Hybrid Materials Formed with Green Metal-Organic Frameworks and Polystyrene as Sorbents in Dispersive Micro-Solid-Phase Extraction for Determining Personal Care Products in Micellar Cosmetics.

Hybrid materials based on polystyrene (PS) and green metal-organic frameworks (MOFs) were synthesized, characterized, and evaluated as potential sorbents in dispersive micro-solid-phase extraction (µ-dSPE). Among the resulting materials, the hybrid PS/DUT-67(Zr) was selected as the adequate extraction material for the monitoring of six personal care products in micellar cosmetic samples, combining the µ-dSPE method with ultra-high performance liquid chromatography (UHPLC) coupled to ultraviolet/visible detection (UV/Vis). Univariate studies and a factorial design were performed in the optimization of the microextraction procedure. The compromise optimum extraction conditions included 20 mg of PS/DUT-67(Zr) for 10 mL of sample, 2 min of extraction time, and two desorption steps using 100 µL of acetonitrile and 5 min assisted by vortex in each one. The validated µ-dSPE-UHPLC-UV/Vis method presented limits of detection and quantification down to 3.00 and 10.0 µg·L-1, respectively. The inter-day precision values were lower than 23.5 and 21.2% for concentration levels of 75 µg·L-1 and 650 µg·L-1, respectively. The hydrophobicity of the resulting PS/DUT-67(Zr) material was crucial for the improvement of its extraction capacity in comparison with its unitary components, showing the advantages of combining MOFs with other materials, getting new sorbents with interesting properties.

Zirconium-Based Metal-Organic Framework Mixed-Matrix Membranes as Analytical Devices for the Trace Analysis of Complex Cosmetic Samples in the Assessment of Their Personal Care Product Content.

A device comprising a zirconium-based metal-organic framework (MOF) mixed-matrix membrane (MMM) framed in a plastic holder has been used to monitor the content of personal care products (PCPs) in cosmetic samples. Seven different devices containing the porous frameworks UiO-66, UiO-66-COOH, UiO-67, DUT-52, DUT-67, MOF-801, and MOF-808 in polyvinylidene fluoride (PVDF) membranes were studied. Optimized membranes reach high adsorption capacities of PCPs, up to 12.5 mg·g-1 benzophenone in a 3.0 mg·L-1 sample. The MMM adsorption kinetics, uptake measurements, and isotherm studies were carried out with aqueous standard solutions of PCPs to ensure complete characterization of the performance. The studies demonstrate the high applicability and selectivity of the composites prepared, highlighting the performance of PVDF/DUT-52 MMM that poses uptakes up to 78% for those PCPs with higher affinity while observing detection limits for the entire method down to 0.03 µg·L-1. The PVDF/DUT-52 device allowed the detection of parabens and benzophenones in the samples, with PCPs found at concentrations of 1.9-24 mg·L-1.

Core-shell microparticles formed by the metal-organic framework CIM-80(Al) (Silica@CIM-80(Al)) as sorbent material in miniaturized dispersive solid-phase extraction.

Core-shell SiO2@CIM-80(Al) microspheres were synthesized, characterized, and used as novel sorbent in a dispersive miniaturized solid-phase extraction (D-µSPE) method for the determination of fourteen polycyclic aromatic hydrocarbons (PAHs) in wastewaters by ultra-high performance liquid chromatography coupled to a fluorescence detector (UHPLC-FD). A Doehlert experimental design permitted to optimize the main parameters affecting the microextraction procedure, intending the obtaining of a simple approach. Optimized extraction conditions include 13 mg of SiO2@CIM-80(Al) microparticles (~2 mg CIM-80(Al)), 2.5 min of extraction time, 0.125 mL of acetonitrile (ACN) as desorption solvent and 0.5 min of desorption time. The entire method showed adequate analytical performance with limits of detection down to 5 ng L-1, and inter-day precision lower than 14.1% for a concentration level of 0.5 µg L-1. The extraction capability of SiO2@CIM-80(Al) microspheres was compared to that obtained with commercially available silica microspheres and the neat MOF CIM-80(Al), demonstrating the advantages of the use of MOF core-shell sorbents in D-µSPE.

Braid solid-phase microextraction of polycyclic aromatic hydrocarbons by using fibers coated with silver-based nanomaterials in combination with HPLC with fluorometric detection.

Authors propose a novel braid support configuration for use in solid-phase microextraction (SPME) fibers. Two different braided supports (double and triple) were prepared and compared with the conventional single support configuration. Three kinds of silver-based nanomaterials that serve as coatings on these supports are described. They included silver dendrites, silver nanoparticles (AgNPs), and silver dendrites decorated with AgNPs (Ag-dendrites@AgNPs). They were prepared by electrodeposition, a layer-by-layer (LBL) method, and a hybrid strategy, respectively. Fibers were used in the direct-immersion (DI) mode of SPME. Five polycyclic aromatic hydrocarbons (PAHs) were studied as model analytes by DI-SPME when analyzing (spiked) underground waters. PAHs were further determined with high-performance liquid chromatography (HPLC) and fluorescence detection. The analytical performance of the fibers was compared to that of the commercial polydimethylsiloxane (PDMS) fiber of 100 µm thickness. AgNPs obtained by LBL was the best coating and the double braid was the best support configuration. The configuration of the SPME support always played an important role independently on the coating material, being always beneficial the use of double-braids. Despite the low coatings volumes of the silver-based fibers compared to that of PDMS, the analytical features of the method were adequate. Figures of merit include: (a) limits of detection down to 20 ng·L-1; (b) intra-day, inter-day, and inter-fiber precisions (expressed as RSDs) of <13%, <12%, and < 13%, respectively; and (c) adequate operational lifetime (>60 extractions). Graphical abstract Schematic presentation of braided solid-phase microextraction support configurations together with different silver-based nanomaterials as coatings.

