Enantiomers separation by capillary electrochromatography using polysaccharide-based stationary phases.

The separation of chiral compounds is an interesting and important topic of research because these compounds are involved in some biological processes, fundamentally in human health. Among the various application fields where enantiomers are remarkable, drug analysis has to be considered. Most of the drugs contain enantiomers and very often one of the two isomers could be pharmacologically more active or even dangerous. Therefore, the separation of these compounds is very important. Among the different analytical techniques usually employed, capillary electrochromatography has demonstrated great capability in enantiomers resolution. The great potential of this electromigration technique stands mainly in its high efficiency due to the use of an electrosmotic flow (flat flow profile) and on the high selectivity because of the use of a stationary phase. Chiral separation can be obtained utilizing several chiral stationary phases including a polysaccharide derivative. The aim of this review paper is to summarize the main features of capillary electrochromatography and polysaccharide derivatives of chiral stationary phase. It also report examples of practical applications utilizing this approach.

Capillary electrochromatography and nano-liquid chromatography coupled to nano-electrospray ionization interface for the separation and identification of estrogenic compounds.

Nano-LC and CEC were coupled to MS through a nanospray or a pressurized liquid-junction interface for the simultaneous separation and determination of 11 estrogenic compounds. Different stationary phases, that is, phenyl, C18, and C18 bidentate silica hydrate, were studied. For both techniques, the phenyl stationary phase was the best option, considering separation efficiency, selectivity, and resolution. Under the optimized conditions, the baseline separation of the target compounds (including estradiol and zearalanol epimers) was achieved in less than 20 min in nano-LC-MS and less than 13 min in CEC-MS. Molecular imprinted polymer SPE was used for extracting the target compounds from mineral water samples with the analysis of nano-LC-MS. The whole molecular imprinted polymer SPE nano-LC-MS method was validated through a recovery study at two levels of concentration. Sensitivity was improved by on-column focusing technique obtaining LODs in the range 1.4-55.4 ng/L.

Evaluation of the combination of a dispersive liquid-liquid microextraction method with micellar electrokinetic chromatography coupled to mass spectrometry for the determination of estrogenic compounds in milk and yogurt.

In this work, the suitability of a methodology based on dispersive liquid-liquid microextraction (DLLME) has been evaluated for the extraction of four endoestrogens (estriol, 17α-estradiol, 17ß-estradiol, and estrone), an exoestrogen (17α-etynylestradiol), and a mycotoxin (zearalenone), together with some of their major metabolites (2-methoxyestradiol, α-zearalanol, ß-zearalanol, α-zearalenol, and ß-zearalenol) from different types of milk (whole and skimmed cow milk and semiskimmed goat milk) and whole natural yogurt. The methodology includes a previous protein precipitation with acidified ACN and a defatting step with n-hexane. Separation of the analytes, determination, and quantification were developed by MEKC coupled to ESI-MS using a BGE containing an aqueous solution of ammonium perfluorooctanoate as MS friendly surfactant. Calibration, precision, and accuracy studies of the described DLLME-MEKC-MS/MS method were evaluated obtaining a good linearity and LODs in the low micrograms per liter range.

Determination of estrogens in environmental water samples using 1,3-dipentylimidazolium hexafluorophosphate ionic liquid as extraction solvent in dispersive liquid-liquid microextraction.

In this work, the potential of a symmetric dialkyl-substituted ionic liquid (IL), 1,3-dipenthylimidazolium hexafluorophosphate ([PPIm][PF6 ]), as extraction solvent in dispersive liquid-liquid microextraction (DLLME) has been studied for the analysis of a group of three natural (estriol, 17ß-estradiol, and 17α-estradiol) and four synthetic (17α-ethynylestradiol, diethylstibestrol, dienestrol, and hexestrol) estrogenic compounds as well as one mycotoxin with estrogenic activity (zearalenone) in different types of water samples (Milli-Q, mineral, and wastewater). Separation, determination, and quantification were developed by HPLC-DAD and a fluorescence detector (FD) connected in series. Factors influencing the IL-DLLME procedure (sample pH, amount of IL, type and volume of disperser solvent, ionic strength, and assistance of vortex agitation) were investigated and optimized by means of a step-by-step approach. Once the optimum extraction conditions were established (10 mL of water at pH 8, 60 mg of [PPIm][PF6 ], 500 µL of ACN as disperser solvent and vortex agitation for 1 min), the calibration curves of the whole method (IL-DLLME-HPLC-DAD/FD) were obtained and precision and accuracy were evaluated. It was demonstrated that the developed methodology was repeatable, accurate, and selective with limits of detection in the 0.30-0.57 µg/L and 13.8-37.1 µg/L range for FD and DAD, respectively. Relative recovery values were higher than 85% for the different types of water samples and the Student's t test demonstrated that there were not significant differences between the added and the found concentration.

