Adenoid cystic carcinoma of the palpebral lobe of the lacrimal gland - case report and literature review.

Epithelial tumors of the lacrimal gland are rare and usually develop in the orbital lobe. We report the exceedingly rare occurrence of a primary adenoid cystic carcinoma in the palpebral lobe of the lacrimal gland. A 26-year-old female was referred for evaluation of a gradually enlarging mass in the lateral upper eyelid, previously diagnosed as a chalazion. Computed tomography revealed a heterogeneous round lesion anterior to the orbital rim. Excisional biopsy was compatible with an adenoid cystic carcinoma. After excluding distant metastasis, and as the patient refused adjuvant radiotherapy, a second surgical procedure, with wide local excision, was indicated. Follow-up showed no recurrence. This case highlights the importance of performing a thorough clinical examination when diagnosing any lateral upper eyelid mass. A high index of suspicion for malignant tumors of the lacrimal gland should always be maintained, and a complete excision with histological analysis should be preferred whenever possible.

Application of a Pillared-Layer Zn-Triazolate Metal-Organic Framework in the Dispersive Miniaturized Solid-Phase Extraction of Personal Care Products from Wastewater Samples.

The pillared-layer Zn-triazolate metal-organic framework (CIM-81) was synthesized, characterized, and used for the first time as a sorbent in a dispersive micro-solid phase extraction method. The method involves the determination of a variety of personal care products in wastewaters, including four preservatives, four UV-filters, and one disinfectant, in combination with ultra-high performance liquid chromatography and UV detection. The CIM-81 MOF, constructed with an interesting mixed-ligand synthetic strategy, demonstrated a better extraction performance than other widely used MOFs in D-µSPE such as UiO-66, HKUST-1, and MIL-53(Al). The optimization of the method included a screening design followed by a Doehlert design. Optimum conditions required 10 mg of CIM-81 MOF in 10 mL of the aqueous sample at a pH of 5, 1 min of agitation by vortex and 3 min of centrifugation in the extraction step; and 1.2 mL of methanol and 4 min of vortex in the desorption step, followed by filtration, evaporation and reconstitution with 100 µL of the initial chromatographic mobile phase. The entire D-µSPE-UHPLC-UV method presented limits of detection down to 0.5 ng·mL-1; intra-day and inter-day precision values for the lowest concentration level (15 ng·mL-1)-as a relative standard deviation (in %)-lower than 8.7 and 13%, respectively; average relative recovery values of 115%; and enrichment factors ranging from ~3.6 to ~34. The reuse of the CIM-81 material was assessed not only in terms of maintaining the analytical performance but also in terms of its crystalline stability.

Salt-induced ionic liquid-based microextraction using a low cytotoxic guanidinium ionic liquid and liquid chromatography with fluorescence detection to determine monohydroxylated polycyclic aromatic hydrocarbons in urine.

A novel ionic liquid (IL)-based microextraction method has been developed for the determination of four hydroxylated polycyclic aromatic hydrocarbons (OHPAHs) in urine samples. The water soluble IL-based surfactant selected as extraction solvent is decylguanidinium chloride (C10Gu-Cl), the cytotoxicity and micellar behavior of which were evaluated. The proposed salt-induced IL-based preconcentration method simply consists in adding NaClO4 to the aqueous medium containing the IL to promote its water insolubility. The entire method was optimized, requiring the use of only 20 µL of C10Gu-Cl for 10 mL of diluted urine sample (1:10) without any pH adjustment, followed by the addition of NaClO4 to ensure a 5% (w/v) content. A cloudy solution was observed immediately, and after the application of 4 min of vortex and 8 min of centrifugation, the droplet was diluted up to 60 µL with a mixture of acetonitrile:water (30:70) and injected into the liquid chromatograph with fluorescence detection. The method was validated using both synthetic urine and human urine as matrix for the determination of the four OHPAHs. The following analytical features were obtained: detection limits down to 1 ng·L-1 in real urine; inter-day reproducibility (as RSD in %) always lower than 17% when dealing with real urine samples spiked at 80 ng·L-1; and average relative recoveries of 102% in real urine samples at such low spiked levels. Despite the simplicity of the proposed method, it performed successfully with complex urine samples. Graphical abstract Salt-induced IL-based microextraction using a low cytotoxic IL for mono-OHPAHs in urine.

