Ionic mobility of the solvated proton and acid-base titration in a four-compartment capillary electrophoresis system

Although H(+) and OH(-) are the most common ions in aqueous media, they are not usually observable in capillary electrophoresis (CE) experiments, because of the extensive use of buffer solutions as the background electrolyte. In the present work, we introduce CE equipment designed to allow the determination of such ions in a similar fashion as any other ion. Basically, it consists of a four-compartment piece of equipment for electrolysis-separated experiments (D. P. de Jesus et at, Anal. Chem., 2005, 77, 607). In such a system, the ends of the capillary are placed in two reservoirs, which are connected to two other reservoirs through electrolyte-filled tubes. The electrodes of the high-voltage power source are positioned in these reservoirs. Thus, the electrolysis products are kept away from the inputs of the capillary. The detection was provided by two capacitively coupled contactless conductivity detectors (CD), each one positioned about 11 cm from the end of the capillary. Two applications were demonstrated: titration-like procedures for nanolitre samples and mobility measurements. Strong and weak acids (pK(a) < 5), pure or mixtures, could be titrated. The analytical curve is linear from 50 mu M up to 10 mM of total dissociable hydrogen (r = 0.99899 for n =10) in 10-nL samples. By including D(2)O in the running electrolyte, we could demonstrate how to measure the mixed proton/deuteron mobility. When H(2)O/D(2)O (9 : 1 v/v) was used as the solvent, the mobility was 289.6 +/- 0.5 x 10(-5) cm(2) V(-1) s(-1). Due to the fast conversion of the species, this value is related to the overall behaviour of all isotopologues and isotopomers of the Zundel and Eigen structures, as well as the Stokesian mobility of proton and deuteron. The effect of neutral (o-phenanthroline) and negatively charged (chloroacetate) bases and aprotic solvent (DMSO) over the H(+) mobility was also demonstrated.

Thermo-solvatochromism in binary mixtures of water and ionic liquids: on the relative importance of solvophobic interactions

The thermo-solvatochromism of 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr(2), has been studied in mixtures of water, W, with ionic liquids, ILs, in the temperature range of 10 to 60 degrees C, where feasible. The objectives of the study were to test the applicability of a recently introduced solvation model, and to assess the relative importance of solute-solvent solvophobic interactions. The ILs were 1-allyl-3-alkylimidazolium chlorides, where the alkyl groups are methyl, 1-butyl, and 1-hexyl, respectively. The equilibrium constants for the interaction of W and the ILs were calculated from density data; they were found to be linearly dependent on N(C), the number of carbon atoms of the alkyl group; van't Hoff equation (log K versus 1/T) applied satisfactorily. Plots of the empirical solvent polarities, E(T) (MePMBr(2)) in kcal mol(-1), versus the mole fraction of water in the binary mixture, chi(w), showed non-linear, i.e., non-ideal behavior. The dependence of E(T) (MePMBr(2)) on chi(w), has been conveniently quantified in terms of solvation by W, IL, and the ""complex"" solvent IL-W. The non-ideal behavior is due to preferential solvation by the IL and, more efficiently, by IL-W. The deviation from linearity increases as a function of increasing N(C) of the IL, and is stronger than that observed for solvation of MePMBr(2) by aqueous 1-propanol, a solvent whose lipophilicity is 12.8 to 52.1 times larger than those of the ILs investigated. The dependence on N(C) is attributed to solute-solvent solvophobic interactions, whose relative contribution to solvation are presumably greater than that in mixtures of water and 1-propanol.

Validation of dot blot hybridization and denaturing high performance liquid chromatography as reliable methods for TP53 codon 72 genotyping in molecular epidemiologic studies

Background: Mutations in TP53 are common events during carcinogenesis. In addition to gene mutations, several reports have focused on TP53 polymorphisms as risk factors for malignant disease. Many studies have highlighted that the status of the TP53 codon 72 polymorphism could influence cancer susceptibility. However, the results have been inconsistent and various methodological features can contribute to departures from Hardy-Weinberg equilibrium, a condition that may influence the disease risk estimates. The most widely accepted method of detecting genotyping error is to confirm genotypes by sequencing and/or via a separate method. Results: We developed two new genotyping methods for TP53 codon 72 polymorphism detection: Denaturing High Performance Liquid Chromatography (DHPLC) and Dot Blot hybridization. These methods were compared with Restriction Fragment Length Polymorphism (RFLP) using two different restriction enzymes. We observed high agreement among all methodologies assayed. Dot-blot hybridization and DHPLC results were more highly concordant with each other than when either of these methods was compared with RFLP. Conclusions: Although variations may occur, our results indicate that DHPLC and Dot Blot hybridization can be used as reliable screening methods for TP53 codon 72 polymorphism detection, especially in molecular epidemiologic studies, where high throughput methodologies are required.

