RESUMEN
The paper presents the results of determining the content of coumarin and its derivatives in the melilot using nuclear magnetic resonance spectroscopy, including the study of the effect of fertilizers on the quantitative content of coumarin and its derivatives in the composition of the melilot treated by phases using the method of 1H and 13C nuclear magnetic resonance spectroscopy. Based on the results of the nuclear magnetic resonance spectroscopy, the possibility of qualitative and quantitative determination of the content of coumarin and its derivatives isolated from extracts of fertilized melilot was evaluated. The effect of eight preparations on the plant and its concentration in solution on the content of coumarin substances in the Altynbas yellow melilot variety was studied. It was shown that the preparations have a slight effect on the coumarin content in the melilot and, accordingly, on the quality of feed based on it. In the control variant (variant 9), the coumarin proton content was 9.85%, and the maximum coumarin proton content was observed in the variant where BioEnergy was used as fertilizer and amounted to 22.44%.
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Cumarinas , Fertilizantes , Espectroscopía de Resonancia Magnética , Cumarinas/análisis , Fertilizantes/análisisRESUMEN
Cinnamomi ramulus (CR) is a common Chinese herbal medicine with a long history. It is often used to treat exogenous wind-cold diseases in clinic, but its chemical compositions remain to be studied. In this study, CR was extracted with 75% ethanol, and UPLC-Q-Orbitrap-MS combined with data post-processing method was used to identify the chemical components in the extract. Through this technology, the components in CR can be separated and accurately identified. A total of 61 compounds were identified, including 14 simple phenylpropanoids, 3 coumarins, 5 lignans, 14 flavonoids, 10 benzoic acids, 8 organic acids, and 7 others. This study confirmed the existence of these compounds in CR and speculated the cleavage pathways of each compound, which enriched the mass spectrometry data and cleavage rules. This study can provide a reference for CR and other research.
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Cumarinas , Medicamentos Herbarios Chinos , Flavonoides , Cromatografía Líquida de Alta Presión/métodos , Medicamentos Herbarios Chinos/química , Medicamentos Herbarios Chinos/análisis , Cumarinas/química , Cumarinas/análisis , Flavonoides/análisis , Flavonoides/química , Lignanos/análisis , Lignanos/química , Espectrometría de Masas/métodos , Cinnamomum/química , Espectrometría de Masas en Tándem/métodosRESUMEN
Hua-ju-hong (HJH) is a Chinese medicinal material obtained from Citrus grandis 'Tomentosa' (CGT) and Citrus grandis (L.) Osbeck (CG) with various commercial specifications. It is known for relieving cough and dispelling phlegm. To reveal the quality marker for distinguishing the various HJH, 215 batches of commercial HJH were studied systematically using multidimensional chemical analysis. Ten major components were identified by high-performance liquid chromatography coupled with quadrupole-time-of-flight mass spectrometry and quantified via high-performance liquid chromatography coupled with diode array detection. In this study, a rapid, efficient, and low-cost chromatographic method was established. Total coumarin-hemiterpene and total coumarin-monoterpene were first classified and analyzed in HJH. The result indicated that the main component, naringin, was not the quality marker for differentiating CGT from CG. For reflecting the unique medicinal and food value of HJH, coumarins should be the more potential quality markers. Flavonoids were the possible quality markers for distinguishing two growth stages of fruit-exocarp and young fruit. For the first time, two chemotypes of HJH were identified in CG. This study provides a convenient yet reliant chromatographic method and novel yet systematic strategies for overall quality control of commercial HJH.
