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1.
Int J Mol Sci ; 25(10)2024 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-38791498

RESUMO

The post-column reaction method enables the evaluation of the antiradical capacity of individual components in a mixture by separating the components using HPLC and measuring stable free radical (e.g., DPPH●) scavenging that occurs after the chromatography column. The equipment typically consists of two detectors. The first records signals of the analytes leaving the column. The second records radical scavenging by the analytes, which appears as a negative band. The recorded signals are found on two separate chromatograms, which must be combined to interpret the results. In this study, a single DAD detector was used behind the post-column reactor, enabling the simultaneous recording of the analyte bands and negative signals, indicating radical scavenging. The objective of this study was to evaluate the antiradical capacity of key compounds found in two herbal raw materials used in traditional Chinese medicine. Saposhnikovia divaricata roots contain phenolic acids, chromones, and furanocoumarins. Chlorogenic acid, rosmarinic acid, and imperatorin demonstrated strong radical scavenging, while prim-O-glucoslocimifugin showed a weaker response, both in standards and in root extracts. However, scavenging was not observed for cimifugin and 4'-O-ß-D-glucosyl-5-O-methylvisamminol. Astragalus mongholicus roots contain astragalosides I-IV (triterpene saponins). None of these showed DPPH● scavenging. Furthermore, additional signals were observed, indicating the presence of unidentified radical scavenging compounds.


Assuntos
Sequestradores de Radicais Livres , Extratos Vegetais , Plantas Medicinais , Plantas Medicinais/química , Extratos Vegetais/química , Cromatografia Líquida de Alta Pressão/métodos , Sequestradores de Radicais Livres/química , Apiaceae/química , Raízes de Plantas/química , Cromonas/análise , Cromonas/química , Furocumarinas/química , Furocumarinas/análise
2.
Environ Res ; 235: 116633, 2023 10 15.
Artigo em Inglês | MEDLINE | ID: mdl-37459949

RESUMO

Current artificial agarwood-inducing techniques yield low quality and quantities of agarwood. On account of unclear agarwood formation mechanism there's still no high-efficiency agarwood inducing method globally spread. In this study, a complete agarwood column was taken out of the live tree trunk at 6 months post-treatment by a novel agarwood-inducing method (Agar-Bit) in cultivated Aquilaria sinensis trees, and was first divided into 8 parts (A1-4, B1-4) involving agarwood layer (A part) and brown inner layer (B part) according to its color and length for analysis. These eight parts were analyzed microscope observation, 6 chromones' contents and characteristic chromatograms by HPLC (high performance liquid chromatography), GC-MS (gas chromatography-mass spectrometer) with to determine chemical changes. Other quality characteristics, TLC (thin-layer chromatography) and alcohol soluble extraction content, were also determined. Our results showed that resin changed with A to B part and microstructure changed with length. Six chromones in the eight parts varied with layers. Result of characteristic chromatograms showed that both A and B parts contained six characteristic peaks. Volatile component distributed mainly in A part, but important chromones were also detected in B parts. Results from TLC and alcohol soluble extraction content also showed that B part contained characteristic compounds of agarwood. In addition, some compounds in the essential oil detected by GC-MS in A part produced by Agar-Bit were similar to that found in natural agarwood, compounds in B parts were similar to BC agarwood, as were the results for the TLC and alcohol soluble extraction content. In conclusion, the chemical distribution obtained here from Agar-Bit could provide some clues to optimize high production and high efficiency stimulating method for whole tree full of resin in Aquilaria sinensis and to reveal the subtle agarwood formation mechanism throughout a whole trunk.


Assuntos
Cromonas , Thymelaeaceae , Ágar/análise , Cromonas/análise , Cromatografia Gasosa-Espectrometria de Massas , Thymelaeaceae/química , Madeira/química
3.
Nat Prod Res ; 37(1): 47-55, 2023 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34519597

RESUMO

Two new chromones named cnidimol G (1) and cnidimol H (2), one new coumarin, 7-methoxy-8-(3-methoxy-3-methyl-2-oxobutyl)coumarin (3), and twenty known compounds were isolated from MeOH extract of the fruit of Cnidium monnieri (L.) Cusson. The structures of compounds were elucidated by extensive spectroscopic analyses including 1 D and 2 D NMR, HRESIMS, IR and UV. Anti-inflammatory activity of the selected isolated compounds were evaluated. Compounds 1 and 8 exhibited inhibitory activities against nitric oxide production.


