CN110186991B - Polyphenol positional isomer qualitative method - Google Patents
Polyphenol positional isomer qualitative method Download PDFInfo
- Publication number
- CN110186991B CN110186991B CN201910407541.9A CN201910407541A CN110186991B CN 110186991 B CN110186991 B CN 110186991B CN 201910407541 A CN201910407541 A CN 201910407541A CN 110186991 B CN110186991 B CN 110186991B
- Authority
- CN
- China
- Prior art keywords
- ion
- secondary mass
- acid
- compound
- relative intensity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention relates to a qualitative method of polyphenol positional isomers, which comprises the following steps: under a positive ion mode, performing secondary mass spectrometry on different position isomers of the compound by using a plurality of collision energies; calculating the relative intensity of the parent ions and the daughter ions in a secondary mass spectrogram, and drawing a change curve of the relative intensity along with the collision energy; and qualitatively judging different positional isomers of the compound according to the change curve of the relative intensity. The deep structure analysis of the flavonol glycoside compounds and the caffeoylquinic acid compounds is realized, and the C-3 and C-7 position isomers of the flavonol glycoside compounds, the monocaffeoylquinic acid and dicaffeoylquinic acid position isomers and the like can be effectively identified.
Description
Technical Field
The invention belongs to the field of separation analytical chemistry, and particularly relates to a qualitative method of polyphenol positional isomers.
Background
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The liquid chromatogram-mass spectrum combined technology takes liquid chromatogram as a separation system and mass spectrum as a detection system. The sample is separated from the flowing phase in the mass spectrum part, ionized, separated by mass analyzer of mass spectrum according to mass number, and the mass spectrum is obtained by detector. The liquid chromatography-mass spectrometry reflects the complementation of the advantages of the chromatogram and the mass spectrum, and combines the advantages of high separation capability of the chromatogram on a complex sample, high selectivity and high sensitivity of the mass spectrum and capability of providing relative molecular mass and structural information. At present, due to the characteristics of high sensitivity and high resolution, the liquid chromatography-mass spectrometry technology is widely applied to many fields such as natural products, pharmaceutical analysis, food analysis, environmental analysis and the like.
Polyphenolic compounds are the most widely distributed class of secondary metabolites in plants with important physiological functions. The polyphenol compounds play a role in eliminating active oxygen free radicals and protecting plants from being damaged when the plants are subjected to adversity stresses such as infection, radiation, drought, high temperature and the like. The polyphenol compounds separated from natural products have the pharmacodynamic activities of resisting inflammation, resisting virus, resisting tumor, reducing blood sugar, reducing blood fat, enhancing immunity and the like, are the active substance basis of the natural medicines for playing the roles, and are also important sources for discovering innovative medicines. The polyphenol compounds often exist in many positional isomers (positional isomers mean the same mass number and different attachment positions of substituents). The difference of the connection position can cause the obvious difference of the physiological function and the pharmacodynamic activity. The accurate characterization of positional isomers of polyphenolic compounds plays a crucial role in plant physiology and the development of modern medicine.
The inventor finds that: polyphenolic compounds, such as: when the flavonol glycoside, the caffeoylquinic acid compound and the like are qualitatively analyzed by using a secondary mass spectrum, the fragment ion types of the position isomers are completely the same, and the accurate qualitative is very difficult.
Disclosure of Invention
In order to overcome the problems, one of the purposes of the invention is to establish a secondary mass spectrometry qualitative method of polyphenol position isomers, and the method realizes the accurate qualitative of the position isomers of flavonol glycoside and caffeoylquinic acid compounds by deep structure analysis of parent ions and daughter ions of secondary mass spectrometry of the flavonol glycoside compounds and the caffeoylquinic acid compounds.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a method for characterizing polyphenol positional isomers, comprising:
under a positive ion mode, performing secondary mass spectrometry on different position isomers of the compound by using a plurality of collision energies;
calculating the relative intensity of the parent ions and the daughter ions in a secondary mass spectrogram, and drawing a change curve of the relative intensity along with the collision energy;
and qualitatively judging different positional isomers of the compound according to the change curve of the relative intensity.