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Citrus , Medicamentos Herbarios Chinos , Cromatografía Líquida de Alta Presión , Medicamentos Herbarios Chinos/análisis , Medicamentos Herbarios Chinos/química , Citrus/química , Cumarinas/análisis , Cumarinas/química , Espectrometría de Masas , Control de Calidad , Estructura MolecularRESUMEN
Citrus fruits are a diverse and economically important group of fruit crops known for their distinctive flavors and high nutritional value. Their cultivation and consumption contribute significantly to the global agricultural economy and offer a wide range of health benefits. Among the genetic diversity of citrus species, Citrus x limon (L.) Osbeck is particularly relevant due to its chemical composition and potential health benefits. Two cultivars from the Sicily region (southern Italy) were compared for their phenolic content and preliminary antioxidant activity to select the distinctive extract with potential biological activity. A detailed characterization revealed the occurrence of phenolics, coumarins, and flavonoids. The quantification of metabolites contained in the selected extract was performed by an ultrahigh-performance liquid chromatographic method coupled with an ultraviolet detector. Different concentrations were tested in vivo through the fish embryo acute toxicity test, and the 50% lethal dose of 107,833 µg mL-1 was calculated. Finally, the effect of the extract on hatching was evaluated, and a dose-dependent relationship with the accelerated hatching rate was reported, suggesting a Femminello Zagara Bianca green peel upregulating effect on the hatching enzymes. PRACTICAL APPLICATION: Citrus fruits and their products continue to be one of the natural food sources with the highest waste output. In this study, we demonstrate how food industry waste, particularly lemon peel, is rich in bioactive compounds with anti-inflammatory and antioxidant properties that may be used in the nutraceuticals industry.
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Antioxidantes , Citrus , Embrión no Mamífero , Flavonoides , Frutas , Metabolómica , Fenoles , Extractos Vegetales , Pez Cebra , Animales , Citrus/química , Extractos Vegetales/farmacología , Extractos Vegetales/química , Frutas/química , Antioxidantes/farmacología , Antioxidantes/análisis , Embrión no Mamífero/efectos de los fármacos , Fenoles/análisis , Fenoles/toxicidad , Metabolómica/métodos , Flavonoides/análisis , Sicilia , Cumarinas/análisis , Cromatografía Líquida de Alta Presión/métodosRESUMEN
Qianggan capsule (QGC) is a complex preparation composed of 16 traditional Chinese medicines (TCM) that can clear heat and dampness, fortify the spleen and blood, typify qi and relieve depression. However, the chemical composition of QGC remains incompletely understood, despite its clinical use in treating chronic hepatitis and liver injury. The objective of this study was to explore the quality markers of QGC through qualitative and quantitative analysis of its chemical components. First, the chemical composition of QGC was qualitatively analyzed using UHPLC-Q-TOF-MS/MS. Subsequently, the LC-sMRM method was developed and optimized to accurately quantify various chemical components of 10 batches of QGC. Finally, the variations in chemical components between batches were analyzed via multivariate statistical analysis. UHPLC-Q-TOF-MS/MS analysis revealed 167 chemical constituents in QGC, comprised of 48 flavonoids, 32 terpenoids, 18 phenolic acids, 9 coumarins, 9 phenylpropanoids, and 51 nucleosides, sugars, amino acids, anthraquinones, and other compounds. The LC-sMRM method was established for the quantitative analysis of 42 chemical components in 10 batches of QGC. The ultrasonic-assisted extraction parameters were optimized using RSM. Compared with conventional MRM, sMRM demonstrated superior sensitivity and precision. PCA and OPLS-DA identified eight chemical components with content differences among batches. This study established the chemical composition of QGC, offering useful guidance for assessing its quality.
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Medicamentos Herbarios Chinos , Espectrometría de Masas en Tándem , Medicamentos Herbarios Chinos/química , Espectrometría de Masas en Tándem/métodos , Cromatografía Líquida de Alta Presión/métodos , Flavonoides/análisis , Flavonoides/química , Cumarinas/química , Cumarinas/análisis , Terpenos/análisis , Hidroxibenzoatos/análisis , Reproducibilidad de los Resultados , Nucleósidos/análisis , Cápsulas/químicaRESUMEN
Sect. tuberculata plant belongs to the Camellia genus and is named for the "tuberculiform protuberance on the surface of the ovary and fruit". It is a species of great ornamental value and potential medicinal value. However, little has been reported on the metabolites of C. tuberculata seeds. Therefore, this study was conducted to investigate the metabolites of C. tuberculata seeds based on UPLC/ESI-Q TRAP-MS/MS with extensively targeted metabolomics. A total of 1611 metabolites were identified, including 107 alkaloids, 276 amino acids and derivatives, 283 flavonoids, 86 lignans and coumarins, 181 lipids, 68 nucleotides and derivatives, 101 organic acids, 190 phenolic acids, 10 quinones, 4 steroids, 17 tannins, 111 terpenoids, and 177 other metabolites. We compared the different metabolites in seeds between HKH, ZM, ZY, and LY. The 1311 identified different metabolites were classified into three categories. Sixty-three overlapping significant different metabolites were found, of which lignans and coumarins accounted for the largest proportion. The differentially accumulated metabolites were enriched in different metabolic pathways between HKH vs. LY, HKH vs. ZM, HKH vs. ZY, LY vs. ZY, ZM vs. LY and ZM vs. ZY, with the most abundant metabolic pathways being 4, 2, 4, 7, 7 and 5, respectively (p < 0.05). Moreover, among the top 20 metabolites in each subgroup comparison in terms of difference multiplicity 7, 8 and 13. ZM and ZY had the highest phenolic acid content. Ninety-six disease-resistant metabolites and 48 major traditional Chinese medicine agents were identified based on seven diseases. The results of this study will not only lead to a more comprehensive and in-depth understanding of the metabolic properties of C. tuberculata seeds, but also provide a scientific basis for the excavation and further development of its medicinal value.
