Linear stability analysis and nonlinear simulations of convective dissolution in an inclined porous layer between impermeable surfaces.

Convective dissolution can occur in porous media when a given solute dissolves in a host layer from above and increases the density of the host solution. Buoyancy-driven fingering can then develop, which increases the transfer flux of the solute. We investigate here numerically the properties of this convective dissolution when the porous host layer is inclined by an angle θ relative to the horizontal direction. We consider an incompressible flow in porous media governed by Darcy's law, driven by density gradients associated with the concentration of the dissolving solute. The model problem focuses on the case of a very long (infinite) tilted porous layer limited by two parallel impermeable surfaces. A linear stability analysis and nonlinear simulations are performed using the Boussinesq approximation. A vorticity-stream function formulation is adopted to solve the two-dimensional hydrodynamic field through the finite element method. We find that the inclination of the interface decreases the growth rate of the instability and the range of unstable wavenumbers, delaying or even suppressing the onset of the fingering instability. Moreover, it introduces a drift velocity on the perturbations, which is characterized here in both the linear stability analysis and the nonlinear simulations.

Silver nanoflower-coated paper as dual substrate for surface-enhanced Raman spectroscopy and ambient pressure mass spectrometry analysis.

Paper-based analytical devices (PADs) have encountered a wealth of applications in recent years thanks to the numerous advantages of paper as a support. A silver nanoflower (AgNF) modified paper-based dual substrate for both surface-enhanced Raman spectroscopy (SERS) and ambient pressure paper spray mass spectrometry (PS-MS) was developed. AgNFs were immobilized on nylon-coated paper modified with silver and ethylenediamine. The developed substrate was characterized via scanning electron microscopy and infrared spectroscopy. The densely packed nanoscale petals of the AgNFs lead to a large number of so-called hot spots at their overlapping points, which result in an enhancement of the Raman signal. In addition, the presence of the AgNFs produces an increase in the sensitivity of the mass spectrometric analysis as compared with bare paper and nylon/Ag-coated paper. The dual substrate was evaluated for the identification and quantification of ketoprofen in aqueous standards as well as human saliva from healthy volunteers. The method enables the determination of ketoprofen with a limit of detection and limit of quantification via PS-MS of 0.023 and 0.076 mg L-1, respectively, with a relative standard deviation (RSD) of 3.4% at a concentration of 0.1 mg L-1. This dual substrate enables the simple and fast detection of ketoprofen with minimal sample preparation, providing complementary Raman and mass spectrometric information. Graphical abstract.

Teaching social responsibility in analytical chemistry.

Analytical chemistry is key to the functioning of a modern society. From early days, ethics in measurements have been a concern and that remains today, especially as we have come to rely more on the application of analytical science in many aspects of our lives. The main aim of this Feature is to suggest ways of introducing the topic of social responsibility and its relation to analytical chemistry in undergraduate or graduate chemistry courses.

Magnetically confined hydrophobic nanoparticles for the microextraction of endocrine-disrupting phenols from environmental waters.

In this article, a solid-phase extraction approach, which takes advantage of the good extraction capabilities of hydrophobic magnetic nanoparticles (MNPs), is presented. The new approach involves the deposition of a thin layer of MNPs in a dedicated stirring unit based on the dual function of a mini-magnet. The system allows the extraction of the analytes in a simple and efficient way. The approach, which reduces the negative effect of the aggregation tendency of hydrophobic MNPs, is characterized for the resolution of a model analytical problem: the determination of some endocrine-disrupting phenols in water by liquid chromatography-photometric detection. All the variables involved in the extraction process have been clearly identified and optimized. The new extraction mode allows the determination of these compounds with limits of detection in the range from 0.15 µg/L (for 4-tert-octylphenol) to 2.7 µg/L (for 4-tert-butylphenol) with a relative standard deviation lower than 5.3 % (for 4-tert-butylphenol).

Determination of non-steroidal anti-inflammatory drugs in urine by the combination of stir membrane liquid-liquid-liquid microextraction and liquid chromatography.