In some embodiments, the compound is a flavonol glycoside or a caffeoylquinic acid compound.
Flavonol is one of the most widely distributed flavonoids, is present in almost all plants except algae, and has wide pharmacological activity and potential medicinal value.
Therefore, the invention also aims to provide the application of the position isomer mass spectrometry method in plant flavonol glycoside characterization.
In some embodiments, the flavonol aglycone of the flavonol glycoside comprises: kaempferol, quercetin, myricetin, isorhamnetin, and luteolin.
In some embodiments, the flavonol glycosides are C-3 and C-7 positional isomers of flavonol glycosides. Different from qualitative differentiation by using aglycon ions and aglycon free radical ions (the mass number difference is 1) in a negative ion mode, the method for analyzing the aglycon ions and the parent ions (molecular ion peaks) in a positive ion mode is based on the size of steric hindrance, so that the detection result is more accurate, the repeatability is good, and the application range is wider.
The caffeoylquinic acid compounds are phenolic acid natural compounds formed by esterification reaction of quinic acid and different numbers of caffeic acid. The caffeoylquinic acid compounds have antioxidant, antiinflammatory, antimicrobial, and enzyme inhibiting effects. The compounds are widely present in plants, such as Compositae, leguminosae, umbelliferae, caprifoliaceae, convolvulaceae and the like, and have wide pharmacological activity and potential medicinal value.
Therefore, the invention also aims to provide the application of the position isomer mass spectrometry method in the determination of caffeoylquinic acid in fruits, vegetables and Chinese medicinal materials.
In some embodiments, the caffeoylquinic acid compounds are monocaffeoylquinic acid and dicaffeoylquinic acid position isomers.
In some embodiments, the plurality of collisions can vary in a gradient.
In some embodiments, the gradient of the plurality of collision energies is in an arithmetic progression.
In some embodiments, the collision energy ranges from 15eV to 45eV.
In some embodiments, the compound is extracted by a method comprising: ultrasonically extracting the plant to be detected in an organic solvent/aqueous solution, centrifuging and taking supernatant fluid to obtain the plant-specific ultrasonic probe.
In some embodiments, the organic solvent is acetonitrile, methanol, or ethanol.
The invention has the beneficial effects that:
(1) The invention realizes the effective identification of C-3 and C-7 position isomers of the flavonol glycoside compound for the first time through a secondary mass spectrum relative intensity change curve of parent ions and daughter ions with 6 collision energies in a positive ion mode.
(2) The method has high accuracy in identifying C-3 and C-7 position isomers of the flavonol glycoside compounds.
(3) According to the invention, the effective identification of the position isomers of the monocaffeoylquinic acid and the dicaffeoylquinic acid is realized for the first time through a secondary mass spectrum relative intensity change curve of 7 parent ions and daughter ions with collision energy in a positive ion mode.
(4) The accuracy for identifying the caffeoylquinic acid position isomer by adopting the method is high.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a graph showing the relative intensity of parent ion 471 and daughter ion 309 at 6 collision energies for kaempferol 3-O-glucoside and kaempferol 7-O-glucoside;
FIG. 2 is a graph of the relative intensity changes of parent ion 539 and daughter ion 377/163 at 7 collision energies for dicaffeoylquinic acid;
FIG. 3 is a graph showing the relative intensity of parent ion 377 and daughter ion 163 at 7 collision energies for monocaffeoylquinic acid.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are conventional products which are commercially available, and are not indicated by manufacturers.
As introduced by the background technology, the problem that the fragment ion species of polyphenol positional isomers in natural medicinal components of plants are completely the same in secondary mass spectrometry and are difficult to accurately determine is solved. Therefore, the invention provides a qualitative method of polyphenol positional isomers based on the characteristics of parent ions and daughter ions of secondary mass spectra with different collision energies in a positive ion mode. The method comprises the following steps:
performing secondary mass spectrometry on different positional isomers of the compound by using a plurality of collision energies;
collecting the relative intensities of the parent ions and the daughter ions in a secondary mass spectrogram, and drawing a change curve of the relative intensities along with the collision energy;
and qualitatively judging different positional isomers of the compound according to the change curve of the relative intensity.