Assuntos
Cnidium , Frutas , Cnidium/química , Frutas/química , Cromonas/farmacologia , Cromonas/análise , Extratos Vegetais/química , Cumarínicos/química
4.
Prog Chem Org Nat Prod ; 118: 47-100, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35416517

RESUMO

The phytochemistry of the fragrant infected heartwood of Aquilaria and Gyrinops species, agarwood (oud), is critically reviewed, highlighting the use of this remarkable natural raw material in perfumery. The chemistry of the two main groups of constituents of agarwood (sesquiterpenoids and chromones) is discussed, focusing particularly on the former structural type. The identities of the main key odorants of agarwood essential oil and of the smoke produced by heating the wood of agarwood are also discussed.


Assuntos
Sesquiterpenos , Thymelaeaceae , Cromonas/análise , Cromonas/química , Odorantes/análise , Sesquiterpenos/química , Thymelaeaceae/química , Madeira/química
5.
Spectrochim Acta A Mol Biomol Spectrosc ; 251: 119388, 2021 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-33503560

RESUMO

Prospective antiviral molecule (2E)-N-methyl-2-[(4-oxo-4H-chromen-3-yl)methylidene]-hydrazinecarbothioamide has been probed using Fourier transform infrared (FTIR), FT-Raman and quantum chemical computations. The geometry equilibrium and natural bond orbital analysis have been carried out with density functional theory employing Becke, 3-parameter, Lee-Yang-Parr method with the 6-311G++(d,p) basis set. The vibrational assignments pertaining to different modes of vibrations have been augmented by normal coordinate analysis, force constant and potential energy distributions. Drug likeness and oral activity have been carried out based on Lipinski's rule of five. The inhibiting potency of 2(2E)-methyl-2-[(4-oxo-4H-chromen-3-yl)methylidene]-hydrazinecarbothioamide has been investigated by docking simulation against SARS-CoV-2 protein. The optimized geometry shows a planar structure between the chromone and the side chain. Differences in the geometries due to the substitution of the electronegative atom and intermolecular contacts due to the chromone and hydrazinecarbothioamide were analyzed. NBO analysis confirms the presence of two strong stable hydrogen bonded NH⋯O intermolecular interactions and two weak hydrogen bonded CH⋯O interactions. The red shift in NH stretching frequency exposed from IR substantiates the formation of NH⋯O intermolecular hydrogen bond and the blue shift in CH stretching frequency substantiates the formation of CH⋯O intermolecular hydrogen bond. Drug likeness, absorption, distribution, metabolism, excretion and toxicity property gives an idea about the pharmacokinetic properties of the title molecule. The binding energy of the nonbonding interaction with Histidine 41 and Cysteine 145, present a clear view that 2(2E)-methyl-2-[(4-oxo-4H-chromen-3-yl)methylidene]-hydrazinecarbothioamide can irreversibly interact with SARS-CoV-2 protease.


Assuntos
Antivirais , Tratamento Farmacológico da COVID-19 , Cromonas , Proteases 3C de Coronavírus/antagonistas & inibidores , Drogas em Investigação , SARS-CoV-2/efeitos dos fármacos , Tioureia , Antivirais/análise , Antivirais/síntese química , Antivirais/química , Antivirais/farmacocinética , Cromonas/análise , Cromonas/síntese química , Cromonas/química , Cromonas/farmacocinética , Química Computacional , Proteases 3C de Coronavírus/metabolismo , Cristalografia por Raios X , Drogas em Investigação/análise , Drogas em Investigação/síntese química , Drogas em Investigação/química , Drogas em Investigação/farmacocinética , Humanos , Hidrazinas/química , Hidrogênio/química , Ligação de Hidrogênio , Modelos Moleculares , Simulação de Acoplamento Molecular , Estrutura Molecular , Ligação Proteica , Teoria Quântica , Espectroscopia de Infravermelho com Transformada de Fourier , Análise Espectral Raman , Tioamidas/análise , Tioamidas/síntese química , Tioamidas/química , Tioamidas/farmacocinética , Tioureia/análise , Tioureia/síntese química , Tioureia/química , Tioureia/farmacocinética , Vibração
6.
Int J Mol Sci ; 23(1)2021 Dec 30.
Artigo em Inglês | MEDLINE | ID: mdl-35008829