CE-MS fingerprinting of Laurencia complex algae (Rhodophyta).

The use of CE-ESI-MS has been considered as a new chemical strategy for the possible discernment of genera and species of the Laurencia complex. After the selection of the CE-MS and the extraction conditions, a total of 28 specimens of the complex, including different species of four genera (Laurencia, Laurenciella, Palisada, and Osmundea) collected from five intertidal locations on the Island of Tenerife (Canary Islands, Spain) were analyzed. CE-MS fingerprints revealed that CE-MS can be used as a useful tool for these studies in order to assess similarities and differences between them and that it constitutes an important starting point for further studies in the field.

Hollow-fiber liquid-phase microextraction for the determination of pesticides and metabolites in soils and water samples using HPLC and fluorescence detection.

A new and simple method has been developed for the determination of a group of four benzimidazole pesticides (carbendazim/benomyl, thiabendazole, and fuberidazole), a carbamate (carbaryl), and an organophosphate (triazophos), together with two of their main metabolites (2-aminobenzimidazole, metabolite of carbendazim/benomyl, and 1-naphthol, metabolite of carbaryl) in soils. First, an ultrasound-assisted extraction (UAE) was performed, followed by evaporation and reconstitution in water. Then, extraction and preconcentration of the analytes was accomplished by two-phase hollow-fiber liquid-phase microextraction (HF-LPME) using 1-octanol as extraction solvent. Parameters that affect the extraction efficiency in HF-LPME technique (organic solvent, pH of the sample, extraction time, stirring speed, temperature, and ionic strength) were deeply investigated. Optimum HF-LPME conditions involved the use of a 2.0 cm polypropylene fiber filled with 1-octanol to extract 10 mL of an aqueous soil extract at pH 9.0 containing 20% (v/v) of NaCl for 30 min at 1440 rpm. Separation and quantification was achieved by HPLC with fluorescence detection (FD). The proposed optimum UAE-HF-LPME-HPLC-FD methodology provided good calibration, precision, and accuracy results for two soils of different physicochemical properties. LODs were in the range 0.001-6.94 ng/g (S/N = 3). With the aim of extending the validation, the HF-LPME method was also applied to different types of waters (Milli-Q, mineral and run-off), obtaining LODs in the range 0.0002-0.57 µg/L.

Dispersive liquid-liquid microextraction of pesticides and metabolites from soils using 1,3-dipentylimidazolium hexafluorophosphate ionic liquid as an alternative extraction solvent.

In this work, the use of the ionic liquid (IL) 1,3-dipentylimidazolium hexafluorophosphate ([PPIm][PF6]) as an alternative extractant for IL dispersive liquid-liquid microextraction (IL-DLLME) of a group of pesticides and metabolites (2-aminobenzimidazole, carbendazim/benomyl, thiabendazole, fuberidazole, carbaryl, 1-naphthol, and triazophos) from soils is described. After performing an initial ultrasound-assisted extraction (USE), the IL-DLLME procedure was applied for the extraction of these organic analytes from soil extracts. Separation and quantification was achieved by high-performance liquid chromatography (HPLC) with fluorescence detection (FD). Calibration, precision, and accuracy of the described USE-IL-DLLME-HPLC-FD method using [PPIm][PF6] as an alternative extractant was evaluated with two soils of different physicochemical properties. Accuracy percentages were in the range 93-118% with RSD values below 20%. A comparison of the performance of [PPIm][PF6] versus that of the so-common 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIm][PF6]) was accomplished. Results indicate a comparable extraction efficiency with both ILs, being slightly higher with [HMIm][PF6] for the metabolite 2-aminobenzimidazole, and slightly higher with [PPIm][PF6] for triazophos. In all cases, LODs were in the low ng/g range (0.02-14.2 ng/g for [HMIm][PF6] and 0.02-60.5 ng/g for [PPIm][PF6]). As a result, the current work constitutes a starting point for the use of the IL [PPIm][PF6] for further analytical approaches.

Pesticide residue analysis in cereal-based baby foods using multi-walled carbon nanotubes dispersive solid-phase extraction.