The invention also provides an application of the qualitative method of the flavonol glycoside positional isomer in the mass spectrum. The method comprises the following steps:
secondary analyses were performed at 6 collision energies (20 eV, 25eV, 30eV, 35eV, 40eV, 45 eV). And identifying C-3 and C-7 positional isomers of the flavonol glycoside compounds through a change curve of relative intensity of the parent ions and the daughter ions along with collision energy in a secondary mass spectrogram.
The method comprises the following specific steps:
(1) Secondary mass spectrum data acquisition: performing secondary mass spectrometry on the sample supernatant under different collision energies;
the collision energies described herein are 20eV, 25eV, 30eV, 35eV, 40eV, 45eV.
The secondary mass spectrometry described herein is in the positive ion mode, and for mass spectrometry, the response of the positive ion mode is generally better than that of the negative ion mode.
(2) Drawing a change curve of relative strength of parent ions and child ions along with collision energy according to the collision energy of the secondary mass spectrum data obtained in the step (1);
the secondary mass spectrum parent ion is [ M + Na ]] + Peak(s).
The secondary mass spectrometer ion is [ M + Na ] of aglycone] + Peak(s).
(3) The method is characterized by accurately determining the difference between the relative intensity of the parent ion and the daughter ion of the flavonol glycoside in a secondary mass spectrogram along with the change of collision energy.
The flavonol aglycone of the flavonol glycoside comprises kaempferol, quercetin, myricetin, isorhamnetin and luteolin.
The parent ion and the daughter ion variation described herein are the parent ion [ M + Na] + The descending order of the relative strength increasing along with the collision energy in the secondary mass spectrum is aglycon-7-O-glucoside and aglycon-3-O-glucoside, and the aglycon ion thereof is [ M + Na ]] + The ascending sequence of the relative intensity along with the collision energy in the secondary mass spectrum is aglycone-7-O-glucoside and aglycone-3-O-glucoside.
The invention also provides an application of the mass spectrometry qualitative method in the qualitative determination of caffeoylquinic acid in fruits, vegetables and traditional Chinese medicinal materials. The method comprises the following steps:
secondary mass spectrometry was performed at 7 collision energies (15 eV, 20eV, 25eV, 30eV, 35eV, 40eV, 45 eV). Identification of the single caffeoylquinic acid positional isomers is performed by the difference in the curves of relative intensity versus collision energy in the secondary mass spectrum of the parent ion 377 and the daughter ion 163. The identification of dicaffeoylquinic acid positional isomers is carried out by the difference in the curves of the relative intensity as a function of the collision energy in the secondary mass spectrum of the parent ion 539 and the daughter ion 377/163.
The above fruits, vegetables and Chinese medicinal materials include Compositae, leguminosae, umbelliferae, caprifoliaceae, and Convolvulaceae.
The method comprises the following specific steps:
(1) Secondary mass spectrum data acquisition: performing mass spectrum secondary analysis on the sample supernatant under different collision energies;
the collision energies described herein are 15eV, 20eV, 25eV, 30eV, 35eV, 40eV, 45eV.
The secondary mass spectrometry described herein is in positive ion mode.
(2) Drawing a change curve of relative strength of parent ions and child ions along with collision energy according to the collision energy of the secondary mass spectrum data obtained in the step (1);
the secondary mass spectrum parent ion, the monocaffeoylquinic acid parent ion, is [ M + Na ]] + 377; dicaffeoylquinic acid parent ion is [ M + Na [)] + ，539。
The secondary mass proton ion described herein, the monocaffeoylquinic acid ion, is 163; dicaffeoylquinic acid ion is 377 and 163.
(3) The method is characterized by accurately determining the relative intensity of the monocaffeoyl and dicaffeoylquinic acid parent ions and daughter ions in a secondary mass spectrogram according to the difference of the change of the relative intensity along with the collision energy.