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Camellia , Hidroxibenzoatos , Lignanos , Camellia/química , Antioxidantes/química , Espectrometría de Masas en Tándem , Flavonoides/análisis , Semillas/química , Metabolómica/métodos , Extractos Vegetales/química , Lignanos/análisis , Cumarinas/análisisRESUMEN
The bark of Fraxinus mandshurica is a traditional folk herb used to clear heat and dry dampness. To investigate the differences in coumarins content in the bark of F. mandshurica, 24 batches of samples from four origins were collected and analyzed. Eight coumarins were obtained by traditional natural product extraction, isolation and identification techniques and quantified by high performance liquid chromatography-photodiode array (HPLC-DAD). The quantitative results showed that the overall content of compound 30 (Fraxinol) was higher at 100.23 mg/g, while the overall content of compound 23 (Cichoriin) was lower, which may be related to environmental factors in different regions. The method validation showed that the linear range of the eight standards was between 10 and 2500 µg/mL with correlation coefficient (R2) values >0.9991; the relative standard deviation (RSD, %) values of intra-day precision were between 0.35 and 1.38, while the RSD values of inter-day precision were between 0. 29-1.78; the RSD (%) values for the reproducibility experiments ranged from 0.29 to 1.87, while the RSD (%) values for the stability experiments ranged from 0.22 to 2.33; the spiked recovery of the samples ranged from 98.65 to 101.34%, and the RSD (%) values ranged from 0.22 to 1.96. The method validation results showed that the instrument used for the analysis had good precision, the reproducibility and stability of the samples were good, and the accuracy of the experimental method was high. In addition, a total of 54 chemical components were identified from F. mandshurica bark by ultra performance liquid chromatography-electrospray quadrupole time-of-flight mass spectrometry (UPLC-ESI-Q-TOF-MS). Based on this, fingerprinting, heatmap and multivariate analysis, including principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA), were established for 24 batches of samples, and four marker compounds that could be used to distinguish different origins of F. mandshurica were screened. To further investigate the bioactivities of the eight coumarins, in vitro enzyme activity inhibition studies were performed, and the results showed that they all exhibited different degrees of inhibition of acetylcholinesterase, tyrosinase and α-glucosidase, thus having potential applications in the treatment of Alzheimer's disease, blemish whitening and anti-diabetes, and becoming a new source of natural enzyme activity inhibitors. This study established an identification and evaluation method applicable to plants of different origins, which provides a strong reference for quality control, origin evaluation and clinical application of traditional medicinal plants.