Silver nanoparticles supported onto a stainless steel wire for direct-immersion solid-phase microextraction of polycyclic aromatic hydrocarbons prior to their determination by GC-FID.

The authors describe a new coating for use in solid-phase microextraction (SPME). Silver nanoparticles (AgNPs) were prepared by using gallic acid or glucose as the reducing agents, and then supported onto a stainless steel wire that was previously coated with a silver mirror. Coating with AgNPs was performed by a layer-by-layer approach of up to eight cycles of consecutive deposition of AgNPs and the thiol linker 1,8-octanedithiol. This procedure allows proper control of the coating thickness. Thicknesses are 3.2 µm and 3.5 µm with AgNPs obtained with gallic acid and glucose, respectively. This is in agreement with theoretical estimations (3.8 µm). The fibers were used in the direct-immersion SPME-GC-FID determination of 16 polycyclic aromatic hydrocarbons (PAHs) from different waters. The performance of the method was compared to the one using polydimethylsiloxane fibers (100 µm), which is the most suitable commercial SPME fiber for PAHs. Despite the low thickness of the AgNP coatings (compared to PDMS), the analytical features of the method using the most adequate coating (AgNPs prepared with gallic acid) include: (a) limits of detection down to 0.6 ng·mL-1; (b) intra-day, inter-day, and inter-fiber precisions (expressed as RSDs) lower than 22, 26 and 25%, respectively; and (c) an operational lifetime of ~150 extractions/desorption cycles. The analysis of various spiked environmental waters using these fibers resulted in adequate analytical performance. Graphical abstract Silver nanoparticle based coatings for solid-phase microextraction fibers were prepared by a layer-by-layer approach. They were used for determination of 16 PAHs in waters by gas chromatography. Limits of detection are < 14 µg·L-1 and intra-day, inter-day, and inter-fiber precisions are <26%.

Influence of vegetable coagulant and ripening time on the lipolytic and sensory profile of cheeses made with raw goat milk from Canary breeds.

Free fatty acids and sensory profiles were obtained for cheeses made with raw goat milk and vegetable coagulant, derived from the cardoon flower ( Cynara cardunculus), at different ripening times (7 and 20 days). A solid-liquid phase extraction method followed by solid-phase extraction and gas chromatography was used. Profiles were also obtained with cheeses made with commercial coagulant, traditional kid rennet paste, and mixture coagulant (vegetable coagulant-kid rennet). The use of vegetable coagulant and vegetable coagulant-kid rennet is common in traditional Protected Designation of Origin cheeses such as " Queso Flor de Guía" and " Queso Media Flor de Guía" (Spain). Contents of short-chain free fatty acids (7.5-22.5 mmol·kg-1), medium-chain free fatty acids (0.4-3.7 mmol·kg-1), and long-chain free fatty acids (0.2-2.1 mmol·kg-1) varied depending on the coagulant type and the ripening time. Vegetable coagulant cheeses present odour intensity and flavour intensity much higher than commercial coagulant cheeses in the sensory analysis for cheeses obtained with seven days of ripening, but the values decrease when increasing the ripening time. Multivariate analysis allowed us to differentiate cheese samples according to the ripening time when using lipolytic profile and according to the coagulant type using the sensory profile.

Gold nanoparticles based solid-phase microextraction coatings for determining organochlorine pesticides in aqueous environmental samples.

The use of solid-phase microextraction coatings based on gold nanoparticles was investigated, focusing the attention on the preparation of nanoparticles with nonclassical reduction agents of HAuCl4 such as gallic acid and H2 O2 , rather than the conventional sodium citrate. All nanoparticles were characterized by diode array spectroscopy, whereas novel nanoparticles prepared with gallic acid and H2 O2 were also characterized by microscopic techniques. Solid-phase microextraction coatings were prepared with a layer-by-layer approach. Gallic acid permitted the preparation of stable nanoparticles with milder experimental conditions (1 min, room temperature) and provided the most uniform coatings (thickness ∼3 µm). Seven organochlorine pesticides were determined in different environmental waters using gas chromatography with electron capture detection. Despite the low thickness of the coatings, limits of detection of the entire method down to 0.13 µg/L were obtained. A comparison with the commercial polyacrylate in terms of the partition coefficients of the analytes to the coatings gave logarithm of the partition coefficient values two times higher with gallic acid than polyacrylate (although the commercial fiber is 28 times thicker). Interfiber relative standard deviation values ranged from 8.67 to 21.3%. Optimum fibers also presented an adequate lifetime (>100 extractions).