RESUMEN

OBJECTIVE: Delta bilirubin (albumin-covalently bound bilirubin) may provide important clinical utility in identifying impaired hepatic excretion of conjugated bilirubin, but it cannot be measured in real-time for diagnostic purposes in clinical laboratories. METHODS: A total of 210 samples were collected, and their delta bilirubin levels were measured four times using high-performance liquid chromatography. Data collected included age, sex, diagnosis code, delta bilirubin, total bilirubin, direct bilirubin, total protein, albumin, globulin, aspartate aminotransferase, alanine transaminase, alkaline phosphatase, gamma-glutamyl transferase, lactate dehydrogenase, hemoglobin, serum hemolysis value, hemolysis index, icterus value (Iv), icterus index (Ii), lipemia value (Lv), and lipemia index. To conduct feature selection and identify the optimal combination of variables, linear regression machine learning was performed 1,000 times. RESULTS: The selected variables were total bilirubin, direct bilirubin, total protein, albumin, hemoglobin, Iv, Ii, and Lv. The best predictive performance for high delta bilirubin concentrations was achieved with the combination of albumin-direct bilirubin-hemoglobin-Iv-Lv. The final equation composed of these variables was as follows: delta bilirubin = 0.35 × Iv + 0.05 × Lv - 0.23 × direct bilirubin - 0.05 × hemoglobin - 0.04 × albumin + 0.10. CONCLUSION: The equation established in this study is practical and can be easily applied in real-time in clinical laboratories.

Asunto(s)

Bilirrubina , Aprendizaje Automático , Bilirrubina/sangre , Humanos , Femenino , Masculino , Persona de Mediana Edad , Adulto , Anciano , Adolescente , Adulto Joven , Niño , Anciano de 80 o más Años , Cromatografía Líquida de Alta Presión , Preescolar , Lactante

RESUMEN

BACKGROUND-AIM: Methylmalonic acid (MMA) is currently the best biomarker of functional vitamin B12 deficiency. However, for a correct interpretation of the patient's results it is necessary to know its biological variation (BV). No BV data are available for urine MMA values, as measured by mass spectrometry. Hence, the aim of this study was to estimate the within- and between-person coefficients of variation (CVw, CVg) for MMA in a healthy population, and the associated index of individuality (II), as well as to define quality specifications based on BV and the reference change value (RCV). METHODS: Random urine samples from 34 healthy volunteers were collected over four consecutive weeks. Samples were stored at -80 °C until analysis in a single analytical run. MMA excretion was quantified by tandem liquid chromatography coupled to mass spectrometry (HPLC-MS/MS). Results were normalized to urine creatinine. The coefficients of variation were estimated by CV-ANOVA. Confidence intervals (95 %) were calculated. Quality specifications were defined according to international recommendations. RESULTS: A total of 128 samples were included. The coefficients of variation were CVw = 35.7 % (26.1-45.3) and CVg = 67.7 % (58.3-77.0). The associated II was 0.5 and the RCV was 88.1 %. CONCLUSION: Considering the II obtained, MMA in urine has high individuality, therefore, RCV is better to evaluate serial clinical results. Our results will contribute to a better clinical interpretation of this biomarker and will represent a great aid when defining analytical performance specifications for this magnitude.

Asunto(s)

Ácido Metilmalónico , Humanos , Ácido Metilmalónico/orina , Masculino , Adulto , Femenino , España , Espectrometría de Masas en Tándem , Persona de Mediana Edad , Adulto Joven , Voluntarios Sanos , Cromatografía Líquida de Alta Presión , Biomarcadores/orina