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Fraxinus , Cumarinas/análisis , Reproducibilidad de los Resultados , Acetilcolinesterasa , Corteza de la Planta/química , Estructura Molecular , Análisis Multivariante , Cromatografía Líquida de Alta Presión/métodosRESUMEN
Cinnamon is one of the most popular spices used in cuisines worldwide. Among its different species, Ceylon cinnamon ("true cinnamon") is the one with the most health benefits due to its high concentration in the antioxidant eugenol and the ultra-low content of the hepatotoxic compound coumarin. However, the higher price of Ceylon cinnamon makes it vulnerable to fraudulent adulteration with more economic species of cinnamon, such as Cassia and Saigon. Thus, for the detection of frauds in cinnamon samples, a HPLC-UV method was developed for the determination of 4 characteristic cinnamon compounds: eugenol, cinnamaldehyde, coumarin and cinnamic acid. The obtained data were analyzed by PLS to attain not only the authentication of cinnamon species but also the detection and quantification of partial adulterations. Several mixtures prepared in the laboratory using different cinnamon powder samples considered 'pure' Ceylon, Cassia or Saigon were tested, concluding that the proposed approach allows a clear identification of Ceylon cinnamon and a suitable quantification of the Ceylon: non-Ceylon ratio regardless of the commercial sample selected (RMSE <0.06 for both training and test sets).
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Cinnamomum zeylanicum , Eugenol , Cromatografía Líquida de Alta Presión/métodos , Quimiometría , Cumarinas/análisisRESUMEN
The Chinese herb Qianghuo is an antiphlogistic herb with many effects and complex components. In this study, the chemical composition of Qianghuo and its components in rat plasma after oral administration were investigated using ultra-high-performance liquid chromatography coupled with quadrupole-time-of-flight tandem mass spectrometry (UPLC-Q-TOF-MS/MS). The extracts, blank plasma, and plasma containing the drug were analyzed by mass spectrometry, and data collected in both positive and negative ion modes were analyzed using Masslynx software, and the structures were confirmed by combining the compound fragment ions and mass spectrometry cleavage pathways. A total of 62 in vitro chemical components were identified, including 27 coumarins, 18 organic acids, 5 amino acids, 5 glycosides, 2 flavonoids, 4 nucleotides, and 1 ester, which were summarized from the obtained compounds in terms of their possible cleavage patterns. Among the identified 31 compounds in rat plasma, 21 were prototypes, mostly coumarins, organic acids, and flavonoids, and 10 were metabolites, which were mainly generated via hydroxylation and methylation pathways. Based on these, this study provides a theoretical foundation for quality control and basic research on Qianghuo medicinal substances.
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Medicamentos Herbarios Chinos , Espectrometría de Masas en Tándem , Ratas , Animales , Espectrometría de Masas en Tándem/métodos , Medicamentos Herbarios Chinos/química , Cromatografía Líquida de Alta Presión/métodos , Estructura Molecular , Flavonoides/análisis , Ácidos , Cumarinas/análisisRESUMEN
Because Ancathia igniaria (Spreng.) DC. (Cirsium igniarium Spreng.) has been segregated as a monotypic genus from the genus Cirsium on the basis of phylogenetic data, chemotaxonomic differences are of interest to detect in the composition of polyphenolic components of aerial plant parts. Phenolic compounds are of chemotaxonomic significance in a number of genera and families. The polyphenolic profile of aerial parts was therefore compared for Cirsium esculentum (Siev.) C.A. Mey., Cirsium serratuloides (L.) Hill, and A. igniaria. The last two species were for the first time examined in this context. The compounds were identified against known standard via high-performance liquid chromatography (HPLC). The species of the genus Cirsium were found to have similar compositions of simple phenols, but differ in the set of flavonoids. Six to eight phenolic compounds were detected in the species, and three simple polyphenols (syringin, chlorogenic acid, and ethyl gallate) proved to be common. The flavonoid profiles of aerial parts included rutin in both Cirsium species. Cymaroside and quercetin-3-O-ß-D-diglucoside-O-α-L-rhamnoside were species specific for C. serratuloides; salipurposide and hyperoside, for C. esculentum. An extract of A. igniaria aerial parts contained cinaroside (like in C. serratuloides), chrysin 7-O-glucoside, and eriodictyol. A greater difference in flavonoid composition was observed between the genera Cirsium and Ancathia. Data on phenolic compound composition are of importance for chemosystematics and use of plants as medicinal raw materials. The total content of coumarins, aglycones, and flavonoid glycosides in the species was determined by a spectrophotometric method. The contents of flavonoids and coumarins in C. esculentum and C. serratuloides were comparable and exceeded their contents in A. igniaria. Thus, A. igniaria proved to differ from the genus Cirsium in the quantitative and qualitative composition of phenolic compounds.