A stir membrane liquid phase microextraction procedure working under the three-phase mode is proposed for the first time for the determination of six anti-inflammatory drugs in human urine. The target compounds are isolated and preconcentrated using a special device that integrates the extractant and the stirring element. An alkaline aqueous solution is used as extractant phase while 1-octanol is selected as supported liquid membrane solvent. After the extraction, all the analytes are determined by liquid chromatography (LC) with ultraviolet detection (UV). The analytical method is optimized considering the main involved variables (e.g., pH of donor and acceptor phases, extraction time, stirring rate) and the results indicate that the determination of anti-inflammatory drugs at therapeutic and toxic levels is completely feasible. The limits of detection are in the range from 12.6 (indomethacin) to 30.7 µg/L (naproxen). The repeatability of the method, expressed as relative standard deviation (RSD, n = 5) varies between 3.4% (flurbiprofen) and 5.7% (ketoprofen), while the enrichment factors are in the range from 35.0 (naproxen) to 72.5 (indomethacin).

Participation of CWI, HOG and Calcineurin pathways in the tolerance of Saccharomyces cerevisiae to low pH by inorganic acid.

AIMS: The present work aimed at identifying the metabolic response to acid stress and the mechanisms that lead to cell tolerance and adaptation. METHODS AND RESULTS: Two strategies were used: screening deletion mutants for cell growth at neutral and acid pH compared to wild type and measurement by qPCR of the expression of yeast genes involved in different pathways. CONCLUSIONS: The results complement our previous findings and showed that the Cell Wall Integrity pathway is the main mechanism for cell tolerance to acid pH, and this damage triggers the protein kinase C (PKC) pathway mainly via the Wsc1p membrane sensor. In addition, cell wall injury might mimic the effects of high osmotic shock and activates the High Osmolarity Glycerol pathway, which amplifies the signal in the upper part of PKC pathway and leads to the activation of Ca(2+) channels by SLT2 overexpression and this Ca(2+) influx further activates calcineurin. Together, these mechanisms induce the expression of genes involved in cell cycle regulation and cell wall regeneration. SIGNIFICANCE AND IMPACT OF THE STUDY: These interactions are responsible for long-term adaptation of yeast cells to the acidic environment, and the results could drive future work on the genetic modification of yeast strains for high tolerance to the stresses of the bioethanol fermentation process.

Unmodified cellulose filter paper, a sustainable and affordable sorbent for the isolation of biogenic amines from beer samples.

While current trends in Green Analytical Chemistry aim at reducing or simplifying sample treatment, food usually comprises complex matrices where direct analysis is not possible in most cases. In this context, sample treatment plays a pivotal role. Biogenic amines are naturally formed in many foodstuffs due to the action of microorganisms, while their presence has been associated with adverse health effects. In this work, the extraction of seven biogenic amines (cadaverine, histamine, phenylethylamine, putrescine, spermidine, spermine, and tyramine) from beer samples has been simplified using laboratory filter paper as sorbent without any further modification. The analysis of the eluates by direct infusion mass spectrometry reduces the time of analysis, increasing the sample throughput. This simple but effective method enabled the determination of the analytes with limits of detection as low as 0.06 mg L-1 and relative standard deviations better than 11.9%. The suitability of the method has been assessed by analyzing eight different types of beers by the standard addition method.

Highly selective and non-conventional sorbents for the determination of biomarkers in urine by liquid chromatography.

Urine is one of the most extensively analysed biological fluids in clinical and toxicological investigations owing to its high availability and non-invasive collection. The chemical nature of the analytes involved (polarity and thermal instability) makes liquid chromatography the separation technique of choice for compound determination. Moreover, sample treatment based on solid-phase extraction is usually carried out owing to its flexibility and the availability of new sorbent materials with increased selectivity and versatility towards the target compounds. Taking into account these three fundamental points, this review focuses on recent developments in urine pretreatment using highly selective and non-conventional sorbents in solid-phase extraction such as affinity sorbents (immunosorbents and molecularly imprinted polymers), restricted access materials and carbon nanotubes, with emphasis on the new synthesis methods. Their main advantages and shortcomings are presented, together with representative examples in this context.

Sensitive in-surface infrared monitoring coupled to stir membrane extraction for the selective determination of total hydrocarbon index in waters.