RESUMEN

ETHNOPHARMACOLOGICAL RELEVANCE: Hypercholesterolemia (HLC) was a key risk factor for cardiovascular disease (CVD) characterized by elevated cholesterol levels, particularly LDL. While traditional Chinese medicine preparations Compound Danshen Pills(CDP) has been clinically used for hypercholesterolemia and coronary heart disease, its specific therapeutic effect on HLC remains understudied, necessitating further investigation into its mechanisms. AIM OF THE STUDY: The aim of this study was to explore the potential of CDP in treating HLC and elucidate its underlying mechanisms and active components. MATERIALS AND METHODS: A hypercholesterolemic lipemia rat model induced by a high-fat diet was employed. Network pharmacology combined with UHPLC-Q exactive orbitrap HRMS technique was used to predict the active components, targets and mechanisms of CDP for HLC. Histological analysis and serum biochemical assays were used to assess the therapeutic effect of CDP and its main active ingredient Sa B on hypercholesterolemic lipemia rat model. Immunofluorescence assays and western blotting were used to verify the mechanism of CDP and Sa B in the treatment of HLC. Metabolomics approach was used to demonstrate that CDP and Sa B affected the metabolic profile of HLC. RESULTS: Our findings demonstrated that both CDP and its main active ingredient Sa B significantly ameliorated hypercholesterolemic lipemic lesions, reducing levels of TC, LDL, AST, ALT, and ALP. Histological analysis revealed a decrease in lipid droplet accumulation and collagen fiber deposition in the liver, as well as reduced collagen fiber deposition in the aorta. Network pharmacology predicted potential targets such as PPARα and CYP27A1. Immunofluorescence assays and western blotting confirmed that CDP and Sa B upregulated the expression of Adipor1, PPARα and CYP27A1. Metabolomics analyses further indicated improvements in ABC transporters metabolic pathways, with differential metabolites such as riboflavin, taurine, and choline showed regression in levels after CDP treatment and riboflavin, L-Threonine, Thiamine, L-Leucine, and Adenosine showed improved expression after Sa B treatment. CONCLUSION: CDP and Sa B have been shown to alleviate high-fat diet-induced hypercholesterolemia by activating the PPAR pathway and improving hepatic lipid metabolism. Our study demonstrated, for the first time, the complex mechanism of CDP, Sa B in the treatment of hypercholesterolemia at the protein and metabolic levels and provided a new reference that could elucidate the pharmacological effects of traditional Chinese medicine on hypercholesterolemia from multiple perspectives.

Asunto(s)

Dieta Alta en Grasa , Medicamentos Herbarios Chinos , Hipercolesterolemia , Metabolómica , Farmacología en Red , Ratas Sprague-Dawley , Salvia miltiorrhiza , Animales , Hipercolesterolemia/tratamiento farmacológico , Medicamentos Herbarios Chinos/farmacología , Medicamentos Herbarios Chinos/uso terapéutico , Masculino , Cromatografía Líquida de Alta Presión , Salvia miltiorrhiza/química , Ratas , Modelos Animales de Enfermedad , Hígado/efectos de los fármacos , Hígado/metabolismo , Hígado/patología , Canfanos , Panax notoginseng

RESUMEN

Curcumae Radix (CR) is a widely used traditional Chinese medicine with significant pharmaceutical importance, including enhancing blood circulation and addressing blood stasis. This study aims to establish an integrated and rapid quality assessment method for CR from various botanical origins, based on chemical components, antiplatelet aggregation effects, and Fourier transform near-infrared (FT-NIR) spectroscopy combined with multivariate algorithms. Firstly, ultra-performance liquid chromatography-photodiode array (UPLC-PDA) combined with chemometric analyses was used to examine variations in the chemical profiles of CR. Secondly, the activation effect on blood circulation of CR was assessed using an in vitro antiplatelet aggregation assay. The studies revealed significant variations in chemical profiles and antiplatelet aggregation effects among CR samples from different botanical origins, with constituents such as germacrone, ß-elemene, bisdemethoxycurcumin, demethoxycurcumin, and curcumin showing a positive correlation with antiplatelet aggregation biopotency. Thirdly, FT-NIR spectroscopy was integrated with various machine learning algorithms, including Artificial Neural Network (ANN), K-Nearest Neighbors (KNN), Logistic Regression (LR), Support Vector Machine (SVM), and Subspace K-Nearest Neighbors (Subspace KNN), to classify CR samples from four distinct sources. The result showed that FT-NIR combined with KNN and SVM classification algorithms after SNV and MSC preprocessing successfully distinguished CR samples from four plant sources with an accuracy of 100%. Finally, Quantitative models for active constituents and antiplatelet aggregation bioactivity were developed by optimizing the partial least squares (PLS) model with interval combination optimization (ICO) and competitive adaptive reweighted sampling (CARS) techniques. The CARS-PLS model achieved the best predictive performance across all five components. The coefficient of determination (R2p) and root mean square error (RMSEP) in the independent test sets were 0.9708 and 0.2098, 0.8744 and 0.2065, 0.9511 and 0.0034, 0.9803 and 0.0066, 0.9567 and 0.0172 for germacrone, ß-elemene, bisdemethoxycurcumin, demethoxycurcumin and curcumin, respectively. The ICO-PLS model demonstrated superior predictive capabilities for antiplatelet aggregation biotency, achieving an R2p of 0.9010, and an RMSEP of 0.5370. This study provides a valuable reference for the quality evaluation of CR in a more rapid and comprehensive manner.