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Asteraceae , Cirsium , Cirsium/química , Filogenia , Flavonoides/análisis , Flavonoides/química , Fenoles/análisis , Fenoles/química , Componentes Aéreos de las Plantas/química , Cumarinas/análisis , Extractos Vegetales/análisis , Extractos Vegetales/químicaRESUMEN
Fermented tea (FT) using a single Eurotium cristatum strain can produce a pleasant fungal-flowery aroma, which is similar to the composite aroma characteristic of minty, flowery, and woody aromas, but its molecular basis is not yet clear. In this study, solvent-assisted flavor evaporation and gas chromatography-mass spectrometry/olfactometry were applied to isolate and identify volatiles from the FT by E. cristatum. The application of an aroma extract dilution analysis screened out 43 aroma-active compounds. Quantification revealed that there were 11 odorants with high odor threshold concentrations. Recombination and omission tests revealed that nonanal, methyl salicylate, decanoic acid, 4-methoxybenzaldehyde, α-terpineol, phenylacetaldehyde, and coumarin were the major odorants in the FT. Addition tests further verified that methyl salicylate, 4-methoxybenzaldehyde, and coumarin were the key odorants for fungal-flowery aroma, each corresponding to minty, woody, and flowery aromas, respectively. 4-Methoxybenzaldehyde and coumarin were newly found odorants for fungal-flowery aroma in FT, and 4-methoxybenzaldehyde had not been reported as a tea volatile compound before. This finding may guide future industrial production optimization of FT with improved flavor.
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Odorantes , Compuestos Orgánicos Volátiles , Odorantes/análisis , Olfato , Aromatizantes/análisis , Compuestos Orgánicos Volátiles/análisis , Olfatometría , Cumarinas/análisis , TéRESUMEN
Anticoagulant rodenticides (ARs) are used to control rodent populations. Poisoning of non-target species can occur by accidental consumption of commercial formulations used for rodent control. A robust method for determining ARs in animal tissues is important for animal postmortem diagnostic and forensic purposes. We evaluated an ultra-performance liquid chromatography coupled with mass spectrometry (UPLC-MS) method to quantify 8 ARs (brodifacoum, bromadiolone, chlorophacinone, coumachlor, dicoumarol, difethialone, diphacinone, warfarin) in a wide range of animal (bovine, canine, chicken, equine, porcine) liver samples, including incurred samples. We further evaluated UPLC-MS in 2 interlaboratory comparison (ILC) studies; one an ILC exercise (ICE), the other a proficiency test (PT). The limits of detection of UPLC-MS were 0.3-3.1 ng/g, and the limits of quantification were 0.8-9.4 ng/g. The recoveries obtained using UPLC-MS were 90-115%, and relative SDs were 1.2-13% for each of the 8 ARs for the 50, 500, and 2,000 ng/g spiked liver samples. The overall accuracy from the laboratories participating in the 2 ILC studies (4 and 11 laboratories for ICE and PT studies, respectively) were 86-118%, with relative repeatability SDs of 3.7-11%, relative reproducibility SDs of 7.8-31.2%, and Horwitz ratio values of 0.5-1.5. Via the ILC studies, we verified the accuracy of UPLC-MS for AR analysis in liver matrices and demonstrated that ILC can be utilized to evaluate performance characteristics of analytical methods.
