Simultaneous analysis of parabens in cosmetic products by stir bar sorptive extraction and liquid chromatography

A sensitive and precise stir bar sorptive extraction (SBSE) combined with LC (SBSE/LC) analysis is described for simultaneous determination of methyl, ethyl, propyl, and butyl parabens in commercial cosmetic products in agreement with the European Union Cosmetics Directive 76/768/EEC. Important factors in the optimization of SB SE efficiency are discussed, such as time and temperature of extraction, pH, and ionic strength of the sample, matrix effects, and liquid desorption conditions by different modes (magnetic stirring, ultrasonic). The LOQs of the SBSE/LC method ranged from 30 to 200 ng/mg, with linear response over a dynamic range, from the LOQ to 2.5 mu g/mg, with a coefficient of determination higher than 0.993. The interday precision of the SBSE/LC method presented a coefficient of variation lower than 5%. The effectiveness of the proposed method was proven for analysis of commercial cosmetic products such as body creams, antiperspirant creams, and sunscreens.

Rifampicin determination in plasma by stir bar-sorptive extraction and liquid chromatography

A sensitive and reproducible stir bar-sorptive extraction and high performance liquid chromatography-UV detection (SBSE/HPLC-UV) method for therapeutic drug monitoring of rifampicin in plasma samples is described and compared with a liquid:liquid extraction (LLE/HPLC-UV) method. This miniaturized method can result in faster analysis, higher sample throughput, lower solvent consumption and less workload per sample while maintaining or even improving sensitivity. Important factors in the optimization of SBSE efficiency such as pH, temperature, extraction time and desorption conditions (solvents, mode magnetic stir, mode ultrasonic stir, time and number of steps) were optimized recoveries ranging from 75 to 80%. Separation was obtained using a reverse phase C(8) column with UV detection (254 nm). The mobile phase consisted of methanol:0.25 N sodium acetate buffer, pH 5.0 (58:42, v/v). The SBSE/HPLC-UV method was linear over a working range of 0.125-50.0 mu g mL(-1). The intra-assay and inter-assay precision and accuracy were studied at three concentrations (1.25, 6.25 and 25.0 mu g mL(-1)). The intra-assay coefficients of variation (CVs) for all compounds were less than 10% and all inter-CVs were less than 10%. Limits of quantification were 0.125 mu g mL(-1). Stability studies showed rifampicin was stable in plasma for 12 h after thawing; the samples were also stable for 24 h after preparation. Based on the figures of merit results, the SBSE/HPLC-UV proved to be adequate to the rifampicin analyses from therapeutic to toxic levels. This method was successfully applied to the analysis of real samples and was as effective as the LLE/HPLC-UV method. (C) 2009 Elsevier B.V. All rights reserved.

Determination of fluoxetine and norfluoxetine enantiomers in human plasma by polypyrrole-coated capillary in-tube solid-phase microextraction coupled with liquid chromatography-fluorescence detection

A sensitive, selective, and reproducible in-tube polypyrrole-coated capillary (PPY) solid-phase microextraction and liquid chromatographic method for fluoxetine and norfluoxetine enantiomers analysis in plasma samples has been developed, validated, and further applied to the analysis of plasma samples from elderly patients undergoing therapy with antidepressants. Important factors in the optimization of in-tube SPME efficiency are discussed, including the sample draw/eject volume, draw/eject cycle number, draw/eject flow-rate, sample pH, and influence of plasma proteins. Separation of the analytes was achieved with a Chiralcel OD-R column and a mobile phase consisting of potassium hexafluorophosphate 7.5 mM and sodium phosphate 0.25 M solution, pH 3.0, and acetonitrile (75:25, v/v) in the isocratic mode, at a flow rate of 1.0 mL/min. Detection was carried out by fluorescence absorbance at Ex/Em 230/290 nm. The multifunctional porous surface structure of the PPY-coated film provided high precision and accuracy for enantiomers. Compared with other commercial capillaries, PPY-coated capillary showed better extraction efficiency for all the analytes. The quantification limits of the proposed method were 10 ng/mL for R- and S-fluoxetine, and 15 ng/mL for R- and S-norfluoxetine, with a coefficient of variation lower than 13%. The response of the method for enantiomers is linear over a dynamic range, from the limit of quantification to 700ng/mL, with correlation coefficients higher than 0.9940. The in-tube SPME/LC method can therefore be successfully used to analyze plasma samples from ageing patients undergoing therapy with fluoxetine. (C) 2009 Elsevier B.V. All rights reserved.