RESUMO

Aqueous-ethanol extracts (70%) from the leaves of Eranthis longistipitata Regel. (Ranunculaceae Juss.)-collected from natural populations of Kyrgyzstan-were studied by liquid chromatography with high-resolution mass spectrometry (LC-HRMS). There was no variation of the metabolic profiles among plants that were collected from different populations. More than 160 compounds were found in the leaves, of which 72 were identified to the class level and 58 to the individual-compound level. The class of flavonoids proved to be the most widely represented (19 compounds), including six aglycones [quercetin, kaempferol, aromadendrin, 6-methoxytaxifolin, phloretin, and (+)-catechin] and mono- and diglycosides (the other 13 compounds). In the analyzed samples of E. longistipitata, 14 fatty acid-related compounds were identified, but coumarins and furochromones that were found in E. longistipitata were the most interesting result; furochromones khelloside, khellin, visnagin, and cimifugin were found in E. longistipitata for the first time. Coumarins 5,7-dihydroxy-4-methylcoumarin, scoparone, fraxetin, and luvangetin and furochromones methoxsalen, 5-O-methylvisammioside, and visamminol-3'-O-glucoside were detected for the first time in the genus Eranthis Salisb. For all the above compounds, the structural formulas are given. Furthermore, detailed information (with structural formulas) is provided on the diversity of chromones and furochromones in other representatives of Eranthis. The presence of chromones in plants of the genus Eranthis confirms its closeness to the genus Actaea L. because chromones are synthesized by normal physiological processes only in these members of the Ranunculaceae family.


Assuntos
Cromonas/análise , Cumarínicos/análise , Compostos Fitoquímicos/análise , Ranunculaceae/química , Cromatografia Líquida , Cromonas/química , Cumarínicos/química , Espectrometria de Massas , Compostos Fitoquímicos/química
7.
Elife ; 92020 07 09.
Artigo em Inglês | MEDLINE | ID: mdl-32644042

RESUMO

Directly modulating the choice between homologous recombination (HR) and non-homologous end joining (NHEJ) - two independent pathways for repairing DNA double-strand breaks (DSBs) - has the potential to improve the efficiency of gene targeting by CRISPR/Cas9. Here, we have developed a rapid and easy-to-score screening approach for identifying small molecules that affect the choice between the two DSB repair pathways. Using this tool, we identified a small molecule, farrerol, that promotes HR but does not affect NHEJ. Further mechanistic studies indicate that farrerol functions through stimulating the recruitment of RAD51 to DSB sites. Importantly, we demonstrated that farrerol effectively promotes precise targeted integration in human cells, mouse cells and mouse embryos at multiple genomic loci. In addition, treating cells with farrerol did not have any obvious negative effect on genomic stability. Moreover, farrerol significantly improved the knock-in efficiency in blastocysts, and the subsequently generated knock-in mice retained the capacity for germline transmission.


Assuntos
Sistemas CRISPR-Cas , Cromonas/análise , Edição de Genes , Ensaios de Triagem em Larga Escala , Animais , Células HEK293 , Humanos , Camundongos
8.
Molecules ; 25(9)2020 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-32354199

RESUMO

The attribution of 1H and 13C NMR signals of a library of 5-, 6- and 7-substituted 2,2-dimethylchroman-4-one derivatives is reported. Substituent effects were interpreted in terms of the Hammett equation, showing a good correlation for carbons para- to the substituent group, not for the meta- ones. Similarly, the Lynch correlation shows the additivity of the substituent chemical shifts in the case of both H and C nuclei, again with the exception of the carbons in the meta- position. Density Functional Theory (DFT)-predicted 1H and 13C chemical shifts correspond closely with experimentally observed values, with some exceptions for C NMR data; however, the correlation is valid only for the aromatic moiety and cannot be extended to the heterocyclic ring of the chroman-4-one scaffold.


