Ultrasonic sensor for the presence of oily contaminants in water

The determination of the complex reflection coefficient of ultrasonic shear-waves at the solid-liquid interface is a technique employed for the measurement of the viscoelastic properties of liquids. An interesting property of the measurement technique is the very small penetration depth of the shear-waves into the liquid sample, which permits measurements with liquid films of some micrometers thick. This property, along with the adhesion of oily substances to surfaces, can be used for the detection of oily contaminants in water. In this work, the employment of the ultrasonic shear-wave reflection technique to the detection of oily contaminants in water is proposed and the theoretical and experimental concepts involved are discussed. Preliminary experimental results show the measurement technique can detect SAE 40 automotive oil in water in volume proportions less than 0.5%.

Liquid-liquid equilibria for systems composed of rice bran oil and alcohol-rich solvents: Application to extraction and deacidification of oil

The liquid-liquid equilibria of systems composed of rice bran oil, free fatty acids, ethanol and water were investigated at temperatures ranging from 10 to 60 degrees C. The results of the present study indicated that the mutual solubility of the compounds decreased with an increase in the water content of the solvent and a decrease in the temperature of the solution. The experimental data set was correlated by applying the UNIQUAC model. The average variance between the experimental and calculated compositions was 0.35%, indicating that the model can accurately predict behavior of the compounds at different temperatures and degrees of hydration. The adjustment of interaction parameters enables both the simulation of liquid-liquid extractors for deacidification of vegetable oil and the prediction of phase compositions for the oil and alcohol-rich phases that are generated during cooling of the stream exiting the extractor (when using ethanol as the solvent). (C) 2012 Elsevier Ltd. All rights reserved.

Formation of thin luminescent Eu3+-LB films by in situ coordination with 2,3,5,6-tetra(2 '-pyridyl)pyrazine and 1-octadecanol in pure and mixed Langmuir monolayers

The in situ complexation between 2,3,5,6-tetra(2-pyridyl)pyrazine (tppz) molecules and europium ions at the air-liquid interface by means of mixed 1-octadecanol Langmuir films is reported. These films were transferred to solid supports by means of the Langmuir-Blodgett (LB) technique. The EDS maps attested the homogeneity of the LB films as well as the presence of the europium ions. The mixed alcohol/tppz LB film contained a larger amount of europium ions as compared to the pure octadecanol LB film. This work reports the production of a thin luminescent Eu3+ film containing europium ions using only alcohol molecules as ligands an unexpected result, since it is well known that there is an occurrence of non-radiative deactivation of excited europium by hydroxyl groups. Europium ion multiple binding sites were detected from lifetime decay measurements of these films in the presence of tppz molecules. (C) 2012 Elsevier B.V. All rights reserved.

Comparison of predicted and experimental DSC curves for vegetable oils

We compare experimental and predicted differential scanning calorimetry (DSC) curves for palm oil (PO), peanut oil (PeO) and grapeseed oil (GO). The predicted curves are computed from the solid-liquid equilibrium modelling and direct minimization of the Gibbs free energy. For PO, the lower the scan rate, the better the agreement. The temperature transitions of PeO and GO were predicted with an average deviation of -0.72 degrees C and -1.29 degrees C respectively, in relation to experimental data from literature. However, the predicted curves showed other peaks not reported experimentally, as computed DSC curves correspond to equilibrium hypothesis which is reached experimentally for an infinitely small scan rate. The results revealed that predicted transitions temperatures using equilibrium hypotheses can be useful in pre-experimental evaluation of vegetable oils formulations seeking for desired melting profiles. (C) 2012 Elsevier B.V. All rights reserved.

Interaction of chitosan and mucin in a biomembrane model environment

Chitosans have been widely exploited in biological applications, including drug delivery and tissue engineering, especially owing to their mucoadhesive properties, but the molecular-level mechanisms for the chitosan action are not known in detail. It is believed that chitosan could affect the mucus by interacting with the proteins mucins, in a process mediated by the cell membrane. In this study we used Langmuir monolayers of dimyristoylphosphatidic acid (DMPA) as simplified membrane models to investigate the interplay between the activity of mucins and chitosan. Surface pressure and surface potential measurements were performed with DMPA monolayers onto which chitosan and/or mucin was adsorbed. We found that the expanding effect from mucin was considerably reduced when chitosan was injected after mucin had been adsorbed on the DMPA monolayer. The results were consistent with the formation of complexes between mucin and chitosan, thus highlighting the importance of electrostatic interactions. Furthermore, chitosan could remove mucin that was co-deposited along with DMPA in Langmuir-Blodgett (LB) films, which could be ascribed to molecular-level interactions between chitosan and mucin inferred from the FTIR spectra of the LB films. In conclusion, the results with Langmuir and LB films suggest that electrostatic interactions are crucial for the mucoadhesive mechanism, which is affected by the complexation between chitosan and mucin. (C) 2012 Elsevier Inc. All rights reserved.

