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1.
J Pharm Biomed Anal ; 177: 112813, 2020 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-31472326

RESUMO

Differentiated composition in precursor ions for different subclasses of ginsenosides in the negative electrospray-ionization mode has been reported, which lays a foundation for the sorted and untargeted identification of ginsenosides. Carboxyl-free ginsenosides simultaneously from Panax ginseng, P. quinquefolius, and P. notoginseng, were comprehensively characterized and statistically compared. A neutral loss/product ion scan (NL-PIS) incorporated untargeted profiling approach, coupled to ultra-high performance liquid chromatography, was developed on a linear ion-trap/Orbitrap mass spectrometer for characterizing carboxyl-free ginsenosides. It incorporated in-source fragmentation (ISF) full scan-MS1, mass tag-MS2, and product ion scan-MS3. Sixty batches of ginseng samples were analyzed by metabolomics workflows for the discovery of ginsenoside markers. Using formic acid (FA) as the additive, carboxyl-free ginsenosides (protopanaxadiol-type, protopanaxatriol-type, and octillol-type) gave predominant FA-adducts, while rich deprotonated molecules were observed for carboxyl-containing ginsenosides (oleanolic acid-type and malonylated) when source-induced dissociation (SID) was set at 0 V. Based on the NL transition [M+FA‒H]- > [M-H]- and the characteristic sapogenin product ions, a NL-PIS approach was established. It took advantage of the efficient full-information acquisition of ISF-MS1 (SID: 50 V), the high specificity of mass tag (NL: 46.0055 Da)-induced MS2 fragmentation, and the substructure fragmentation of product ion scan-MS3. We could characterize 216 carboxyl-free ginsenosides, and 21 thereof were potentially diagnostic for the species differentiation. Conclusively, sorted and untargeted characterization of the carboxyl-free ginsenosides was achieved by the established NL-PIS approach. In contrast to the conventional NL or PIS-based survey scan strategies, the high-accuracy MSn data obtained can enable more reliable identification of ginsenosides.


Assuntos
Ginsenosídeos/análise , Espectrometria de Massas/métodos , Panax/química , Cromatografia Líquida de Alta Pressão/métodos , Íons/análise , Panax/classificação
2.
Front Pharmacol ; 10: 845, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31417403

RESUMO

The sourcing of plants from multiple botanical origins is a common phenomenon in traditional Chinese medicines. Uncaria Stem with Hooks (UHs) are approved for using five botanical origins in the Chinese Pharmacopoeia (2015 Edition). All five UHs are commonly used for treating hypertension even though the plants have different chromatographic fingerprints based on our previous study. However, their hypotensive effects and metabolic phenotypes have not been fully studied. In the present study, spontaneously hypertensive rats (SHRs) were orally administered five aqueous extracts (4 g crude drug/kg) prepared from the different UHs over a 6-week period. Systolic blood pressure (SBP) was measured every week, and urine was collected after SBP measurement. Untargeted metabonomics was performed using ultra performance liquid chromatography (UPLC) coupled with an LTQ-Orbitrap mass spectrometer. Bidirectional orthogonal projection to latent structures discriminant analysis (O2PLS-DA), Student's t test, and correlation analysis were used for pattern recognition and the selection of significant metabolites. A similar and prolonged reduction in SBP was observed in each of the groups given the five different UHs, while the metabolic profiles were perturbed slightly compared with that of SHR. Further analysis has shown that only a few common, different components were observed within the five groups, which showed the similar antihypertensive effect in spite of the distinct metabolic pathways due to their different alkaloid composition. These results help in understanding the mechanisms of the phenomenon "different species, same effect" of UHs.

