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Biomedical and food analysis has always been an important topic that closely relates to health [...].
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Análisis de los Alimentos , Análisis de los Alimentos/métodos , Espectrometría de Masas/métodosRESUMEN
Dinotefuran (DNT) belongs to the third-generation neonicotinoid pesticides, which are among the most common residuals in a variety of food commodities. To guarantee accurate quantification and traceability of results in food samples, certified reference materials (CRMs) are the indispensable benchmark. In this work, a DNT CRM was characterized and its purity was assessed by two independent methods, including mass balance (MB) and quantitative nuclear magnetic resonance spectroscopy (qNMR). The mass fraction of moisture was 0.33 mg/g, the inorganic impurity was 0.01 mg/g, and no detectable organic solvent was detected. Benzoic acid was chosen as the internal standard for qNMR. Its mass fraction was 997.9 mg/g and 992.9 mg/g by MB and qNMR, respectively. Eventually, the DNT CRM was assigned a mass fraction of 995 mg/g, with expanded uncertainty of 5 mg/g (k = 2). This CRM can be used to prepare calibrant solutions and is applicable to national routine monitoring of DNT residuals in agro-products and food.
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Imagen por Resonancia Magnética , Estándares de Referencia , Espectroscopía de Resonancia Magnética/métodosRESUMEN
Ochratoxin A is a highly toxic mycotoxin and has posed great threat to human health. Due to its serious toxicity and wide contamination, great efforts have been made to develop reliable determination methods. In this review, analytical methods are comprehensively summarized in terms of sample preparation strategy and instrumental analysis. Detailed method is described according to the food commodities in the order of cereal, wine, coffee, beer, cocoa, dried fruit and spice. This review mainly focuses on the recent advances, especially reported in the last decade. At last, challenges and perspectives are also discussed to achieve better advancement and promote practical application in this field.
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Contaminación de Alimentos , Ocratoxinas , Cromatografía Líquida de Alta Presión/métodos , Contaminación de Alimentos/análisis , Humanos , Espectrometría de MasasRESUMEN
Thiamethoxam (TMX) is a widely used neonicotinoid insecticide in pest control. Identification of structurally related impurities is very important during certified reference material development and pesticide registration, thus it needs to be carefully characterized. In this study, a combined strategy with liquid chromatography-high resolution mass spectrometry and computer assisted elucidation (SIRIUS) has been developed for the impurity elucidation in TMX material. MS and MS/MS spectra were used to score the impurity candidates by isotope score and fragment tree in SIRIUS. TMX, the main component, worked as an anchor for formula identification and structure elucidation of impurity. With this strategy, four impurities were identified, including two byproducts (TMX-OCH3 and TMX-Cl) and two metabolites (clothianidin and TMX-urea). Their fragmentation pathways were concluded, and mechanism of impurity formation was also proposed. This result showed successful application of combining human intelligence with machine learning in impurity identification from chemicals.
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Insecticidas , Plaguicidas , Cromatografía Líquida de Alta Presión/métodos , Computadores , Humanos , Insecticidas/química , Neonicotinoides , Espectrometría de Masas en Tándem/métodos , Tiametoxam , UreaRESUMEN
In this study, a trans-zearalenone (trans-ZEN) calibrant in acetonitrile as certified reference material (CRM) was prepared and intensively investigated the stability by high performance liquid chromatography coupled diode array detection and triple quadrupole tandem mass spectrometry (HPLC-DAD-MS/MS). The photoisomerization and degradation of main component and related impurities in trans-ZEN calibrant CRM was studied in detail under different light conditions such as UV light (254 nm), sunlight, and visible light. Trans-ZEN in acetonitrile was confirmed a significant shift toward cis-ZEN up to a 52% cis-isomerization rate after exposing to UV light (254 nm) in transparent ampule for 1 day. The unsaturated double bond photosensitive groups of trans-ZEN and cis-ZEN will further undergo photoreaction to generate more isomers and related products with the increase of UV irradiation time. The calibrant in amber ampules was relatively stable after exposing to sunlight for 28 days, with only 0.35% cis-isomer observed. The results indicated that trans-ZEN solution calibrant should be packed in amber ampules to avoid UV rays. Thermal stability test exhibited this calibrant was stable over 6 weeks even at 60 °C. Trans-ZEN was found to be more stable in acetonitrile than in methanol since an unknown impurity was observed in methanol after 6 weeks placed at 25 °C. The stability study of trans-ZEN calibrant provided a basis for the usage, storage, and transportation of the CRM. A concentration and expanded uncertainty of the trans-ZEN calibrant CRM of 11.01 ± 0.18 µg/mL was developed.