In the present study, a new analytical method has been developed for the simultaneous quantification of 15 organophosphorus pesticides, including some of their metabolites, (disulfoton-sulfoxide, ethoprophos, cadusafos, dimethoate, terbufos, disulfoton, chlorpyrifos-methyl, malaoxon, fenitrothion, pirimiphos-methyl, malathion, chlorpyrifos, terbufos-sulfone, disulfoton-sulfone and fensulfothion) in three different types of commercial cereal-based baby foods. Dispersive solid-phase extraction (dSPE) with multi-walled carbon nanotubes (MWCNTs) was used together with gas chromatography with nitrogen phosphorus detection. Most favorable conditions involved a previous ultrasound-assisted extraction of the sample with acetonitrile containing formic acid. After evaporation of the extract and redissolution in water, a dSPE procedure was carried out with MWCNTs. The whole method was validated in terms of repeatability, linearity, precision and accuracy and matrix effect was also evaluated. Absolute recoveries were in the range 64-105 % with relative standard deviation values below 7.6 %. Limits of quantification achieved ranged from 0.31 to 5.50 µg/kg, which were lower than the European Union maximum residue limits for pesticide residues in cereal-based baby foods.

Pesticide analysis in toasted barley and chickpea flours.

Analytical potentiality of a modified version of the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method has been studied and validated for the extraction of a group of 11 pesticides (ethoprophos, cadusafos, dimethoate, terbufos, disulfoton, chlorpyrifos-methyl, fenitrothion, pirimiphos-methyl, malathion, chlorpyrifos and fensulfothion) and some of their metabolites (malaoxon, disulfoton sulfoxide, terbufos sulfone and disulfoton sulfone) in toasted barley and chickpea flours. The method involves separation and quantification by gas chromatography (GC) with nitrogen phosphorus detection (NPD) using triphenylphosphate as the internal standard. Matrix-matched calibration was carried out for both flours due to the existence of a matrix effect. Linearity, recovery, precision and accuracy studies of the proposed QuEChERS-GC-NPD method were evaluated in each sample matrix. Mean recovery values were in the range of 73-118% with relative standard deviation values below 10%. Limits of detection of the whole method were between 0.07 and 57.39 µg/kg. The method was finally applied for the analysis of 14 samples collected in different zones of the Tenerife island. The residues of pirimiphos-methyl were found in 13 of them, confirming its unequivocal presence by mass spectrometry.

Diffuse CO2 degassing precursors of the January 2020 eruption of Taal volcano, Philippines.

On January 12, 2020, Taal volcano in Philippines erupted, 43 years after its previous eruption in 1977. This eruption was preceded by diffuse CO2 degassing precursory signals. Significant temporal variations in diffuse CO2 emission from Taal Main Crater Lake (TMLC) were observed across the ~ 12 years reaching high CO2 degassing rates in 2011 and 2017, with values typical of plume degassing volcanoes. In addition to these CO2 surveys at the TCML, soil CO2 efflux continuous monitoring was implemented at Taal volcano since 2016 and a clear increasing trend of the soil CO2 efflux in 2017 was observed. These geochemical observations are most simply explained by magma recharge to the system, and represent the earliest warning precursor signals to the January 2020 eruptive activity.

Multi-walled carbon nanotubes-dispersive solid-phase extraction combined with nano-liquid chromatography for the analysis of pesticides in water samples.

In this work, the simultaneous separation of a group of 12 pesticides (carbaryl, fensulfothion, mecoprop, fenamiphos, haloxyfop, diclofop, fipronil, profenofos, fonofos, disulfoton, nitrofen, and terbufos) by nano-liquid chromatography with UV detection is described. For the analyses, a 100 µm internal diameter capillary column packed with silica modified with phenyl groups was used. Experimental parameters, including the use of a trapping column for increasing the sensitivity, were optimized and validated. A preliminary study of the applicability of a rapid and practical dispersive solid-phase extraction (DSPE) procedure was developed for the extraction of some of these pesticides (carbaryl, fensulfothion, fenamiphos, fipronil, profenofos, fonofos, disulfoton, nitrofen, and terbufos) from Milli-Q water samples using multi-walled carbon nanotubes (MWCNTs). The method was validated through a recovery study at three different levels of concentration, obtaining limits of detection in the range 0.016-0.067 µg/L (below European Union maximum residue limits) for the majority of the pesticides. In this work, MWCNTs were reused up to five times, representing an important reduction of the waste of stationary phase. Furthermore, DSPE permitted a clear diminution of the total sample treatment time with respect to conventional SPE.

