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The use of electric fields as additional driving forces in sample preparation techniques is an innovative approach that is environmentally friendly, straightforward, and able to overcome several limitations of conventional sample preparation procedures. In this work, the advantages of electric field-assisted solid phase extraction (E-SPE) using syringe-type cartridges were demonstrated for the extraction of four fluoroquinolones (FQs) in their anionic forms. The FQs were extracted from eggs and subsequently determined by UHPLC–MS/MS. The use of electric fields during the washing and final elution steps resulted in a significant improvement of the extraction efficiencies for almost all FQs when compared to conventional SPE. Intra- and inter-day assays showed coefficients of variation below 10%. The better cleanup also resulted in the appearance of less precipitated matter in the final eluate, as well as reduced matrix effects. The results showed that the electrophoretic forces derived from electric fields are a promising way of significantly increasing the extraction efficiency of ionic analytes, while minimizing matrix effects associated with complex samples.

A semiautomated solid-phase extraction manifold for multiple extractions is presented. The manifold utilizes commercial solid-phase syringe cartridges and automatically introduces and elutes all the solvents during the extraction, reducing the typical workload and stress of the analyst. The manifold consists of a peristaltic pump with solenoid valves in a flow circuit that contains transmissive photomicrosensors. The photomicrosensors were used to control the solvent dispenser and the solvent level inside the cartridge. As solvent-level sensors, the photomicrosensors determined the exact time the solvent reached the top frit to avoid sorbent drying and accurately perform the solvent exchange. The repeatability of the manifold to introduce a particular volume of solvent into the cartridges was measured, and the precisions were between 0.05 and 2.89% (RSD). To evaluate the manifold, the amount of two fluoroquinolones in a fortified blank milk sample was determined. The results of the intra- and inter-day precision of multiple extractions from the fortified milk samples resulted in precisions better than 9.0% (RSD) and confirmed that the arrangement of the semiautomated manifold could adequately be used in solid-phase extraction with commercial cartridges.

An automated system for liquid-liquid extraction flow analysis (LLE-FA) for the determination of Sb(V) in antileishmanial drugs is presented. The method is based on extraction in a 5mL glass extraction chamber of an ion pair formed between hexachloroantimoniate anion and rhodamine B cation into toluene. The detection system consists of a green light emitting diode (LED) and a photodiode. The system is controlled by a microcomputer using a program written in Visual Basic 3.0. The extraction process was optimized and the following experimental parameters were established: sample loop of 150muL; reagent loop of 900muL; stirring time of 100s; phase separation time of 80s; volumetric ratio of 1:1 (aqueous/organic). The method was in-house validated for the determination of Sb(V) in meglumine antimoniate. The following performance criteria were obtained: linearity of 0.9989, linear range of 7.0x10(-5) to 7.2x10(-4)mol Sb(V)L(-1), sensitivity of 1.61x10(6)+/-2 arbitrary units Lmol(-1) (P0.05), intra-assay precision of 3.5% (n=5; 4.1x10(-4)molL(-1) Sb(V). Whereas the method is selective in the presence of Sb(III), As(III) and Pb(II) at concentrations up to one tenth of the concentration of Sb(V), As(V) interferes. The accuracy of the method was evaluated through comparison of results obtained from analyses of pharmaceutical formulations by the proposed LLE-FA method with those obtained by inductively coupled plasma optic emission spectrometry (ICP OES) and differential pulse polarography for total antimony and Sb(III), respectively. The proposed method presented an analytical frequency of eight analysis per hour and is suitable for Sb(V) determination in the quality control of drugs employed for the treatment of leishmaniasis.

In this work a stainless steel electrode was prepared, characterised and used as indicator electrode in a potentiometric flow cell. Due to its versatility, it was possible to study different electrode geometries and flow cell arrangements. After optimising the system, mixtures of succinic and oxalic acids were determined by titration. Partial least squares (PLS) regression as multivariate calibration tool was applied for data treatment. The predicted results obtained in a test set showed a relative error of 4.3% for succinic acid and 5.5% for oxalic acid.

Near infrared (NIR) spectroscopy was employed for simultaneous determination of methanol and ethanol contents in gasoline. Spectra were collected in the range from 714 to 2500 nm and were used to construct quantitative models based on partial least squares (PLS) regression. Samples were prepared in the laboratory and the PLS regression models were developed using the spectral range from 1105 to 1682 nm, showing a root mean square error of prediction (RMSEP) of 0.28% (v/v) for ethanol for both PLS-1 and PLS-2 models and of 0.31 and 0.32% (v/v) for methanol for the PLS-1 and PLS-2 models, respectively. A RMSEP of 0.83% (v/v) was obtained for commercial samples. The effect of the gasoline composition was investigated, it being verified that some solvents, such as toluene and o-xylene, interfere in ethanol content prediction, while isooctane, o-xylene, m-xylene and p-xylene interfere in the methanol content prediction. Other spectral ranges were investigated and the range 1449-1611 nm showed the best results.