Asunto(s)

Curcuma , Inhibidores de Agregación Plaquetaria , Agregación Plaquetaria , Espectroscopía Infrarroja Corta , Curcuma/química , Espectroscopía Infrarroja Corta/métodos , Agregación Plaquetaria/efectos de los fármacos , Espectroscopía Infrarroja por Transformada de Fourier/métodos , Inhibidores de Agregación Plaquetaria/análisis , Inhibidores de Agregación Plaquetaria/química , Animales , Cromatografía Líquida de Alta Presión/métodos , Medicamentos Herbarios Chinos/química , Medicamentos Herbarios Chinos/análisis , Algoritmos , Extractos Vegetales/química

RESUMEN

ETHNOPHARMACOLOGICAL RELEVANCE: Jinye Baidu granules (JYBD) have been used to treat acute respiratory tract infections and demonstrated clinical efficacy for the treatment of emerging or epidemic respiratory viruses such as SARS-CoV-2 and influenza virus. AIM OF THE STUDY: This study is to investigate the antiviral effect of JYBD against influenza A viruses (IAV) in vitro and in vivo and elucidate its underlying mechanism. MATERIALS AND METHODS: Ultra-high-performance liquid chromatography connected with Orbitrap mass spectrometer (UHPLC-Orbitrap MS) was employed to describe the chemical profile of JYBD. The potential pathways and targets involved in JYBD against IAV infection were predicted by network pharmacology. The efficacy and mechanism of JYBD were validated through both in vivo and in vitro experiments. Moreover, combination therapy with JYBD and the classic anti-influenza drugs was also investigated. RESULTS: A total of 126 compounds were identified by UHPLC-Orbitrap MS, of which 9 compounds were unambiguously confirmed with reference standards. JYBD could significantly inhibit the replication of multiple strains of IAV, especially oseltamivir-resistant strains. The results of qRT-PCR and WB demonstrated that JYBD could inhibit the excessive induction of pro-inflammatory cytokines induced by IAV infection and regulate inflammatory response through inhibiting JAK/STAT, NF-κB and MAPK pathways. Moreover, both JYBD monotherapy or in combination with oseltamivir could alleviate IAV-induced severe lung injury in mice. CONCLUSIONS: JYBD could inhibit IAV replication and mitigate virus-induced excessive inflammatory response. Combinations of JYBD and neuraminidase inhibitors conferred synergistic suppression of IAV both in vitro and in vivo. It might provide a scientific basis for clinical applications of JYBD against influenza virus infected diseases.

Asunto(s)

Antivirales , Medicamentos Herbarios Chinos , Virus de la Influenza A , Farmacología en Red , Infecciones por Orthomyxoviridae , Antivirales/farmacología , Animales , Medicamentos Herbarios Chinos/farmacología , Medicamentos Herbarios Chinos/química , Virus de la Influenza A/efectos de los fármacos , Perros , Ratones , Humanos , Infecciones por Orthomyxoviridae/tratamiento farmacológico , Infecciones por Orthomyxoviridae/virología , Células de Riñón Canino Madin Darby , Replicación Viral/efectos de los fármacos , Células A549 , Ratones Endogámicos BALB C , Masculino , Femenino , Cromatografía Líquida de Alta Presión

RESUMEN

The extraction of bioactive compounds is based on the application of various extraction techniques. Therefore, the stem and root bark of the plant species Morinda lucida L. were used in this research, while the extraction procedure was performed using three extraction techniques: HAE (homogenizer extraction), UAE (ultrasound extraction) as modern, and MAC (maceration) as conventional extraction technique. The presence of different classes of secondary metabolites was determined using the UHPLC method, while the content of total phenols and flavonoids was determined spectrophotometrically. The biological potential was investigated by in vitro antioxidant and enzyme assays. Different extraction technologies showed significant differences in only two classes of phenols, namely lignans and phenolic acids, which were significantly higher in HAE than in UAE and MAC. These findings highlight the significant effect of stem and bark extracts of M. lucida, opening the way for innovative industrial exploitation of these matrices.

Asunto(s)

Antioxidantes , Morinda , Fenoles , Extractos Vegetales , Morinda/química , Extractos Vegetales/química , Extractos Vegetales/aislamiento & purificación , Extractos Vegetales/farmacología , Fenoles/química , Fenoles/aislamiento & purificación , Fenoles/farmacología , Antioxidantes/química , Antioxidantes/aislamiento & purificación , Antioxidantes/farmacología , Cromatografía Líquida de Alta Presión , Flavonoides/química , Flavonoides/aislamiento & purificación , Corteza de la Planta/química , Fraccionamiento Químico/métodos , Tallos de la Planta/química , Raíces de Plantas/química