3.
J Chromatogr A ; 1603: 179-189, 2019 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-31255247

RESUMO

Comprehensive analysis and identification of chemical components are very important to evaluate the efficacy and safety of traditional Chinese medicine (TCM). Meanwhile, the discovery of new natural compounds is of great significance for drug exploitation and development. Although two-dimensional liquid chromatography (2D LC) systems expand the peak capacity and improve selectivity and resolution, interpreting the post-processing data is tedious and time-consuming. In this study, an off-line two-dimensional liquid chromatography/ultra-high performance supercritical fluid chromatography tandem quadrupole time-of-flight mass spectrometry (2D LC/UHPSFC-Q-TOF/MS) system was established for systematic chromatographic separation and identification of bufadienolides. Subsequently, the Global Natural Product Social Molecular Networking (GNPS) was applied for dereplication of chemical components of adjacent fractions with high efficiency and accuracy. The key parameters which affected separation and detection with respect to chromatographic conditions and mass spectrometry conditions were optimized. The extract of Venenum Bufonis was fractionated into forty fractions by first-dimensional reversed phase high-performance liquid chromatography (HPLC), which were further analyzed by the second-dimensional UHPSFC-Q-TOF/MS in positive ion mode. The data of forty fractions was imported into GNPS and processed automatically within about five hours. Furthermore, the chemical components with similar featured fragments were classified into the same cluster, which was helpful for components identification. A total of 229 bufadienolides were characterized and two subclasses of compounds (bufogenins conjugated with carboxylic acid and N-heterocyclic bufogenins) were found in Venenum Bufonis for the first time. In addition, UHPSFC exhibited powerful separation ability of isomers in Venenum Bufonis. In this analysis, two new compounds were isolated and fully characterized by NMR verifying the feasibility of this combined analytical strategy. This integrated strategy can improve the efficiency in the detection of new compounds and offer greater observation of isomers from medicinal herbs and other natural sources.


Assuntos
Bufanolídeos/isolamento & purificação , Animais , Produtos Biológicos/análise , Bufanolídeos/química , Bufonidae , Cromatografia Líquida de Alta Pressão , Cromatografia de Fase Reversa , Espectroscopia de Ressonância Magnética , Espectrometria de Massas em Tandem
4.
J Ethnopharmacol ; 237: 215-235, 2019 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-30905791

RESUMO

ETHNOPHARMACOLOGICAL RELEVANCE: The animal medicine of Venenum Bufonis (VB), a product of the secretions of Bufo gargarizans Cantor or B. melanostictus Schneider, has long been used as a traditional Chinese medicine (TCM) for the treatment of sunstroke and faint, acute filthy disease - abdominal pain or vomiting and diarrhea, etc. AIM OF THE REVIEW: This review is aimed at providing the comprehensive and up-to-date information of VB as regards its ethnopharmacological uses, constituents and their metabolism, pharmacokinetics, pharmacology and toxicology, all of which could be used as fundamental data for future research as well as development of new drugs. MATERIALS AND METHODS: The information and data about the studies of VB were collected from scientific journals, material medica, historical documents, library, and electronic databases (PubMed, Google Scholar, Science Direct, Researchgate, Web of Science and CNKI). RESULTS: To date, about 142 bufadienolides and 16 indole alkaloids have been isolated from VB in total. The extract and isolated compounds showed a wide range of in vitro and in vivo pharmacologic effects, such as cardiotonic, anti-tumor, antinociceptive, anti-inflammatory, anesthetic and antimicrobial activities. Especially, bufadienolides have been extensively studied due to its powerful anti-tumor activities against various cancer cells. Furthermore, their metabolites and metabolic pathways were concluded in detail, and the main metabolic pathways of bufadienolides were hydroxylation, 3-isomerization, 3-keto, 16-hydrolyzation, 3-O-sulfate and 3-O-glucuronide. CONCLUSIONS: Although VB possesses significant anti-tumor effect against various cancer cell lines, the development of new drugs still remains to be a challenge due to its pharmacodynamic effects in vivo, druggability and toxicology. The main problem lies in its side effects in vivo, poor bioavailability, fast metabolism, cardiotoxicity and neurovirulence. Besides, studies on its metabolism and toxicology in vitro and in vivo, as well as clinical trials should be further conducted for the new drug development and the establishment of optimal dosage of consumption of its administration.


Assuntos
Bufanolídeos , Medicina Tradicional Chinesa , Animais , Bufanolídeos/química , Bufanolídeos/farmacologia , Bufanolídeos/uso terapêutico , Humanos , Compostos Fitoquímicos/análise
5.
Molecules ; 23(11)2018 Nov 19.
Artigo em Inglês | MEDLINE | ID: mdl-30463184

RESUMO

The mass spectrometry (MS) has been widely used for profiling chemical components of traditional Chinese medicine (TCM). However, there are few studies reporting quality control of TCM based on mass spectrometry fingerprint (MSF) due to its complicated operation and high cost. The aim of this study was to extend the application of MSF for quality evaluation of TCM. In this study, an MSF based on single quadrupole mass spectrometry method was established, and was successfully used for the quality control of Venenum bufonis (VB), a famous TCM which was used clinically for cancer treatment in China. The results showed that the superiority of MSF for more chemical information exposure and the finding of more potential chemical markers (eight versus four) compared with the traditional photo-diode array (a kind of ultra violet detector, PDA). Besides, the performance of MSF was also validated by similarity and principle component analysis (PCA) of MS data acquired on two other mass spectrometry (low-resolution, triple quadrupole, QQQ, and high-resolution, quadruple time-of-flight, Q-TOF), showing high consistency with QQQ and Q-TOF, but robustness with few parameters' settings. Based on our study, MSF could be widely applied for the quality control of TCM.