Automated determination of rifampicin in plasma samples by in-tube solid-phase microextraction coupled with liquid chromatography

A sensitive and automated method is described for determination of rifampicin in plasma samples for therapeutic drug monitoring by in-tube solid-phase microextraction coupled with liquid chromatography (in-tube SPME/LC). Important factors in the optimization of in-tube SPME are discussed, such as coating type, sample pH, sample draw/eject volume, number of draw/eject cycles, and draw/eject flow rate. Analyte pre-concentrated in the polyethylene glycol phase was directly transferred to the liquid chromatographic column by percolation of the mobile phase, without carryover. The method was linear over the 0.1-100 mu g/mL range, with a linear coefficient value (r(2)) of 0.998. The inter-assay precision presented coefficient of variation <= 1.7%. The effectiveness and practicability of the proposed method are proven by analysis of plasma samples from ageing patients undergoing therapy with rifampicin. (C) 2011 Elsevier B.V. All rights reserved.

Purification and Partial Characterization of an Exo-polygalacturonase from Paecilomyces variotii Liquid Cultures

An extracellular polygalacturonase (PG) produced from Paecilomyces variotii was purified to homogeneity through two chromatography steps using DEAE-Fractogel and Sephadex G-100. The molecular weight of P. variotii PG was 77,300 Da by gel filtration and SDS-PAGE. PG had isoelectric point of 4.37 and optimum pH 4.0. PG was very stable from pH 3.0 to 6.0. The extent of hydrolysis of different pectins by the purified enzyme was decreased with an increase in the degree of esterification. PG had no activity toward non-pectic polysaccharides. The apparent K (m) and V (max) values for hydrolyzing sodium polypectate were 1.84 mg/mL and 432 A mu mol/min/mg, respectively. PG was found to have temperature optimum at 65 A degrees C and was totally stable at 45 A degrees C for 90 min. Half-life at 55 A degrees C was 50.6 min. Almost all the examined metal cations showed partial inhibitory effects under enzymatic activity, except for Na(+1), K(+1), and Co(+2) (1 mM) and Cu(+2) (1 and 10 mM).

On the solute coupling at the moving solid/liquid interface during equiaxed solidification

Integral mass conservation was widely accepted for the solute coupling to solve solute redistribution during equiaxed solidification so far. The present study revealed that the integral form was invalid for moving boundary problems as it could not represent the mass balance at the moving interface. Accordingly, differential mass conservation at the solid/liquid interface was used to solve solute diffusion for spherical geometry. The model was applied for hydrogen diffusion in solidification to validate that the hydrogen enrichment was significant and depended on the growth rate. (c) 2006 American Institute of Physics.

Percutaneous absorption of sunscreen agents from liquid paraffin: Self-association of octyl salicylate and effects on skin flux

This study provides an investigation of the availability of octyl salicylate (OS), a common sunscreen agent, from liquid paraffin and the effect of OS on skin permeability. A model membrane system to isolate the vehicle effect from membrane permeability has been developed. Partitioning of OS between liquid paraffin and aqueous receptor phases was conducted. Partition coefficients increased with increase in OS concentration. A range of OS concentrations in liquid paraffin was diffused across human epidermis and synthetic membranes into 4% bovine serum albumin in phosphate-buffered saline and 50% ethanol. Absorption profiles of OS obtained from silicone and low-density polyethylene (LDPE) membranes were similar to each other but higher than for the high-density polyethylene [HDPE (3 times)] membrane and human epidermis (15 times). The steady state fluxes and apparent permeability coefficients (K-p') obtained from the diffusion studies showed the same trends with all membranes, except for the HDPE membrane which showed greater increase in flux and K-p' at concentrations above 30%. IR spectra showed that several bands of OS were shifted with concentrations, and the molecular models further suggested that the main contribution to the self-association is from non-1,4 van der Waals interactions.

