RESUMEN
Polycyclic Aromatic Hydrocarbons (PAHs) are organic compounds with two or more condensed aromatic rings, formed from incomplete organic matter combustion. PAHs pose potential health risks due to their carcinogenic and mutagenic properties, accumulating in edible tissues of aquatic organisms, such as shrimp, which is extensively produced in the southern region of Rio Grande do Sul state (Brazil) and it is the most consumed seafood globally. Therefore, this study aimed to optimize and validate an analytical method for extracting 16 priority PAHs from shrimp samples using Vortex-Assisted Matrix Solid-Phase Dispersion (VA-MSPD) with determination by Gas Chromatography Tandem Mass Spectrometry (GC-MS/MS). The optimized method, which uses a reused solid support, was validated according to INMETRO and SANTE guidelines. PAHs demonstrated adequate linearity with correlation coefficients > 0.99. The matrix effect was assessed, and 12 out of the 16 PAHs showed a matrix effect of less than ±20%. The method's quantification limits ranged from 6.67 to 33.35 ng g-1. Accuracy and precision showed recovery values ranging from 55 to 115% with relative standard deviation (RSD) lower than 17% for all PAHs. In the applicability, 11 PAHs were detected, such as benzo[a]pyrene and benzo[b]fluoranthene, and the ∑PAHs ranged from 25.14 to 79.52 ng g-1, confirming the environmental contamination in the region and the need for monitoring these contaminants in shrimp destined for human consumption.
Asunto(s)
Cromatografía de Gases y Espectrometría de Masas , Penaeidae , Hidrocarburos Policíclicos Aromáticos , Extracción en Fase Sólida , Espectrometría de Masas en Tándem , Hidrocarburos Policíclicos Aromáticos/análisis , Hidrocarburos Policíclicos Aromáticos/aislamiento & purificación , Animales , Cromatografía de Gases y Espectrometría de Masas/métodos , Espectrometría de Masas en Tándem/métodos , Extracción en Fase Sólida/métodos , Penaeidae/química , Límite de Detección , Brasil , Alimentos Marinos/análisis , Contaminación de Alimentos/análisis , Reproducibilidad de los Resultados , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/aislamiento & purificaciónRESUMEN
In the present paper, the assessment of vortex-assisted dispersive magnetic solid-phase extraction using amino-functionalized mesoporous combined with direct magnetic sorbent sampling (DMSS) in flame or furnace atomic absorption spectrometry (FAAS or FF-AAS) was demonstrated for highly sensitive silver determination in water samples. The developed method showed significant enrichment factors compared to conventional pneumatic nebulization by FAAS, 607 for DMSS-FF-AAS and 114 for DMSS-FAAS. The analytical curve showed linearity in the range from 5.0 to 70.0 µg L- 1 and 1.0 to 15.0 µg L- 1 and limits of detection of 0.59 and 0.09 µg L- 1 for DMSS-FAAS and DMSS-FF-AAS, respectively. The intra and inter-day precision evaluated as a percentage of the relative standard deviation (RSD,%) ranged from 1.89 to 4.71% for levels of 25.0 and 65.0 µg L- 1. The method was applied in different kinds of water samples without matrix effects, yielding recovery values from 90 to 110%.
Asunto(s)
Plata , Extracción en Fase Sólida , Espectrofotometría Atómica , Contaminantes Químicos del Agua , Extracción en Fase Sólida/métodos , Plata/química , Contaminantes Químicos del Agua/análisis , Monitoreo del Ambiente/métodos , Límite de DetecciónRESUMEN
Magnetic particle spray mass spectrometry (MPS-MS), an innovative ambient ionization technique proposed by our research group, was employed to determine beta-blockers in human plasma samples. A dispersive solid phase extraction of atenolol, metoprolol, labetalol, propranolol, nadolol, and pindolol was carried out using magnetic molecularly imprinted polymer (M-MIP) particles that were attached to the tip of a metal probe, which was placed in the mass spectrometer inlet. A solvent (1% formic acid in methanol) was dispensed on the particles, and the Taylor cone was formed around them (in high voltage). The analytes were desorbed/ionized and determined by a triple quadrupole mass spectrometer. M-MIP was synthesized with oxprenolol as a pseudo-template, demonstrating good selectivity to beta-blockers compared with no-analog molecules, with an adsorption process occurring in monolayers, according to isotherm studies. Kinetic experiments indicated chemisorption as the predominant M-MIP/analyte interaction. The analytical curves were linear (R2 > 0.98), and the limit of quantification was 3 µg L-1 for all the analytes. Limits of detection ranged from 0.64 to 2.41 µg L-1. Precisions (relative standard deviation) and accuracies (relative error) ranged from 3.95 to 21.20% and -17.05 to 18.93%, respectively. MPS-MS proved to be a simple, sensitive, and advantageous technique compared with conventional approaches. The analyses were fast, requiring no chromatographic separation and without ionic suppression. The method is aligned with green chemistry principles, requiring minimal sample, solvent, and sorbent amounts. MPS-MS successfully integrates sample preparation and ambient ionization mass spectrometry and holds great potential for application with other sorbents, samples, and analytes.
