Standard pH values for phosphate buffer reference solutions in acetonitrile-water mixtures up to 50% (m/m)

Reference pH_ps values for 0.025 mol/kg potassium dihydrogen phosphate + 0.025 mol/kg disodium hydrogen phosphate primary standard buffer solutions in 10, 30, 40 and 50% (m/m) acetonitrile-water mixtures at 298.15 K have been determined from reversible e.m.f. measurements of the cell Pt/Ag/AgCl/primary standard buffer + KCl in acetonitrile-water/glass electrode. The consistency of the results is confirmed by multilinear regression analysis of the pH_ps values obtained for each solution composition. Considering the high number of possible acetonitrile-water mixtures, the methodology of linear solvation energy relationships (LSER) was applied and pH_ps data have been correlated with the Kamlet-Taft solvatochromic parameters of the acetonitrile-water mixtures over the whole of the experimental range.     

Evaluation of electrodeposited tungsten chemical modifier for direct determination of chromium in urine by ETAAS

The direct determination of chromium in urine by electrothermal atomic absorption spectrometry (ETAAS) using graphite tubes modified with tungsten is proposed. Modification of the graphite is made by tungsten electrodeposition over the whole surface atomizer followed by carbide formation by heating the tube inside its own furnace. For tungsten electrocoating, the graphite tube and a platinum electrode were connected to a power supply as cathode and anode, respectively, and immersed in a solution containing 2 mg of W in 0.1% v/v HNO₃. Then, 5 V was applied between the electrodes during 20 min for tungsten electrodeposition over the whole atomizer. A SpectrAA 220 Varian atomic absorption spectrometer equipped with a deuterium background corrector was used throughout. Undiluted urine (20 μl) was delivered over the tungsten-treated tube and the chromium-integrated absorbance was measured after applying a suitable heating program with maximum pyrolysis at 1300 °C and atomization at 2500 °C. With electrodeposited tungsten modifier, the tube lifetime increased up to four times when compared to previous published methods for Cr determination in urine by ETAAS, reaching 800 firings. Method detection limit (3 S.D.) was 0.10 μg l⁻¹, based on 10 integrated absorbance measurements of a urine sample with low Cr concentration. Two reference materials of urines (SRM 2670) from National Institute of Standards and Technology (NIST) were analyzed for method validation. For additional validation, results obtained from eight human urine samples were also analyzed in a spectrometer with Zeeman effect background correction.     

Unified mechanistic concept of electrophilic aromatic nitration: convergence of computational results and experimental data

The mechanism of electrophilic aromatic nitration was revisited. Based on the available experimental data and new high-level quantum chemical calculations, a modification of the previous reaction mechanism is proposed involving three separate intermediates on the potential energy diagram of the reaction. The first, originally considered an unoriented pi-complex or electron donor acceptor complex (EDA), involves high electrostatic and charge-transfer interactions between the nitronium ion and the pi-aromatics. It explains the observed low substrate selectivity in nitration with nitronium salts while maintaining high positional selectivity, as well as observed oxygen transfer reactions in the gas phase. The subsequent second intermediate originally considered an oriented "pi-complex" is now best represented by an intimate radical cation-molecule pair, C(6)H(6)(+)(*)()/NO(2), that is, a SET complex, indicative of single-electron transfer from the aromatic pi-system to NO(2)(+). Subsequently, it collapses to afford the final sigma-complex intermediate, that is, an arenium ion. The proposed three discrete intermediates in electrophilic aromatic nitration unify previous mechanistic proposals and also contribute to a better understanding of this fundamentally important reaction. The previously obtained ICR data of oxygen transfer from NO(2)(+) to the aromatic ring are also accommodated by the proposed mechanism. The most stable intermediate of this reaction on its potential energy surface is a complex between phenol and NO(+). The phenol.NO(+) complex decomposes affording C(6)H(6)O(+)(*)/PhOH(+) and NO, in agreement with the ICR results.     