Recent food safety and food quality applications of CE-MS.

The first on-line coupling of CE with MS detection more than 20 years ago provided a very powerful technique with a wide variety of applications, among which food analysis is of special interest, especially that dealing with food safety and food quality applications, the major topics of public interest nowadays. With this review article, we would like to show the most recent applications of CE-MS in both fields by recompiling and commenting articles published between January 2004 and October 2008. Although both applications are difficult to separate from each other, we have included in this work two main sections dealing with each specific field. Future trends will also be discussed.

Food analysis: a continuous challenge for miniaturized separation techniques.

One of the current trends of modern analytical chemistry is the miniaturization of the various tools daily used by a large number of researchers. Ultrafast separations, consumption of small amounts of both samples and reagents as well as a high sensitivity and automation are some of the most important goals desired to be achieved. For many years a large number of research laboratories and analytical instrument manufacturing companies have been investing their efforts in this field, which includes miniaturized extraction materials, sample pre-treatment procedures and separation techniques. Among the separation techniques, capillary electromigration methods (which also include CEC), microchip and nano-LC/capillary LC have received special attention. Besides their well-known advantages over other separation tools, the role of these miniaturized techniques in food analysis is still probably in an early stage. In fact, applications in this field carried out by CEC, microchip, nano-LC and capillary LC are only a few when compared with other more established procedures such as conventional GC or HPLC. The scope of this review is to gather and discuss the different applications of such miniaturized techniques in this field. Concerning CE, microchip-CE and CEC works, emphasis has been placed on articles published after January 2007.

Recent applications of carbon nanotube sorbents in analytical chemistry.

Carbon nanotubes (CNTs) are still awakening scientists' interest because of their inherent properties as well as their applications in a wide variety of fields. Regarding Analytical Chemistry, and although they have also been used as stationary phases in chromatography or pseudostationary phases in capillary electrophoresis, they have also found a particular place in sorbent-based extraction techniques. In fact, they are currently used as sorbents in solid-phase extraction, solid-phase microextraction, stir-bar sorptive extraction and matrix solid-phase dispersion, for analyte enrichment or storage, sample fractionation or clean-up as well as support for derivatization reactions. CNT surface is tuneable and, as a result, they can be suitably functionalized, aggregated or linked to other supports which increase their potential use as sorbents. They can also be arranged under different formats (cartridges, fibers, stir bars, disks, etc.) or even combined with magnetic nanoparticles, which clearly enlarge their applications. This review article overviews the most recent applications of CNTs as sorbent materials, covering the period from 2010 to early 2014.

Analysis of oestrogenic compounds in dairy products by hollow-fibre liquid-phase microextraction coupled to liquid chromatography.

In this work, the potential of a hollow-fibre liquid-phase microextraction (LPME)-based method has been studied and validated for the extraction of a group of nine oestrogenic compounds four of them being natural (oestriol, 17ß-oestradiol, 17α-oestradiol and oestrone), four being synthetic (17α-ethynyloestradiol, diethylstilbestrol, dienestrol and hexestrol) and one metabolite (2-hydroxyoestradiol) in different dairy products (whole and skimmed natural yogurt, a probiotic yogurt-type drink and cheese). The methodology includes a prior protein precipitation with acidified acetonitrile for all samples and an additional defatting step with n-hexane for cheese, the matrix with the highest fat content. Later separation, determination and quantification were done by high-performance liquid chromatography coupled to a diode array detector and a fluorescence detector set in series. Calibration, sensitivity, precision and accuracy of the method were carried out in the selected matrices, providing good linearity, LODs in the low µg/kg or µg/L range, good precision and appropriate accuracy.

Estrogenic compounds determination in water samples by dispersive liquid-liquid microextraction and micellar electrokinetic chromatography coupled to mass spectrometry.