Asunto(s)
Antagonistas Adrenérgicos beta , Antagonistas Adrenérgicos beta/sangre , Antagonistas Adrenérgicos beta/química , Humanos , Límite de Detección , Polímeros Impresos Molecularmente/química , Extracción en Fase Sólida/métodos , Espectrometría de Masas/métodos , AdsorciónRESUMEN
The instrumental development of tandem mass spectrometers fosters the actual trend in the trace analysis of organic compounds to the development of methods that allow the analysis of contaminants of the most diverse origin in a single analytical sample. The multiclass methods are aligned with the Who's One Health initiative while accomplishing the concepts of green chemistry. However, there are few reports of wide scope multiclass methods for the analysis of contaminants in this matrix. In this work, a method for the simultaneous determination of 62 compounds in bovine fat, was developed and validated following DG-SANTE/11813/2021 guidance. Liquid nitrogen milled fat was extracted with toluene and acetonitrile. Then a clean-up in a cryogenic bath, followed by dispersive solid phase extraction was performed. Residue determination was done using liquid chromatography for 44 compounds and gas chromatography for 18 compounds, both coupled to tandem mass spectrometry in MRM mode. The method was first developed and validated for two ectoparasiticides, then the scope was expanded for the analysis of 13 veterinary drugs and 49 pesticides. Recovery percentages were in the range of 60-134%, high matrix effect was observed in 50% of the scope of the method. Most compounds presented limits of quantification of 10 µg kg-1 in compliance with international requirements. The method was applied to monitor 49 commercial samples to evaluate its performance. Eighty percent of samples contained ethion and 10% had fluazuron, both within MRLs, highlighting the need for proper withdrawal times.
Asunto(s)
Espectrometría de Masas en Tándem , Animales , Bovinos , Espectrometría de Masas en Tándem/métodos , Drogas Veterinarias/análisis , Cromatografía Liquida/métodos , Límite de Detección , Extracción en Fase Sólida/métodos , Contaminación de Alimentos/análisisRESUMEN
The use of pesticides is often regarded as a fundamental aspect of conventional agriculture. However, these compounds have gained recognition as some of the oldest and most widely employed xenobiotic contaminants, necessitating effective strategies for human biomonitoring. In this context, a method was developed for the determination of 16 legacy organochlorine pesticides, 6 metabolites of current pesticides (2,4-D, malathion, parathion, fipronil, pyraclostrobin, cypermethrin, permethrin, cyfluthrin), and 1 triazine herbicide (atrazine) in serum. Samples were prepared with water, formic acid, acetonitrile, and ultrasound irradiation, followed by solid-phase extraction with Oasis Prime HLB. Subsequently, metabolites from current pesticides underwent derivatization using MTBSTFA with 1% TBDMSCl for analysis via gas chromatography-tandem mass spectrometry (GC-MS/MS), employing an SLB-5MS fused silica capillary column. Analytical curves were generated with limits of quantification from 0.3 to 4.0 ng.mL-1. Accuracy ranged from 69 to 124%, and the coefficient of variation from 2 to 28%. Moreover, determining 1-(4-chlorophenyl)-1H-pyrazol-3-ol was suggested as a biomarker for pyraclostrobin biomonitoring. This analytical approach facilitated the determination of both legacy and metabolites of current pesticides in the same serum sample, presenting an interesting and cost-effective option for large cohorts, and multi-omics studies that evaluate time-dependent biomarkers in blood samples, thereby enabling biomonitoring within the same matrix. Furthermore, a proof-of-concept involving 10 volunteers demonstrated exposure to 9 pesticides at mean concentrations measured in ng mL-1, consistent with findings from various biomonitoring initiatives.