Assuntos
Isótopos de Carbono/análise , Química/métodos , Cromonas/síntese química , Espectroscopia de Ressonância Magnética/métodos , Algoritmos , Carbono/química , Cromonas/análise , Elétrons , Hidrogênio , Modelos Lineares , Distribuição Normal , Software , Espectrofotometria
9.
Biomed Chromatogr ; 34(7): e4829, 2020 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-32170766

RESUMO

Qu-feng-sheng-shi Granules (QFSSG), a common prescription for the treatment of chronic inflammation and allergic rhinitis, is widely used in the clinic as a traditional Chinese medicine. Chemical analysis and quality control studies of this formulation are relatively limited compared with pharmacological studies. In this study, a high-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (HPLC-ESI-Q/TOF-MSn ) was used to identify the components in this prescription. Next, to quantify six major compounds, an HPLC-UV method was developed and validated. The results showed that 53 compounds were identified based on the MSn data, retention time and previous reports, including 17 coumarins, 14 lignans, 10 chromones, nine phenylethanoid glycosides and three other compounds, were identified or tentatively assigned. Contents of six major bioactive compounds (4'-O-ß-glucopyranosyl-5-O-methylvisamminol, Prim-O-glucosylcimifugin, forsythin, magnolin, imperatorin, isoimperatorin) could be determined by HPLC simultaneously. In addition, the potential anti-inflammatory activity of six major compounds was determined too, and we found that four compounds (4'-O-ß-glucopyranosyl-5-O-methylvisamminol, Prim-O-glucosylcimifugin, forsythin, imperatorin) have a potent nitric oxide inhibitory effect. In conclusion, this work provided comprehensive information on the quality control of QFSSG and evaluated the potential biological activity of the main components in QFSSG, which can contribute to understanding and using it more scientifically.


Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Medicamentos de Ervas Chinesas , Espectrometria de Massas por Ionização por Electrospray/métodos , Animais , Sobrevivência Celular/efeitos dos fármacos , Cromonas/análise , Cromonas/química , Cumarínicos/análise , Cumarínicos/química , Medicamentos de Ervas Chinesas/análise , Medicamentos de Ervas Chinesas/química , Medicamentos de Ervas Chinesas/farmacologia , Glicosídeos/análise , Glicosídeos/química , Lignanas/análise , Lignanas/química , Limite de Detecção , Modelos Lineares , Camundongos , Células RAW 264.7 , Reprodutibilidade dos Testes , Espectrofotometria Ultravioleta
10.
J Sep Sci ; 43(7): 1284-1296, 2020 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-31916672

RESUMO

Agarwood, a species of resinous heartwood, is a precious medicinal plant and a type of rare natural spice, which is widely used in medicine, cosmetics, religious activities, and other fields. In this study, agarwood samples from eight different regions across four countries were analyzed by comprehensive two-dimensional gas chromatography-quadrupole time-of-flight mass spectrometry. A total of 232 species were identified (the match factors of these compounds were above 750). The main compounds of agarwood are oxygenated sesquiterpenes and chromones. The compositions of India1 and Malaysia2 were significantly different from those of other samples, which might be attributed to the different production processes of agarwood. For further investigation, factor analysis was conducted for six agarwood samples. The results showed that the data classification possessed a regional characteristic; according to the retention time and relative content, characteristic compositions were determined by factor scores. Finally, the differences of characteristic compositions were simply analyzed, and the reasons were speculated.


Assuntos
Cromonas/análise , Sesquiterpenos/análise , Thymelaeaceae/química , Cromatografia Gasosa-Espectrometria de Massas/instrumentação
11.
J Nat Med ; 74(1): 170-188, 2020 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-31578667

RESUMO

Saposhnikoviae Radix (SR) is a commonly used crude drug that is obtained from the root and rhizome of Saposhnikovia divaricata which is distributed throughout China, Korea, Mongolia, and Russia. To evaluate the quality of Mongolian S. divaricata, metabolomic profiling of 43 plant specimens from different regions of Mongolia, as well as 8 SR samples and 2 plant specimens from China, were conducted by liquid chromatography-ion-trap-time-of-flight-mass spectrometer (LC-IT-TOF-MS). LC-MS profiles of the specimens showed uniformity and 30 compounds were tentatively identified, including 13 chromones and 17 coumarins. Among them, 16 compounds were isolated and unambiguously verified by comparing them with the spectroscopic data of standard compounds. Orthogonal partial least squares-discriminant analysis (OPLS-DA) based on LC-MS data from 7 Mongolian specimens and 8 Chinese SR samples as well as 2 plant specimens revealed that these 2 groups were clearly distinguishable and that Mongolian specimens were characterized by an abundance of prim-O-glucosylcimifugin (1). Moreover, the OPLS-DA of the Mongolian specimens showed that they can be discriminated by their growing regions based on the content of 8 chromones. The total content of dihydrofurochromones 1-3 was relatively higher in the specimens from Khalkhgol in the far eastern part of Mongolia, while contents of 10, 11, 15, and 16 were higher in those from Holonbuir in the eastern part. Based on this research, the roots of S. divaricata from Mongolia have potential as a new resource of SR in Kampo medicine.