RESUMEN

To improve the adsorption affinity and selectivity of fipronils (FPNs), including fipronil, its metabolites and analogs, a magnetic covalent organic framework (Fe3O4@COF-F) with copious fluorine affinity sites was innovatively designed as an adsorbent of magnetic solid-phase extraction (MSPE). The enhanced surface area, pore size, crystallinity of Fe3O4@COF-F and its exponential adsorption capacities (187.3-231.5 mg g-1) towards fipronils were investigated. Combining MSPE with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), an analytical method was established for the selective determination of fipronils in milk and milk powder samples. This method achieved high sensitivity (LODs: 0.004-0.075 ng g-1), satisfactory repeatability and accuracy with spiked recoveries ranging from 89.9% to 100.3% (RSDs≤5.1%). Overall, the constructed Fe3O4@COF-F displayed great potential for the selective enrichment of fipronils, which could be ascribed to fluorine­fluorine interaction. This method proposed a feasible and promising strategy for the development of functionalized COF and broadened its application in fluorine containing hazards detection.

Asunto(s)

Flúor , Contaminación de Alimentos , Estructuras Metalorgánicas , Leche , Pirazoles , Extracción en Fase Sólida , Espectrometría de Masas en Tándem , Pirazoles/química , Contaminación de Alimentos/análisis , Flúor/química , Leche/química , Animales , Estructuras Metalorgánicas/química , Adsorción , Cromatografía Líquida de Alta Presión , Insecticidas/química , Insecticidas/análisis , Límite de Detección

RESUMEN

This study presents the contents of α-methylenecyclopropylglycine, a potentially toxic amino acid, in the peel, pulp and seed fractions of two well-known litchi varieties, namely Shahi and China, over a span of three harvest-seasons. For analysing α-methylenecyclopropylglycine, an LC-MS/MS-based method was validated. The method-accuracies fell within 75-110 % (RSD, <15 %) at 0.1 mg/kg (LOQ) and higher levels. A comparative evaluation of the results in peel, pulp and seed at 30 days before harvest (DBH), 15-DBH, and edible-ripe stage revealed that α-methylenecyclopropylglycine content increased as the litchi seeds grew towards maturity, regardless of the cultivar. In arils, at maturity, the concentration of α-methylenecyclopropylglycine ranged from not-detected to 11.7 µg/g dry weight. The Shahi cultivar showed slightly higher α-methylenecyclopropylglycine content in comparison to China litchi. This paper presents the first known analysis of combined seasonal data on different fruit components at various growth stages for the two chosen litchi cultivars grown in India.

Asunto(s)

Frutas , Litchi , Semillas , Espectrometría de Masas en Tándem , Litchi/química , Litchi/crecimiento & desarrollo , Litchi/metabolismo , Frutas/química , Frutas/crecimiento & desarrollo , China , Semillas/química , Semillas/crecimiento & desarrollo , Glicina/análogos & derivados , Glicina/análisis , Cromatografía Líquida de Alta Presión , Ciclopropanos/análisis

RESUMEN

Harvest season exerts great influence on tea quality. Herein, the variations in non-volatile flavor substances in spring and summer fresh tea leaves of four varieties were comprehensively investigated by integrating UHPLC-Q-Exactive based lipidomics and metabolomics. A total of 327 lipids and 99 metabolites were detected, among which, 221 and 58 molecules were significantly differential. The molecular species of phospholipids, glycolipids and acylglycerolipids showed most prominent and structure-dependent seasonal changes, relating to polar head, unsaturation and total acyl length. Particularly, spring tea contained higher amount in aroma precursors of highly unsaturated glycolipids and phosphatidic acids. The contents of umami-enhancing amino acids and phenolic acids, e.g., theanine, theogallin and gallotannins, were increased in spring. Besides, catechins, theaflavins, theasinensins and flavone/flavonol glycosides showed diverse changes. These phytochemical differences covered key aroma precursors, tastants and colorants, and may confer superior flavor of black tea processed using spring leaves, which was verified by sensory evaluation.

Asunto(s)

Camellia sinensis , Aromatizantes , Lipidómica , Espectrometría de Masas , Metabolómica , Hojas de la Planta , Estaciones del Año , Camellia sinensis/química , Camellia sinensis/metabolismo , Hojas de la Planta/química , Hojas de la Planta/metabolismo , Cromatografía Líquida de Alta Presión , Aromatizantes/química , Aromatizantes/metabolismo , Humanos , Gusto , Odorantes/análisis , Lípidos/análisis , Lípidos/química

RESUMEN

Chemicals from packaging materials might be transferred into food resulting in consumer exposure. Identifying these migrated chemicals is highly challenging and crucial to perform their safety assessment, usually starting by the understanding of the chemical composition of the packaging material itself. This study explores the use of the Molecular Networking (MN) approach to support identification of the extracted chemicals. Two formulations of bioplastics were analyzed using Liquid Chromatography hyphenated to High-Resolution Mass Spectrometry. Data processing and interpretation using a conventional manual method was performed as a point of comparison to understand the power of MN. Interestingly, only the MN approach facilitated the identification of unknown chemicals belonging to a novel oligomer series containing the azelaic acid monomer. The MN approach provided a faster visualization of chemical families in addition to the highlight of unrelated chemicals enabling to prioritize chemicals for further investigation improving the safety assessment of packaging materials.