Asunto(s)
Cromatografía de Gases y Espectrometría de Masas , Límite de Detección , Plaguicidas , Espectrometría de Masas en Tándem , Humanos , Plaguicidas/sangre , Cromatografía de Gases y Espectrometría de Masas/métodos , Espectrometría de Masas en Tándem/métodos , Extracción en Fase Sólida/métodos , Exposición a Riesgos Ambientales/análisis , Monitoreo del Ambiente/métodos , Monitoreo Biológico/métodos , AdultoRESUMEN
Liquid chromatography-mass spectrometry (LC-MS) has emerged as a powerful analytical technique for analyzing complex biological samples. Among various chromatographic stationary phases, porous graphitic carbon (PGC) columns have attracted significant attention due to their unique properties-such as the ability to separate both polar and non-polar compounds and their stability through all pH ranges and to high temperatures-besides the compatibility with LC-MS. This review discusses the applicability of PGC for SPE and separation in LC-MS-based analyses of human biological samples, highlighting the diverse applications of PGC-LC-MS in analyzing endogenous metabolites, pharmaceuticals, and biomarkers, such as glycans, proteins, oligosaccharides, sugar phosphates, and nucleotides. Additionally, the fundamental principles underlying PGC column chemistry and its advantages, challenges, and advances in method development are explored. This comprehensive review aims to provide researchers and practitioners with a valuable resource for understanding the capabilities and limitations of PGC columns in LC-MS-based analysis of human biological samples, thereby facilitating advancements in analytical methodologies and biomedical research.
Asunto(s)
Grafito , Espectrometría de Masas , Humanos , Grafito/química , Cromatografía Liquida/métodos , Porosidad , Espectrometría de Masas/métodos , Extracción en Fase Sólida/métodos , Biomarcadores/análisis , Proteínas/análisis , Polisacáridos/análisis , Cromatografía Líquida con Espectrometría de MasasRESUMEN
Pesticides has transformed the agricultural industry, primarily by enhancing productivity. However, the indiscriminate use of such compounds can adversely affect human health and disrupt ecosystem balance. Limited knowledge exists regarding the removal of these compounds from water, particularly for organophosphate pesticides when employing conventional treatment technologies. Therefore, this study aimed to assess the removal of acephate (ACE) and methamidophos (MET) - considered priority pesticides in Brazil - from waters with high and low turbidity during the clarification process carried out with aluminum sulfate (AS) and ferric chloride (FC), either alone or combined with powdered activated carbon (PAC) adsorption. All water samples were submitted to solid phase extraction (SPE C18 cartridges) prior to acephate and methamidophos analysis by HPLC MS/MS. The clarification process with either AS or FC coagulant did not efficiently remove acephate or methamidophos and maximum average removal (27 %) was observed with waters of high turbidity when using ferric chloride as coagulant. Addition of mineral PAC was also ineffective for removing both pesticides. However, the use of vegetable PAC (10 mg/L) resulted in better removal percentages, up to 80%, but only for methamidophos. The limited removal rates were attributed to the high hydrophilicity of acephate and methamidophos, along with their neutral charge at coagulation pH. These factors hinder the interaction of such organophosphorus pesticides with the flocs formed during coagulation as well as with PAC surface.