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Zearalenona , Ámbar , Cromatografía Líquida de Alta Presión/métodos , Metanol , Espectrometría de Masas en Tándem/métodos , Zearalenona/análisisRESUMEN
A series of functional metal-organic frameworks (MOFs) were facilely prepared through an one-pot procedure or post-synthetic modification strategy and used as matrices in laser desorption ionization mass spectrometry (LDI-MS). Compared with traditional organic matrices and other MOFs, maltose-functional MOF MIL-101-maltose demonstrated ultrahigh ionization efficiency, free matrix background, uniform crystallization, and good dispersibility. A simple, general, and efficient LDI-MS platform was developed for rapid detection of various small biomolecules using MIL-101-maltose as matrix, providing several advantages including low sample consumption of 500 nL, short analysis time of few seconds, strong salt tolerance (500 mM NaCl), and satisfactory reproducibility. The MIL-101-maltose matrix was used for serum glucose determination and successfully distinguished the diabetic patients from the healthy controls. This work provides a generic LDI-MS platform for fast determination of small biomolecules with high potential in clinical diagnosis and disease monitoring.
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Estructuras Metalorgánicas , Humanos , Rayos Láser , Maltosa , Estructuras Metalorgánicas/química , Reproducibilidad de los Resultados , Espectrometría de Masa por Láser de Matriz Asistida de Ionización Desorción/métodosRESUMEN
A simple, fast and reliable analytical method was developed for 20 free amino acids (FAAs) determination in honey samples through a dilute-and-shoot strategy and hydrophilic interaction liquid chromatography tandem mass spectrometry. Compared with previous reports, direct dilution by water has significantly reduced the matrix effect and facilitated full extraction of FAAs. Further, a 5 min determination method was established with an acetonitrile-water mobile phase system with 0.1% formic acid addition. The established method was validated and demonstrated several advantages including short detection time, wide linear range over 3-4 orders of magnitude, high sensitivity down to 0.1 ng/mL and negligible matrix effect. Twenty FAAs were determined in 10 honey samples from different botanical origins by this method, and 19 FAAs were found. This general applicable method was also promising for fast determination of FAAs in other practical samples.
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Aminoácidos/análisis , Cromatografía Liquida/métodos , Miel/análisis , Espectrometría de Masas en Tándem/métodos , Límite de Detección , Reproducibilidad de los ResultadosRESUMEN
Dinotefuran (DNT) is a neonicotinoid insecticide widely used in pest control. Identification of structurally related impurities is indispensable during material purification and pesticide registration and certified reference material development, and therefore needs to be carefully characterized. In this study, a combined strategy with liquid chromatography high-resolution mass spectrometry and SIRIUS has been developed to elucidate impurities from DNT material. MS and MS/MS spectra were used to score the impurity candidates by isotope score and fragment tree in the computer assisted tool, SIRIUS. DNT, the main component, worked as an anchor for formula identification and impurity structure elucidation. With this strategy, two by-product impurities and one stereoisomer were identified. Their fragmentation pathways were concluded, and the mechanism for impurity formation was also proposed. This result showed a successful application for combined human intelligence and machine learning, in the identification of pesticide impurities.
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Plaguicidas , Espectrometría de Masas en Tándem , Cromatografía Líquida de Alta Presión/métodos , Contaminación de Medicamentos , Guanidinas , Humanos , Neonicotinoides , Nitrocompuestos , Espectrometría de Masas en Tándem/métodosRESUMEN
Ochratoxin A (OTA) is a highly toxic mycotoxin and poses great threat to human health. Due to its serious toxicity and widespread contamination, great efforts have been made to evaluate its human exposure. This review focuses on the OTA occurrence and contamination level in nine plant and animal derived food commodities: cereal, wine, coffee, beer, cocoa, dried fruit, spice, meat, and milk. The occurrence and contamination level varied greatly in food commodities and were affected by many factors, including spices, geography, climate, and storage conditions. Therefore, risk monitoring must be routinely implemented to ensure minimal OTA intake and food safety.