In this paper, the direct coupling between stir membrane extraction and infrared spectroscopy working under transmission mode is presented for the sensitive and selective determination of the total hydrocarbon index in waters. For this purpose, a new extraction unit was built using stainless steel in order to maximize the adsorption of the target analytes in the 40-microm-thick polytetrafluoroethylene membrane. The method allows the determination of hydrocarbons in the presence of grease, using hexadecane and stearic acid as model compounds, respectively. The proposal is optimized in depth, taking into account the main experimental variables such as membrane thickness, extraction time, and stirring and sample volume. Later on, the method was characterized on the basis of its linearity, precision, and limits of detection. The combination allows the determination of the hydrocarbon index with a limit of detection of 18 microg L(-1), the precision being (expressed as relative standard deviation) better than 4.3%. The analytical method provides a high sample throughput since some extractions can be performed in parallel, the relative standard deviation between devices being better than 8%. The proposed analytical method is finally compared in terms of analytical figures with counterpart ASTM method, recently presented.

Effects of Bermudagrass hay and soybean hulls inclusion on performance of sheep fed cactus-based diets.

The objective of this experiment was to determine the effects of replacing corn with soybean hulls (SH) or Bermudagrass tifton hay (TH) on performance of sheep fed cactus-based diets. Three ruminally fistulated sheep were used in a 3 x 3 Latin square experiment with 21-day periods. All diets contained 75% spineless cactus (dry matter basis, DM) and formulated to be isonitrogenous. Fiber source had no influence on nutrient intakes except for the intake of neutral detergent fiber (NDF) which was lower (p<0.05) for animals fed corn relative to those fed SH or TH. Time expended in rumination and total chewing time were higher (p<0.05) for animals fed TH than those fed SH or corn. In vivo nutrient digestibilities were similar for all dietary treatments and averaged 69.6%, 74.8%, 69.9%, and 61.8% for DM, organic matter, crude protein, and NDF, respectively. Feeding SH relative to TH and corn decreased ruminal pH (p<0.05) and increased concentration of total volatile fatty acids (p<0.05). However, ruminal NH3-N concentration was higher (p<0.05) for animal fed TH than for those fed SH or corn. Abdominal distension and ruminal biofilm production were greater (p<0.05) in animals fed corn or SH than in those fed TH. It was concluded that replacing corn with SH or TH up to 15% of the diet DM in a cactus-based diet had no effect on nutrient intakes or total tract nutrient utilization. Changes in ruminal fermentation parameters reflected differences in ruminal degradability between the two fiber sources. Bermudagrass tifton hay was more effective than SH in reducing the risk of bloat associated with feeding high levels of spineless cactus to ruminants.

Steroid-sparing effect of mycophenolate mofetil in the treatment of a subepidermal blistering autoimmune disease in a dog.

A 7-year-old female Cocker spaniel-cross was referred with an 8-month history of mucocutaneous erosive dermatitis. On physical examination, skin lesions affected the eyelids and periocular area, lips and vulva. Lesions were symmetrical with small diffuse superficial ulcers, haemorrhagic crusts, adherent purulent exudation in haired skin, and alopecia with hyperpigmentation and scarring. Histopathologic evaluation showed multiple, non-intact dermoepidermal junction vesicles and ulceration associated with a dermal lichenoid infiltrate. Immunohistochemistry showed strong to moderate reactivity in the dermoepidermal junction for the antibodies directed against canine IgG, human IgG lambda light chains and C3, respectively. A diagnosis of autoimmune subepidermal blistering dermatosis was made. Treatment with oral prednisone at 2 mg/kg and mycophenolate mofetil (MMF) at 20 mg/kg twice daily was initiated and after 4 weeks the ulcers and erosions were cured. During the rest of treatment, MMF was maintained at 10 mg/kg twice daily and prednisone could be tapered to 0.25 mg/kg once every other day without recurrences. In conclusion, this case report shows that MMF was well tolerated and might be effective as steroid-sparing agent in the long-term treatment of this autoimmune subepidermal blistering disease.

Cotton fibers functionalized with ß-cyclodextrins as selectivity enhancer for the direct infusion mass spectrometric determination of cocaine and methamphetamine in saliva samples.