Asunto(s)

Embalaje de Alimentos , Embalaje de Alimentos/instrumentación , Contaminación de Alimentos/análisis , Espectrometría de Masas , Cromatografía Líquida de Alta Presión

RESUMEN

Different scented teas provide various choices for consumers from appearance, aroma, flavor and others. Aiming to define advantages and market positions of different scented teas and promote optimization of market structure, characteristics for scented tea favored by consumers and outstanding attributes of different scented teas should be clarified. Rose tea was taken as study object. Sensory evaluation and consumer acceptance were investigated. GC-MS and HPLC fingerprints were established. Physicochemical characteristics were determined. RGB integration analysis was inventively proposed for correlation analysis. The volatile compounds with spicy, green or herbal odor as camphene, ß-phenethyl acetate, eugenol, and physicochemical parameters as antioxidant capacity, reducing sugar content, pH showed positive correlation with popular sensory properties. Six models for consumer preference by objective description were built through GA-SVR (accuracy = 1), and APP was developed. The research mode of scented tea has been successfully established to study multiple subjective characteristics with measurable objective parameters.

Asunto(s)

Odorantes , Gusto , Odorantes/análisis , Humanos , Compuestos Orgánicos Volátiles/química , Compuestos Orgánicos Volátiles/análisis , Té/química , Cromatografía de Gases y Espectrometría de Masas , Comportamiento del Consumidor , Antioxidantes/química , Antioxidantes/análisis , Rosa/química , Cromatografía Líquida de Alta Presión

RESUMEN

A modified QuEChERS method was developed to determine multi-class pesticide and veterinary residues in aquatic products. Chitosan microspheres were conveniently synthesized and utilized as the cleanup adsorbent in the QuEChERS procedure, showcasing rapid filtration one-step pretreatment ability for the determination of drug multi-residues in aquatic products. Compared to conventional synthetic sorbents, chitosan microspheres not only have good purification performance, but also have renewable and degradable properties. This novel sorbent worked well in the simultaneous determination of 95 pesticides and veterinary drug residues in aquatic products after being combined with an improved one-step vortex oscillating cleanup method. We achieved recoveries ranging from 64.0% to 115.9% for target drugs in shrimp and fish matrix. The limits of detection and quantification were 0.5-1.0 and 1.0-2.0 µg kg-1, respectively. Notably, hydrocortisone was detected with considerable frequency and concentration in the tested samples, underscoring the necessity for stringent monitoring of this compound in aquatic products.

Asunto(s)

Quitosano , Peces , Microesferas , Espectrometría de Masas en Tándem , Drogas Veterinarias , Animales , Quitosano/química , Cromatografía Líquida de Alta Presión , Drogas Veterinarias/análisis , Drogas Veterinarias/aislamiento & purificación , Contaminación de Alimentos/análisis , Residuos de Medicamentos/análisis , Residuos de Medicamentos/aislamiento & purificación , Residuos de Medicamentos/química , Plaguicidas/aislamiento & purificación , Plaguicidas/análisis , Plaguicidas/química , Residuos de Plaguicidas/aislamiento & purificación , Residuos de Plaguicidas/análisis , Residuos de Plaguicidas/química , Adsorción , Extracción en Fase Sólida/métodos , Extracción en Fase Sólida/instrumentación , Contaminantes Químicos del Agua/aislamiento & purificación , Contaminantes Químicos del Agua/química , Contaminantes Químicos del Agua/análisis , Alimentos Marinos/análisis , Mariscos/análisis , Cromatografía Líquida con Espectrometría de Masas

RESUMEN

Australian honey samples from four botanical genera (Lophostemon, Eucalyptus, Macadamia and Corymbia) were investigated for their phenolic content. An improved phenolic extraction and high-performance liquid chromatography-diode array detection (HPLC-DAD) analysis method allowed for the rapid and reliable identification of phenolic compounds. A concentrated liquid-liquid extraction method with an acidified aqueous solution and acetonitrile was optimised to isolate phenolic compounds from the honey matrix. The concentrated extraction method improved sensitivity and permitted the identification of phenolics present at low concentrations (LOD: 0.012-0.25 mg/kg and LOQ: 0.040-2.99 mg/kg). The optimised HPLC-DAD chromatographic conditions gave stable retention times, improved peak separation and allowed for the inexpensive detection of each of the 109 phenolic compounds at their maximum absorbance wavelength. Out of the 109 phenolic compounds included in this study, 49 were identified in the Australian honeys tested. Furthermore, 25 of the 49 compounds were determined to be markers specific to honey floral origin.