Assuntos
Apiaceae/química , Cromonas/análise , Cromonas/química , Cumarínicos/química , Monossacarídeos/química , Xantenos/química , China , Cromatografia Líquida de Alta Pressão/métodos , Cromatografia Líquida , Medicamentos de Ervas Chinesas/química , Medicina Kampo , Mongólia , Raízes de Plantas/química , Rizoma/química , Espectrometria de Massas em Tandem/métodos
12.
J Nat Med ; 74(1): 98-105, 2020 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-31392566

RESUMO

Agarwood, which is used as medicine and incense, contains sesquiterpenes and chromones. Agarotetrol is a chromone derivative found in high concentrations in the water-extract fraction of agarwood and thus may be present in pharmaceutical products made from decoctions of agarwood. Agarotetrol has been reported to be present at the early stages of cell death in calli. We therefore examined the presence of agarotetrol in medical- and incense-grade agarwood, in agarwood-source plants lacking resin deposits, and in artificially made agarwood. Agarotetrol appeared as a large peak in the HPLC chromatograms of all samples of medical-grade and artificially made agarwood, and in most incense-grade agarwood samples. In contrast, agarwood samples lacking resin deposits did not contain agarotetrol. These results show that agarotetrol is characteristic of resin formation. Agarotetrol was also detected in decoctions of agarwood. A newly developed TLC method for the detection of agarotetrol in agarwood is described.


Assuntos
Cromonas/análise , Cromonas/química , Resinas Vegetais/análise , Thymelaeaceae/química , Cromatografia Líquida de Alta Pressão , Extratos Vegetais , Resinas Vegetais/química , Sesquiterpenos/metabolismo
13.
PLoS One ; 14(10): e0224575, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31661523

RESUMO

Limonoids, quinolone alkaloids and chromones have been reported as constituents of Dictyoloma vandellianum Adr. Juss. (Rutaceae). Although those compounds are known for their biological activities, only the anti-inflammatory activity of chromones isolated from the underground parts has been evaluated. There are no studies of the pharmacological properties of the aerial parts of D. vandellianum. The present study was carried out to determine the phytochemical profile and antinociceptive activity of the methanol extract, fractions and isolated compounds of leaves of D. vandellianum. The phytochemical profile was performed by HLPC-DAD-ESIMSn and pure substances obtained were characterized by MS and NMR spectroscopy. The antinociceptive activity was assessed using the formalin assay in mice, and the motor function in the rotarod test. ME and all the fractions obtained from ME produced antinociceptive effects. Among them, the ethyl ether fraction was the most active. Data from HPLC-DAD-ESIMSn showed that the ethyl ether fraction presented 42 compounds. The major compounds isolated from this fraction-gallic acid, methyl gallate and 1,2,6-tri-O-galloyl-ß-d-glucopyranose-were tested and produced antinociceptive effects. Gallic acid, methyl gallate and 1,2,6-tri-O-galloyl-ß-d-glucopyranose at antinociceptive doses did not affect the motor performance in mice in the rotarod test. This work is the first report of the occurrence of gallotanins in D. vandellianum. In addition, the pharmacological study showed that D. vandellianum leaves present antinociceptive activity, probably induced by gallic acid, methyl gallate and 1,2,6-tri-O-galloyl-ß-d-glucopyranose.