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Análisis de los Alimentos , Contaminación de Alimentos/análisis , Alimentos , Ocratoxinas/análisis , Animales , Humanos , Ocratoxinas/toxicidadRESUMEN
BACKGROUND: Patulin is a mycotoxin that mainly contaminates apple juice, which is a typical high sugar matrix. Many different adsorbents have been utilized to develop a sample pretreatment method to minimize the matrix interference from apple juice. RESULTS: A simple and reliable extraction method for the determination of patulin in apple juice has been developed. The sample preparation involves a simple one-step cleanup procedure using amine-functionalized polymeric solid-phase extraction cartridges (Retain AX) that effectively remove interferences and facilitate the quantification. Isotope dilution liquid chromatography tandem mass spectrometry (ID-LC-MS/MS) was employed to minimize the matrix effect and ensure reliable results. The limit of detection was as low as 0.2 µg kg-1 , which was satisfactory with regard to current European, US, and Chinese legislation. Matrix-matched linearity (r2 = 0.9997) was established in the range of 1-400 µg kg-1 . Recovery was performed in samples spiked at three levels, and results were between 97.2% and 100.2%. CONCLUSION: The results indicated that, with one-step cleanup, the matrix effect was negligible and sensitivity was satisfactory. Our work provided a simple and reliable method for patulin detection in apple juice and is also very promising in routine quality control. © 2020 Society of Chemical Industry.
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Cromatografía Líquida de Alta Presión/métodos , Jugos de Frutas y Vegetales/análisis , Malus/química , Patulina/análisis , Patulina/aislamiento & purificación , Extracción en Fase Sólida/métodos , Espectrometría de Masas en Tándem/métodos , Aminas/química , Contaminación de Alimentos/análisis , Frutas/química , Extracción en Fase Sólida/instrumentaciónRESUMEN
The merger of photoredox-initiated enamine-imine tautomerization and nucleophilic addition processes to access ß-substituted pyrroles from pyrrolidines has been achieved. The significant advantage of this method is suppressing the Friedel-Crafts reaction, which usually occurs between N-aryl pyrrolidines and the highly electrophilic ketoesters. The good functional group tolerance, high atom economy, and high regioselectivity as well as easy handling conditions make it an appealing alternative to synthesize ß-substituted pyrroles.
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A Brønsted acid-catalyzed α-C(sp3)-H amination of cyclic amines using hydrazines as coupling partners has been reported. This methodology provides a unique protocol to the one-step assembly of tetrahydro[1,3,4]triazepines via [1,5]-hydride transfer-initiated C(sp3)-H amination. This reaction features mild conditions, good yields, and high atom economy.
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B-type natriuretic peptide (BNP) is a circulating biomarker that is mainly applied in heart failure (HF) diagnosis and to monitor disease progression. Because some identical amino acid sequences occur in the precursor and metabolites of BNP, undesirable cross-reactions are common in immunoassays. This review first summarizes current analytical methods, such as immunoassay- and mass spectrometry (MS)-based approaches, including the accuracy of measurement and the inconsistency of the results. Second, the review presents some promising approaches to resolve the current barriers in clinical BNP measurement, such as how to decrease cross-reactions and increase the measurement consistency. Specific approaches include research on novel BNP assays with higher-specificity chemical antibodies, the development of International System of Units (SI)-traceable reference materials, and the development of structure characterization methods based on state-of-the-art ambient and ion mobility MS technologies. The factors that could affect MS analysis are also discussed, such as biological sample cleanup and peptide ionization efficiency. The purpose of this review is to explore and identify the main problems in BNP clinical measurement and to present three types of approaches to resolve these problems, namely, materials, methods and instruments. Although novel approaches are proposed here, in practice, it is worth noting that the BNP-related peptides including unprocessed proBNP were all measured in clinical BNP assays. Therefore, approaches that aimed to measure a specific BNP or proBNP might be an effective way for the standardization of a particular BNP form measurement, instead of the standardization of "total" immunoreactive BNP assays in clinical at present.