Influence of Ligand Functionalization of UiO-66-Based Metal-Organic Frameworks When Used as Sorbents in Dispersive Solid-Phase Analytical Microextraction for Different Aqueous Organic Pollutants.

Four metal-organic frameworks (MOFs), specifically UiO-66, UiO-66-NH2, UiO-66-NO2, and MIL-53(Al), were synthesized, characterized, and used as sorbents in a dispersive micro-solid phase extraction (D-µSPE) method for the determination of nine pollutants of different nature, including drugs, phenols, polycyclic aromatic hydrocarbons, and personal care products in environmental waters. The D-µSPE method, using these MOFs as sorbents and in combination with high-performance liquid chromatography (HPLC) and diode-array detection (DAD), was optimized. The optimization study pointed out to UiO-66-NO2 as the best MOF to use in the multi-component determination. Furthermore, the utilization of isoreticular MOFs based on UiO-66 with the same topology but different functional groups, and MIL-53(Al) to compare with, allowed us for the first time to evaluate the influence of such functionalization of the ligand with regards to the efficiency of the D-µSPE-HPLC-DAD method. Optimum conditions included: 20 mg of UiO-66-NO2 MOF in 20 mL of the aqueous sample, 3 min of agitation by vortex and 5 min of centrifugation, followed by the use of only 500 µL of acetonitrile as desorption solvent (once the MOF containing analytes was separated), 5 min of vortex and 5 min of centrifugation. The validation of the D-µSPE-HPLC-DAD method showed limits of detection down to 1.5 ng·L-1, average relative recoveries of 107% for a spiked level of 1.50 µg·L-1, and inter-day precision values with relative standard deviations lower than 14%, for the group of pollutants considered.

Double salts of ionic-liquid-based surfactants in microextraction: application of their mixed hemimicelles as novel sorbents in magnetic-assisted micro-dispersive solid-phase extraction for the determination of phenols.

The use of mixed hemimicelles of ionic liquid (IL)-based surfactants in a magnetic-based micro-dispersive solid-phase extraction (m-µdSPE) approach is described. Not only is the symmetric monocationic IL-based surfactant 1,3-didodecylimidazolium bromide (C12C12Im-Br) studied for first time in m-µdSPE, but double-salt (DS) IL (DSIL)-based surfactants are also examined. Nine DSIL-based surfactants were formed by combination of C12C12Im-Br with other IL-based surfactants, including nonsymmetric monocationic and dicationic ILs combined at three different molar fractions. The analytical application was focused on the determination of a group of eight phenols, including bisphenol A, in water samples. The best results were obtained with the DSIL formed by C12C12Im-Br (molar fraction 0.5) and 1-hexadecyl-3-methylimidazolium bromide (C16MIm-Br), after proper optimization of the overall method in combination with high-performance liquid chromatography (HPLC) and diode-array detection (DAD). The optimum conditions for 100 mL of water samples require a small amount (10 mg) of Fe3O4 magnetic nanoparticles, a low content (5.0 mg of C12C12Im-Br and 3.9 mg of C16MIm-Br) of the selected DSIL, pH 11, a sonication time of 2.5 min, and an equilibration time of 5 min with the aid of NdFeB magnets, followed by elution of phenols, evaporation, and reconstitution with 0.5 mL of acetonitrile. The overall m-µdSPE-HPLC-DAD method is characterized for limits of detection down to 1.3 µg · L(-1), intraday relative standard deviations lower than 13 % (n = 3), and interday relative standard deviations lower than 17 % (n = 9), with a spiking level of 15 µg · L(-1); with enrichment factors between 15.7 and 141, and average relative recoveries of 99.9 %.

Automated direct-immersion solid-phase microextraction using crosslinked polymeric ionic liquid sorbent coatings for the determination of water pollutants by gas chromatography.