Assuntos
Bufanolídeos/análise , Medicamentos de Ervas Chinesas/análise , Espectrometria de Massas/métodos , Análise de Componente Principal/métodos , Bufanolídeos/química , Cromatografia Líquida de Alta Pressão/métodos , Medicamentos de Ervas Chinesas/química , Extratos Vegetais/análise , Extratos Vegetais/química , Controle de Qualidade
6.
J Chromatogr A ; 1571: 213-222, 2018 Oct 12.
Artigo em Inglês | MEDLINE | ID: mdl-30146372

RESUMO

Specific analytical approaches that enable untargeted profiling of modified metabolites are in great need. An untargeted profiling strategy, by integrating in-source collision-induced dissociation (ISCID)-MS1, mass tag-MS2, and neutral loss scan-MS3, is established on a linear ion-trap/Orbitrap mass spectrometer coupled to ultra-high performance liquid chromatography. This strategy is applied to screen malonylginsenosides from three reputable Panax species (P. ginseng, P. quinquefolius, and P. notoginseng). In light of the preferred neutral elimination of CO2 and entire malonyl substituent (C3H2O3) in the negative electrospray ionization mode, a pseudo-neutral loss scan (PNL) method was established by applying ISCID energy 40 V in MS1, mass tag 43.9898 Da oriented CID-MS2 at normalized collision energy (NCE) 30%, and neutral loss 43.9898 Da-triggered high-energy C-trap dissociation-MS3 at NCE 70%. The PNL approach achieved a high coverage of targeted malonylginsenosides but introduced less false positives. It displayed comparable performance to a precursor ions list-driven targeted approach we have reported in the profiling and characterization of malonylginsenosides, but could avoid complex data processing. Totally 178 malonylginsenosides were characterized from the roots, leaves, and flower buds of P. ginseng, P. quinquefolius, and P. notoginseng, and most of them possess potentially new structures. The compositions of malonylginsenosides identified from these three Panax species are similar, and only malonylginsenoside Rb2 and some minor may have potential chemotaxonomic significance. In conclusion, we provide a potent analytical strategy for the direct and efficient screening of modified metabolites, which may have broad applications in the fields of metabolomics, drug metabolism, and natural product research.


Assuntos
Ginsenosídeos/análise , Panax/química , Espectrometria de Massas por Ionização por Electrospray/métodos , Cromatografia Líquida de Alta Pressão , Flores/química , Flores/metabolismo , Ginsenosídeos/química , Panax/metabolismo , Folhas de Planta/química , Folhas de Planta/metabolismo , Raízes de Plantas/química , Raízes de Plantas/metabolismo
7.
J Sep Sci ; 41(8): 1888-1895, 2018 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-29333638

RESUMO

Phenolic acids are the major water-soluble components in Salvia miltiorrhiza (>5%). According to previous studies, many of them contribute to the cardiovascular effects and antioxidant effects of S. miltiorrhiza. Polymeric phenolic acids can be considered as the tanshinol derived metabolites, e.g., dimmers, trimers, and tetramers. A strategy combined with tanshinol-based expected compounds prediction, total ion chromatogram filtering, fragment ion searching, and parent list-based multistage mass spectrometry acquisition by linear trap quadropole-orbitrap Velos mass spectrometry was proposed to rapid profile polymeric phenolic acids in S. miltiorrhiza. More than 480 potential polymeric phenolic acids could be screened out by this strategy. Based on the fragment information obtained by parent list-activated data dependent multistage mass spectrometry acquisition, 190 polymeric phenolic acids were characterized by comparing their mass information with literature data, and 18 of them were firstly detected from S. miltiorrhiza. Seven potential compounds were tentatively characterized as new polymeric phenolic acids from S. miltiorrhiza. This strategy facilitates identification of polymeric phenolic acids in complex matrix with both selectivity and sensitivity, which could be expanded for rapid discovery and identification of compounds from complex matrix.