Asunto(s)

Eucalyptus , Miel , Fenoles , Miel/análisis , Cromatografía Líquida de Alta Presión , Fenoles/análisis , Fenoles/química , Eucalyptus/química , Australia , Flores/química

RESUMEN

Making health-enhancing tea from Forsythia suspensa leaves has been a tradition of Chinese folk culture for centuries. However, these leaves were not officially recognized as a new food source until 2017 by the Chinese government. In this study, ethyl acetate fractions from Forsythia suspensa fruit and leaves exhibited excellent antioxidant activity in vitro antioxidant assays and in vivo D-galactose-induced aging mice model. The antioxidant activity of the leaves was higher than that of fruit both in vitro and in vivo. The chemical constituents present in these ethyl acetate fractions were comprehensively analyzed using UHPLC-Q-Exactive-Orbitrap/MS. A total of 20 compounds were identified, among which forsythoside E, (+)-epipinoresinol, dihydromyricetin, chlorogenic acid, and ursolic acid were exclusively detected in the ethyl acetate fraction of Forsythia suspensa leaves, but absent in the ethyl acetate fraction derived from its fruit. This study provides theoretical support for the utilization of Forsythia suspensa fruit and leaves.

Asunto(s)

Envejecimiento , Antioxidantes , Forsythia , Frutas , Galactosa , Extractos Vegetales , Hojas de la Planta , Animales , Forsythia/química , Hojas de la Planta/química , Ratones , Frutas/química , Extractos Vegetales/química , Cromatografía Líquida de Alta Presión , Antioxidantes/química , Antioxidantes/farmacología , Envejecimiento/efectos de los fármacos , Masculino , Humanos , Espectrometría de Masas

RESUMEN

Aromatic amino acid oxidation products (AAAOPs) are newly discovered risk substances of thermal processes. Due to its significant polarity and trace level in food matrices, there are no efficient pre-treatment methods available to enrich AAAOPs. Herein, we proposed a magnetic cationic covalent organic framework (Fe3O4@EB-iCOF) as an adsorbent for dispersive magnetic solid-phase extraction (DMSPE). Benefiting from the unique charged characteristics of Fe3O4@EB-iCOF, AAAOPs can be enriched through electrostatic interaction and π-π interactions. Under the optimal DMSPE conditions, the combined HPLC-MS/MS method demonstrated good linearity (R2 ≥ 0.990) and a low detection limit (0.11-7.5 µg·kg-1) for AAAOPs. In addition, the method was applied to real sample and obtained satisfactory recoveries (86.8 % âˆ¼ 109.9 %). Especially, we applied this method to the detection of AAAOPs in meat samples and conducted a preliminarily study on its formation rules, which provides a reliable basis for assessing potential dietary risks.

Asunto(s)

Aminoácidos Aromáticos , Oxidación-Reducción , Extracción en Fase Sólida , Extracción en Fase Sólida/métodos , Aminoácidos Aromáticos/química , Aminoácidos Aromáticos/análisis , Aminoácidos Aromáticos/aislamiento & purificación , Espectrometría de Masas en Tándem , Estructuras Metalorgánicas/química , Calor , Contaminación de Alimentos/análisis , Cromatografía Líquida de Alta Presión , Animales , Adsorción , Carne/análisis , Alimentos Procesados

RESUMEN

The impact of seasonal variations on the quality of oolong tea products remains a subject of ongoing exploration. This study delves into the intricate relationships between seasonality, metabolites, and sensory characteristics in finished oolong tea products. Metabolomic data from 266 Tieguanyin oolong tea products harvested in both spring and autumn, along with corresponding sensory evaluations, were acquired. Using OPLS-DA and PLS-DA models with UPLC-QToF/MS data, our findings showed that seasonal effects were notably more pronounced in light-scented Tieguanyin products (lightly-roasted) compared to strong-scented products (moderately-roasted). Furthermore, over half of the identified key seasonal discriminant metabolites happened to be crucial for determining the sensory grade. The study marks the first-time recognition of triterpene saponins as critical factors in determining both the harvest season and the sensory grade of oolong tea. These insights deepen our understanding of the interplays between seasonal variations, metabolites, and sensory attributes in oolong tea products.