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Anticoagulantes , Técnicas de Química Analítica , Cumarinas , Indanos , Rodenticidas , Animales , Técnicas de Química Analítica/métodos , Técnicas de Química Analítica/normas , Técnicas de Química Analítica/veterinaria , Rodenticidas/análisis , Anticoagulantes/análisis , Hígado/química , Cromatografía Líquida con Espectrometría de Masas , Indanos/análisis , Cumarinas/análisis , Límite de Detección , Reproducibilidad de los ResultadosRESUMEN
The present study explored the consistency of the content proportions of active components of Aurantii Fructus and analyzed the influencing factors based on three-dimensional multi-component analysis. A total of 839 Aurantii Fructus samples in 65 research articles were analyzed using the three-dimensional multi-component analysis mode. The content data of flavonoid components(naringin, hesperidin, neohesperidin, narirutin, and nobiletin), coumarin components(meranzin and gluconolactone), and alkaloid(synephrine) in 386 samples which met the criteria of 2020 edition of the Chinese Pharmacopoeia were extracted and adjusted to percentages, and the content ratios between components were calculated. The influencing factors of Aurantii Fructus quality were analyzed. The results showed content ratios of components as follows: neohesperidinâ¶naringin in the range of 0.4-1.2; narirutinâ¶naringin in the range of 0.02-0.16; hesperidinâ¶naringin in the range of 0.01-0.3; nobiletinâ¶naringin in the range of 0.000 588 3-0.069 68; synephrineâ¶naringin in the range of 0.02-0.042; gluconolactoneâ¶naringin in the range of 0.001-0.01; meranzinâ¶naringin in the range of 0.000 4-0.035. The quality of Aurantii Fructus was closely related to the origin, variety, harvesting time, and processing method of medicinal materials. Harvesting time had a greater impact on the quality of Aurantii Fructus, and the origin and variety had a certain impact on the quality of Aurantii Fructus. The findings of this study indicated that the ratios between flavonoid components, flavonoids and coumarin components, and flavonoids and alkaloids fluctuated. The production base should optimize the varieties, harvesting period, and processing methods of Aurantii Fructus to provide a scientific basis for the production of high-quality Aurantii Fructus.
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Citrus , Medicamentos Herbarios Chinos , Flavonoides/análisis , Frutas/química , Cumarinas/análisis , Cromatografía Líquida de Alta Presión/métodosRESUMEN
There is an urgent need to develop highly sensitive and selective fluorescence probes for ONOO- in mitochondria. Herein, we reported a ratiometric fluorescent probe COUS with coumarin-cyanine hybrid as fluorophore and C = C bonds as reaction sites of ONOO-. The probe COUS was sensitive and selective to ONOO-, and had a large fluorescence emission shift (239 nm) as well as a low detection limit (41.88 nM). Moreover, COUS showed the mitochondrial targeting ability, and the targeting moiety could dissociate from the probe when reacting with ONOO-, which enabled COUS to accurately detect ONOO- in mitochondria.
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Colorantes Fluorescentes , Ácido Peroxinitroso , Colorantes Fluorescentes/química , Ácido Peroxinitroso/análisis , Mitocondrias/química , Cumarinas/análisis , FluorescenciaRESUMEN
BACKGROUND: Skimmin, a potential agent for treating postpartum stroke, is one of the most important coumarins extracted from the leaves of skimmia. OBJECTIVE: In this study, a specific, sensitive, and simple high-performance liquid chromatography with tandem mass spectrometry (HPLC-MS/MS) method for the simultaneous determination of skimmin and its metabolite umbelliferone in rat plasma was established and validated. METHOD: Chromatographic separation was performed by an Inertsil ODS-3 column (50 mm × 4.6 mm, 5 µm) with a mobile phase consisting of 0.1% formic acid in distilled water-acetonitrile at a flow rate of 0.5 mL/min with gradient elution mode. All analytes were detected and quantified in negative multiple reaction monitoring (MRM). RESULTS: All calibration curves showed good linearity (r > 0.995) over the concentration range of 10-10â000 and 2.0-2000 ng/mL for skimmin and umbelliferone, respectively. The selectivity, sensitivity, extraction recovery, matrix effect, and stability met all requirements. CONCLUSIONS: The analysis method was successfully applied to the pharmacokinetic study of skimmin and umbelliferone in rats following oral administration of skimmin at the doses of 10, 30, and 90 mg/kg. With the exception of AUC(0-∞) and Cmax, MRT and Cl/F of skimmin had significant statistical difference with the increasing doses. Skimmin might exhibit nonlinear pharmacokinetic characteristics in rats. HIGHLIGHTS: This was the first study to investigate the pharmacokinetic characteristics of skimmin as a candidate agent for treating postpartum stroke.