Four different crosslinked polymeric ionic liquid (PIL)-based sorbent coatings were evaluated in an automated direct-immersion solid-phase microextraction method (automated DI-SPME) in combination with gas chromatography (GC). The crosslinked PIL coatings were based on vinyl-alkylimidazolium- (ViCnIm-) or vinylbenzyl-alkylimidazolium- (ViBzCnIm-) IL monomers, and di-(vinylimidazolium)dodecane ((ViIm)2C12-) or di-(vinylbenzylimidazolium)dodecane ((ViBzIm)2C12-) dicationic IL crosslinkers. In addition, a PIL-based hybrid coating containing multi-walled carbon nanotubes (MWCNTs) was also studied. The studied PIL coatings were covalently attached to derivatized nitinol wires and mounted onto the Supelco assembly to ensure automation when acting as SPME coatings. Their behavior was evaluated in the determination of a group of water pollutants, after proper optimization. A comparison was carried out with three common commercial SPME fibers. It was observed that those PILs containing a benzyl group in their structures, either in the IL monomer and crosslinker (PIL-1-1) or only in the crosslinker (PIL-0-1), were the most efficient sorbents for the selected analytes. The validation of the overall automated DI-SPME-GC-flame ionization detector (FID) method gave limits of detection down to 135 µg · L(-1) for p-cresol when using the PIL-1-1 and down to 270 µg · L(-1) when using the PIL-0-1; despite their coating thickness: ~2 and ~5 µm, respectively. Average relative recoveries with waters were of 85 ± 14 % and 87 ± 15 % for PIL-1-1 and PIL-0-1, respectively. Precision values as relative standard deviation were always lower than 4.9 and 7.6 % (spiked level between 10 and 750 µg · L(-1), as intra-day precision). Graphical Abstract Automated DI-SPME-GC-FID using crosslinked-PILs sorbent coatings for the determination of waterpollutants.

Utilization of an ionic liquid in situ preconcentration method for the determination of the 15 + 1 European Union polycyclic aromatic hydrocarbons in drinking water and fruit-tea infusions.

An ionic liquid (IL) in situ preconcentration method was optimized and applied to the monitoring of the 15 + 1 European Union polycyclic aromatic hydrocarbons in water and fruit-tea infusions. The optimized method utilizes 10 mL of water (or infusion) containing 38 µL of the IL 1-butyl-3-methylimidazolium chloride and a content of 36.1 g/L NaCl, which are mixed with Li-NTf2 (340 µL, 0.2 g/mL), followed by vortex (4 min) and centrifugation (5 min). The obtained microdroplet containing hydrocarbons is diluted with acetonitrile and injected into an HPLC with UV/Vis and fluorescence detection. The method presented average enrichment factors of 127 for water (tap water and bottled water) and 27 for two fruit-tea infusions; with average relative recoveries of 86.7 and 106% for water and fruit-tea infusions, respectively. The method was sensitive, with detection limits ranging from 0.001 to 0.050 ng/mL in water, and from 0.010 to 0.600 ng/mL in fruit-tea infusions, for the fluorescent hydrocarbons. Real extraction efficiencies ranged from 12.7 to 58.7% for water, and from 20.2 to 117% for the infusions. The method was also fast (~12 min) and free of organic solvents in the extraction step.

Monitoring polycyclic aromatic hydrocarbons in seawaters and wastewaters using a dispersive liquid-liquid microextraction method.

An evaluation has been made of a dispersive liquid-liquid microextraction (DLLME) procedure for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) in different environmental waters including seawaters and wastewaters, using gas-chromatography (GC) with flame-ionization detection (FID). The optimized method requires 18 microL of the extractant solvent tetrachloroethylene (C2Cl4), 1 mL of acetonitrile as dispersive solvent, and 5 mL of aqueous sample. After centrifugation (5 min), 2 microL of the obtained micro-droplet containing the extracted PAHs, which varied from - 15 microL for seawaters to - 9 microL for wastewaters, is directly injected in the GC-FID. The performance of the method is characterized for average extraction efficiencies of 99.0% and 98.1% when analysing real seawaters and wastewaters, respectively, at low spiked levels (3 ng x mL(-1)); and average precision values of 8.4% as relative standard deviation. The performance of the method was also compared with conventional liquid-liquid extraction. The DLLME calibrations have been obtained in different aqueous matrices to thoroughly evaluate the matrix effect. The application of the joint-confidence ellipse F-test showed that seawaters can be simply analysed using DLLME calibrations obtained in the laboratory using deionized water. However, important caution must be taken into account when dealing with wastewater, because of matrix effects.

Developing qualitative extraction profiles of coffee aromas utilizing polymeric ionic liquid sorbent coatings in headspace solid-phase microextraction gas chromatography-mass spectrometry.