Flow‐Injection Pulsed‐Amperometric Determination of Free Glycerol in Biodiesel at a Gold Electrode

This work reports the highly‐sensitive amperometric determination of free glycerol in biodiesel at a gold electrode adapted in a flow‐injection analysis (FIA) cell. The amperometric method involved the continuous application of three sequential pulses to the working electrode (+250 mV, +700 mV, and ?200 mV, for 100 ms each). This sequence of potential pulses eliminated electrode passivation and dramatically increased the analytical signal. The proposed FIA‐amperometric method presented low relative standard deviation between injections (1.5 %, n=15), high analytical frequency (85 h^?1), satisfactory recovery values (93–118 %) for spiked samples, wide linear range (from 1 to 300 µmol L^?1), and low detection limit (0.5 µmol L^?1).     

Visualisation and modelling studies of churn flow in a vertical pipe

Churn flow is an important flow regime intermediate between slug flow and annular flow. A feature of this regime is the occurrence of very large waves travelling upwards over a liquid film substrate which may intermittently travel downwards. These waves are often formed close to the liquid inlet where their behaviour is usually difficult to observe. This paper describes a series of experiments using a test section with a specially constructed transparent liquid inlet. High-speed video recordings show clearly the process of wave formation and analysis of the recordings gave data on wave frequencies and typical velocities. Also, predictions of velocity and distance travelled by the waves were obtained via the application of a simple mathematical model that takes into account the forces acting on a circumferentially coherent wave.     

Study of 1,4-dihydroxyanthraquinone as an acid-base indicator in isopropyl alcohol medium Evaluation of colour-change limits through complementary chromaticity parameters

The use of 1,4-dihydroxyanthraquinone as an acid-base indicator in isopropyl alcohol medium is proposed. The acid dissociation constants of the indicator in isopropyl alcohol solution are pK(a1) = 12.95 +/- 0.03 and pK(a2) = 15.96 +/- 0.07. The sharpness of the indicator transition is described by means of complementary chromaticity parameters. The indicator is used for determination of weak organic acids, with errors of less than 1%.     

Capillary electrophoresis and matrix-assisted laser desorption/ionization-time of flight-mass spectrometry for analysis of the novel erythropoiesis-stimulating protein (NESP)

NESP (novel erythropoiesis-stimulating protein) is a recently approved hyperglycosylated analogue of human erythropoietin (EPO) with a long-lasting effect. In this work, the capillary electrophoresis (CE) methodology proposed by the European Pharmacopoeia for the separation of EPO glycoforms has been modified for the separation of NESP glycoforms. Optimization of pH of the separation electrolyte has been fundamental in order to achieve baseline resolution of seven peaks corresponding to NESP glycoforms. Intact NESP has also been characterized by matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS). An accurate approximation to an average molecular mass of the NESP molecule has been obtained, taking into account the strong influence of laser intensity upon the MALDI-TOF mass spectra found.     

Electrochemical behaviour of Ni-Co amorphous alloys in alkaline solutions

The dissolution processes of amorphous G15 (Ni₅₈Co₂₀B₁₂Si₁₀) and G16 (Ni₂₅Co₅₀B₁₀Si₁₅) alloys in carbonate-bicarbonate buffers (8.9≤pH≤10.5) have been studied using voltammetry and stationary polarization techniques combined with electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy (XPS) measurements. Results indicate that the electrochemical processes are dependent on the applied potential, the alloy composition, and the pH and ionic strength of the electrolyte. An enhancement of the corrosion processes is observed when the pH and the ionic strength are increased and when the Co content of the alloy diminishes. Furthermore, XPS provided information about the composition of the surface layer. Electronic Publication     

Methomyl Detection by Inhibition of Laccase Using a Carbon Ceramic Biosensor

A sol–gel derived carbon ceramic biosensor was used for methomyl determination in vegetable extract samples based on the immobilization of laccase from Aspergillus oryzae. Esculetin was chosen as the substrate for laccase in order to measure inhibition by this pesticide. The analytical curve was linear for methomyl concentrations of 0.5 to 12.2 µM with a detection limit of 0.2 µM. The lifetime of the proposed biosensor was 60 days and the recovery from vegetable extract samples ranged from 98.0 to 104.2 %. The results using the proposed method are in agreement with those using HPLC at the 95 % confidence level.