Asunto(s)
Compuestos Organotiofosforados , Fosforamidas , Contaminantes Químicos del Agua , Purificación del Agua , Compuestos Organotiofosforados/química , Contaminantes Químicos del Agua/análisis , Adsorción , Purificación del Agua/métodos , Compuestos Férricos/química , Brasil , Compuestos de Alumbre/química , Extracción en Fase Sólida/métodos , Plaguicidas , ClorurosRESUMEN
Haff disease typically develops after eating contaminated marine or freshwater species, especially fish. Despite still having an unknown etiology, recent reports have suggested its possible correlation with palytoxins. Therefore, the present work aimed to optimize and perform a validation of a sensitive method using liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) for the analysis of palytoxin and some of its analogs, with the main purpose of investigating their presence in marine and freshwater food samples associated with Haff disease in Brazil. The method optimization was performed using a central composite rotatable design and fish samples fortified with the palytoxin standard. Then, the optimized method was validated for different food matrices, including freshwater and marine fish, mollusks, and crustaceans. The sample preparation involved a solid-liquid extraction using methanol and water, solid-phase extraction using Strata-X cartridges, and on-column palytoxin oxidation. The detection of the main oxidized fragments (amino and amide aldehydes) was achieved by LC-MS/MS with electrospray ionization in positive mode, using a C18 column, as well as acetonitrile and water as mobile phases, both acidified with 0.1 % of formic acid. After optimization and validation, the etiological investigation involved the analysis of 16 Brazilian Haff disease-related food samples (in natura and leftover meals) from 2022. The method was demonstrated to be appropriate for quantitative analysis of freshwater and marine species. So far, it has proven to be one of the most sensitive methods related to palytoxin detection (LOD 10 µg/kg), being able to work in a range that includes the provisional ingestion limit (30 µg/kg). Regarding the Haff disease-related samples analysis, there is a strong indication of palytoxin contamination since the amino aldehyde (common fragment for all palytoxins) was detected in 15 of the 16 samples. Selected results were confirmed using liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS).
Asunto(s)
Acrilamidas , Venenos de Cnidarios , Contaminación de Alimentos , Agua Dulce , Alimentos Marinos , Animales , Acrilamidas/análisis , Brasil , Peces , Contaminación de Alimentos/análisis , Agua Dulce/química , Límite de Detección , Cromatografía Líquida con Espectrometría de Masas/métodos , Toxinas Poliéteres , Reproducibilidad de los Resultados , Alimentos Marinos/análisis , Extracción en Fase Sólida/métodos , Espectrometría de Masas en Tándem/métodosRESUMEN
Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic organic pollutants found in various environments, notably aquatic ecosystems and the food chain, posing significant health risks. Traditional methods for detecting PAHs in food involve complex processes and considerable reagent usage, raising environmental concerns. This study explores eco-friendly approaches suing solid phases derived from natural sources in matrix solid phase dispersion. We aimed to develop, optimize, and validate a sample preparation technique for seafood, employing natural materials for PAH analysis. Ten natural phases were compared with a commercial reference phase. The methodology involved matrix solid phase dispersion and pressurized liquid extraction, followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Three solid phases (perlite, sweet manioc starch, and barley) showed superior performance in LC-MS/MS and were further evaluated with gas chromatography-tandem mass spectrometry (GC-MS/MS), confirming perlite as the most effective phase. Validation followed Brazilian regulatory guidelines and European Community Regulation 2021/808/EC. The resulting method offered advantages in cost-effectiveness, reduced environmental impact, cleaner extracts, and enhanced analytical performance compared to the reference solid phase and LC-MS/MS. Proficiency analysis confirmed method reliability, with over 50% alignment with green analytical chemistry principles. In conclusion, this study developed an environmentally sustainable sample preparation technique for seafood analysis using natural solid phases, particularly perlite, for PAH determination.
Asunto(s)
Contaminación de Alimentos , Cromatografía de Gases y Espectrometría de Masas , Hidrocarburos Policíclicos Aromáticos , Alimentos Marinos , Espectrometría de Masas en Tándem , Hidrocarburos Policíclicos Aromáticos/análisis , Alimentos Marinos/análisis , Espectrometría de Masas en Tándem/métodos , Cromatografía de Gases y Espectrometría de Masas/métodos , Cromatografía Liquida/métodos , Contaminación de Alimentos/análisis , Extracción en Fase Sólida/métodos , Reproducibilidad de los Resultados , Brasil , Tecnología Química Verde/métodosRESUMEN
A film composed of agarose and graphene (G) and magnetic nanoparticles (G-MNPs) is proposed as a sorbent for the extraction and determination of medroxyprogesterone (MED), levonorgestrel (LEV), norethisterone (NOR) and progesterone (PRO) in natural water samples. Both the preparation of the film and the extraction procedure were optimized. The optimal extraction parameters were as follows: isopropyl alcohol as activation solvent, sample pH value of 3.0, extraction time of 30 min, 1.00 mL of acetonitrile as eluent, elution time of 5 min and sample volume of 100.00 mL. HPLC with photodiode array detector was used for the separation and determination. The method presented a linear range between 2.50 and 75.0 µg L-1 for all analytes, and the LODs were between 1.40 and 1.80 µg L-1. The method was applied to natural water samples, obtaining satisfactory recovery values (75-111 %). In conclusion, for the immobilization of the G-MNPs, agarose was used, which is a non-toxic, renewable and biodegradable material. The G-MNPs-agarose film was reused up to 70 times, without losing its extraction capacity significantly and presenting excellent sorbent properties, which allow the extraction and preconcentration of the progestogens under study.