Two solid-phase microextraction (SPME) sorbent coatings based on polymeric ionic liquids (PILs) have been utilized for the analysis of complex coffee aroma samples. The PIL-based SPME coatings examined, namely, poly(1-(4-vinylbenzyl)-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonyl]imide) [poly(VBHDIm(+) NTf(2)(-))], with ~14-µm thickness, and poly(1-vinyl-3-hexylimidazolium chloride) [poly(ViHIm(+)Cl(-))], with ~8-µm thickness, were employed for the headspace determination of up to 49 analytes from four different coffee beans: two French roast coffees of different brands, Sumatra coffee, and decaffeinated Sumatra coffee. The analysis was conducted using gas chromatography coupled to mass spectrometry. For comparative purposes, the commercial polyacrylate (PA, 85-µm film thickness) SPME coating was utilized under the same extraction conditions. The three SPME coatings tested behaved quite differently as a function of the families of compounds extracted. Thus, the poly(VBHDIm(+) NTf(2)(-) ) coating was extremely selective for aldehydes while also exhibiting good extraction efficiencies for acids. The poly-(ViHIm(+) Cl(-)) coating exhibited superior performance for aromatic alcohols, and the PA coating worked better for heterocyclic aromatics. Both PIL-based SPME sorbent coatings demonstrated exceptional selectivity and extraction efficiency when dealing with complex coffee aromas in spite of their small film thicknesses.

Suitability of ionic liquids as mobile-phase additives in HPLC with fluorescence and UV detection for the determination of heterocyclic aromatic amines.

The effects of several ionic liquids (ILs) as mobile-phase additives in HPLC with fluorescence and UV-Vis detection for the determination of six heterocyclic aromatic amines were evaluated using two different C(18) stationary phases with moderate silanol activity. The studied ILs were 1-butyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium tetrafluoroborate and 1-methyl-3-octylimidazolium tetrafluoroborate. The optical behaviour of heterocyclic aromatic amines in presence of ILs was studied and the silanol-suppressing potency of ILs was evaluated for the two stationary phases studied. Several chromatographic parameters were evaluated in the presence or absence of ILs, or using triethylamine, the most common mobile-phase additive. The best results were achieved using 1 mM 1-butyl-3-methylimidazolium tetrafluoroborate as mobile-phase additive and NovaPak column. In these conditions and with 18% of ACN in the mobile phase, analytical performance of the chromatographic methods using fluorescence and UV-Vis were evaluated, obtaining good precision in all cases (RSD lower than 6.6%) and low LOD (0.001-0.147 microg/mL with UV-Vis and 0.001-0.006 ng/mL with fluorescence detection).

Use of a pH-sensitive polymer in a microextraction and preconcentration method directly combined with high-performance liquid chromatography.

A pH-sensitive polymer based on the poly(styrene-alt-maleic anhydride) co-polymer serves as basis to develop a microextraction method (pH-HGME) in direct combination with high-performance liquid chromatography (HPLC) and fluorescence detection (FD) for the determination of seven organic compounds, including three polycyclic aromatic hydrocarbons (PAHs), three monohydroxylated PAHs and one alkylphenol, in urine. The method bases on the structural modification of the pH-sensitive polymer in the aqueous sample at a high pH value, followed by the formation and insolubilization of a hydrogel containing the preconcentrated analytes by decreasing the pH, and the direct injection of the hydrogel-rich phase in the HPLC-FD system. The optimization of the main variables permitted the selection of low amounts of aqueous sample (10 mL), which was mixed with 10 mg of co-polymer also present in a low volume (150 µL) of concentrated NaOH. The method further requires the addition of 200 µL of concentrated HCl, 3 min of stirring, and 15 min of centrifugation. This pH-HGME-HPLC-FD method presented low limits of detection, ranging from 0.001 µg L-1 to 0.09 µg L-1 in ultrapure water, average relative recoveries of 96.9% for the concentration level of 0.60 µg L-1, and enrichment factors between 1.50 and 17.7. The proposed method also exhibited high precision, with intermediate relative standard deviations lower than 16% for a concentration level of 0.60 µg L-1. The developed pH-HGME-HPLC-FD method performed adequately when analyzing two human urine samples provided by a non-smoker male and a smoker female, respectively. One of the target analytes (2-hydroxynaphthalene) was quantified in both samples using the standard addition method, with a predicted concentration of 7.3 ± 0.4 µg L-1 in the non-smoker male urine and 19.3 ± 0.6 µg L-1 in the smoker female urine.