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Cumarinas , Espectrometría de Masas en Tándem , Femenino , Ratas , Animales , Cromatografía Liquida/métodos , Espectrometría de Masas en Tándem/métodos , Cumarinas/análisis , Cumarinas/farmacocinética , Umbeliferonas/análisis , Cromatografía Líquida de Alta Presión/métodos , Reproducibilidad de los ResultadosRESUMEN
In this paper, we report about the application of a sensitive fluorescent derivatization reagent Coumarin151-N-Hydroxysuccinimidyl Carbamate (Cou151DSC) for amino compounds using high-performance liquid chromatography (HPLC) compatible with ultraviolet (UV), fluorescence detector (FLD) and electrospray ionization - tandem mass spectrometry (ESI-MS/MS)-positive mode. We optimized derivatization procedure and validated an analytical method to determine 24 amino acids in Kvass drink using Norvaline as an internal standard. Compared to 6-Aminoquinolyl-N-Hydroxysuccinimidyl Carbamate (6-AQC), the derivatization with Cou151 DSC is faster and milder, for 5 min at 40°C instead of 15 min at 55°C. The limit of quantitation (LOQ, pmol on column) for 21 amino acids in this work is lower 1.1-30.0 times than values obtained with 6-AQC. The derivatives have excitation wavelength at 355 nm and emission wavelength at 486 nm. Their MS/MS fragmentation behaviors were examined together with 23 other amino compounds. We found three possibilities to lose a neutral group which can be Coumarin 151 isocyanate Cou151NCO (255 Da), amine Coumarin 151 (229 Da) or urea Cou151CONH2 (272 Da). The accuracy of the proposed method was within 83-107% with good relative standard deviations (RSDs) of equal or less than 6%. The recoveries were from 82 to 120% in four spiked concentrations, repeatability was between 0 and 14%. The intra- and inter-day precision are less than 13% and 18%, respectively.
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Aminoácidos , Espectrometría de Masas en Tándem , Cromatografía Liquida/métodos , Aminoácidos/análisis , Indicadores y Reactivos , Cromatografía Líquida de Alta Presión/métodos , Aminas , Cumarinas/análisisRESUMEN
Qijiao Shengbai Capsules(QJ) are a common Miao medicine serving as an adjuvant cancer therapy in clinical practice.QJ consists of seven medicinal materials such as Astragalus membranaceus and Lespedeza buergeri.Its chemical components have not been clarified and the quality control needs to be improved.In this study, LC-IT-TOF-MS was used to comprehensively collect MS~1 and MS~2 fragment information of QJ and rapidly identify the chemical compositions.The chromatographic separation was performed on the Capcell core ADME column(2.1 mm×150 mm, 2.7 µm) with 0.1% formic acid aqueous solution(A) and acetonitrile(B) as mobile phases for gradient elution.High-resolution mass spectrometric information was obtained by scanning in the positive and negative ion ESI modes.A total of 107 compounds were structurally identified according to the deduced MS fragmentation patterns and comparison with standards and data reported in the literature, including 54 flavonoids, 16 phthalides, 13 alkaloids, 12 phenolic acids, 7 saponins, 2 coumarins, 2 condensed tannins, and 1 purine.This study clarified the chemical composition of QJ and provided references for the improvement of its quality standards and the elucidation of its medicinal substances.
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Alcaloides , Medicamentos Herbarios Chinos , Proantocianidinas , Saponinas , Acetonitrilos , Cápsulas , Cromatografía Líquida de Alta Presión , Cumarinas/análisis , Medicamentos Herbarios Chinos/química , Flavonoides/análisis , Formiatos , Proantocianidinas/análisis , Purinas , Espectrometría de Masas en TándemRESUMEN
Shengjiang Xiexin decoction, a traditional Chinese medical formula, has been utilized to alleviate the delayed-onset diarrhea induced by irino tecan. However, the chemical constituents of this formula and the activities of its constituents remain unclear. In this study, ultrahigh-performance liquid chromatography-quadrupole/orbitrap high-resolution mass spectrometry was employed to comprehensively analyze the chemical constituents of Shengjiang Xiexin decoction. A total of 270 components, including flavonoids, coumarins, triterpenoids, alkaloids, diarylheptanoids and others, were identified or characterized. Multidrug resistance-associated protein 2 is an efflux transporter responsible for regulating drug absorption. A total of 20 characteristic components from the formula were selected to evaluate their effects on the function of multidrug resistance-associated protein 2 using the vesicular transport assay. Glycyrrhizic acid and glycyrrhetinic acid were identified as potential multidrug resistance-associated protein 2 inhibitors, while 9 flavonoid aglycones increased the uptake of the substrate [3 H]-estradiol 17-ß-glucuronide in the vesicles. This was the first systematic investigation of the chemical constituents from Shengjiang Xiexin decoction and the effect of its characteristic components on the transporter. The results offered a basis for further exploring the detoxification mechanisms of this formula and its interactions with other drugs.