Assuntos
Hidroxibenzoatos/análise , Polímeros/análise , Salvia miltiorrhiza/química , Íons/análise , Espectrometria de Massas
8.
Planta Med ; 84(6-07): 449-456, 2018 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-29216668

RESUMO

It remains a challenge to establish new monographs for herbal drugs derived from multiple botanical sources. Specifically, the difficulty involves discriminating and quantifying these herbs with components whose levels vary markedly among different samples. Using Uncaria stem with hooks as an example, a characteristic chromatogram was proposed to discriminate its five botanical origins and to quantify its characteristic components in the chromatogram. The characteristic chromatogram with respect to the components of Uncaria stem with hooks with the five botanical origins was established using 0.02% diethylamine and acetonitrile as the mobile phase. The total analysis time was 50 min and the detection wavelength was 245 nm. Using the same chromatogram parameters, the single standard to determine multicomponents method was validated to simultaneously quantify nine indole alkaloids, including vincosamide, 3α-dihydrocadambine, isocorynoxeine, corynoxeine, isorhynchophylline, rhynchophylline, hirsuteine, hirsutine, and geissoschizine methyl ether. The results showed that only the Uncaria stem with hooks from Uncaria rhynchophylla, the most widely used in the herbal market, showed the presence of these nine alkaloids. The conversion factors were 1.27, 2.32, 0.98, 1.04, 1.00, 1.02, 1.26, 1.33, and 1.25, respectively. The limits of quantitation were lower than 700 ng/mL. The total contents of 31 batches of Uncaria stem with hooks were in the range of 0.1 - 0.6%, except for Uncaria hirsuta Havil and Uncaria sinensis (Oliv.) Havil. The results also showed that the total content of indole alkaloids tended to decrease with an increase in the hook diameter. This showed that the characteristic chromatogram is practical for controlling the quality of traditional Chinese medicines with multiple botanical origins.


Assuntos
Caules de Planta/química , Uncaria/química , Cromatografia Líquida de Alta Pressão/métodos , Medicina Herbária/métodos , Alcaloides Indólicos/análise , Controle de Qualidade
9.
Planta Med ; 83(6): 557-564, 2017 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-27992941

RESUMO

Salvia miltiorrhiza is one of the most used herbal medicines for the treatment of a wide range of diseases in China. Decoction pieces and Chinese patent medicines from S. miltiorrhiza are the two main types of products used by patients. Other relatively new products of S. miltiorrhiza, like injections and ultrafine granular powder (D90 < 45 µm before granulation), are also increasingly used nowadays. With the growing usage of new products of S. miltiorrhiza, their chemical components and pharmacological effects, compared to the traditional decoction pieces, are attracting attention. In this work, the chemical profiles of two types of products from S. miltiorrhiza (one is traditional "decoction pieces", the other is modern "ultrafine granular powder") were compared via similarity analysis and discriminated via multivariate analysis, e.g., hierarchical cluster analysis, principal component analysis, and partial least squares discrimination analysis. A new adamantane stationary phase column was used to establish informative chemical profiles of them. The mean similarity correlation coefficient (> 0.987) revealed that ultrafine granular powder and decoction pieces of S. miltiorrhiza were consistent between each other and stable between different batches. Two types of S. miltiorrhiza products were clearly resolved from each other by hierarchical cluster analysis, principal component analysis, and partial least squares discrimination analysis. Compounds responsible for the discrimination results were further characterized by ESI-MS/MS. Eventually, 62 compounds selected as characteristic markers for evaluation were characterized or tentatively characterized. This result will facilitate the further comparison of these two types of S. miltiorrhiza products in pharmacology and pharmacokinetics.


Assuntos
Medicamentos de Ervas Chinesas/química , Salvia miltiorrhiza/química , Medicamentos de Ervas Chinesas/isolamento & purificação , Análise dos Mínimos Quadrados , Pós , Análise de Componente Principal , Espectrometria de Massas em Tandem
10.
J Pharm Biomed Anal ; 134: 149-157, 2017 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-27915192