Solid-phase microextraction coatings based on the metal-organic framework ZIF-8: Ensuring stable and reusable fibers.

Chemical vapor deposition of MOFs (MOF-CVD) has been used to coat solid-phase microextraction (SPME) fibers with ZIF-8, by exposing ZnO layers to the linker vapor (2-methylimidazole). This ZIF-8 coating has been used as a seed layer in a following solvothermal MOF growth step in order to increase the ZIF-8 thickness. The combined MOF-CVD and solvothermal growth of ZIF-8 on the fibers result in a thickness of ~3 µm, with adequate thermal stability, and mechanical integrity when tested with methanol and acetonitrile ultrasonic treatments. The fibers have been evaluated in direct immersion mode using gas chromatography and flame ionization detection (GC-FID), for a group of target analytes including three polycyclic aromatic hydrocarbons (PAHs) and five personal care products (PCPs). The optimized conditions of the SPME-GC-FID methods include low amount of aqueous sample (5 mL), stirring for 45 min at 35 °C, and desorption at 280 °C for 5 min. The method presents limits of detection down to 0.6 µg L-1; intra-day, inter-day and inter-batch relative standard deviation values lower than 16%, 19%, and 23%, respectively; and a lifetime higher than 70 cycles.

Ionic liquids as desorption solvents and memory effect suppressors in heterocyclic aromatic amines determination by SPME-HPLC fluorescence.

The beneficial effects of 1-butyl-3-methylimidazolium tetrafluoroborate (BMIm-BF(4)) ionic liquid (IL) as mobile phase additive, desorption solvent, and memory effect suppressor in solid-phase microextraction (SPME)-high-performance liquid chromatography with fluorescence detection for the determination of six heterocyclic aromatic amines have been evaluated for the first time. Several chromatographic parameters have been evaluated in the presence or absence of IL or using triethylamine as the most common mobile phase additive, with a Nova-Pak C18 stationary phase. This IL was found to be clearly superior to triethylamine for efficiency as well as peak shape enhancement and sensitivity increase. SPME was chosen because it is faster than conventional extraction techniques and allowed us to minimize the use of organic solvents. However, memory effect may become a problem when a high-sensitivity detector is used. The appropriate conditions for the desorption step and to eliminate the memory effect involving BMIm-BF(4) were established and optimized. The method was applied for the determination of these compounds in commercial meat extracts.

Determination of carbonyl compounds in smoke samples: strategies for sampling and standardization.

There are significant drawbacks to the calibration procedure recommended in the normalized Spanish or American methods used to determine carbonyl compounds in ambient air by quantifying hydrazones that form with 2,4-dinitrophenylhydrazine. The impurities present in 2,4-dinitrophenylhydrazine, as well as the lack of quantitativity and the slow kinetics of some derivatization reactions can lead to considerable errors in quantification. This work proposes two alternative systems for sampling biomass smoke in order to analyze aldehydes and ketones. The standardization process used by both systems requires standard solutions to be reacted with 2,4-dinitrophenylhydrazine under experimental conditions similar to those used to collect the sample. The resulting calibration curve slopes differ between 8% and 74% from the curves used in methods that employ commercial standard hydrazone solutions. The detection limits reached by using the proposed methods are between 0.07 and 0.47 mg L(-1). Both methods are complementary for smoke samples that have significant differences in the concentrations of aldehydes or ketones.

[Seroprevalence of rubella in urban and rural populations, Guaratinguetá]. / Soroprevalência da rubéola na população urbana e rural de Guaratinguetá