Mechanical Measurements Of Two Exogenous Surfactants Using A Langmuir Film Balance:A Comparative Study

Rationale: The primary function of surfactant is to reduce the surface tension at air-liquid interface. In this study, the surface tension behavior of two commercial surfactants, poractant alfa (ChiesiFarmaceuticals,ltaly) and beractant (Abbott Laboratories,USA), were evaluated,using new parameters. Methods: We used a Langmuir film balance (Minitrough,KSV lnstruments,Finland) to measure of surface tension of both poractant alfa and beractant samples. For both samples,we prepared a solution of 1 mg/mdl dissolved in chloroform. The solution (1uL) was applied over a subphase of milli-Q water (175 ml) in the chamber of the balance. The chamber has two moving barriers that can change its surface area between a maximum value of 112.5 cm2 anda minimum value of 22.5 cm2, defining a balance cycle.lhree sample's films were evaluated for each sample, during 20 balance cycles. Here quantify two new variables, which is the mean hysteresis area of the measured curve surface tension of the last 16 balance cycles,defined here as Mean Work Cycle (MWC), and the moment that the surfactant is active in the surface, this measure is defined here as Active Surface Area Critical in the compression (ASACC) and the expansion (ASACE). The test was applied to compare the statistical significance of the results.

Determination of anticonvulsants in human plasma using SPME in a heated interface coupled online to liquid chromatography (SPME-LC)

A simple and sensitive method using solid phase microextraction (SPME) and liquid chromatography (LC) with heated online desorption (SPME-LC) was developed and validated to analyze anticonvulsants (AEDs) in human plasma samples. A heated lab-made interface chamber was used in the desorption procedure, which allowed the transference of the whole extracted sample. The SPME conditions were optimized by applying an experimental design. Important factors are discussed such as fiber coating types, pH, extraction time and desorption conditions. The drugs were analyzed by LC, using a C18 column (150 mm x 4.6 mm x 5 mm); and 50 mmol L-1, pH 5.50 ammonium acetate buffer : acetonitrile : methanol (55 : 22 : 23 v/v) as the mobile phase with a flow rate of 0.8 mL min(-1). The suggested method presented precision (intra-assay and inter-assay), linearity and limit of quantification (LOQ) all adequate for the therapeutic drug monitoring (TDM) of AEDs in plasma.

Evaluation of Solid-Phase Microextraction using a Polythiophene Film and Liquid Chromatography with Spectrophotometric Detection for the Determination of Antidepressants in Plasma Samples

Polythiophene (PTh) phase electropolymerized on the stainless steel wire was evaluated as solid-phase microextraction (SPME), and analysis by liquid chromatography with spectrophotometric detection (LC-UV) for determination of new-generation antidepressants, selective serotonin reuptake inhibitors (SSRIs) (citalopram, paroxetine, fluoxetine and sertraline), in plasma samples. The influence of electropolymerization variables (scan rate, potential range and scan cycles) was evaluated on SPME performance. The SPME variables (extraction time, temperature, matrix pH, ionic strength and desorption procedure), as well as the influence of plasma proteins on sorption mechanisms were also evaluated. The SPME/LC-UV method developed for determination of antidepressants in plasma sample presented a linear range between the limit of quantification (LOQ, 200-250 ng mL(-1)) to 4000 ng mL(-1), and interday precision with coefficient of variation (CV) ranged from 11 to 15%. The proposed method can be a useful tool for the determination of antidepressants in human plasma samples in urgent toxicological analysis after the accidental or suicidal intake of higher doses of medications.