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Espectrometría de Masas/métodos , Péptido Natriurético Encefálico/análisis , Biomarcadores/análisis , Insuficiencia Cardíaca/diagnóstico , HumanosRESUMEN
A D-A-D' type pure organic molecule, named ODFRCZ, has unique triple-emission character covering fluorescence, phosphorescence, and delayed fluorescence (DF). The phosphorescence of ODFRCZ has a rather long lifetime of about 350â ms at room temperature. One dimer of ODFRCZ with enhanced parallel molecular packing acts more effectively to prompt ISC processes, which further generates room-temperature phosphorescence (RTP), owing to the larger transition dipole moment and closer energy level between S1 and Tn . ODFRCZ is a rare example of an organic RTP molecule that shows dual-stimuli responsiveness of dual-mode mechanochromism (fluorescence red-shift and RTP/DF on-off switch) and reversible crystal-state photochromism. This work may broaden the knowledge for stimuli-responsive RTP organic molecules and lay the foundation for their wide-scale applications.
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Ambient mass spectrometry provides great convenience for fast screening, and has showed promising potential in analytical chemistry. However, its relatively low sensitivity seriously restricts its practical utility in trace compound analysis. In this review, we summarize the sampling and analyte enrichment strategies coupled with nine modes of representative ambient mass spectrometry (desorption electrospray ionization, paper vhspray ionization, wooden-tip spray ionization, probe electrospray ionization, coated blade spray ionization, direct analysis in real time, desorption corona beam ionization, dielectric barrier discharge ionization, and atmospheric-pressure solids analysis probe) that have dramatically increased the detection sensitivity. We believe that these advances will promote routine use of ambient mass spectrometry. Graphical abstract Scheme of sampling stretagies for ambient mass spectrometry.
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Glycosides are a kind of highly important natural aromatic precursors in tobacco leaves. In this study, a novel HKUST-1-coated monolith dip-it sampler was designed for the fast and sensitive analysis of trace glycosides using direct analysis in real-time mass spectrometry. This device was prepared in two steps: in situ polymerization of monolith in a glass capillary of dip-it and layer-by-layer growth of HKUST-1 on the surface of monolith. Sufficient extraction was realized by immersing the tip to solution and in situ desorption was carried out by plasma direct analysis in real time. Compared with traditional solid-phase microextraction protocols, sample desorption was not needed anymore, and only extraction conditions were needed to be optimized in this method, including the gas temperature of direct analysis in real time, extraction time, and CH3 COONH4 additive concentration. This method enabled the simultaneous detection of six kinds of glycosides with the limits of detection of 0.02-0.05 µg/mL and the linear ranges covering two orders of magnitude with the limits of quantitation of 0.05-0.1 µg/mL. Moreover, the developed method was applied for the glycosides analysis of three tobacco samples, which only took about 2 s for every sample.
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Técnicas de Química Analítica/métodos , Glicósidos/análisis , Espectrometría de Masas , Microextracción en Fase Sólida , Técnicas de Química Analítica/instrumentación , Límite de Detección , Estructuras Metalorgánicas , Compuestos OrganometálicosRESUMEN
The study on sulfated beta-cyclodextrin binding to uranyl ion helps to get a better understanding of uranyl compounds' intermolecular interaction mechanism and facilitates the structure-based design of uranyl binding molecules. Here we investigated the electromigration of the inclusion complex by using affinity capillary electrophoresis in acidic solution. The binding constant was determined to be logK = 2.96 ± 0.02 (R2 = 0.996) through nonlinear regression approach. The possible configurations and structural features of the inclusion complex were further studied by molecular dynamics simulation. The results suggest the distinctions of coordination environment and hydration compared with bare uranyl ion in aqueous solution. Thus, two water oxygen atoms coordinated with uranyl in the first hydration shell at 2.55 angstrom instead of five in the same distance range. The binding free energy was calculated as -12.10 ± 1.46 kcal/mol by means of thermodynamic perturbation method. The negative value indicates that the process of S-ß-CD capture uranyl ion in the aqueous media is spontaneous.