Asunto(s)
Progestinas , Contaminantes Químicos del Agua , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/aislamiento & purificación , Contaminantes Químicos del Agua/química , Progestinas/aislamiento & purificación , Progestinas/análisis , Progestinas/química , Adsorción , Nanopartículas de Magnetita/química , Extracción en Fase Sólida/métodos , Sefarosa/química , Cromatografía Líquida de Alta PresiónRESUMEN
This study outlines the development and optimization of an analytical method using Disposable Pipette Extraction (DPX) followed by high performance liquid chromatography-mass spectrometry (HPLC-MS) analysis to determine NAs in medicines. HPLC-MS analysis utilized a reversed-phase and positive mode electrospray ion source. DPX parameters were optimized through univariate and multivariate analyses, including extraction phase, desorption solvent, sample pH, equilibrium time, and extraction/desorption cycles. The optimized conditions included a C18 extraction phase, methanol desorption solvent, pH at 7, an equilibrium time of 30 seconds, 2 extraction cycles, and 5 desorption cycles. Considering this method, it was possible to achieve a sample preparation step for the analysis of NAs in medicines using a minimal amount of extraction phase, sample, and desorption solvent. Furthermore, the total extraction procedure enables the extraction of NAs in around 4 minutes with NA recovery up to 98%. Analytical performance demonstrated precision and accuracy below 15% and a quantification limit of 1 ng mL-1, meeting validation requirements set by regulations worldwide. Thus, the DPX/HPLC-MS technique offers a faster and cost-effective method for analyzing NAs in medicines compared to traditional approaches. Besides, this method reduces solvent consumption and residue generation, enhancing environmental sustainability according to green chemistry principles.
Asunto(s)
Nitrosaminas , Cromatografía Líquida de Alta Presión/métodos , Nitrosaminas/análisis , Nitrosaminas/aislamiento & purificación , Límite de Detección , Espectrometría de Masas/métodos , Reproducibilidad de los Resultados , Extracción en Fase Sólida/métodos , Cromatografía Líquida con Espectrometría de MasasRESUMEN
The aim of this study was to develop a high-performance liquid chromatography-tandem mass spectrometry method for the determination of 6-cyanodopamine, 6-nitrodopamine, 6-nitrodopa, 6-nitroadrenaline and 6-bromodopamine in human plasma samples. Strata-X 33 µm solid-phase extraction cartridges were used for the extraction of the catecholamines from human plasma samples. The catecholamines were separated in a 150 × 3 mm Shim-pack GIST C18-AQ column with 3 µm particle size, placed in an oven at 40°C and perfused with 82% mobile phase A (acetonitrile-H2O; 90:10, v/v) + 0.4% acetic acid and 18% mobile phase B (deionized H2O) + 0.2% formic acid at a flow rate of 340 µl/min in isocratic mode. The injected volume was 4 µl and the run lasted 4 min. The method was linear from 0.1 to 20 ng/ml and the lower limit of quantification was 0.1 ng/ml for all analytes. The method was applied to evaluate the plasma levels of catecholamines in plasma of patients with chronic kidney disease and allowed the detection for the first time of circulating levels of the novel catecholamines 6-bromodopamine and 6-cyanodopamine.
