Simultaneous determination of third-generation synthetic cannabinoids in oral fluids using cyclodextrin-silica porous sorbents
Abstract A microporous material made of cyclodextrin units covalently immobilized into a silica network has found an innovative bioanalytical application in the sample clean-up and simultaneous isolation of three synthetic cannabinoids (ADB-CHMICA, MMB-CHMICA, and MDMB-CHMCZCA) from human oral fluid through solid-phase extraction. The subsequent quantitation is carried out using liquid chromatography coupled to fluorescence detection. The optimized experimental procedure gives recoveries ranging from 76% to 96% in oral fluid samples spiked with the studied cannabinoids at the µg L-1 level. High selectivity is obtained through the extraction procedure due to the presence of cyclodextrin in t…
Mesoporous iron phosphate/phosphonate hybrid materials
Abstract Relatively high surface area pure mesoporous iron-phosphorus oxide-based derivatives have been synthesized through an S + I − surfactant-assisted cooperative mechanism by means of a one-pot preparative procedure from aqueous solution and starting from iron atrane complexes and phosphoric and phosphonic acids. A soft chemical extraction procedure allows opening the pore system of the parent as-prepared materials by exchanging the surfactant without mesostructure collapse. The nature of the pore wall can be modulated from iron phosphate up to hybrids involving approximately 30% of organophosphorus entities (phosphonates or diphosphonates). X-ray powder diffraction, transmission elect…
Enlarged pore size in nanoparticulated bimodal porous silicas: Improving accessibility
Abstract Mass-transfer kinetics seems to be highly favored in siliceous materials constructed from the aggregation of mesoporous nanoparticles. Besides intra-particle mesopores, over the course of the aggregation process an inter-particle (textural) large pore system is generated. Diffusion constrains through the resulting hierarchically structured pore systems mainly depend on the characteristics of the intra-particle mesopores. By using alkanes as swelling agents, we have been able to significantly increase the intra-particle mesopore size in previously well characterized UVM-7 materials. The Winsor-III-like behavior associated with the presence of alkanes in the hydro-alcoholic reaction …
Bimodal porous silica nanomaterials as sorbents for an efficient and inexpensive determination of aflatoxin M1 in milk and dairy products
Abstract An extraction procedure was developed for the determination of aflatoxin M1 in milk and dairy products. A sorbent based on UVM-7 mesoporous silica was used as solid phase for the sample clean-up, and the analyte determination was carried out by HPLC coupled to a fluorescence detector. The material architecture was characterized by transmission electronic microscopy, X-ray diffraction, 29Si NMR and nitrogen adsorption-desorption. After the optimization of extraction parameters, the influence of the matrix has been evaluated, obtaining recoveries in the range 78–105% for whole and skimmed milk and yogurt matrix. The reusability of the material was also proved. The sensitivity of the …
Comparative evaluation of liquid chromatography versus gas chromatography using a β-cyclodextrin stationary phase for the determination of BTEX in occupational environments
An HPLC method for the determination of benzene, toluene, ethylbenzene and o-xylene, m-xylene and p-xylene in occupational environments was developed and compared with a GC-MS method. Chromatographic analysis using a beta-cyclodextrin stationary phase was performed after active and passive air sampling by adsorption on activated charcoal and pressurized fluid extraction. The analytes were completely separated and quantified using both methods, although GC-MS provided better resolutions and lower detection limits than HPLC. The HPLC method was unsuccessfully applied to the determination of benzene in real samples because its sensitivity was too low. Both methods were applied to the analysis …
Host-guest interactions for extracting antibiotics with a γ-cyclodextrin poly(glycidyl-co-ethylene dimethacrylate) hybrid sorbent
Abstract A procedure for the solid-phase extraction of antibiotics (enoxacin, ofloxacin, norfloxacin, ciprofloxacin, and sparfloxacin) in water has been developed. The sorbent used is based on a poly(glycidyl-co-ethylene dimethacrylate) network, whose previously modified surface has been functionalized with γ-cyclodextrin through a click-chemistry reaction. The architecture of the material has been characterized by thermogravimetric analysis, N2 adsorption-desorption, Raman spectroscopy, confocal microscopy, and scanning electron microscopy, showing good capability to be used as a filler for extraction cartridges. The optimization of the extraction methodology shows good intra-day and inter…
Application of pressurized fluid extraction to determine cadmium and zinc in plants
Abstract A procedure for the determination of Cd and Zn in plants is proposed. The metals are extracted by pressurized fluid extraction (PFE). Operational conditions are: pressure 1500 psi, temperature 75 °C, static time 5 min, flush volume 35%, purge time 60 s, cycles 1 and 1,2-diaminocyclohexane- N , N , N ′, N ′-tetraacetic acid (CDTA) 0.01 M at pH 4.5 as extracting solution. Determination of Zn is carried out by flame atomic absorption spectroscopy and depending on the concentration level, Cd content is determined by flame or electrothermal atomic absorption spectroscopy. Certified samples of Virginia tobacco leaves, tea leaves, spinach leaves, poplar leaves, a commercial spinach sample…
Cyclodextrins as a Key Piece in Nanostructured Materials: Quantitation and Remediation of Pollutants
Separation and pre-concentration of trace pollutants from their matrix by reversible formation of inclusion complexes has turned into a widely studied field, especially for the benefits provided to different areas. Cyclodextrins are non-toxic oligosaccharides that are well known for their host–guest chemistry, low prices, and negligible environmental impact. Therefore, they have been widely used as chiral selectors and delivery systems in the pharmaceutical and food industry over time. However, their use for extraction purposes is hampered by their high solubility in water. This difficulty is being overcome with a variety of investigations in materials science. The setting-up of novel solid…
Enhancing extraction performance of organophosphorus flame retardants in water samples using titanium hierarchical porous silica materials as sorbents.