Sequential injection analysis implementing multiple standard additions for As speciation by liquid chromatography and atomic fluorescence spectrometry (SIA-HPLC-AFS)

An analytical procedure for multiple standard additions of arsenic species using sequential injection analysis (SIA) is proposed for their quantification in seafood extracts. SIA presented flexibility for generating multiple specie standards at the ng mL(-1) concentration level by adding different volumes of As(III), As(V), monomethylarsonic (MMA) and dimethylarsinic (DMA) to the sample. The mixed sample plus standard solutions were delivered from SIA to fill the HPLC injection loop. Subsequently, As species were separated by HPLC and analyzed by atomic fluorescence spectrometry (AFS). The proposed system comprised two independently controlled modules, with the HPLC loop acting as the intermediary device. The analytical frequency was enhanced by combining the actions of both modules. While the added sample was flowing through the chromatographic column towards the detection system, the SIA program started performing the standard additions to another sample. The proposed method was applied to spoiled seafood extracts. Detection limits based on 3 sigma for As(III), As(V), MMA and DMA were 0.023, 0.39, 0.45 and 1.0 ng mL(-1), respectively. (C) 2011 Elsevier B.V. All rights reserved.

Liquid-liquid microextraction without phase separation in a multicommuted flow system for diltiazem determination in pharmaceuticals

Liquid-liquid microextraction without phase segmentation was implemented in a multicommuted flow system for determination of the anti-hypertensive diltiazem. The procedure was based on ion pair formation between the drug and the dye bromothymol blue at pH 3.5. The detection was performed without phase separation in a glass tube coupled to a fiber-optics spectrophotometer. The total volume of chloroform was reduced to 50 mu L in comparison with 10 mL consumed in batch. A linear response was observed between 9 and 120 mu mol L(-1), with a detection limit of 0.9 mu mol L(-1) (99.7% confidence level). The coefficient of variation (n = 10), sampling rate and extraction efficiency were estimated as 0.6%, 78 determinations per hour and 61%, respectively. About 30 mu g of bromothymol blue was consumed and the waste volume was 380 mu L per determination. The results for pharmaceutical samples agreed with those obtained by the reference procedure at the 95% confidence level. (C) 2011 Elsevier B.V. All rights reserved.

A critical evaluation of a flow-cell based on a liquid core waveguide for chemiluminescence measurements

Liquid-core waveguides (LCWs), devices that constrain the emitted radiation minimizing losses during the transport, are an alternative to maximize the amount of detected radiation in luminescence. In this work, the performance of a LCW flow-cell was critically evaluated for chemiluminescence measurements, by using as model the oxidation of luminol by hydrogen peroxide or hypochlorite. An analytical procedure for hypochlorite determination was also developed, with linear response in the range 0.2-3.8 mg/L (2.7-51 mu mol/L), a detection limit estimated as 8 mu g/L (0.64 mu mol/L) at the 99.7% confidence level and luminol consumption of 50 mu g/determination. The coefficients of variation were 3.3% and 1.6% for 0.4 and 1.9 mg/L CIO(-), respectively, with a sampling rate of 164 determinations/h. The procedure was applied to the analysis of Dakin`s solution samples, yielding results in agreement with those obtained by iodometric titration at the 95% confidence level. Copyright (c) 2008 John Wiley & Sons, Ltd.

An improved procedure for flow-based turbidimetric sulphate determination based on a liquid core waveguide and pulsed flows

An improved flow-based procedure is proposed for turbidimetric sulphate determination in waters. The flow system was designed with solenoid micro-pumps in order to improve mixing conditions and minimize reagent consumption as well as waste generation. Stable baselines were observed in view of the pulsed flow characteristic of the systems designed with solenoid micro-pumps, thus making the use of washing solutions unnecessary. The nucleation process was improved by stopping the flow prior to the measurement, thus avoiding the need of sulphate addition. When a 1-cm optical path flow cell was employed, linear response was achieved within 20-200 mg L(-1), described by the equation S = -0.0767 + 0.00438C (mg L(-1)), r = 0.999. The detection limit was estimated as 3 mg L(-1) at the 99.7% confidence level and the coefficient of variation was 2.4% (n = 20). The sampling rate was estimated as 33 determinations per hour. A long pathlength (100-cm) flow cell based on a liquid core waveguide was exploited to increase sensitivity in turbidimetry. Baseline drifts were avoided by a periodical washing step with EDTA in alkaline medium. Linear response was observed within 7-16 mg L(-1), described by the equation S = -0.865 + 0.132C (mg L(-1)), r = 0.999. The detection limit was estimated as 150 mu g L(-1) at the 99.7% confidence level and the coefficient of variation was 3.0% (n = 20). The sampling rate was estimated as 25 determinations per hour. The results obtained for freshwater and rain water samples were in agreement with those achieved by batch turbidimetry at the 95% confidence level. (C) 2008 Elsevier B.V All rights reserved.