Low liquid-solid ratio (LSR) hot water pretreatment of sugarcane bagasse

Low liquid-solid ratio (LSR) can be used to obtain high-content xylo-oligosaccharide (XOS) spend liquor by hot water pretreatment. Developing a technology based on low LSR results in more efficient water usage in the system and thus in lower capital and operating costs. Xylans from xylan rich agro-industrial waste are abundant hemicellulosic polymers with enormous potential for industrial applications. Currently, freeze-dried xylo-oligosaccharides are used as bio-based polymers and hydrolysates containing high xylose contents are converted to several chemical products. In this study, sugarcane bagasse was treated with water at low LSRs and mild temperatures in order to assess the effects of varying the pretreatment conditions on the xylo-oligosaccharide and xylose concentrations, and use a central composite experimental design to optimize the process parameters. The pretreatments were performed in the ranges temperature: 143.3-176.7 degrees C, time: 20-70 min and LSR: 1 : 1 to 11 : 1 (g g(-1)). The maximum concentrations of xylose and xylan were 13.76 and 36.18 g L-1 (equivalent to 48.29 g L-1 of xylan), respectively, which were achieved by treating bagasse at 170 degrees C for 60 min, with LSR of 3 g g(-1). The amount of xylan removed under these conditions was almost 57%. The soluble xylan consisted mainly of xylo-oligosaccharides (74 wt% of the identified compound in the spent liquor).

Esophageal contractions, bolus transit and perception of transit after swallows of liquid and solid boluses in normal subjects

CONTEXT: Esophageal dysphagia is the sensation that the ingested material has a slow transit or blockage in its normal passage to the stomach. It is not always associated with motility or transit alterations. OBJECTIVES: To evaluate in normal volunteers the possibility of perception of bolus transit through the esophagus after swallows of liquid and solid boluses, the differences in esophageal contraction and transit with these boluses, and the association of transit perception with alteration of esophageal contraction and/or transit. METHODS: The investigation included 11 asymptomatic volunteers, 4 men and 7 women aged 19-58 years. The subjects were evaluated in the sitting position. They performed swallows of the same volume of liquid (isotonic drink) and solid (macaroni) boluses in a random order and in duplicate. After each swallow they were asked about the sensation of bolus passage through the esophagus. Contractions and transit were evaluated simultaneously by solid state manometry and impedance. RESULTS: Perception of bolus transit occurred only with the solid bolus. The amplitude and area under the curve of contractions were higher with swallows of the solid bolus than with swallows of the liquid bolus. The difference was more evident in swallows with no perception of transit (n = 12) than in swallows with perception (n = 10). The total bolus transit time was longer for the solid bolus than for the liquid bolus only with swallows followed by no perception of transit. CONCLUSION: The results suggest that the perception of esophageal transit may be the consequence of inadequate adaptation of esophageal transit and contraction to the characteristics of the swallowed bolus.

Evaluation of solid-phase microextraction using a polythiophene film and liquid chromatography with spectrophotometric detection for the determination of antidepressants in plasma samples

Polythiophene (PTh) phase electropolymerized on the stainless steel wire was evaluated as solid-phase microextraction (SPME), and analysis by liquid chromatography with spectrophotometric detection (LC-UV) for determination of new-generation antidepressants, selective serotonin reuptake inhibitors (SSRIs) (citalopram, paroxetine, fluoxetine and sertraline), in plasma samples. The influence of electropolymerization variables (scan rate, potential range and scan cycles) was evaluated on SPME performance. The SPME variables (extraction time, temperature, matrix pH, ionic strength and desorption procedure), as well as the influence of plasma proteins on sorption mechanisms were also evaluated. The SPME/LC-UV method developed for determination of antidepressants in plasma sample presented a linear range between the limit of quantification (LOQ, 200-250 ng mL-1) to 4000 ng mL-1, and interday precision with coefficient of variation (CV) ranged from 11 to 15%. The proposed method can be a useful tool for the determination of antidepressants in human plasma samples in urgent toxicological analysis after the accidental or suicidal intake of higher doses of medications.