Assuntos
Analgésicos/química , Folhas de Planta/química , Rutaceae/química , Alcaloides/química , Animais , Cromatografia Líquida de Alta Pressão/métodos , Cromatografia Líquida/métodos , Cromonas/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Limoninas/análise , Masculino , Metanol/análise , Camundongos , Compostos Fitoquímicos/análise , Extratos Vegetais/farmacologia , Folhas de Planta/metabolismo , Rutaceae/genética
14.
Phytomedicine ; 64: 153076, 2019 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-31473579

RESUMO

BACKGROUND: Long-term exposure to aeroallergens such as house dust mite (HDM) could result in airway inflammation and airway remodeling, characteristic features of allergic asthma. Huangqi-Fangfeng (HF), an important "couplet medicines" of Yu-Ping-Feng-San (YPFS), mediates allergen-induced airway inflammation in mice, but its role in the airway remodeling is not known. PURPOSE: To evaluate the effects of HF on airway remodeling of allergic asthma in a murine model and to investigate the underlying mechanisms in vivo and in vitro. METHODS: The main components of HF were analyzed by HPLC. The HDM-induced asthma mice model was established to study the effects of HF on airway inflammation and airway remodeling in vivo. Enhanced pause (Penh) index value was used as an indicator of airway hyper-reactivity. Bronchoalveolar lavage fluid (BALF) was processed for differential cell counting and determination of cytokines production. The lungs were fixed in 4% paraformaldehyde for histological examination after staining with H&E, trichrome and IHC. Production of interleukin (IL)-4, IL-5, IL-13, and transforming growth factor beta-1 (TGF-ß1) in BALF and lung tissues, IgE in serum were measured by ELISAs. Expression of epithelial markers and mesenchymal markers were detected by immunohistochemistry and western blots. The effects of HF and its components on epithelial-mesenchymal transition (EMT) were detected in human bronchial epithelial cells (16HBE) treated with TGF-ß1 and HDM. RESULTS: The main components of Huangqi-Fangfeng detected by HPLC were Calycosin, Formononetin and Cimifugin. In HDM-induced allergic asthma mice model, respiratory exposure to HDM lead to airway hyperresponsiveness and thickening of the smooth muscle layer in the airway. TGF-ß1 levels increased in mice airways while epithelial cells lost expression of E-cadherin and gained expression of the mesenchymal proteins N-cadherin, α-SMA and collagen І. These changes were relieved by treatment with HF. Furthermore, restored epithelial markers expression treated with individual components were also detectable in 16HBE cells. CONCLUSION: These results demonstrated that Huangqi-Fangfeng protected against allergic airway remodeling through inhibiting epithelial-mesenchymal transition process in mice via regulating epithelial derived TGF-ß1.


Assuntos
Remodelação das Vias Aéreas/efeitos dos fármacos , Antiasmáticos/farmacologia , Medicamentos de Ervas Chinesas/farmacologia , Transição Epitelial-Mesenquimal/efeitos dos fármacos , Animais , Antiasmáticos/química , Apiaceae/química , Asma/etiologia , Asma/patologia , Astragalus propinquus , Brônquios/citologia , Líquido da Lavagem Broncoalveolar , Cromonas/análise , Modelos Animais de Doenças , Medicamentos de Ervas Chinesas/análise , Medicamentos de Ervas Chinesas/química , Células Epiteliais/efeitos dos fármacos , Humanos , Isoflavonas/análise , Pulmão/efeitos dos fármacos , Pulmão/patologia , Masculino , Camundongos Endogâmicos BALB C , Fator de Crescimento Transformador beta1/metabolismo
15.
Anal Chim Acta ; 1080: 95-103, 2019 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-31409479

RESUMO

Structural analysis of biomolecules is essential to natural product discovery, especially for precious biomaterials such as agarwood. However, one of the greatest challenges to the characterization of natural products is the profound cost in time and manpower to the structural elucidation of these highly diverse compounds. Here, we demonstrate a multi-modal mass spectrometric strategy, integrating matrix-assisted laser desorption ionization (MALDI) mass spectrometry imaging (MSI) and mass spectral molecular networking, to uncover agarwood natural products of Aquilaria sinensis trees. A simple workflow for preparing wood sections for MALDI-MSI analysis was demonstrated. Notably, tens of natural products in the agarwood region in wood stem section of A. sinensis were spatially revealed by MALDI-MSI. For the first time, such a great number of plant specialized metabolites is obtained by a single wood section MSI. Guided by the spatially resolved features, mass spectral molecular networking was subsequently applied for structural analysis of the agarwood natural products, in which three major classes of 2-(2-phenylethyl)chromones and their analogues were putatively characterized. These results suggest an efficient strategy to the dereplication of plant natural products.