Influence of Sensory Cues on the Stimulability for Liquid Sounds in Brazilian Portuguese-Speaking Children

Objective: Stimulability is the ability to produce an adequate sound under specific conditions. This study aimed to describe the stimulability of Brazilian Portuguese-speaking children with and without phonological disorders for the production of liquid sounds with the aid of visual and tactile cues. Patients and Methods: The study sample included 36 children between 5; 0 and 11; 6 years of age, 18 with phonological disorder and 18 without any speech-language disorders. Stimulability was measured for syllable imitation. The stimulability test employed includes 63 syllables with the sounds [1], [(sic)], and [(sic)], as well as seven oral vowels. If the subject was unable to imitate a sound, a visual cue was given. When necessary, a tactile cue was also given. Results: The sound [(sic)] required greater use of sensory cues. Children with phonological disorder needed a greater number of cues. Conclusion: The use of sensory cues seemed to facilitate sound stimulability, making it possible for the children with phonological disorder to accurately produce the sounds modeled. Copyright (C) 2009 S. Karger AG, Basel

Anisotropic Reversible Aggregation of Latex Nanoparticles Suspended in a Lyotropic Nematic Liquid Crystal: Effect of Gradients of Biaxial Order

We studied the anisotropic aggregation of spherical latex particles dispersed in a lyotropic liquid crystal presenting three nematic phases; calamitic, biaxial, and discotic. We observed that in the nematic calamitic phase aggregates of latex particles are formed, which become larger and anisotropic in the vicinity of the transition to the discotic phase, due to a coalescence process. Such aggregates are weakly anisotropic and up to 50 mu m long and tend to align parallel to the director field. At the transition to the discotic phase, the aggregates dissociated and re-formed when the system was brought back to the calamitic phase. This shows that the aggregation is due to attractive and repulsive forces generated by the particular structure of the nematic phase. The surface-induced positional order was investigated by surface force apparatus experiments with the lyotropic system confined between mica surfaces, revealing the existence of a presmectic wetting layer around the surfaces and oscillating forces of increasing amplitude as the confinement thickness was decreased. We discuss the possible mechanisms responsible for the reversible aggregation of latex particles, and we propose that capillary condensation of the N(C) phase, induced by the confinement between the particles, could reduce or remove the gradient of order parameter, driving the transition of aggregates from solidlike to liquidlike and gaslike.

Enantioselective Determination of Mexiletine and Its Metabolites p-Hydroxymexiletine and Hydroxymethylmexiletine in Rat Plasma by Normal-Phase Liquid Chromatography-Tandem Mass Spectrometry: Application to Pharmacokinetics

Mexiletine (MEX), hydroxymethylmexiletine (HMM) and P-hydroxy-mexiletine (PHM) were analyzed in rat plasma by LC-MS/MS. The plasma samples were prepared by liquid-liquid extraction using methyl-tert-butyl ether as extracting solvent. MEX, HMM, and PHM enantiomers were resolved on a Chiralpak (R) AD column. Validation of the method showed a relative standard deviation (precision) and relative errors (accuracy) of less than 15% for all analytes studied. Quantification limits were 0.5 ng ml(-1) for the MEX and 0.2 ng ml(-1) for the HMM and PHM enantiomers. The validated method was successfully applied to quantify the enantiomers of MEX and its metabolites in plasma samples of rats (n = 6) treated with a single oral dose of racemic MEX. Chirality 21:648-656, 2009. (C) 2008 Wiley-Liss, Inc.

A sensitive and specific assay for glutathione with potential application to glutathione disulphide, using high-performance liquid chromatography-tandem mass spectrometry