Asunto(s)

Camellia sinensis , Estaciones del Año , Gusto , Té , Camellia sinensis/química , Camellia sinensis/metabolismo , Té/química , Té/metabolismo , Humanos , Metabolómica , Cromatografía Líquida de Alta Presión , Odorantes/análisis , Espectrometría de Masas

RESUMEN

Dried citrus peel (DCP), also called "Chen Pi", has edible and medicinal value. However, the specific differences among various sources remain unknown. Herein, we collected six DCP species, namely, one Citrus reticulata 'Chachi' (CZG) and five Citrus reticulata Blanco (CRB). Targeted high-performance liquid chromatography and untargeted ultra-high-performance liquid chromatography-tandem mass spectrometry were employed to comprehensively compare the phenolic compounds and metabolites in DCP. Interestingly, 13 different phenolic compounds were noted in DCP. The total phenolic compound content in all CRB samples (58.86-127.65 mg/g) was higher than that of CZG (39.47 mg/g). Untargeted metabolomic revealed 1495 compounds, with 115 differentially expressed metabolites for CRBs and CZG, particularly flavonoids (38), terpenoids (15), and phenolic acids and derivatives (9). Lastly, antioxidant assays revealed that all CRB samples exhibited higher antioxidant activities compared with CZG. Therefore, our study results provide a theoretical basis for the high-value utilization of citrus peels and their metabolites.

Asunto(s)

Antioxidantes , Citrus , Frutas , Metabolómica , Extractos Vegetales , Espectrometría de Masas en Tándem , Citrus/química , Citrus/metabolismo , Antioxidantes/química , Antioxidantes/metabolismo , Antioxidantes/análisis , Cromatografía Líquida de Alta Presión , Frutas/química , Frutas/metabolismo , Extractos Vegetales/química , Extractos Vegetales/metabolismo , Fenoles/metabolismo , Fenoles/química , Fenoles/análisis , Flavonoides/metabolismo , Flavonoides/química , Flavonoides/análisis

RESUMEN

BACKGROUND: ß-nicotinamide mononucleotide stands out as an essential breakthrough in "anti-aging" and consistently leads the list of top-selling nutritional supplements in terms of quantity. As the metabolites of ß-nicotinamide mononucleotide, the detection of nicotinamide and N1-methylnicotinamide is of great significance for evaluating the nutritional effect of dietary supplements of ß-nicotinamide mononucleotide. However, due to the extremely low concentration of nicotinamide and N1-methylnicotinamide in vivo and the serious matrix interference in biological samples, there is an increasing demand for materials and methods of pre-treatment. RESULTS: In this study, Fe3O4@hydroxypropyl methyl cellulose@dodecylbenzenesulfonic acid magnetic fluid was synthesized for the first time, and it was used as pretreatment material to detect nicotinamide and N1- methylnicotinamide in urine samples by high performance liquid chromatography. Compared with other adsorption materials, Fe3O4@hydroxypropyl methyl cellulose@dodecylbenzenesulfonic acid nanoparticles are a kind of uniform magnetic fluid. Furthermore, they have more types and quantities of interaction sites (electrostatic interactions, hydrophobic interactions, hydrogen bonding interactions, and π-π interactions), so they own greater adsorption capacity. When the pH of the solution is 4, they can be adsorbed quickly within 10 s. The method successfully detected trace nicotinamide and N1-methylnicotinamide in urine samples in the linear range of 0.1-80 µg mL-1, the low detection limits were 0.30 ng mL-1 and 1.5 ng mL-1 respectively, and the quantification limits were 1.0 ng mL-1 and 5.0 ng mL-1, respectively. At the same time, the standard urine samples of nicotinamide and N1-methylnicotinamide showed satisfactory recovery rate 94.50-109.1 %. The results indicated that the established method can accurately and quantitatively determine trace nicotinamide and N1-methylnicotinamide in urine samples. SIGNIFICANCE: Consequently, low concentration of ß-nicotinamide mononucleotide metabolites can be detected simultaneously, and the interference can be eliminated during the detection process, which provides an efficient and convenient pretreatment method and a rapid and sensitive detection method for the analysis of ß-nicotinamide mononucleotide metabolites. What's more, it has a wide application prospect in the analysis of other similar metabolites in biological samples.