Asunto(s)
Límite de Detección , Insuficiencia Renal Crónica , Espectrometría de Masas en Tándem , Humanos , Espectrometría de Masas en Tándem/métodos , Reproducibilidad de los Resultados , Modelos Lineales , Insuficiencia Renal Crónica/sangre , Cromatografía Líquida de Alta Presión/métodos , Masculino , Cromatografía Liquida/métodos , Extracción en Fase Sólida/métodos , Dopamina/sangre , Dopamina/análogos & derivados , Catecolaminas/sangre , Persona de Mediana Edad , Cromatografía Líquida con Espectrometría de MasasRESUMEN
Caffeine is present in a large number of beverages and is an additive used in dietary supplements. Therefore, the concern about its quality and safety for consumers has been increasing and hence requires faster and simpler analytical methods to determine the caffeine amount. The high-throughput analysis is an appropriate solution to pharmaceuticals, bioanalysis, forensic and food laboratory routines. In this sense, Venturi easy ambient sonic-spray ionization mass spectrometry (V-EASI-MS), a specific ambient ionization source, is suitable to enable direct analysis of sample solutions in real time and is appropriate to be coupled to liquid chromatography (LC). The development of an on-line solid phase extraction system coupled to V-EASI-MS optimizes the advantages of LC-MS hyphenation by enhancing the figures of merit of the analytical method according to AOAC guidelines and simultaneously minimizing the runtime analysis to 1.5 min per sample, as well as sample preparation steps and solvent consumption, which is currently a challenge for quantitative applications of ambient ionization MS.
Asunto(s)
Cafeína , Suplementos Dietéticos , Extracción en Fase Sólida , Espectrometría de Masa por Ionización de Electrospray , Cafeína/análisis , Extracción en Fase Sólida/métodos , Suplementos Dietéticos/análisis , Espectrometría de Masa por Ionización de Electrospray/métodos , Ensayos Analíticos de Alto Rendimiento/métodos , Cromatografía Liquida/métodosRESUMEN
Cocaine and antidepressants rank high globally in substance consumption, emphasizing their impact on public health. The determination of these compounds and related substances in biological samples is crucial for forensic toxicology. This study focused on developing an innovative analytical method for the determination of cocaine, antidepressants, and their related metabolites in postmortem blood samples, using unmodified commercial Fe3O4 nanoparticles as a sorbent for dispersive magnetic solid-phase extraction (m-d-SPE), coupled with liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) analysis. An aliquot of 100 µL of whole blood and 5 µL of the internal standard pool were added to 30 mg of nanoparticles. The nanoparticles were separated from the sample using a neodymium magnet inserted into a 3D-printed microtube rack. The liquid was then discarded, followed by desorption with 300 µL of 1/1/1 acetonitrile/methanol/ethyl acetate. The sample was vortexed and separated, and 1.5 µL of the organic supernatant was injected into the LC-MS/MS. The method was acceptably validated and successfully applied to 263 postmortem blood samples. All samples evaluated in this study were positive for at least one substance. The most frequent analyte was benzoylecgonine, followed by cocaine and cocaethylene. The most common antidepressants encountered in the analyzed samples were citalopram and fluoxetine, followed by fluoxetine's metabolite norfluoxetine. This study describes the first report of this sorbent in postmortem blood analysis, demonstrating satisfactory results for linearity, precision, accuracy, and selectivity for all compounds. The method's applicability was confirmed, establishing it as an efficient and sustainable alternative to traditional techniques for forensic casework.
Asunto(s)
Antidepresivos , Cocaína , Toxicología Forense , Nanopartículas de Magnetita , Extracción en Fase Sólida , Espectrometría de Masas en Tándem , Humanos , Cocaína/sangre , Cocaína/análogos & derivados , Antidepresivos/sangre , Espectrometría de Masas en Tándem/métodos , Toxicología Forense/métodos , Extracción en Fase Sólida/métodos , Nanopartículas de Magnetita/química , Cromatografía Liquida/métodos , Límite de Detección , Detección de Abuso de Sustancias/métodos , Masculino , Femenino , AdultoRESUMEN
An ultrafast, efficient, and eco-friendly method combining magnetic solid phase extraction and capillary electrophoresis with diode array detection have been developed to determine ractopamine residues in food samples. A restricted access material based on magnetic and mesoporous molecularly imprinted polymer has been properly synthesized and characterized, demonstrating excellent selectivity and high adsorbent capacity. Short-end injection capillary electrophoresis method was optimized: 75 mM triethylamine pH 7 as BGE, -20 kV, 50 mbar by hydrodynamic injection during 8 s, and capillary temperature at 25 °C; reaching ultrafast ractopamine analysis (â¼0.6 min) with good peak asymmetry, and free from interfering and/or baseline noise. After sample preparation optimization, the conditions were: 1000 µL of sample at pH 6, 20 mg of adsorbent, stirring time of 120 s, 250 µL of ultrapure water as washing solvent, 1000 µL of methanol: acetic acid (7: 3, v/v) as eluent, and the adsorbent can be reused four times. In these conditions, the analytical method showed recoveries around to 100 %, linearity ranged from 9.74 to 974.0 µg kg-1, correlation coefficient (r) ≥ 0,99 in addition to adequate precision, accuracy, and robustness. After proper validation, the method was successfully applied in the analysis ractopamine residues in bovine milk and bovine and porcine muscle.
