microg/g using 1 g of meconium per assay. Mean recoveries ranged between 61.1 and 87.2% for different analytes. The quantification limits were 0.005 microg/g meconium for amphetamine, methamphetamine, and 4-hydroxy-3-methoxymethamphetamine and 0.004 microg/g meconium for 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine, 3,4-methylenedioxyethylamphetamine, and N-methyl-1-(3,4-methylenedioxyphenyl)-2-butanamine. The method was applied to analysis of meconium in newborns to assess eventual fetal exposure to amphetamine derivatives.     

Structural and spectroscopic characteristics of synthetic hydrohaematite

In order to investigate the identity of water-containing haematite, a method of preparation has been elaborated which leads to samples of hydrohaematite which are structurally pure and free of amorphous iron hydroxide. Differential thermal analysis by a lack of endothermic effect at 423 to 473 K on the DTA-curves and by a steady fall of the TG curves up to 1150 K revealed that water in the preparations must be tightly held in the lattice of haematite. Measurements of intensities of X-ray reflections of the (1 0 4) and (0 2 4) planes in relation to the (1 1 3) plane confirmed Fe³⁺-deficiency in the haematite cationic sublattice brought about by the presence of OH^– ions in the anionic sublattice. The infrared spectrum of hydrohaematite, in addition to six bands from Fe-O variations, exhibits three bands from hydroxyl groups. The effect of silicates on the pattern of the infrared spectra of natural and synthetic hydrohaematites and the discrepancies in the infrared spectra of haematites published to date are discussed.     

Microwave-assisted photochemical reactor for the online oxidative decomposition and determination of p-hydroxymercurybenzoate and its thiolic complexes by cold vapor generation atomic fluorescence detection

We developed a photochemical method for the online oxidation of p-hydroxymercurybenzoate (PHMB), an organic mercury species widely used for mercaptan and thiolic compound labeling. The method is based on a fully integrated online UV/microwave (MW) photochemical reactor for the digestion of PHMB, followed by cold vapor generation atomic fluorescence spectrometry (CVG-AFS) detection. The MW/UV process led to the quantitative conversion of PHMB and thiol-PHMB complexes to Hg(II), with a yield between 91% and 98%, without using chemical oxidizing reagents and avoiding the use of toxic carcinogenic compounds. This reaction was followed by the reduction of Hg(II) to Hg(0), performed in a knitted reaction coil with NaBH(4) solution, and AFS detection in an Ar/H(2) miniaturized flame. The low MW power applied (18 W) allowed us to keep constant the temperature of the photochemical reactor (21 ± 1 °C), using a flowing water bath. This avoided peak widening due to diffusion processes generally occurring at high temperatures and in the additional cooling coil. This method has been applied to the determination of thiols in human plasma, blood, and wine.     

Dithizone modified gold nanoparticles films for potentiometric sensing

For the first time, application of a membrane composed of gold nanoparticles decorated with complexing ligand for potentiometric sensing is shown. Gold nanoparticles drop cast from a solution form a porous structure on a substrate electrode surface. Sample cations can penetrate the gold nanoparticles layer and interact with ligand acting as a charged ionophore, resulting in Nernstian potentiometric responses. Anchoring of complexing ligand on the gold surface abolishes the necessity of ionophore application. Moreover, it opens the possibility of preparation of potentiometric sensors using chelators of significantly different selectivity patterns further enhanced by the absence of polymeric membrane matrix. This was clearly seen, for example, for gold nanoparticles stabilizing the applied ligand-dithizone-thiol conformation leading to a high potentiometric selectivity toward copper ions, much higher than that of ionophores typically used to induce selectivity for polymeric ion-selective membranes.     

Effect of cooking and germination on phenolic composition and biological properties of dark beans (Phaseolus vulgaris L.)

Legumes are the base´s diet in several countries. They hold a high nutritional value, but other properties related to human health are nowadays being studied. The aim of this work was to study the influence of processes (boiling or germination) on the phenolic composition of dark beans (Phaseolus vulgaris L. c.v. Tolosana) and their effect on their antioxidant, neuroprotective and anticancer ability. Phenolic composition of raw and processed dark beans was analysed by HPLC-PAD and HPLC–ESI/MS. The antioxidant activity was evaluated by ORAC. Astrocytes cultures (U-373) have been used to test their neuroprotective effect. Anticancer activities were evaluated on three different cell lines (renal adenocarcinoma (TK-10), breast adenocarcinoma (MCF-7) and melanoma (UACC-62)) by sulphorhodamine B method. Qualitative and quantitative differences in phenolic composition have been observed between raw and processed dark beans that influence the antioxidant activity, mainly for germinated samples which show a decrease of antioxidant capacity. Although every assayed extracts decreased reactive oxygen species release and exhibited cytotoxicity activities on cancer cell lines, raw beans proved to be the most active in neuroprotective and antitumoral effects; this sample is especially rich in phenolic compounds, mainly anthocyanins. This study further demonstrated that phenolic composition of dark beans is related with cooking process and so with their neuroprotective and anticancer activity; cooking of dark beans improves their digestion and absorption at intestinal level, while maintaining its protective ability on oxidative process at cellular level.     

Neuroprotective properties of Spanish red wine and its isolated polyphenols on astrocytes

The neuroprotective effect of Merlot red wine and its isolated polyphenols was evaluated in an oxidative stress model induced by Fenton reaction and hydrogen peroxide in the human astrocytoma U373 MG cell line. Compared with cells treated only with oxidative stress inductors, the pre-incubation with Merlot red wine for 24 h caused a significant increase in cell viability for all concentrations assayed. The most abundant polyphenols found in Merlot red wine were the flavonoids catechin (37.8 mg/l), epicatechin (52.3 mg/l), quercetin (5.89 mg/l) and procyanidins (15.2 mg/l), the hydroxybenzoic acid gallic acid (16.7 mg/l), and the phenolic alcohol tyrosol (31.4 mg/l). The potential protective role of these polyphenols when isolated was then assessed in treated Fenton reaction U373 MG cells. Polyphenols decreased reactive oxygen species generation and increased the activity and the protein expression of the antioxidant enzymes catalase, superoxide dismutase, glutathione reductase and glutathione peroxidase. Of the polyphenols, quercetin and procyanidins showed the highest neuroprotective effect.     

Electrochemical performance of carbon gels with variable surface chemistry and physics

This study describes the electrochemical characterization of N-doped carbon xerogels in the form of microspheres and of carbon aerogels with varied porosities and surface oxygen complexes. The interfacial capacitance of N-doped carbon xerogels decreased with increased micropore surface area as determined by N₂ adsorption at ?196 °C. The interfacial capacitance showed a good correlation with the areal N_XPS concentration, and the best correlation with the areal concentration of pyrrolic or pyridonic nitrogen functionalities. The gravimetric capacitance decreased with greater xerogel microsphere diameter. The interfacial capacitance of carbon aerogels increased with higher percentage of porosity as determined from particle and true densities. The interfacial capacitance showed a linear relationship with the areal oxygen concentration and with the areal concentrations of CO- and CO₂-evolving groups.     

Postfailure Mechanics of Landslides: Laboratory Investigation of Flowslides in Pyroclastic Soils

Of all landslides, subaerial flowslides are the most dangerous. According to the literature, flowslides in saturated granular deposits are caused by static liquefaction induced by loss of stability. However, the catastrophic flowslides that occurred on steep slopes in Campania (southern Italy) in 1998, 1999, and 2005 were triggered by rainwater infiltration into shallow deposits of pyroclastic soils, which were initially unsaturated. Starting from the experience collected during the investigations of some of these landslides, the writers consider flowslide evolution as a result of a mechanical chain process characterized by saturation increase due to rainwater infiltration, mechanical degradation, volumetric collapse, and static liquefaction, culminating in complete fluidization of the soil. In the paper this chain process is investigated through wetting tests both in suction controlled triaxial apparatuses and in a well-equipped small scale slope model.     

Porcelain Faucet Handle Failure Analysis

A porcelain faucet handle failed after years of use in a residential rental property. Determining the cause of failure was hampered by the fact that the failed handle was no longer available. The analysis included mechanical testing of exemplar faucet handles to measure the reasonable forces that could be applied by hand and the forces necessary to cause failure. Interface geometry between the porcelain handle and the interior metal nut was a factor. Finite Element Analysis facilitated the study. Results showed that if the faucet handle had sustained damage during a gasket repair, then the failure could be accounted for.