Abstract A sorbent for the extraction of organophosphorus flame retardants has been proposed, based on UVM-7 (University of Valencia Materials) mesoporous silica doped with titanium. Designed cartridges have been applied to the extraction and preconcentration of flame retardants in water samples, followed by gas chromatography coupled to a mass spectrometry detector. Firstly, UVM-7 materials with different contents of titanium were synthesized and characterized by several techniques, thus confirming the proper mesoporous architecture. The potential of these materials was assessed in comparison with their morphological properties, resulting Ti50-UVM-7 the best solid phase. Several extraction…
Identification and determination of amphetamine and methamphetamine in street drugs
Abstract A procedure to identify and quantify amphetamine and/or methamphetamine in street drugs is proposed. The procedure is based on the application of the ACC method (Apparent content curves method) to emission and absorption data of samples. Discrimination and quantification of amphetamine and methamphetamine in samples is carried out based on their different behavior in acid and basic medium. Potential interfering drugs are tested and the accuracy of the method is verified in prepared and real samples. Results obtained are in agreement with a HPLC procedure used as reference.
Fluorimetric determination of amphetamine in urine by flow injection with on-line liquid–liquid extraction
Abstract Determination of amphetamine in urine was performed by batch and flow injection methodologies. The suitable experimental conditions for fluorimetric measurements were established. The liquid–liquid extraction was carried out at pH 13 using diethyl ether as extracting reagent. The measurement conditions were 260 nm and 277 nm for excitation and emission wavelengths, respectively. The method requires standard addition calibration and Youden blank correction. The influence of the main metabolites of amphetamine and metamphetamine were studied. The accuracy and precision of the proposed method was tested and the method is adapted to the flow injection procedure with on-line extraction.
A new proposal for the determination of polychlorinated biphenyls in environmental water by using host-guest adsorption
Abstract Polychlorinated biphenyls (PCBs) are ubiquitous environmental pollutants whose wide industrial use has been banned over the years in most countries due to their persistence and bioaccumulation. In fact, the International Agency for Research on Cancer defined them in 2016 as carcinogenic to humans based on sufficient evidence of an increased risk of cancer, being children and pregnant or lactating women the most vulnerable population subgroups. In this work, a new alternative for the determination of polychlorinated biphenyls (PCB28, PCB52, PCB101, PCB138, PCB153, and PCB180) in water samples has been developed by using a cyclodextrin-containing silica microparticulated material as …
Preconcentration and speciation of chromium in waters using solid-phase extraction and atomic absorption spectrometry
Abstract A method for the preconcentration and speciation of chromium was developed. After formation of an anionic compound with ethylenediaminetetraacetic acid (CrY − ), Cr (VI) and Cr (III) are retained on a strong anionic phase (SAX) and controlled elution with 0.5 M NaCl permits their speciation. The retention and elution conditions were optimised, and interferences due to the presence of other ions such as Mg(II), Mn(II), Sn(II), Fe(III), Ba(II), Al(III), Ca(II), chloride, iodine, bromide, fluoride, sulphate, phosphate, bicarbonate and nitrate were studied. The detection limits were 0.4 μg l −1 and 1.1 μg l −1 for Cr(III) and Cr(VI), respectively, and reproducibility was 9%. The result…
Comparison of the solid-phase extraction efficiency of a bounded and an included cyclodextrin-silica microporous composite for polycyclic aromatic hydrocarbons determination in water samples.
Solid-phase extraction is one of the most important techniques for sample purification and concentration. A wide variety of solid phases have been used for sample preparation over time. In this work, the efficiency of a new kind of solid-phase extraction adsorbent, which is a microporous material made from modified cyclodextrin bounded to a silica network, is evaluated through an analytical method which combines solid-phase extraction with high-performance liquid chromatography to determine polycyclic aromatic hydrocarbons in water samples. Several parameters that affected the analytes recovery, such as the amount of solid phase, the nature and volume of the eluent or the sample volume and …
Comparison of silica-based materials for organophosphorus pesticides sampling and occupational risk assessment.