Asunto(s)
Impresión Molecular , Polímeros Impresos Molecularmente , Fenetilaminas , Animales , Porcinos , Extracción en Fase Sólida/métodos , Electroforesis Capilar/métodos , Fenómenos Magnéticos , Impresión Molecular/métodos , Cromatografía Líquida de Alta Presión/métodosRESUMEN
According to green analytical chemistry principles, the use of agricultural byproducts as sorbent phases is an interesting topic due to their lignocellulosic origin, as they are biodegradable and inexpensive. To the best of our knowledge, this is the first study in which avocado seed and avocado seed activated carbon are proposed as sustainable sorbents for solid-phase microextraction technologies, which were used to assess the proof of concept. Rotating disk sorptive extraction (RDSE) was used as a model technology and ibuprofen (Ibu) and 1-hydroxy-ibuprofen (1-OH-Ibu) as representative analytes. It was found that activated carbon (AC) prepared at 600 °C with an impregnation ratio (raw material/activating agent (ZnCl2), w/w) of 1:1.2 had better extraction efficiency than other ACs obtained at different temperatures, impregnation ratios, and activating agents (K2CO3). Characterization revealed several differences between natural avocado seed, biochar prepared at 600 °C, and selected AC since the typical functional groups of the natural starting material begin to disappear with pyrolysis and increasing the surface area and pore volume, suggesting that the main interactions between analytes and the sorbent material are pore filling and π-π stacking. By using this AC as the sorbent phase, the optimal extraction conditions in RDSE were as follows: the use of 50 mg of sorbent in the disk, 30 mL of sample volume, pH 4, 90 min of extraction time at a rotation velocity of the disk of 2000 rpm, and methanol as the elution solvent. The extracts were analyzed via gas chromatography coupled to mass spectrometry (GC-MS). The method provided limits of detection of 0.23 and 0.07 µg L-1 and recoveries of 81% and 91% for Ibu and 1-OH-Ibu, respectively. When comparing the extraction efficiency of the selected activated carbon with those provided by Oasis® HLB and C18 in RDSE, nonsignificant differences were observed, indicating that avocado seed activated carbon is a suitable alternative to these commercial materials.
Asunto(s)
Carbón Orgánico , Persea , Ibuprofeno , Solventes/química , Tecnología , Extracción en Fase Sólida/métodosRESUMEN
BACKGROUND: Determining metals in complex biological samples, such as milk, typically involves dry or wet decomposition. However, these techniques have limitations, including low selectivity, risk of contamination, and the use of large reagent volumes. To solve these problems, solid-phase extraction (SPE) using multifunctional sorbents has been extensively explored. In this context, this work proposed synthesizing a new restricted double access ionic imprinted polymer (RAIIP-BSA), for online SPE and determination of Cu2+ from untreated milk samples via flow injection analysis and flame atomic absorption spectrometry (FIA-FASS). RESULTS: Firstly, the polymer was obtained by bulk polymerization using Cu2+ as a template, 4-vinyl pyridine as a functional monomer, and glycidyl methacrylate as a hydrophilic comonomer. Subsequently, it was covered with bovine serum albumin, creating the restricted double access barrier. The obtained material could exclude 97 % of the proteins from milk samples. RAIIP-BSA was chemically and physically characterized. The main extraction variables were optimized via multivariate optimization. The method showed good figures of merit, such as linearity ranging from 0.05 to 1.0 mg L-1, LoD and LoQ of 0.03 and 0.05 mg L-1, intra- and interday precision ranging from 0.73 to 4.14 % and 0.16-3.68 %, and an intra- and interday accuracy ranging from 97.0 to 115.0 % and 103.0-119.0 %, respectively. SIGNIFICANCE: The developed method demonstrates the effective extraction of Cu2+ from untreated milk samples, exhibiting selectivity, high extraction capacity, prolonged sorbent (RAIIP-BSA) durability, simplicity, and swift operation. This method holds promise as an alternative to conventional metal analysis approaches in complex matrices.