Asunto(s)

Niacinamida , Mononucleótido de Nicotinamida , Mononucleótido de Nicotinamida/química , Mononucleótido de Nicotinamida/orina , Mononucleótido de Nicotinamida/metabolismo , Humanos , Niacinamida/orina , Niacinamida/análogos & derivados , Niacinamida/metabolismo , Niacinamida/análisis , Niacinamida/química , Cromatografía Líquida de Alta Presión , Nanopartículas de Magnetita/química , Adsorción , Límite de Detección

RESUMEN

BACKGROUND: Paclitaxel is a promising anticancer drug for patients with ovarian, breast, lung, gastrointestinal, genitourinary, prostate, and head-and-neck cancers. Paclitaxel follows nonlinear pharmacokinetics. The major metabolite of paclitaxel is 6-alpha-hydroxy paclitaxel, mediated by CYP2C8, while metabolism to two of its minor metabolites, 3'-p-hydroxypaclitaxel and 6a, 3'- p-dihydroxypaclitaxel, is catalyzed by CYP3A4. Therapeutic drug monitoring of paclitaxel could be a promising approach to improve the efficacy and safety of paclitaxel correct personalized doses and improve the overall benefit-risk ratio. A novel and highly sensitive chromatographic method for the detection of paclitaxel and its metabolite has been proposed that allows quantification in human plasma with 100% accuracy in terms of recovery without significant intraday or interday variations. MATERIALS AND METHODS: The present study was planned following bioanalytical method validation guidance according to the U.S. Food and Drug Administration requirements. The validation of the analytical procedure was performed as per ICH Q2(R1) guidelines. It was done to assure the reliability of the results obtained for various parameters such as linearity, accuracy, precision, limit of detection (LOD), limit of quantification, robustness, stability, and system suitability. RESULTS: The specificity of the method was established by ensuring no interference with peak obtained from paclitaxel and 6-alpha-hydroxy paclitaxel. LOD was found to be 0.05 and 0.033 while the limit of quantitation was 0.14 and 0.099 for paclitaxel and 6-alpha-hydroxy paclitaxel, respectively. Median (±interquartile range) accuracy for paclitaxel and 6-alpha-hydroxy paclitaxel was found to be 102.73 (±13.581) and 100.87 (±7.573), respectively. CONCLUSION: This novel method of simultaneous detection of paclitaxel and its major metabolite 6-alpha-hydroxy paclitaxel demonstrated significant resolution and was sensitive enough for its quantification in human plasma.

Asunto(s)

Antineoplásicos Fitogénicos , Límite de Detección , Paclitaxel , Paclitaxel/sangre , Paclitaxel/farmacocinética , Paclitaxel/análogos & derivados , Humanos , Cromatografía Líquida de Alta Presión/métodos , Reproducibilidad de los Resultados , Antineoplásicos Fitogénicos/sangre , Antineoplásicos Fitogénicos/farmacocinética , Monitoreo de Drogas/métodos

RESUMEN

In the mirabegron (MIR) synthesis, the N-nitroso mirabegron (NNM) is obtained during synthetic process of MIR; water is being used in reaction under acidic condition. Nitrite source is from water, and secondary amine source is from MIR as it has secondary amine; NNM is generated as an impurity during the synthesis of MIR. The presence of NNM in MIR could potentially affect its effectiveness. The purpose of this study was to establish a Ultra-performance liquid chromatography-mass spectrometry/mass spectrometry (UPLC-MS/MS) methodology to identify NNM in MIR samples. The method for NNM analysis was developed on Acquity HSS T3 (100*2.1) mm 1.8 µm column with gradient elution using mobile phase consisted of 0.1% formic acid in water (mobile phase A) and 0.1% formic acid in methanol (mobile phase B). Mass spectrometer with electrospray ionization operated in the MRM mode was used in the analysis of NNM (m/ z 426.20 → 170.00). The UPLC-MS/MS methodology proposed showed a good linearity (0.02 to 0.72 ppm), good system precision (RSD = 0.57%), good method precision (RSD = 0.87%), acceptable accuracy (94.5-116.5%), low detection limit (0.006 ppm) and low quantification limit (0.02 ppm) for NNM. The UPLC-MS/MS methodology proposed can be utilized to assess the quality of MIR sample for the presence of NNM impurity.

Asunto(s)

Acetanilidas , Espectrometría de Masas en Tándem , Tiazoles , Espectrometría de Masas en Tándem/métodos , Acetanilidas/análisis , Acetanilidas/química , Cromatografía Líquida de Alta Presión/métodos , Tiazoles/análisis , Tiazoles/química , Reproducibilidad de los Resultados , Límite de Detección , Modelos Lineales , Contaminación de Medicamentos , Compuestos Nitrosos/análisis , Compuestos Nitrosos/química , Cromatografía Líquida con Espectrometría de Masas