Abstract A novel air sampler has been designed containing a sorbent based on UVM-7 mesoporous silica doped with Ti. The sorbent has been applied for the determination of organophosphorus pesticides in occupational air, followed by gas chromatography with mass spectrometry detection. Thus, several silica materials with different structures (mesoporous UVM-7 and microporous xerogels) were synthesized, and modified with the addition of Ti and Fe. The structure of these materials was proved by transmission electronic microscopy, energy-dispersive X-ray, X-ray diffraction, nitrogen adsorption-desorption and UV–Vis and Raman spectroscopy. The potential of these materials for the retention of pest…
A smartphone-based innovative approach to discriminate red pigments in roman frescoes mock-ups
The characterization of red pigments in frescoes wall paintings has been of great interest for researchers to better understand raw material procurement dynamics, pigment receipts, stylistic evolution and to assess their conservation state. In this study a non-destructive colorimetric approach implementing a smartphone-based method was developed in order to be able to distinguish between three pigments made from minium, haematite and cinnabar minerals, and also mixed pigments, preparing frescoes mock-ups following the roman receipt described by Vitruvius. Portable FT-IR, Raman spectroscopy, portable XRF and visible reflectance spectra analyses were carried out as reference methods for smart…
Detection of bias errors in ETAASDetermination of copper in beer and wine samples
A method that evidences changes in the shape of the absorbance profiles obtained by graphite furnace atomic absorption spectrometry (ETAAS) is proposed. The method is based upon the apparent content curves model previously described for molecular spectroscopy and it permits the detection of possible sources of bias errors. Moreover, a procedure that allows to detect the existence of constant and/or proportional errors is also described. Both models has been applied to the determination of copper in wine and beer samples with and without pre-treatment of the samples. Results obtained evidence the usefulness of the proposed models.
Design, characterization and comparison of materials based on β and γ cyclodextrin covalently connected to microporous silica for environmental analysis
Abstract Determination of organic pollutants in environmental samples presents great difficulties due to the lack of sensitivity and selectivity in many of the existing analytical methods. In this work, the efficiency of materials based on silica structures containing bounded γ-cyclodextrin has been evaluated to determinate phenolic compounds and polycyclic aromatic hydrocarbons in air and water samples, respectively, in comparison with materials made of β-cyclodextrin. According to the results obtained for the material characterization, the new γ-cyclodextrin solid phase does not apparently present any porosity when used in air samples, but it has been shown to work efficiently for the pre…
Samplers for VOCs in air based on cyclodextrin–silica hybrid microporous solid phases
Samplers for VOCs in air based on cyclodextrin-silica hybrid microporous solid phases are proposed. The solid phase preparation is very easy and inexpensive. Proposed samplers compared with other solid phases present the advantages of a wider range of operative conditions for VOCs desorption. Samplers are tested based on results for the determination of benzene, toluene, ethylbenzene and o-xylene, m-xylene and p-xylene (BTEX) in air. Operational parameters are optimized and quantitative recovery is obtained using a solid phase from 2-hydroxypropyl-β-cyclodextrin and acetonitrile as the extraction solvent. The recoveries obtained are 89 ± 4%, 90 ± 6%, 91 ± 2%, 87.0 ± 0.9%, 88 ± 4%, and 88 ± …
Chromatographic Separation of Cresol Isomers by a β‐Cyclodextrin: Application for the Determination of Volatile Phenols in Alcoholic Beverages
Abstract The chromatographic separation of o‐cresol, m‐cresol, and p‐cresol by using β‐cyclodextrin as a chiral reagent has been studied. Conditions for the chromatographic separation of these isomers by using the cyclodextrin in the mobile phase or bonded in the stationary phase were optimized, and both procedures provided good results for the resolution of the chromatographic peaks. The use of fluorimetric detection (λexc 275 nm λem 300 nm) allows detection and quantification limits of the µg/L for eight studied phenols by using both procedures. The determination of volatile phenols in alcoholic beverages must be carried out using the cyclodextrin in the mobile phase because of the co‐elu…
Determination of phenolic compounds in air by using cyclodextrin-silica hybrid microporous composite samplers
An analytical method for the determination of phenolic compounds in air samples based on the use of cyclodextrin-silica hybrid microporous composite samplers is proposed. The method allows the determination of phenol, guaiacol, cresol isomers, eugenol, 4-ethylphenol and 4-ethylguaiacol in workplaces according to the Norm UNE-EN 1076:2009 for active sampling. Therefore, the proposed method offers an alternative for the assessment of the occupational exposure to phenol and cresol isomers. The detection limits of the proposed method are lower than those for the NIOSH Method 2546. Storage time of samples almost reaches 44 days. Recovery values for phenol, guaiacol, o-cresol, m-cresol, p-cresol,…
Study of silica-structured materials as sorbents for organophosphorus pesticides determination in environmental water samples
Abstract A novel sorbent based on a UVM-7 mesoporous silica doped with Ti has been synthesized and used for solid-phase extraction of several organophosphorus pesticides in environmental water samples followed by gas chromatography coupled to a nitrogen-phosphorus selective detector. Thus, mesoporous silica materials doped with Ti and Fe as well as immobilized cyclodextrin silica-based supports were prepared and morphologically characterized by several techniques such as transmission electronic microscopy, nitrogen adsorption-desorption and X-ray diffraction. These sorbents were comparatively evaluated, and Ti25-UVM-7 material was selected as the best solid phase. After optimization of extr…