OBJECTIVE: To investigate seroprevalence of rubella antibodies in a 15 to 39 year old population in the municipal district of Guaratinguetá. METHODS: The 996 samples studied were collected in urban and rural zones, after informed and elucidated consent from men and women stratified by age (15 -39 years). Rubella IgG antibodies were detected by ELISA using the commercial kit Rubenostika IgGII (Organon Teknika THE, Holland). Age groups were stratified in 3 categories: 15-19; 20-29 and 30-39 years of age. Statistical analyses were accomplished with the software MINITAB version 14.0 (Minitab Inc, USA). RESULTS: The proportion of seropositives for antibodies of the IgG class were: 92.7.% positive for 15-19 years; 82.4% for 20 to 29 years and 90.7% for 30-39 years, with a significant difference in the seropositive proportions by age group (p <0.001). Variation of intensity of antibody response was calculated and results show a significant difference (p = 0.002) between means of the 3 age groups studied. In relation to rural and urban zone average of the ratio DO/CO for each age group, a significant tendency towards a lower average was observed in the rural zone. The same was true when the seropositive proportions were calculated. CONCLUSION: Results showed that the percentage and individuals with antibodies of the IgG class against rubella in the 20-29 year age group was lower than that in the younger and older age groups. Furthermore, the difference between seropositivity in the urban and rural zones discloses susceptibility with a potential for continued circulation of the virus in this zone.

Ionic liquid-based miniaturized aqueous biphasic system to develop an environmental-friendly analytical preconcentration method.

Two ILs containing guanidinium cations (butylguanidinium chloride -C4Gu-Cl- and hexylguanidinium chloride -C6Gu-Cl-) were synthesized and characterized. Their cytotoxicity was also assessed, obtaining adequate CC50 values of 680 ±â€¯99 mg·L-1 for C4Gu-Cl and 135 ±â€¯8 mg·L-1 for C6Gu-Cl. Miniaturized aqueous biphasic systems (µ-ABSs) were developed using amounts lower than 1% (w/w) of these synthesized guanidinium-based ILs, K3PO4 as salting-out agent, and ultrapure water. The phases diagrams of both systems were determined, and the C4Gu-Cl-based µ-ABS was selected for the development of a microextraction method in combination with high performance liquid chromatography (HPLC) with fluorescence detection (FD) for the determination of five polycyclic aromatic hydrocarbons (PAHs) as model analytes. A point of the biphasic region of the C4Gu-Cl-based µ-ABS corresponding to a mixture of 0.75% (w/w) of the IL, 37.7% (w/w) of K3PO4 and 61.55% (w/w) of ultrapure water, and 30 min of equilibrium time, were selected as optimum conditions to obtain high enrichment factors and proper analytical microextraction performance. The C4Gu-Cl-based µ-ABS-HPLC-FD method exhibited low limits of detection, between 0.010 ng·L-1 and 2.0 ng·L-1, average relative recoveries of 96.7%, high enrichment factors ranging from 44.1 to 60.4, average extraction efficiencies of 61.7%, and intermediate precision relative standard deviations lower than 17% for a concentration level of 12 ng·L-1. The developed method was applied successfully in the analysis of different tap water samples.

Coupling the extraction efficiency of imidazolium-based ionic liquid aggregates with solid-phase microextraction-gas chromatography-mass spectrometry. Application to polycyclic aromatic hydrocarbons in a certified reference sediment.

Three ionic liquid (IL)-based aggregates, 1-hexadecyl-3-methylimidazolium bromide (HDMIm-Br), 1-hexadecyl-3-butylimidazolium bromide (HDBIm-Br), and 1,3-didodecylimidazolium bromide (DDDDIm-Br) have been applied to the development of a quantitative solid-phase microextraction (SPME)-gas chromatography (GC)-mass spectrometry (MS) method. A sensitivity factor (SF) is defined and introduced for the first time to quantitatively compare the efficiency of the IL-based aggregates by SPME-GC-MS and to evaluate the partitioning strength of several polycyclic aromatic hydrocarbons (PAHs) to the three IL-aggregates. The ILs HDBIm-Br and HDMIm-Br have been used successfully to extract seven PAHs from the certified reference sediment BCR-535 using focused microwave-assisted extraction followed by SPME-GC-MS. Average recoveries for six of the seven certified PAHs were 84.6% for HDMIm-Br and 101% for HDBIm-Br, with relative standard deviation values (RSDs) lower than 19%. The overall extraction method requires short extraction times (around 7 min for the microwave step) and avoids the use of organic solvents.

The ionic liquid 1-hexadecyl-3-methylimidazolium bromide as novel extracting system for polycyclic aromatic hydrocarbons contained in sediments using focused microwave-assisted extraction.