Asunto(s)
Cobre , Impresión Molecular , Animales , Cobre/química , Leche/química , Impresión Molecular/métodos , Polímeros/química , Extracción en Fase Sólida/métodosRESUMEN
In the present study, a magnetic ion-imprinted polymer based on n-allylthiourea in the presence of 1-(2-pyridylazo)-2-naphthol (MIIP-PAN) was synthesized, characterized, and applied in the preconcentration of nickel ions by dispersive magnetic solid phase extraction (DMSPE) with FAAS detection. For comparison, non-imprinted polymer (MNIP-PAN) and imprinted polymer without PAN were synthesized. The characterization of the polymers was performed by FT-IR, DRX, TEM, TGA, VSM, and BET. Selectivity studies were performed comparing the competitive adsorption of Ni2+ with other cations on MIIP-PAN and MNIP-PAN, achieving higher relative selectivity coefficients for MIIP-PAN than for MNIP-PAN and NIP. Under optimized conditions, the method provided a preconcentration factor of 76.70, detection limit of 0.25 µg/L and intra-day (2.06 - 2.33 %) and inter-day (1.82 - 4.90 %) precision. The developed method was applied to samples of water, teas, and chocolate powder, and its precision was evaluated through tests of recovery and analysis of certified materials.
Asunto(s)
Impresión Molecular , Níquel , Propanolaminas , Níquel/análisis , Agua , Espectroscopía Infrarroja por Transformada de Fourier , Polímeros , Adsorción , Fenómenos Magnéticos , Extracción en Fase Sólida/métodosRESUMEN
Through density functional theory calculations was studied theoretically the formation process of a magnetic and mesoporous molecularly imprinted polymer for ractopamine (RAC), evaluating the molecular electrostatic potential map, functional monomers, functional monomer / template stoichiometry and crosslink agents. The results revealed that the best conditions for the synthesis were established with acrylic acid as functional monomer in a 1: 4 stoichiometry using acetonitrile as the solvent and ethylene glycol dimethacrylate as crosslink agent. It was observed that nine hydrogen bonds established between the RAC and acrylic acid play a key role on the pre-polymerization complex. In addition, three analytical methods using HPLC, UHPLC and CE instruments were optimized for rapid analysis. The adsorbent was experimentally synthesized considering the best conditions found at the molecular level and characterized by FTIR, DRX, TGA, SEM, TEM, surface analysis, and wettability. After that, the synthesized material was used in magnetic solid phase extraction combined with capillary electrophoresis in a preliminary RAC recovery study from milk samples. Finally, greenness metric with a score of 0.55 have been obtained for the sample preparation procedure using the online AGREEprep metric.
Asunto(s)
Impresión Molecular , Polímeros Impresos Molecularmente , Impresión Molecular/métodos , Adsorción , Extracción en Fase Sólida/métodos , Cromatografía Líquida de Alta Presión/métodos , Fenómenos MagnéticosRESUMEN
A new hybrid bionanomaterial composed of graphene oxide (GO) and Spirulina maxima (SM) algae was synthesized and applied to develop a preconcentration method based on the dispersive micro-solid phase extraction (D-µ-SPE) technique for the determination of Pb in water and infant beverages. In this work, Pb(II) was extracted with 3 mg of the hybrid bionanomaterial (GO@SM) followed by a back-extraction step using 500 µL of 0.6 mol L-1 HCl. Then, a 1.5 × 10-3 mol L-1 dithizone solution was added to the sample containing the analyte to form a purplish red-colored complex for its detection by UV-Vis spectrophotometry at 553 nm. An extraction efficiency of 98% was obtained after optimization of experimental variables such as GO@SM mass, pH, sample volume, type, and time of agitation. A detection limit of 1 µg L-1 and a relative standard deviation of 3.5% (at 5 µg L-1 Pb(II), n = 10) were achieved. The calibration linear range was obtained between 3.3 and 95 µg L-1 Pb(II). The proposed method was successfully applied for the preconcentration and determination of Pb(II) in infant beverages. Finally, the greenness degree of the D-µ-SPE method was evaluated using the Analytical GREEnness calculator (AGREE), obtaining a score of 0.62.