A flow-based analytical procedure for salbutamol determination exploiting chemiluminescence in a liquid-core waveguide

Salbutamol is a bronchodilator whose use is restricted due to its anabolic effects. A flow-based procedure for salbutamol determination based on the inhibition of chemiluminescence of the luminol/hypochlorite system was developed. A flow cell constructed with a liquid-core waveguide was employed to constrain the emitted radiation, minimizing losses during transport to detector. Linear response was observed within 2.5 x 10(-6) and 1.0 x 10(-5) mol L-1 with a detection limit estimated as 1 x 10(-7) mol L-1 at the 99.7% confidence level. The coefficient of variation (n = 20), sampling rate, and luminol consumption per determination were estimated as 2.8%, 164 determinations h(-1), and 50 mu g, respectively. Results for pharmaceutical samples were in agreement with those obtained by reference procedures at the 95% confidence level.

Determination of Cr, Fe, Co, Ni, Cu, Zn, As and Pb in liquid chemical waste by energy dispersive X-ray fluorescence

A method for simultaneous determination of Cr, Fe, Co, Ni, Cu, Zn, As e Pb in liquid chemical waste using Energy Dispersive X-Ray Fluorescence (EDXRF) technique was evaluated. A small sample amount (200 mu L) was dried on a 6.35 mu m thickness Mylar film at 60 degrees C and the analyses were carried out using an EDXRF spectrometer operated with an X-ray Mo tube (Zr filter) at 30 kV/20 mA. The acquisition time was 300 s and the Ga element was utilized as internal standard at 25 mg/L for quantitative analysis. The method trueness was assessed by spiking and the detection limit for those elements ranged from 0.39 to 1.7 mg/L. This method is notable because it assists the choice of the more appropriated waste treatment procedure, in which inter elemental interference is a matter of importance. In addition, this inexpensive method allows a non-destructive determination of the elements from (19)K to (92)U simultaneously.

Mechanical properties of Y-TPZ ceramics obtained by liquid phase sintering using bioglass as additive

Yttria stabilized tetragonal zirconia (Y-TZP) ceramics were sintered by liquid phase sintering at low temperatures using bioglass as sintering additive. ZrO2-bioglass ceramics were prepared by mixing a ZrO2 stabilized with 3 Mol%Y2O3 and different amounts of bioglass based on 3CaO center dot P2O5-MgO-SiO2 system. Mixtures were compacted by uniaxial cold pressing and sintered in air, at 1200 and 1300 degrees C for 120 min. The influence of the bioglass content on the densification, tetragonal phase stability, bending strength, hardness and fracture toughness was investigated. The ceramics sintered at 1300 degrees C and prepared by addition of 3% of bioglass, exhibited the highest strength of 435 MPa, hardness of 1170 HV and fracture toughness of 6.3 MPa m(1/2). These results are related to the low monoclinic phase content, high relative density and the presence of the thermal residual stress generated between the ZrO2-matrix and bioglass grain boundary, contributing to the activation of the toughening mechanisms. (c) 2007 Elsevier B.V. All rights reserved.

Linoleic acid peroxidation and lignin degradation by enzymes produced by Ceriporiopsis subvermispora grown on wood or in submerged liquid cultures

Ceriporiopsis subvermispora is a white-rot fungus used in biopulping processes and seems to use the fatty acid peroxidation reactions initiated by manganese-peroxidase (MnP) to start lignin degradation. The present work shows that C. subvermispora was able to peroxidize unsaturated fatty acids during wood biotreatment under biopulping conditions. In vitro assays showed that the extent of linoleic acid peroxidation was positively correlated with the level of MnP recovered from the biotreated wood chips. Milled wood was treated in vitro by partially purified MnP and linoleic acid. UV spectroscopy and size exclusion chromatography (SEC) showed that soluble compounds similar to lignin were released from the milled wood. SEC data showed a broad elution profile compatible with low molar mass lignin fractions. MnP-treated milled wood was analyzed by thioacidolysis. The yield of thioacidolysis monomers recovered from guaiacyl and syringyl units decreased by 33% and 20% in MnP-treated milled wood, respectively. This has suggested that lignin depolymerization reactions have occurred during the MnP/linoleic acid treatment. (C) 2009 Elsevier Inc. All rights reserved.