Assuntos
Produtos Biológicos/análise , Thymelaeaceae/química , Madeira/química , Produtos Biológicos/química , Cromatografia Líquida/métodos , Cromonas/análise , Cromonas/química , Isomerismo , Caules de Planta/química , Espectrometria de Massas por Ionização e Dessorção a Laser Assistida por Matriz/métodos , Espectrometria de Massas em Tandem/métodos
16.
Molecules ; 23(12)2018 Nov 26.
Artigo em Inglês | MEDLINE | ID: mdl-30486289

RESUMO

To clarify the role of the B-ring in antioxidant flavonols, we performed a comparative study between galangin with a null B-ring and 3,5,7-trihydroxychromone without a B-ring using five spectrophotometric assays, namely, •O2--scavenging, 1,1-diphenyl-2-picrylhydrazyl radical (DPPH•)-scavenging, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide radical-scavenging, 2,2'-azino-bis(3-ethylbenzo-thiazoline-6-sulfonic acid) radical-scavenging, and Fe3+-reducing activity. The DPPH•-scavenging reaction products of these assays were further analyzed by ultra-performance liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry (UPLC-ESI-Q-TOF-MS/MS) technology. In the five spectrophotometric assays, galangin and 3,5,7-trihydroxychromone dose-dependently increased their radical-scavenging (or Fe3+-reducing) percentages. However, galangin always gave lower IC50 values than those of 3,5,7-trihydroxychromone. In the UPLC-ESI-Q-TOF-MS/MS analysis, galangin yielded galangin-DPPH adduct MS peaks (m/z 662, 434, 301, 227,196, and 151) and galangin-galangin dimer MS peaks (m/z 538, 385, 268, 239, 211, 195, and 151). 3,5,7-Trihydroxychromone, however, only generated m/z 3,5,7-trihydroxychromone-DPPH adduct MS peaks (m/z 586, 539, 227, 196, and 136). In conclusion, both galangin and 3,5,7-trihydroxychromone could similarly undergo multiple antioxidant pathways, including redox-dependent pathways (such as electron transfer (ET) and ET plus proton transfer (PT)) and a non-redox-dependent radical adduct formation (RAF) pathway; thus, the null B-ring could hardly change their antioxidant pathways. However, it did improve their antioxidant levels in these pathways. Such improvement of the B-ring toward an antioxidant flavonol is associated with its π-π conjugation, which can provide more resonance forms and bonding sites.


Assuntos
Antioxidantes/análise , Cromonas/análise , Flavonoides/análise , Flavonóis/análise , Antioxidantes/química , Compostos de Bifenilo/química , Cromonas/química , Flavonóis/química , Radicais Livres/química , Concentração Inibidora 50 , Modelos Moleculares , Picratos/química , Espectrometria de Massas por Ionização por Electrospray , Espectrometria de Massas em Tandem
17.
Yakugaku Zasshi ; 138(4): 571-579, 2018 Apr 01.
Artigo em Japonês | MEDLINE | ID: mdl-29386422

RESUMO

 Saposhnikoviae Radix ("Boufu") is an important crude drug used in Kampo formulation. It is extracted from wild-type plants. However, recently, extraction has become difficult because of a decrease in wild-type plants. Therefore, cultivated plants account for the majority of the market, from which the crude drug is extracted. However, the cultivation techniques used are not sufficient to obtain the desirable extracts. In this study, we compared the contents of the extract and the quantitative values of characteristic constituents obtained from wild-type and cultivated plants, and found a remarkable difference. Therefore, it is considered that these indicators play an important role in the establishment of better cultivation technology.


Assuntos
Apiaceae/química , Técnicas de Cultura/métodos , Extratos Vegetais/química , Raízes de Plantas/química , Cromatografia Líquida de Alta Pressão , Cromonas/análise , Cromonas/química , Cromonas/isolamento & purificação , Glucosídeos/análise , Glucosídeos/química , Glucosídeos/isolamento & purificação , Conformação Molecular , Monossacarídeos/análise , Monossacarídeos/química , Monossacarídeos/isolamento & purificação , Xantenos/análise , Xantenos/química , Xantenos/isolamento & purificação
18.
Nat Prod Res ; 32(8): 898-901, 2018 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-28817985

RESUMO

Saposhnikoviae Radix (SR), the dried root of Saposhnikovia divaricata (Turcz.) Schischk. (Umbelliferae), is commonly used as a traditional Chinese medicine. In this study, a rapid and accurate method was firstly, developed for the qualitative analysis of SR by high-performance liquid chromatography coupled with electrospray ionisation quadrupole time-of-flight mass spectrometry (HPLC-ESI-Q-TOF-MS/MS). A total of 45 compounds were identified or tentatively characterised, including 13 chromones, 28 coumarins and four others. Among them, 16 compounds were identified from SR for the first time. In addition, six chromones reference standards, including two isolated compounds of 3'-O-angeloylhamaudol and norcimifugin from the extraction of SR, were used to study the fragmentation pathways of chromones. The developed method was effective for characterising the compounds of SR, and the results of the study enriched the understanding of the chemical connotation.