A monosegmented volumetric Karl Fischer titrator is described to mechanize the determination of water content in organic solvents. The system is based on the flow-batch characteristics of the monosegmented analysis concept and employs biamperometry to monitor the progress of the titration. The system shows accuracy and precision that are highly independent of the flow rate, does not require calibration, and is carried out in a closed system capable of minimizing contact of the sample and reagents with ambient moisture. Sample volumes in the range of 40-300muL are employed, depending on the water concentration. An automatic dilution is provided to deal with concentrated samples. The consumption of Karl Fischer reagent depends on the water content of the sample but is not larger than 100muL. The system was evaluated for determination of water in ethanol and methanol in the range 0.02-0.5% (w/w). The average relative precision estimated in that range (9-3%) is comparable to that obtained with a larger volume commercial system and no significant difference was observed between the results obtained for the two systems at the 95% confidence level. A complete titration can be performed in less than 5min employing the proposed system.

This paper presents two methodologies for monitoring the service condition of diesel-engine lubricating oils on the basis of infrared spectra. In the first approach, oils samples are discriminated into three groups, each one associated to a given wear stage. An algorithm is proposed to select spectral variables with good discriminant power and small collinearity for the purpose of discriminant analysis classification. As a result, a classification accuracy of 93% was obtained both in the middle (MIR) and near-infrared (NIR) ranges. The second approach employs multivariate calibration methods to predict the viscosity of the lubricant. In this case, the use of absorbance measurements in the NIR spectral range was not successful, because of experimental difficulties associated to the presence of particulate matter. Such a problem was circumvented by the use of attenuated total reflectance (ATR) measurements in the MIR spectral range, in which an RMSEP of 3.8 cSt and a relative average error of 3.2% were attained.

A monosegmented flow system was employed for the determination of low contents of phosphate in natural water. In this approach, sample and reagents are simultaneously injected to a PTFE reaction coil where the homogenization of the mixture occurs while the monosegment is pumped forwards the photometric detector. The proposed system was evaluated by determining phosphate ion, based on the reaction of association between molybdophosphate and malachite green. It was evaluated individually the best concentration of the reagent solution in relation to blank signal (absorbance of the blank) and the sensitivity of the method. A factorial design was proposed to explain the contribution of each component on the formation of the ion association complex, evaluating the individual contributions as well as the synergistic and antagonistic effects. With the established conditions, phosphorous is determined in the concentration range of 5.0-75mug P PO(4)(3-)l(-1) (r=0.9992), with a detection limit of 0.70mug P PO(4)(3-)l(-1) and a relative standard deviation of 2% (20mug P PO(4)(3-)l(-1), n=8). The proposed method has a sampling frequency of 72h(-1).

In liquid–liquid extraction performed by monosegmented flow analysis (MSFA), the aqueous sample is introduced between two air bubbles and flows, under restricted dispersion, through a glass extraction tube where the analyte is retained, usually at pH higher than 8. The retained analyte is removed to a small volume of an organic phase containing a ligand which is introduced after the second air bubble. In this work, the effect of the organic phase composition on the extraction of Cu(II), Zn(II) and Cd(II) in MSFA systems was investigated by changing the ethanol content (0.1–4% v/v) in toluene, chloroform and carbon tetrachloride. The extracting efficiency of the organic phases containing ethanol was evaluated by using dithizone (DT), 1-2-pyridylazo-2 naphthol (PAN) and sodium diethyldithiocarbamate (DDTC) as ligands for the metals. The MSFA extraction system was improved by introducing a new syringe-based device for organic phase delivery. The presence of ethanol in the organic phase shows a remarkable (up to ten times) effect on the extraction efficiency of the flow system when DT is employed. Its presence is mandatory if DDTC is used, as it accounts for ligand solubility in the organic phase. The extraction efficiency also increases with the pH of the aqueous phase as a consequence of higher ionisation of the glass silanols, where the analytes are adsorbed before extraction. The system has been evaluated for determination of Zn(II) in drugs showing a mean R.S.D. of 2.2% and mean relative accuracy of 4.4%, when compared with atomic absorption spectrometry results. Typical sample frequency, sample and organic phase consumption are 30 samples per hour, 200 and 100 μl, respectively.

A titrimetric method for determination of lead(II), based on the reaction between plumbite and silver ions, is described. Sodium hydroxide solution is added to the sample until the precipitate of lead hydroxide has redissolved. The solution is then made 0.025M in sodium chloride and titrated with silver nitrate. The titration is monitored with a silver electrode. An error smaller than 0.5% has been obtained for 0.05M lead (II).