Asunto(s)
Alcaloides , Medicamentos Herbarios Chinos , Ácido Glicirretínico , Cromatografía Líquida de Alta Presión/métodos , Cromatografía Liquida , Cumarinas/análisis , Diarilheptanoides , Medicamentos Herbarios Chinos/química , Estradiol , Flavonoides/análisis , Glucurónidos , Ácido Glicirrínico/análisis , Espectrometría de Masas/métodos , Proteína 2 Asociada a Resistencia a Múltiples MedicamentosRESUMEN
In present study, an integrating UPLC-QTOF-MS/MS chemical profiling and UPLC-TQ-MS/MS quantification strategy was developed for the holistic quality evaluation of Hibisci Mutabilis Folium (HMF), a traditional Chinese medicinal herb. Using UPLC-QTOF-MS/MS, a total of 58 components were characterized in HMF sample, of which 36 flavonoids, 3 coumarins, 7 organic acids and 4 triterpene acids were unambiguously identified by comparing the chromatographic behavior and mass spectrum with that of reference compounds, or tentatively assigned by comparing the fragmentation pathways and characteristic fragment ions with that of reference substances and/or published literatures together with mass defect filtering (MDF) screening. Meanwhile, 29 representative major components, including 16 flavonoids, 3 coumarins, 7 organic acids and 3 triterpene acids, were quantified by a newly established UPLC-TQ-MS/MS method that was validated in terms of linearity, sensitivity, precision, repeatability, accuracy and stability. The integrated strategy was applied to simultaneously qualifying and quantifying HMF commercial samples and self-prepared samples harvested in difference periods and dried with different methods. It was found that the contents of 29 major components were obviously different in commercial samples or self-prepared samples, suggesting that the holistic quality of HMF commercial samples was inconsistent, and harvesting period and drying method might be the main factors that affect the holistic quality consistency of commercial HMF samples. Standardized harvesting period and drying method should be established for ensuring the holistic quality consistency of HMF.
Asunto(s)
Medicamentos Herbarios Chinos , Triterpenos , Cromatografía Líquida de Alta Presión/métodos , Cumarinas/análisis , Medicamentos Herbarios Chinos/química , Flavonoides/análisis , Espectrometría de Masas en Tándem/métodos , Triterpenos/análisisRESUMEN
INTRODUCTION: The genus Stachys L., belonging to the family Lamiaceae, is one of the largest genera with remarkable medicinal properties. Plants of this genus produce a broad range of secondary metabolites. OBJECTIVES: Due to the incomplete comprehensive assessment of chemical profiles in Stachys species, we conducted an untargeted metabolomics study and identified potential biomarkers in the six sections of Stachys with chemotaxonomic importance. MATERIAL AND METHODS: Dried leaves of 17 taxa were utilized for analysis of all the constituents using HPLC-MQ-API-MS. The obtained data were processed and analyzed using multivariate statistical methods, including heatmaps, PLS-DA score plots, functional analysis of metabolic pathways, metabolite set enrichment analysis, and biomarker and network analysis. RESULTS: Among the 129 metabolites, 111 flavonoids and 18 non-flavonoids were recognized. The most represented flavonoids, including 41 flavones and 20 flavonols, displayed remarkable abundance. In non-flavonoid compounds, a total of six coumarins and six phenolic acids were present at high levels. In terms of approved markers in six sections, 76 chemical compounds, mainly flavonoids, coumarins, quinic acids, and cinnamic acids, were identified as potential biomarkers or chemotaxonomic indicators. Accordingly, the taxonomic complexities of some Stachys species in sections Fragilicaulis, Aucheriana, and Setifolia were properly resolved. CONCLUSION: An HPLC-MS/MS-based metabolomics approach integrated with multivariate statistical methods was employed to identify (1) valuable markers and analyze metabolic diversity and (2) predict the pharmaceutical properties of Stachys species. The obtained chemical profiles provide a new perspective for investigation of the Stachys genus.