Interaction of the meso-tetrakis (4-N-methylpyridyl) porphyrin with gel and liquid state phospholipid vesicles

The interaction of the cationic meso-tetrakis 4-N-methylpyridyl porphyrin (TMPyP) with large unilamellar vesicles (LUVs) was investigated in the present study. LUVs were formed by mixtures of the zwitterionic 1,2-dipalmitoyl-sn-glycero-phosphatidylcholine (DPPC) and anionic 1,2-dipalmitoyl-sn-glycero-3-phosphoglycerol (DPPG) phospholipids, at different DPPG molar percentages. All investigations were carried out above (50 degrees C) and below (25 degrees C) the main phase transition temperature of the LUVs (similar to 41 degrees C). The binding constant values, K-b, estimated from the time-resolved fluorescence study, showed a significant increase of the porphyrin affinity at higher mol% DPPG. This affinity is markedly increased when the LUVs are in the liquid crystalline state. For both situations, the increase of the K-b value was also followed by a higher porphyrin fraction bound to the LUVs. The displacement of the vesicle-bound porphyrins toward the aqueous medium, upon titration with the salt potassium chloride (KCl), was also studied. Altogether, our steady-state and frequency-domain fluorescence quenching data results indicate that the TMPyP is preferentially located at the LUVs Stern layer. This is supported by the zeta potential studies, where a partial neutralization of the LUVs surface charge, upon porphyrin titration, was observed. Dynamic light scattering (DLS) results showed that, for some phospholipid systems, this partial neutralization leads to the LUVs flocculation. (C) 2012 Elsevier Inc. All rights reserved.

Automated analysis of lidocaine and its metabolite in plasma by in-tube solid-phase microextraction coupled with LC-UV for pharmacokinetic study

A sensitive, selective, and reproducible in-tube solid-phase microextraction and liquid chromatographic (in-tube SPME/LC-UV) method for determination of lidocaine and its metabolite monoethylglycinexylidide (MEGX) in human plasma has been developed, validated, and further applied to pharmacokinetic study in pregnant women with gestational diabetes mellitus (GDM) subjected to epidural anesthesia. Important factors in the optimization of in-tube SPME performance are discussed, including the draw/eject sample volume, draw/eject cycle number, draw/eject flow rate, sample pH, and influence of plasma proteins. The limits of quantification of the in-tube SPME/LC method were 50 ng/mL for both metabolite and lidocaine. The interday and intraday precision had coefficients of variation lower than 8%, and accuracy ranged from 95 to 117%. The response of the in-tube SPME/LC method for analytes was linear over a dynamic range from 50 to 5000 ng/mL, with correlation coefficients higher than 0.9976. The developed in-tube SPME/LC method was successfully used to analyze lidocaine and its metabolite in plasma samples from pregnant women with GDM subjected to epidural anesthesia for pharmacokinetic study.

CdSe/CdTe interface band gaps and band offsets calculated using spin-orbit and self-energy corrections

We performed ab initio calculations of the electronic structures of bulk CdSe and CdTe, and their interface band alignments on the CdSe in-plane lattice parameters. For this, we employed the LDA-1/2 self-energy correction scheme [L.G. Ferreira, M. Marques, L.K. Teles, Phys. Rev. B 78 (2008) 125116] to obtain corrected band gaps and band offsets. Our calculations include the spin-orbit effects for the bulk cases, which have shown to be of importance for the equilibrium systems and are possibly degraded in these strained semiconductors. Therefore, the SO showed reduced importance for the band alignment of this particular system. Moreover, the electronic structure calculated along the transition region across the CdSe/CdTe interface shows an interesting non-monotonic variation of the band gap in the range 0.8-1.8 eV, which may enhance the absorption of light for corresponding frequencies at the interface between these two materials in photovoltaic applications. (C) 2012 Elsevier B.V. All rights reserved.

Solid phase microextraction and LC-MS/MS for the determination of paliperidone after stereoselective fungal biotransformation of risperidone

The present work describes for the first time the use of SPME coupled to LC-MS/MS employing the polar organic mode in a stereoselective fungal biotransformation study to investigate the fungi ability to biotransform the drug risperidone into its chiral and active metabolite 9-hydroxyrisperidone (9-RispOH). The chromatographic separation was performed on a Chiralcel OJ-H column using methanol:ethanol (50:50, v/v) plus 0.2% triethylamine as the mobile phase at a flow rate of 0.8 mL min(-1). The SPME process was performed using a C18 fiber, 30 min of extraction time and 5 min of desorption time in the mobile phase. The method was completely validated and all parameters were in agreement with the literature recommendations. The Cunninghamella echinulata fungus was able to biotransform risperidone into the active metabolite, (+)-9-RispOH, resulting in 100% of enantiomeric excess. The Cunninghamella elegans fungus was also able to stereoselectively biotransform risperidone into (+)- and (-)-9-RispOH enantiomers at different rates. (C) 2012 Elsevier B.V. All rights reserved.