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Electroforesis Capilar/métodos , Simulación de Dinámica Molecular , Uranio/química , beta-Ciclodextrinas/química , Simulación por Computador , Oxígeno/química , TermodinámicaRESUMEN
RATIONALE: With the amounts and types of new psychoactive substances (NPSs) increasing rapidly in recent years, an excellent high-throughput method for the analysis of these compounds is urgently needed. In this article, a rapid screening method and a quantitative analysis method for 11 NPSs are described and compared, respectively. METHOD: A simple direct analysis in real time mass spectrometry (DART-MS) method was developed for the analysis of 11 NPSs including three categories of these substances present on the global market such as four cathinones, one phenylethylamine, and six synthetic cannabinoids. In order to analyze these compounds quantitatively with better accuracy and sensitivity, another rapid analytical method with a low limit of detection (LOD) was also developed using liquid chromatography/electrospray ionization quadrupole time-of-flight mass spectrometry (LC/QTOFMS). RESULTS: The 11 NPSs could be determined within 0.5 min by DART-MS. Furthermore, they could also be separated and determined within 5 min by the LC/QTOFMS method. The two methods both showed good linearity with correlation coefficients (r(2) ) higher than 0.99. The LODs for all these target NPSs by DART-MS and LC/QTOFMS ranged from 5 to 40 ng mL(-1) and 0.1 to 1 ng mL(-1) , respectively. Confiscated samples, named as "music vanilla" and "bath salt", and 11 spiked samples were firstly screened by DART-MS and then determined by LC/QTOFMS. CONCLUSIONS: The identification of NPSs in confiscated materials was successfully achieved, and the proposed analytical methodology could offer rapid screening and accurate analysis results. Copyright © 2016 John Wiley & Sons, Ltd.
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Cromatografía Liquida/métodos , Espectrometría de Masas/métodos , Psicotrópicos/análisis , Cannabinoides/análisis , Ensayos Analíticos de Alto Rendimiento/métodos , Límite de Detección , Fenetilaminas/análisis , Reproducibilidad de los Resultados , Espectrometría de Masa por Ionización de Electrospray/métodosRESUMEN
A bifunctional monolith dip-it was fabricated and applied for improving the sensitivity of direct analysis in real time mass spectrometry (DART-MS). This monolith dip-it device was prepared by in situ polymerization of poly(BMA-EDMA-MAA) monolith in the glass capillary of dip-it. As a solid-phase microextraction (SPME) device, it showed strong affinity to four Sudan dyes through hydrophilic interaction and hydrogen bond interaction. As a sample loading device, it could be directly analyzed by DART-MS without organic solvent elution or laser desorption. As a result, this device is environmentally friendly, and used for fast analysis. Under optimized conditions, the limits of detection for four analytes were 5-10 ng mL(-1) and the linear ranges covered more than two orders of magnitude. Finally, the developed method has been applied for the analysis of chili powder and the recoveries for spiked analytes were in the range of 83.2% to 115.1% demonstrating that this device is an efficient sampler for DART-MS analysis and the proposed method could find more applications in different areas like food analysis.
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The online coupling of surface plasmon resonance (SPR) with mass spectrometry (MS) has been highly desired for the complementary information provided by each of the two techniques. In this work, a novel interface for direct and online coupling of SPR to direct analysis in real time (DART) MS was developed. A spray tip connected with the outlet of the SPR flow solution was conducted as the sampling part of the DART-MS, with which the online coupling interface of SPR-MS was realized. Four model samples, acetaminophen, metronidazole, quinine, and hippuric acid, dissolved in three kinds of common buffers were used in the SPR-DART-MS experiments for performance evaluation of the interface and the optimization of DART conditions. The results showed consistent signal changes and high tolerance of nonvolatile salts of this SPR-MS system, demonstrating the feasibility of the interface for online coupling of SPR with MS and the potential application in the characterization of interaction under physiological conditions.