RESUMO

Drug metabolites identification and construction of metabolic profile are meaningful work for the drug discovery and development. The great challenge during this process is the work of the structural clarification of possible metabolites in the complicated biological matrix, which often resulting in a huge amount data sets, especially in multi-samples in vivo. Analyzing these complex data manually is time-consuming and laborious. The object of this study was to develop a practical strategy for screening and identifying of metabolites from multiple biological samples efficiently. Using hirsutine (HTI), an active components of Uncaria rhynchophylla (Gouteng in Chinese) as a model and its plasma, urine, bile, feces and various tissues were analyzed with data processing software (Metwork), data mining tool (Progenesis QI), and HR-MSn data by ultra-high performance liquid chromatography/linear ion trap-Orbitrap mass spectrometry (U-HPLC/LTQ-Orbitrap-MS). A total of 67 metabolites of HTI in rat biological samples were tentatively identified with established library, and to our knowledge most of which were reported for the first time. The possible metabolic pathways were subsequently proposed, hydroxylation, dehydrogenation, oxidation, N-oxidation, hydrolysis, reduction and glucuronide conjugation were mainly involved according to metabolic profile. The result proved application of this improved strategy was efficient, rapid, and reliable for metabolic profiling of components in multiple biological samples and could significantly expand our understanding of metabolic situation of TCM in vivo.


Assuntos
Alcaloides/metabolismo , Medicamentos de Ervas Chinesas/metabolismo , Espectrometria de Massas em Tandem/métodos , Uncaria , Alcaloides/análise , Animais , Cromatografia Líquida de Alta Pressão/métodos , Medicamentos de Ervas Chinesas/análise , Masculino , Espectrometria de Massas/métodos , Redes e Vias Metabólicas/fisiologia , Ratos , Ratos Wistar
11.
Anal Bioanal Chem ; 408(14): 3881-90, 2016 05.
Artigo em Inglês | MEDLINE | ID: mdl-27055884

RESUMO

Animal-derived medicines have been a vital component for traditional Chinese medicine. However, their quality control remains challenging due to the large polarity of the contained endogenous small molecules (ESMs) that are difficult to separate by reversed-phase HPLC. Herein, an intelligentized strategy by ultra-high performance hydrophilic interaction chromatography/quadrupole time-of-flight mass spectrometry (HILIC/QTOF-MS(E)) is presented, and used for the ESMs characterization and differentiation of two geographic origins of earthworm (Guang Di-long, GD; Hu Di-long, HD) as a case study. Chromatographic separation was performed on a BEH Amide column (2.1 × 100 mm, 1.7 µm). The MS(E) data in both negative and positive ion modes were acquired to record the high-accuracy MS and MS/MS data of all precursor ions. Automatic data processing was enabled by use of Progenesis QI software. As a consequence, 926 metabolites among 4705 features and 761 among 3418 features were characterized in the negative and positive modes, respectively, by searching the human metabolome database (HMDB). To reduce the false positive identifications, structural confirmation was conducted by comparison with the reference standards (tR and MS, MS/MS data) or matching with theoretical data or commercial library. Principal component analysis (PCA) of the GD and HD samples showed distinct classifications. Further orthogonal partial least squares discriminant analysis (OPLS-DA) and variable importance in projection (VIP) plot revealed the potential discriminatory markers between GD and HD. The present study provides a powerful and practical strategy that facilitates the primary metabolites characterization and quality evaluation of animal-derived medicines more efficiently. Graphical Abstract A general flowchart illustrating the application of ultra-high performance HILIC/QTOFMS(E) coupled with data processing by Progenesis QI to characterization of the endogenous small molecules and discriminatory analysis of animal-derived traditional medicine: earthworm as a case study.


Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Espectrometria de Massas/métodos , Oligoquetos/química , Animais , Geografia , Padrões de Referência
12.
Nat Prod Res ; 28(8): 551-4, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-24547738

RESUMO

A new aromatic glycoside (1) was isolated from the roots of Glehnia littoralis Fr. Schmidtex Miq. Its structure was elucidated as vanillic acid 1-O-[ß-D-apiofuranosyl-(1 → 6)-ß-D-glucopyranoside] ester mainly by analysing the NMR and MS spectral data. In the in vitro assays, compound 1 displayed some TNF-α secretion inhibitory activity.


Assuntos
Apiaceae/química , Medicamentos de Ervas Chinesas/isolamento & purificação , Glicosídeos/isolamento & purificação , Ácido Vanílico/análogos & derivados , Medicamentos de Ervas Chinesas/química , Medicamentos de Ervas Chinesas/farmacologia , Glicosídeos/química , Glicosídeos/farmacologia , Ressonância Magnética Nuclear Biomolecular , Raízes de Plantas/química , Fator de Necrose Tumoral alfa/antagonistas & inibidores , Fator de Necrose Tumoral alfa/metabolismo , Ácido Vanílico/química , Ácido Vanílico/isolamento & purificação , Ácido Vanílico/farmacologia
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