3-O-caffeoylquinic acid, 4-O-caffeoylquinic acid and 5-O-caffeoylquinic acid, the descending order of the relative intensity of the parent ion 377 increasing with collision energy in the secondary mass spectrum is 5-O-caffeoylquinic acid, 4-O-caffeoylquinic acid and 3-O-caffeoylquinic acid, and the ascending order of the relative intensity of the ion 163 increasing with collision energy in the secondary mass spectrum is 5-O-caffeoylquinic acid, 4-O-caffeoylquinic acid and 3-O-caffeoylquinic acid;
3,5-O-dicaffeoylquinic acid, 4,5-O-dicaffeoylquinic acid, 3,4-O-dicaffeoylquinic acid, the descending order of the relative strength of parent ion 539 increasing with collision energy in the secondary mass spectrum is 3,5-O-dicaffeoylquinic acid, 3,4-O-dicaffeoylquinic acid, 4,5-O-dicaffeoylquinic acid, the ascending order of the relative strength of child ion 377 increasing with collision energy in the secondary mass spectrum is 3,5-O-dicaffeoylquinic acid, 3,4-O-dicaffeoylquinic acid, 4,5-O-dicaffeoylquinic acid, the ascending order of the relative strength of the child ion ions in the secondary mass spectrum increasing with collision energy is 3,4-O-dicaffeoylquinic acid, 3482-dicaffeoylquinic acid, and 3434.
In order to obtain the plant, fruit and vegetable and traditional Chinese medicine extract, the application also provides a preparation method of the fruit and vegetable and traditional Chinese medicine extract: ultrasonic extracting 100mg of fruits, vegetables and Chinese medicinal materials with 1mL of organic solvent/water solution for 30min, centrifuging, and collecting supernatant for mass spectrometry. The extraction solvent is selected from acetonitrile, methanol, and ethanol.
The organic solvent comprises one of acetonitrile, methanol and ethanol.
The ratio of the organic solvent to the water is 1:2-2:1.
The scheme of the application is described by specific examples below.
Example 1:
characterization of positional isomers in tobacco leaves:
(1) Preparing tobacco leaf extract
Adding 100mg of tobacco leaves into 1mL of methanol/water (v/v, 1:1) solution, performing ultrasonic treatment for 30min, centrifuging for 10min, and collecting supernatant.
(2) Second order mass spectrometry
The supernatant was subjected to liquid chromatography-mass spectrometry, and secondary mass spectrometry in the positive ion mode was performed using collision energies of 20eV, 25eV, 30eV, 35eV, 40eV, and 45eV. Time-of-flight mass spectrometry (Q-TOF-MS) was used, mass number range 50-1000, capillary voltage 3500eV, drying gas flow rate 8L/min, drying gas temperature 200 deg.C, collision cell transit time 60 μ s, RF750Vpp, isolation width 4.
(3) Characterization of kaempferol glucoside:
as shown in figure 1, kaempferol-3-O-glucoside and kaempferol-7-O-glucoside are qualitatively obtained in tobacco leaf by the variation of relative intensity of parent ion and daughter ion with collision energy in secondary mass spectrogram, and parent ion [ M + Na ] is] + 471, with relative intensities of 100% and 53% in 35eV collision energy secondary mass spectrometry and daughter ion 309 of 88% and 100% in 35eV collision energy secondary mass spectrometry.
Example 2
The position isomer of caffeoylquinic acid in honeysuckle is characterized:
(1) Preparing honeysuckle extract
Adding 1g of flos Lonicerae extract into 10mL of methanol/water (v/v, 1:1) solution, performing ultrasonic treatment for 30min, centrifuging for 10min, and collecting supernatant.
(2) Second order mass spectrometry
The supernatant was subjected to liquid chromatography-mass spectrometry, and secondary mass spectrometry in the positive ion mode was performed using collision energies of 15eV, 20eV, 25eV, 30eV, 35eV, 40eV, and 45eV. Time-of-flight mass spectrometry (Q-TOF-MS) was used, mass number range 50-1000, capillary voltage 3500eV, drying gas flow rate 8L/min, drying gas temperature 200 deg.C, collision cell transit time 60 μ s, RF750Vpp, isolation width 4.