A method to extract PAHs from sediments is carried out using aqueous solutions containing aggregates of the ionic liquid (IL) 1-hexadecyl-3-methylimidazolium bromide (HDMIm-Br) as the extracting medium. Focused microwave-assisted extraction has been used to accelerate the extraction step, followed by HPLC with fluorescence detection without clean-up steps to remove the IL prior to injection. The method has been applied to certified reference sediment BCR-535 and marine sediments from Tenerife (Canary Islands) with successful results. The optimized method gave average absolute recoveries of 91.1% for six of the seven PAHs studied, with relative standard deviations lower than 10.4%. The overall method is characterized for presenting low extraction times (6min), low amounts of the sediment (0.1g), low amounts of IL (45mM), and low volumes of aqueous extractant solution (9mL). The use of small amounts of both IL and aqueous extractant solution allows the method to be considered environmental-friendly.

Micelle-mediated extractions using nonionic surfactant mixtures and HPLC-UV to determine endocrine-disrupting phenols in seawaters.

An environmentally friendly method to extract endocrine-disrupting phenols (EDPs) from seawaters was realized using nonionic surfactant mixtures and micelle-mediated extractions. The preconcentration step was achieved directly in the seawater matrix, and was followed by high-performance liquid chromatography (HPLC) with ultraviolet (UV) detection without any clean-up steps to remove the surfactant mixture prior to injection. Various nonionic surfactant mixtures were used, and polyoxyethylene-10-laurylether (POLE) with polyoxyethylene-4-laurylether (Brij 30) was found to be the best to work with. Method optimization involved maximizing the preconcentration factor using the studied mixtures. The proposed method gave extraction recoveries ranging from 83.3 to 114.4% for an EDP spiking level of 46.7 microg L(-1), and from 63.4 to 112.4% for a spiking level of 4.7 microg L(-1) for EDPs studied in real seawater matrices, with relative standard deviations of <12.1%. The detection limits of the method varied from 0.18 microg L(-1) for bisphenol A (BPA) to 1.17 microg L(-1) for 4-cumylphenol (4-CP). The method was applied to seawaters from the Canary Islands with successful results.

Guanidinium ionic liquid-based surfactants as low cytotoxic extractants: Analytical performance in an in-situ dispersive liquid-liquid microextraction method for determining personal care products.

The IL-based surfactant octylguanidinium chloride (C8Gu-Cl) was designed and synthetized with the purpose of obtaining a less harmful surfactant: containing guanidinium as core cation and a relatively short alkyl chain. Its interfacial and aggregation behavior was evaluated through conductivity and fluorescence measurements, presenting a critical micelle concentration value of 42.5 and 44.6mmolL-1, respectively. Cytotoxicity studies were carried out with C8Gu-Cl and other IL-based and conventional surfactants, specifically the analogue 1-octyl-3-methylimidazolium chloride (C8MIm-Cl), and other imidazolium- (C16MIm-Br) and pyridinium- (C16Py-Cl) based surfactants, together with the conventional cationic CTAB and the conventional anionic SDS. From these studies, C8Gu-Cl was the only one to achieve the classification of low cytotoxicity. An in situ dispersive liquid-liquid microextraction (DLLME) method based on transforming the water-soluble C8Gu-Cl IL-based surfactant into a water-insoluble IL microdroplet via a simple metathesis reaction was then selected as the extraction/preconcentration method for a group of 6 personal care products (PCPs) present in cosmetic samples. The method was carried out in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD). The method was properly optimized, requiring the use of only 30µL of C8Gu-Cl for 10mL of aqueous sample with a NaCl content of 8% (w/v) to adjust the ionic strength and pH value of 5. The metathesis reaction required the addition of the anion exchange reagent (bis[(trifluoromethyl)sulfonyl]imide - 1:1 molar ratio), followed by vortex and centrifugation, and dilution of the final microdroplet up to 60µL with acetonitrile before the injection in the HPLC-DAD system. The optimum in situ DLLME-HPLC-DAD method takes ∼10min for the extraction step and ∼22min for the chromatographic separation, with analytical features of low detection limits: down to 0.4µgL-1; high reproducibility: with RSD values lower than 10% (intra-day) and 16% (inter-day) for a spiked level of 15µgL-1; and an average enrichment factor of 89. The requirement of low volumes (30µL) of a low cytotoxic IL-based surfactant allows the method to be considered less harmful than other common analytical microextraction approaches.