We have utilised the combination of sensitivity and specificity afforded by coupling high-performance liquid chromatography (HPLC) to a tandem mass spectrometer (MS-MS) to produce an assay which is suitable for assaying glutathione (GSH) concentrations in liver tissue. The sensitivity suggests it may also be suitable for extrahepatic tissues, The method has been validated for GSH using mouse liver samples and also allows the assay of GSSG. The stability of GSH under conditions relevant to the assay has been determined. A 20-mul amount of a diluted methanol extract of tissue is injected with detection limits of 0.2 pmol for GSH and 2 pmol for GSSG. The HPLC uses an Altima C-18 (150X4.6 mm, 5 mum) column at 35 degreesC. Chromatography utilises a linear gradient from 0 to 10% methanol in 0.1% formic acid over 5 min, with a final isocratic stage holding at 10% methanol for 5 min. Total flow rate is 0.8 ml/min. The transition from the M+H ion (308.1 m/z for GSH, and 613.3 m/z for GSSG) to the 162.0 m/z (GSH) and 355.3 m/z (GSSG) fragments are monitored. (C) 2001 Elsevier Science B.V. All rights reserved.

A modified pore-filling isotherm for liquid-phase adsorption in activated carbon

This article modifies the usual form of the Dubinin-Radushkevich pore-filling model for application to liquid-phase adsorption data, where large molecules are often involved. In such cases it is necessary to include the repulsive part of the energy in the micropores, which is accomplished here by relating the pore potential to the fluid-solid interaction potential. The model also considers the nonideality of the bulk liquid phase through the UNIFAC activity coefficient model, as well as structural heterogeneity of the carbon. For the latter the generalized adsorption integral is used while incorporating the pore-size distribution obtained by density functional theory analysis of argon adsorption data. The model is applied here to the interpretation of aqueous phase adsorption isotherms of three different esters on three commercial activated carbons. Excellent agreement between the model and experimental data is observed, and the fitted Lennard-Jones size parameter for the adsorbate-adsorbate interactions compares well with that estimated from known critical properties, supporting the modified approach. On the other hand, the model without consideration of bulk nonideality, or when using classical models of the characteristic energy, gives much poorer bts of the data and unrealistic parameter values.

The use of liquid phase adsorption isotherms for characterization of activated carbons

The characterization of three commercial activated carbons was carried out using the adsorption of various compounds in the aqueous phase. For this purpose the generalized adsorption isotherm was employed, and a modification of the Dubinin-Radushkevich pore filling model, incorporating repulsive contributions to the pore potential as well as bulk liquid phase nonideality, was used as the local isotherm. Eight different flavor compounds were used as adsorbates, and the isotherms were jointly fitted to yield a common pore size distribution for each carbon. The bulk liquid phase nonideality was incorporated through the UNIFAC activity coefficient model, and the repulsive contribution to the pore potential was incorporated through the Steele 10-4-3 potential model. The mean micropore network coordination number for each carbon was also determined from the fitted saturation capacity based on percolation theory. Good agreement between the model and the experimental data was observed. In addition, excellent agreement between the bimodal gamma pore size distribution and density functional theory-cum-regularization-based pore size distribution obtained by argon adsorption was also observed, supporting the validity of the model. The results show that liquid phase adsorption, using adsorptive molecules of different sizes, can be an effective means of characterizing the pore size distribution as well as connectivity. Alternately, if the carbon pore size distribution is independently known, the method can be used to measure critical molecular sizes. (C) 2001 Elsevier Science.

Characterization of activated carbons using liquid phase adsorption

A modification of the Dubinin-Radushkevich pore filling model by incorporation of the repulsive contribution to the pore potential, and of bulk non-ideality, is proposed in this paper for characterization of activated carbon using liquid phase adsorption. For this purpose experiments have been performed using ethyl propionate, ethyl butyrate, and ethyl isovalerate as adsorbates and the microporous-mesoporous activated carbons Filtrasorb 400, Norit ROW 0.8 and Norit ROX 0.8 as adsorbents. The repulsive contribution to the pore potential is incorporated through a Lennard-Jones intermolecular potential model, and the bulk-liquid phase non-ideality through the UNIFAC activity coefficient model. For the characterization of activated carbons, the generalized adsorption isotherm is utilized with a bimodal gamma function as the pore size distribution function. It is found that the model can represent the experimental data very well, and significantly better than when the classical energy-size relationship is used, or when bulk non-ideality is neglected. Excellent agreement between the bimodal gamma pore size distribution and DFT-cum-regularization based pore size distribution is also observed, supporting the validity of the proposed model. (C) 2001 Elsevier Science Ltd. All rights reserved.