(3) Characterization of monocaffeoyl and dicaffeoylquinic acids:
through the variation difference of the relative intensities of the parent ions and the daughter ions along with the collision energy in a secondary mass spectrogram, as shown in figure 2, 3-O-caffeoylquinic acid, 4-O-caffeoylquinic acid and 5-O-caffeoylquinic acid are qualitatively obtained in honeysuckle, and the relative intensities of the secondary mass spectrogram of the parent ions 377 at the collision energy of 30eV are respectively 100%, 82% and 30%; the relative intensities of the secondary mass spectra of its ion 163 at 25eV collision energy were 3%, 17% and 43%, respectively.
As shown in FIG. 3, 3,5-O-dicaffeoylquinic acid, 4,5-O-dicaffeoylquinic acid, 3,4-O-dicaffeoylquinic acid, which has a parent ion 539 having a relative intensity of the secondary mass spectrum at 35eV collision energy of 29%, 65% and 43%, respectively, and a daughter ion 377 having a relative intensity of the secondary mass spectrum at 30eV collision energy of 100%, 52% and 86%, respectively, and a daughter ion 163 having a relative intensity of the secondary mass spectrum at 40eV collision energy of 50%, 74% and 100%, respectively, were characterized from Lonicera japonica.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (3)
1. A mass spectrometry method for polyphenol positional isomers is characterized by comprising the following steps:
under a positive ion mode, performing secondary mass spectrometry on different position isomers of the polyphenol compound by using a plurality of collision energies;
drawing a change curve of relative intensity of the parent ions and the daughter ions along with collision energy in a secondary mass spectrogram; qualitatively judging different position isomers of the compound according to the change curve of the relative intensity; the compound is flavonol glycoside or caffeoyl quinic acid compound, the flavonol glycoside is C-3 and C-7 position isomers of flavonol glycoside, and the caffeoyl quinic acid compound is monocaffeoyl quinic acid and dicaffeoyl quinic acid position isomers;
the flavonol aglycone of the flavonol glycoside includes: kaempferol, quercetin, myricetin, isorhamnetin, luteolin kaempferol, luteolin;
wherein, for the flavonol glycoside compound, the two-stage analysis is carried out by 6 collision energies, and the change gradients of the 6 collision energies are in an arithmetic progression and are 20eV, 25eV, 30eV, 35eV, 40eV and 45eV;
the secondary mass spectrum mother ion is [ M + Na ]] + Peak, secondary mass spectrometer ion is [ M + Na ] of aglycone] + A peak; for the caffeoylquinic acid compound, performing secondary mass spectrometry with 7 collision energies, wherein the 7 collision energies have a gradient of 15eV, 20eV, 25eV, 30eV, 35eV, 40eV and 45eV in an arithmetic progression;
the parent ions of the second-order mass spectrum,the monocaffeoylquinic acid parent ion is [ M + Na] + 377; dicaffeoylquinic acid parent ion is [ M + Na [)] + 539; the secondary mass proton ion, the monocaffeoylquinic acid ion, is 163; dicaffeoylquinic acid daughter ions were 377 and 163.
2. The method of claim 1, wherein the compound is extracted by a method comprising:
ultrasonically extracting the plant to be detected in an organic solvent/aqueous solution, centrifuging and taking supernatant to obtain the plant extract.