Cotton is a natural material with good mechanical and chemical properties. It presents a hydrophilic surface that must be modified by the introduction of appropriate groups, if semi-polar or non-polar analytes are intended to be isolated from an aqueous matrix. In this article, cotton is modified with ß-cyclodextrins, which presents a hydrophobic cavity where target molecules can be hosted. The cavity size restricts the access of larger or less accessible molecules due to their conformation, thus improving the extraction selectivity. The modified cotton fibers are packed in a disposable syringe device where all the steps of the extraction take place. The ensuing fibers were evaluated for the extraction of several drugs providing the best results for cocaine (CO) and methamphetamine (MTA). These targets were extracted from saliva samples and finally determined by direct infusion mass spectrometry. The method provides limits of detection and quantification of 0.6 and 2 µg L-1 for CO and 0.8 and 2.7 µg L-1 for MTA, with precision values at the quantification level better than the 9% (expressed as relative standard deviation). Also, relative recoveries ranged from 115% to 111% for CO and MTA, respectively, demonstrating the applicability of the proposed method. Matrix effect, which has been statistically evaluated, is not significant, showing that the extraction selectivity can compensate the circumvent of the chromatographic separation.

Paper-based sorptive phases for microextraction and sensing.

The simplification of the analytical procedures, including cost-effective materials and detectors, is a current research trend. In this context, paper has been identified as a useful material thanks to its low price and high availability in different compositions (office, filter, chromatographic). Its porosity, flexibility, and planar geometry permit the design of flow-through devices compatible with most instrumental techniques. This article provides a general overview of the potential of paper, as substrate, on the simplification of analytical chemistry methodologies. The design of paper-based sorptive phases is considered in-depth, and the different functionalization strategies are described. Considering our experience in sample preparation, special attention has been paid to the use of these phases under the classical microextraction-analysis workflow, which usually includes a chromatographic separation of the analytes before their determination. However, the interest of these materials extends beyond this field as they can be easily implemented into spectroscopic and electrochemical sensors. Finally, the direct analysis of paper substrates in mass spectrometry, in the so-called paper-spray technique is also discussed. This review is more focused on presenting ideas rather than the description of specific applications to draw a general picture of the potential of these materials.

Dispersive solid phase extraction for in-sorbent surface attenuated total reflection infrared detection.

The combination of dispersive solid phase extraction (DSPE) and attenuated total reflection (ATR) infrared spectroscopy is presented using the joint determination of sorbic and benzoic acids in juice samples as a model analytical problem. The dispersive extraction process allows the selective extraction of the target analytes from the sample matrix allowing their preconcentration prior to their infrared detection. The extraction efficiency is improved compared to the conventional procedures since the interaction between sorbent and analytes is favored with the stirring process. Moreover, the extracted analytes are directly determined in the sorbent. As no elution step is required, analyte dilutions and consumption of organic solvents are avoided. The proposed approach has been qualitative and quantitative studied. The hierarchical cluster analysis permits the sample classification according to the relative concentration of the analytes. The precision of the quantitative analysis was better than 6% with analyte recoveries in the range 87-90%. The proposed method was applied to the analysis of different commercial fruit juice samples. Finally, the main advantages and limitations of the new proposal are presented and compared with existing alternatives.

Stir membrane extraction: a useful approach for liquid sample pretreatment.

In this paper, a novel extraction approach based on the use of a polymeric membrane as the extraction medium is described. For this aim, an original unit which allows the magnetic stirring of the membrane during the extraction process has been designed, optimized, and practically evaluated. On one hand, the main variables affecting the extraction process such as the unit design, the stirring rate, the extraction time, the sample volume, and the elution conditions were deeply studied. Once optimized, a model analytical problem, the determination of polycyclic aromatic hydrocarbons in water samples, was selected for practical evaluation of the stir membrane extraction procedure. The method was characterized on the basis of its linearity, precision, and limits of detection. The novel approach was sensitive and precise enough for the detection of the target analytes in the low nanogram per liter range using 25 mL of sample. In fact, limits of detection ranged from 0.8 ng/L (fluoranthene) to 7.6 ng/L (benzo-anthracene) with relative standard deviations lower than 8%.

Determination of phenothiazine derivatives in human urine by using ionic liquid-based dynamic liquid-phase microextraction coupled with liquid chromatography.

A simple and rapid method for the determination of seven phenothiazines derivatives (chlorpromazine, promethazine, levomepromazine, prochlorperazine, trifluoperazine, fluphenazine and thioridazine) in human urine samples is presented. The analytes are extracted from the sample in 50 microL of the ionic liquid 1-butyl-3-methyl-imidazolium hexafluorophosphate working in an automatic flow system under dynamic conditions. The chemical affinity between the extractant and the analytes allows a good isolation of the drugs from the sample matrix achieving at the same time their preconcentration. The separation and detection of the extracted compounds is accomplished by liquid chromatography and UV detection. The proposed method is a valuable alternative for the analysis of these drugs in urine within the concentration range 0.07-10 microg mL(-1). Limits of detection were in the range from 21 ng mL(-1) (thioridazine) to 60 ng mL(-1) (levomepromazine). The repeatability of the proposed method expressed as RSD (n=5) varied between 2.2% (levomepromazine) and 3.9% (chlorpromazine).

Effect of Enterococcus faecium SF68 on serum cobalamin and folate concentrations in healthy dogs.

OBJECTIVE: To study the effect of a 14-day administration of the probiotic Enterococcus faecium SF68 on serum concentrations of cobalamin and folate in healthy dogs. MATERIALS AND METHODS: Thirty-six healthy dogs were randomly allocated between probiotic and control groups. Enterococcus faecium SF68 was administered to the probiotic group for 14 days whereas the control group did not receive any product. A blood sample was taken from all dogs when starting the administration (day 1), when the administration ended (day 14) and 14 days later (day 28). Serum cobalamin and folate concentrations and the canine inflammatory bowel disease activity index scores were determined at each time point. RESULTS: There was a progressive reduction of mean serum cobalamin in the probiotic group during the 28-day study, with significantly lower concentration at day 28 compared to baseline and day 14 concentrations. Moderate hypocobalaminaemia was observed in eight dogs at day 28. Probiotic administration was associated with a non-significant increase in mean serum folate concentration at day 14, and a significant decrease at day 28 compared with day 1. The canine inflammatory bowel disease activity index score remained unaltered during the study. CLINICAL SIGNIFICANCE: Short-term Enterococcus faecium SF68 administration caused a significant reduction of mean cobalamin concentration and moderate hypocobolaminaemia in eight of 18 dogs. Monitoring serum folate appears unnecessary because the probiotic caused a non-significant increase that returned to baseline values after administration was discontinued.

Swainsonine-induced lysosomal storage disease in goats caused by the ingestion of Turbina cordata in Northeastern Brazil.

A disease of the central nervous system in goats was observed in the municipalities of Juazeiro, Casa Nova and Curaça, state of Bahia, and Petrolina, state of Pernambuco, Northeastern Brazil. The disease was produced experimentally in two goats by the administration of dry Turbina cordata mixed with grain. Clinical signs were observed after the ingestion of 62 and 106 g/kg body weight in 28 and 54 days, respectively. The concentration of swainsonine in the plant varied from less than 0.001% to 0.14% (dry weight). Clinical signs of natural and experimental cases included difficulties in standing, ataxia, hypermetria, wide-based stance, intention tremors, spastic paresis mainly in the hind legs, nystagmus, abnormal postural reactions, head tilting, and falling. Diffuse vacuolation of neurons, epithelial cells of pancreas, thyroids, and renal tubules were observed on the histology. From the electron microscopy of Purkinje cells the vacuoles represented dilated lysosomes. These findings demonstrated that T. cordata causes an acquired glycoprotein lysosomal storage disease. The intoxication occurs at least in an area of 27,000 km2 causing severe losses in goats, and some farmers report the disease also in cattle.

In-syringe dispersive micro-solid phase extraction using carbon fibres for the determination of chlorophenols in human urine by gas chromatography/mass spectrometry.

In this article, carbon fibres (CFs) are presented as sorbent material for the dispersive micro-solid phase extraction of twelve chlorophenols from urine samples. CFs are synthesized by a reagentless and green procedure consisting of heating raw cotton, a natural precursor, at high temperature (400°C) in an inert atmosphere (Ar) during 2h. The resulting fibres, which present good water dispersibility, are finally loaded on an in-syringe device. This device, which integrates the extraction and final elution of the analytes, is disposable and it is adapted to process low sample volumes. Working at the optimum conditions, the extraction procedure in combination with gas chromatography/mass spectrometry allows the determination of the analytes in urine at the low µg/L range. In fact, the limits of quantification (LOQs) of the analytes were in the interval from 1µg/L to 2.5µg/L with precision values, expressed as relative standard deviations (RSD), better than 13%. Relative recovery values, ranging from 74.5% to 113%, demonstrate the applicability of the proposed method.