In this work, a group of 12 estrogenic compounds, i.e., four natural sexual hormones (estrone, 17ß-estradiol, 17α-estradiol and estriol), an exoestrogen (17α-ethynylestradiol), a synthetic stilbene (dienestrol), a mycotoxin (zearalenone) and some of their major metabolites (2-methoxyestradiol, α-zearalanol, ß-zearalanol, α-zearalenol and ß-zearalenol) have been separated and determined by micellar electrokinetic chromatography (MEKC) coupled to electrospray ion trap mass spectrometry. For this purpose, a background electrolyte containing an aqueous solution of 45 mM of perfluorooctanoic acid (PFOA) adjusted to pH 9.0 with an ammonia solution, as MS friendly surfactant, and methanol (10% (v/v)), as organic modifier, was used. To further increase the sensitivity, normal stacking mode was applied by injecting the sample dissolved in an aqueous solution of 11.5mM of ammonium PFO (APFO) at pH 9.0 containing 10% (v/v) of methanol for 25s. Dispersive liquid-liquid microextraction, using 110 µL of chloroform and 500 µL of acetonitrile as extraction and dispersion solvents, respectively, was employed to extract and preconcentrate the target analytes from different types of environmental water samples (mineral, run-off and wastewater) containing 30% (w/v) NaCl and adjusted to pH 3.0 with 1M HCl. The limits of detection achieved were in the range 0.04-1.10 µg/L. The whole method was validated in terms of linearity, precision, recovery and matrix effect for each type of water, showing determination coefficients higher than 0.992 for matrix-matched calibration and absolute recoveries in the range 43-91%.

Hollow-fiber liquid-phase microextraction for the determination of natural and synthetic estrogens in milk samples.

In this work, a group of nine estrogens, four of them being natural (estriol, 17ß-estradiol, 17α-estradiol and estrone), four being synthetic (17α-ethynylestradiol, diethylstibestrol, dienestrol and hexestrol) and one metabolite (2-hydroxyestradiol) have been extracted and preconcentrated from milk samples with different fat content (whole, semi-skimmed and skimmed). After protein precipitation with acetonitrile containing acetic acid, evaporation of the supernatant and reconstitution of the residue in water, hollow-fiber liquid-phase microextraction (HF-LPME) using 1-octanol as extraction solvent was applied to further preconcentrate the analytes. Separation, determination and quantification were achieved by high-performance liquid chromatography coupled to a diode array detector and a fluorescence detector set in series. Deproteinization conditions, as well as parameters affecting the extraction efficiency in HF-LPME (pH of the sample, ionic strength, extraction time, stirring speed, temperature and desorption conditions) were investigated and optimized. Calibration, precision and accuracy studies were carried out to validate the methodology in different types of milk providing LODs in the low µg/L range.

Liquid phase microextraction applications in food analysis.

Over the last years, liquid-phase microextraction (LPME) in its different application modes (single drop microextraction, dispersive liquid-liquid microextraction and hollow fiber-LPME) has been increasingly applied for the extraction of both inorganic and organic analytes from different matrices. Its advantages over conventional extraction procedures (simplicity, effectiveness, rapidity and low consumption of organic solvents) has also attracted its application in the complex food analysis field, in which it has clearly provided good and challenging results. A comprehensive review dealing with those articles published since its introduction till the end of March 2011 is presented, offering also a critical vision of the analytical potential of LPME for the analysis of foods.

Ionic liquid-dispersive liquid-liquid microextraction for the simultaneous determination of pesticides and metabolites in soils using high-performance liquid chromatography and fluorescence detection.

In this work, an ionic liquid-dispersive liquid-liquid microextraction (IL-DLLME) procedure was developed for the extraction of a group of pesticides (carbendazim/benomyl, thiabendazole, fuberidazole, carbaryl and triazophos) and some of their key metabolites in soils (2-aminobenzimidazole, metabolite of carbendazim and 1-naphthol, metabolite of carbaryl) from aqueous soil extracts, using high performance liquid chromatography (HPLC) with fluorescence detection (FD). Analytes were previously extracted from four soils with different physicochemical properties (forestal, ornamental, garden and lapilli soils) by ultrasound-assisted extraction (USE). The IL 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIm][PF(6)]) and methanol (MeOH) were used as extraction and dispersion solvent, respectively, for the DLLME procedure. Factors affecting IL-DLLME (sample pH, IL amount, volume of dispersion solvent and sodium chloride percentage) were optimized by means of an experimental design, obtaining the most favorable results when using 117.5 mg of IL and 418 µL of MeOH to extract the compounds from the aqueous soil extracts at pH 5.20 containing 30% (w/v) NaCl. Calibration of the USE-IL-DLLME-HPLC-FD method was carried out for every type of soil and accuracy and precision studies were developed at two levels of concentration, finding that no significant differences existed between real and spiked concentrations (Student's t test). LODs achieved were in the low ng/g range.