3. The method of claim 2, wherein the organic solvent is acetonitrile, methanol, or ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910407541.9A CN110186991B (en) | 2019-05-15 | 2019-05-15 | Polyphenol positional isomer qualitative method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910407541.9A CN110186991B (en) | 2019-05-15 | 2019-05-15 | Polyphenol positional isomer qualitative method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110186991A CN110186991A (en) | 2019-08-30 |
| CN110186991B true CN110186991B (en) | 2022-12-02 |
Family
ID=67716606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910407541.9A Active CN110186991B (en) | 2019-05-15 | 2019-05-15 | Polyphenol positional isomer qualitative method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110186991B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106770803A (en) * | 2017-02-27 | 2017-05-31 | 江苏江大源生态生物科技股份有限公司 | Polyphenols HPLC/Q TOF MS detection methods in a kind of propolis |
| CN107764891B (en) * | 2017-10-16 | 2020-03-13 | 杭州先导医药科技有限责任公司 | Method for distinguishing and measuring entecavir chiral isomers |
-
2019
- 2019-05-15 CN CN201910407541.9A patent/CN110186991B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110186991A (en) | 2019-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kumar | Application of HPLC and ESI-MS techniques in the analysis of phenolic acids and flavonoids from green leafy vegetables (GLVs) | |
| Stobiecki | Application of mass spectrometry for identification and structural studies of flavonoid glycosides | |
| Ahmad et al. | Plant metabolites and regulation under environmental stress | |
| Harnly et al. | Profiling methods for the determination of phenolic compounds in foods and dietary supplements | |
| Wojakowska et al. | Structural analysis and profiling of phenolic secondary metabolites of Mexican lupine species using LC–MS techniques | |
| Lee et al. | Mass spectrometry-based metabolite profiling and antioxidant activity of Aloe vera (Aloe barbadensis Miller) in different growth stages | |
| Xu et al. | An integrated exact mass spectrometric strategy for comprehensive and rapid characterization of phenolic compounds in licorice | |
| Farag et al. | Metabolomics driven analysis of 11 Portulaca leaf taxa as analysed via UPLC-ESI-MS/MS and chemometrics | |
| Yang et al. | Identification of the chemical compositions of Ponkan peel by ultra performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry | |
| Zhang et al. | A target and nontarget strategy for identification or characterization of the chemical ingredients in Chinese herb preparation Shuang‐Huang‐Lian oral liquid by ultra‐performance liquid chromatography–quadrupole time‐of‐flight mass spectrometry | |
| Zhang et al. | Phytochemical profiles and screening of α-glucosidase inhibitors of four Acer species leaves with ultra-filtration combined with UPLC-QTOF-MS/MS | |
| Gates et al. | Characterisation of flavonoid aglycones by negative ion chip-based nanospray tandem mass spectrometry | |
| CN106596800B (en) | A kind of a variety of flavone component rapid assay methods of Herba Epimedii based on UPLC/Q-TOF | |
| Gouveia-Figueira et al. | Phenolic screening by HPLC–DAD–ESI/MSn and antioxidant capacity of leaves, flowers and berries of Rubus grandifolius Lowe | |
| CN108107126B (en) | Method for detecting flavonoid components in peony petals | |
| Soininen et al. | The combined use of constrained total-line-shape 1H NMR and LC–MS/MS for quantitative analysis of bioactive components in yellow onion | |
| CN112526047B (en) | Method for quantitatively detecting flavonoid compounds in sea buckthorn based on ultra-high performance liquid chromatography-high resolution mass spectrometry technology | |
| Kachlicki et al. | Profiling isoflavone conjugates in root extracts of lupine species with LC/ESI/MSn systems | |
| Xu et al. | Identification of new dianthrone glycosides from Polygonum multiflorum Thunb. using high-performance liquid chromatography coupled with LTQ-Orbitrap mass spectrometry detection: a strategy for the rapid detection of new low abundant metabolites from traditional Chinese medicines | |
| Stobiecki et al. | Application of LC/MS systems to structural characterization of flavonoid glycoconjugates | |
| Yang et al. | Simultaneous determination of 15 components in Radix Glehniae by high performance liquid chromatography–electrospray ionization tandem mass spectrometry | |
| Knittel et al. | Simultaneous determination of bufadienolides and phenolic compounds in sea squill (Drimia maritima (L.) Stearn) by HPLC-DAD-MS n as a means to differentiate individual plant parts and developmental stages | |
| Luo et al. | Fingerprint analysis of Ginkgo biloba extract and Ginkgo semen in preparations by LC-Q-TOF/MS | |
| Wojtanowski et al. | Study of a complex secondary metabolites with potent anti-radical activity by two dimensional TLC/HPLC coupled to electrospray ionization time-of-flight mass spectrometry and bioautography | |
| Sertić et al. | Analysis of aucubin and catalpol content in different plant parts of four Globularia species |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |