Simultaneous determination of the urinary metabolites of benzene, toluene, xylene and styrene using high-performance liquid chromatography/hybrid quadrupole time-of-flight mass spectrometry

A simple and rapid method using reversed-phase liquid chromatography/tandem mass spectrometry (LC/MS/MS) for the simultaneous determination of the urinary metabolites of benzene, toluene, xylene and styrene in human urine specimens and standard solutions is described. A hybrid quadrupole/time-of-flight (QqTOF) mass spectrometer was compared for the determination of metabolite of aromatic solvents in urine samples. The metabolites selected were: trans,trans-muconic acid, hippuric acid, o-, m- and p-methylhippuric acid and phenylglyoxylic acid. The compounds were well separated from each other on narrow-bore 1-mm i.d. reversed-phase LC C-18 columns. Average recoveries for loading 100 microL of urine samples varied from 88-110% and the quantification limits were less than 30 ng/mL for each analyte (3 ng/mL for trans,trans-muconic acid). The qualitative information obtained (mass accuracy, resolution and full-scan spectra) with the QqTOF mass spectrometer allows a secure identification of analytes in biological matrices.     

Construction of a singular elliptic-harmonic measure

The authors study an example, suggested by E. De Giorgi, of a second-order uniformly elliptic partial differential operator in divergence form with continuous coefficients on a smooth domain in the plane such that the associated harmonic measure on the boundary is not absolutely continuous with respect to the ordinary surface measure.     

Plasma antioxidant capacity determination: comparative evaluation of chemiluminescent and spectrophotometric assays

All aerobic organisms have developed different mechanisms for neutralising the free radicals, mostly produced by the monoelectronic reduction of O(2), and preventing the severe damages these can provoke. The efficiency of these mechanisms can be assessed, in different matrices, by a simple and direct chemiluminescent assay (CL) based on luminol oxidation catalysed by horseradish peroxidase. Light emission is mediated by the production of free radicals and it is inhibited after a sample addition in a way that is directly proportional to the sample total content of molecules displaying antioxidant activity. The performances of this chemiluminescent assay were compared with those of two spectrophotometric methods already applied in clinical practice. First spectrophotometric method measures, like CL assay, the total antioxidant capacity, whereas the second one determines free thiol groups content. The chemiluminescent assay has a linearity interval between 0.60 and 9.46 mumol l(-1) of Trolox (y=34.91x+3.10; r=0.999; n=5) with an imprecision, expressed as CV, of 3.8% and an inaccuracy, expressed as percentage recovery, of 109%. The first spectrophotometric method, based on the same reference standard, the Trolox molecule, has a linearity interval between 0.2 and 2.5 mmol l(-1) of Trolox (y=-0.01x+4.54; r=0.95; n=5); the thiol groups assay has a linearity interval between 0.1 and 1 mmol l(-1) of l-cysteine (y=1.68x-47.09; r=0.998; n=5). Different clinical samples of plasma from healthy individuals, obese subjects and patients with liver diseases were tested. Interesting correlations were obtained among the three methods, but no significant correlations emerged between antioxidant capacity and clinical parameters. Significant differences were there only between men and women among obese subjects and between drinkers and non-drinkers among liver disease patients.     

High-intensity ultrasound and microwave, alone or combined, promote Pd/C-catalyzed aryl-aryl couplings

Pd-catalyzed homo- and cross-couplings of boronic acids and aryl halides were successfully carried out both in aqueous media under high-intensity ultrasound (US) and in DME under microwave (MW). Heterogeneous catalysis with Pd/C was employed, avoiding phosphine ligands and phase-transfer catalysts. In a trial series involving 15 different iodo- and bromoaryls and 7 boronic acids, both energy sources drastically reduced reaction times affording biaryls in acceptable to good yields. With palladium(II) acetate as catalyst, electron-deficient aryl chlorides also reacted, affording a few biaryls in acceptable yields. Ullmann-type zinc-mediated homocoupling of iodo- and bromoaryls in the presence of Pd/C under CO₂ atmosphere was achieved in aqueous media under US, though not under MW. Suzuki homo- and cross-couplings were also carried out in a new reactor developed in our laboratory, featuring combined US and MW irradiation, further improving a green synthetic method.     

Evaluation of behaviour of linear monoamines CH3-(CH2)n−1-NH2 (n=1-6) in ion chromatography

This paper reports the results on a study of ion chromatography (IC) behaviour on strong cationic exchange column of CH₃-(CH₂)_n−1-NH₂ (n=1-6) type linear monoamines. The eluents were mixtures of HCl-NaCl, HNO₃-NaNO₃, HClO₄-NaClO₄, H₂SO₄-Na₂SO₄, HClO₄-NaClO₄-CH₃CN. Amines were revealed with an amperometric detector. The influence of different counter-ions on retention factors, k′, is discussed. Relationships between k′ and pE (E=sum of Na⁺ and H⁺ concentrations), and length of alkylic chain, and sensitivity coefficient S, are reported and discussed. The addition of acetonitrile (ACN) in the eluent was also taken into account. Suitable considerations are derived from these data. An example of monoamines separation is given.     

Separation of fluorescent 1,N6 ethenoderivatives of diadenosine polyphosphates and their enzymatic degradation products by reversed-phase high-performance liquid chromatography

Summary The retention, selectivity and elution order of fluorescent 1,N⁶-etheno derivatives of diadenosine polyphosphates and their enzymatic degradation products on octadecyl and phenyl-bonded silica columns have been studied as a function of mobile phase pH, ionic strength and organic modifier content. Good separations of the compounds of interest were achieved using mobile phases of around 0.1M potassium phosphate buffers at neutral pH containing approximately 10% methanol or 4% acetonitrile for C₁₈ columns and 5% methanol or 1.5% acetonitrile for phenyl columns. The data obtained were used to establish isocratic assays for diadenosine polyphosphate cleaving activities from chromaffin cells using Di(1,N⁶-ethenoadenosine) polyphosphates as fluorogenic substrate analogues followed by fluorescence detection.     

Hydrolysis of (CH3)3Sn+ in Various Salt Media

The hydrolysis of trimethyltin(IV) has been studied by potentiometry (H⁺ -glass electrode) and calorimetry in various salt media (NaNO₃, NaCl, KCl, Na₂SO₄, and NaNO₃—NaCl mixtures). The effect of ionic strength on the hydrolysis constants is accounted for by a simple Debye–Hückel type equation and by Pitzer equations. The results allow us to obtain H for hydrolysis and the temperature dependence of the Pitzer parameters. The resulting coefficients can be used to examine the speciation of (CH₃)₃Sn⁺ in multicomponent electrolyte solutions, such as natural waters, over a wide range of temperature and ionic strength.     

Mapping the sites for selective oxidation of guanines in DNA

The effective energy of a positive charge when it is localized at a specific guanine nucleobase in DNA was calculated using density functional theory. The results demonstrate that the efficiency of a guanine to act as a hole-trap in DNA strongly depends on the nature of the flanking nucleobases. The presence of a pyrimidine base at the 3' position adjacent to a guanine significantly increases the localization energy of the positive charge. The calculated distributions of a positive charge in sequences of two or three adjacent guanines, flanked by other nucleobases, provide an explanation for experimental literature data on the site-selective oxidation of DNA.     

Reaction of thiete 1,1-dioxide with α-chlorobenzalphenylhydrazine and methyl phenylhydrazonochloroacetate

Thiete 1,1-dioxide reacts with 2 moles of α-chlorobenzalphenylhydrazine and methyl phenylhydrazonochloroacetate in the presence of triethylamine leading to the pyrazole derivatives 6 and 7 whose structure and mechanism of formation are discussed.     

Ultrasound effects on the Mn(III) - promoted addition of amidoalkyl radicals to olefins

Amidoalkyl radicals, generated from amides by Mn(OAc)₃ in acetic acid react with phenyl substituted alkenes to generate five-membered lactones or lactams. Ultrasound at ambient temperature significantly accelerates these single electron transfer reactions even when compared with conventional conditions under reflux or simple mechanical stirring. In some cases sonication leads to unusual products.