Assuntos
Apiaceae/química , Cromatografia Líquida de Alta Pressão/métodos , Raízes de Plantas/química , Espectrometria de Massas por Ionização por Electrospray/métodos , Cromonas/análise , Cromonas/química , Cumarínicos/análise , Cumarínicos/química , Medicamentos de Ervas Chinesas/química , Medicina Tradicional Chinesa , Espectrometria de Massas em Tandem/métodos
19.
Biotechnol Lett ; 40(2): 413-418, 2018 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-29185164

RESUMO

OBJECTIVES: To explore the potentiality of undifferentiated Pimpinella anisum L. cell cultures for the production of secondary metabolites by means of elicitation. RESULTS: Two chromone compounds were secreted to the medium of undifferentiated cultures of P. anisum: 4-methoxyfuro[3,2-g]chromen-7-one, known as bergapten, which is constitutive to anise, and 5-hydroxy-7-methoxy-2-methylchromen-4-one, the rare chromone eugenin, not yet described in P. anisum. Caffeoyl quinic acid species were also identified in the biomass. Elicitation with methyl jasmonate enhanced chromone accumulation in the medium and stimulated phenolic acid metabolism in the biomass (11 mg caffeoyl quinic acids g-1 DW cells). The application of 2,6-dimethyl-ß-cyclodextrins to cultures led to an intense accumulation of chromones, with nearly 10 mg l-1 bergapten and 150 mg l-1 eugenin being accumulated extracellularly after optimal elicitation conditions. CONCLUSIONS: The significant amounts of eugenin obtained in the anise cultures and the stability of production over long periods of time can be of interest for its biotechnological production and for future studies on biosynthesis regulation.


Assuntos
Acetatos/farmacologia , Cromonas/metabolismo , Ciclopentanos/farmacologia , Oxilipinas/farmacologia , Pimpinella/efeitos dos fármacos , Pimpinella/metabolismo , beta-Ciclodextrinas/farmacologia , 5-Metoxipsoraleno , Técnicas de Cultura de Células , Cromanos/análise , Cromanos/metabolismo , Cromonas/análise , Espaço Extracelular/química , Espaço Extracelular/metabolismo , Metoxaleno/análogos & derivados , Metoxaleno/análise , Metoxaleno/metabolismo , Pimpinella/citologia
20.
J Sep Sci ; 41(7): 1682-1690, 2018 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-29280307

RESUMO

Ultra-performance convergence chromatography is an environmentally friendly analytical technique that employs dramatically reduced amounts of organic solvents compared to conventional chromatographic methods. In this study, a rapid, sensitive, and environmentally friendly method based on ultra-performance convergence chromatography was developed for the quantification of four major chromones present in the roots of Saposhnikovia divaricata (Turcz.) Schischk. Using this method, the analysis time was significantly shortened compared to conventional high-performance liquid chromatography techniques. In addition, the influence of cosolvent type, cosolvent ratio, column temperature, system pressure, and flow rate on the peak resolution was investigated. The proposed method was validated in terms of its limits of detection, limits of quantitation, linearity, precision, and accuracy. More specifically, the limits of detection of the four chromones ranged from 0.006 to 0.033 µg/mL, while the limits of quantitation ranged from 0.019 to 0.101 µg/mL. Our method also exhibited a good regression (r2  > 0.999), excellent precision (RSD < 0.60%), and acceptable recoveries (99.48-102.89%). Finally, the quantities of these four chromones present in 20 commercial samples from Korea and China were successfully evaluated using the developed method, indicating that the proposed method is suitable for the rapid and accurate quality control of Saposhnikovia divaricata.


Assuntos
Apiaceae/química , Cromonas/análise , Cromatografia Líquida de Alta Pressão , Conformação Molecular , Controle de Qualidade
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