Nitrogen removal in a sequencing batch biofilm reactor with liquid circulation: Effect of feed strategy and carbon source in the denitrifying step

Ammonium nitrogen removal from a synthetic wastewater by nitrification and denitrification processes were performed in a sequencing batch biofilm reactor containing immobilized biomass on polyurethane foam with circulation of the liquid-phase. It was analyzed the effect of four external carbon sources (ethanol, acetate, carbon synthetic medium and methanol) acting as electron donors in the denitrifying process. The experiments were conducted with intermittent aeration and operated at 30+/-1 degrees C in 8-h cycles. The synthetic wastewater (100 mgCOD/L and 50 mgNH(4)(+)-N/L) was added batch-wise, while the external carbon sources were added fed-batch-wise during the periods where aeration was suspended. Ammonium nitrogen removal efficiencies obtained were 95.7, 94.3 and 97.5% for ethanol, acetate and carbon synthetic medium, respectively. As to nitrite, nitrate and ammonium nitrogen effluent concentrations, the results obtained were, respectively: 0.1, 5.7 and 1.4 mg/L for ethanol; 0.2, 4.1 and 1.8 mg/L for acetate and 0.2, 6.7 and 0.8 for carbon synthetic medium. On the other hand using methanol, even at low concentrations (50% of the stoichiometric value calculated for complete denitrification), resulted in increasing accumulation of nitrate and ammonium nitrogen in the effluent over time.

Numerical solution of the two-phase expansion of a metastable flashing liquid jet using the dispersion-controlled dissipative scheme

This paper presents a study of the stationary phenomenon of superheated or metastable liquid jets, flashing into a two-dimensional axisymmetric domain, while in the two-phase region. In general, the phenomenon starts off when a high-pressure, high-temperature liquid jet emerges from a small nozzle or orifice expanding into a low-pressure chamber, below its saturation pressure taken at the injection temperature. As the process evolves, crossing the saturation curve, one observes that the fluid remains in the liquid phase reaching a superheated condition. Then, the liquid undergoes an abrupt phase change by means of an oblique evaporation wave. Across this phase change the superheated liquid becomes a two-phase high-speed mixture in various directions, expanding to supersonic velocities. In order to reach the downstream pressure, the supersonic fluid continues to expand, crossing a complex bow shock wave. The balance equations that govern the phenomenon are mass conservation, momentum conservation, and energy conservation, plus an equation-of-state for the substance. A false-transient model is implemented using the shock capturing scheme: dispersion-controlled dissipative (DCD), which was used to calculate the flow conditions as the steady-state condition is reached. Numerical results with computational code DCD-2D vI have been analyzed. Copyright (C) 2009 John Wiley & Sons, Ltd.

Reduction of Chromium from Al(2)O(3)-CaO-SiO(2)-CrOx Slags by Carbon Dissolved in Liquid Iron

The goal of this work is to investigate the reduction of chromium from a quaternary slag by carbon dissolved in liquid steel. Laboratory scale experiments were conducted to study the reduction of chromium oxides in the slag by carbon dissolved in the melt. These experiments were made under different conditions of slag basicity and amount of added carbon. Thermodynamic calculations based on Double Sublattice model were applied using the commercial software Thermo-Calc, with the IRSID database. The results obtained showed good correlation with practical and calculated results, making it possible to predict equilibrium conditions of the system and to determine the activities of chromium oxides in the slag.

Batch Liquid-Liquid Extraction of Phenol from Aqueous Solutions

The aim of this work is the study of batch liquid-liquid extraction of phenol from aqueous solutions in a bench-scale well-mixed reactor. The influence of the ratio of phase volumes, temperature, and rotational speed on phenol removal (0.72-1.1% w/w) was investigated using methyl isobutyl ketone as an extracting solvent. For this purpose, the ratio of phase volumes were set at 0.1 and 0.2, the temperature at 10, 20, and 30 degrees C, and the rotational speed at 300, 400, and 500 rpm. A physical model based on the material balance of the phases as well as the equation of mass flux between the phases allowed the estimation of the overall coefficient of mass transfer coupled with the superficial area. Moreover, it proved to fit, satisfactorily well, the experimental data of residual phenol concentration in the organic phase versus time under all the conditions investigated.