CN114441680A - Method for distinguishing traditional Chinese medicine fructus aurantii from garden balsam based on high-resolution mass spectrometry technology - Google Patents
Method for distinguishing traditional Chinese medicine fructus aurantii from garden balsam based on high-resolution mass spectrometry technology Download PDFInfo
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- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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- G01N30/26—Conditioning of the fluid carrier; Flow patterns
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Abstract
The invention discloses a method for distinguishing traditional Chinese medicine fructus aurantii from a garden based on a high-resolution mass spectrometry technology. The method is mainly used for quickly identifying the traditional Chinese medicine fructus aurantii and the garden balsam. The invention develops a method for distinguishing traditional Chinese medicine fructus aurantii from a garden based on an ultra-high performance liquid quadrupole time-of-flight mass spectrometry technology, establishes a special identification method of traditional Chinese medicine-characteristic components, finds a characteristic compound capable of distinguishing fructus aurantii from the garden, namely, hydrated oxypeucedanin, and can quickly and effectively identify the fructus aurantii and the garden; the method adopts a conventional experience identification method based on morphological appearance different from the conventional methods of bitter orange and a fragrance garden, avoids subjective fault tolerance, enhances the specificity of the method, can effectively solve the problem that the traditional Chinese medicine bitter orange and the fragrance garden are difficult to distinguish in actual work, and provides a technical method and a basis for fighting the illegal action that a fragrance garden counterfeit product fakes as the traditional Chinese medicine bitter orange.
Description
Technical Field
The invention relates to the technical field of drug analysis and detection, in particular to a method for distinguishing traditional Chinese medicine bitter orange from a fragrant garden based on a high-resolution mass spectrometry technology.
Background
The fructus Aurantii is dried immature fruit of Citrus aurantium L.of Rutaceae and its cultivar. The garden is dry mature fruit of Citrus wilsonii Tanaka, a rutaceae plant, and is one of the sources of traditional Chinese medicine citron. The appearance of the dried immature fruits in the garden is very similar to that of the bitter oranges, and the dosage and the price of the bitter oranges are higher than those of the sweet dumplings, so that the sweet dumplings are often taken as the bitter oranges by drug vendors to be sold after being faked, and the conventional experience identification based on morphological appearance is difficult to distinguish and identify the situations. In addition, due to the lack of professional appraisers of traditional Chinese medicines, Chinese patent medicine production enterprises are difficult to control the authenticity of the raw medicinal materials of the bitter orange, and finished Chinese patent medicines destroy the integrity of the raw medicinal materials, so that the difficulty of traditional Chinese medicine inspectors in identifying and distinguishing the bitter orange and the Chinese patent medicines is increased to a certain extent. In clinical practice of traditional Chinese medicine, fructus aurantii has the effects of regulating qi, relieving epigastric distention, activating stagnancy and relieving distension, and is commonly used for treating qi stagnation in chest and hypochondrium, fullness and pain, indigestion, phlegm-fluid retention, viscera prolapse and other diseases. The Xiangyuan has the effects of soothing liver, regulating qi, relieving epigastric distention and resolving phlegm, and is commonly used for treating qi stagnation of liver and stomach, distending pain in chest and hypochondrium, fullness and fullness in stomach and abdomen, vomiting of belching, excessive phlegm and cough, etc. The former is good at relieving distension, the latter is good at soothing liver and resolving phlegm, the indication efficacy of the two are quite different, and the clinical efficacy is seriously affected by the mixed use.
At present, the identification means of the traditional Chinese medicine false-mixing product mainly comprises methods such as thin-layer chromatography identification, microscopic identification, traditional Chinese medicine characteristic spectrum or fingerprint identification, Polymerase Chain Reaction (PCR) method and the like, but most of the means are the identification of the authenticity of the traditional Chinese medicine raw materials, and the false negative condition is easy to occur to the species with similar patent medicines or provenances, so the identification methods are not suitable for the identification of the bitter orange and the fragrant garden.
Therefore, it is very important to find an efficient and specific method for identifying the traditional Chinese medicine fructus aurantii and the garden balsam.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the technical defects of the background technology and provides a method for distinguishing traditional Chinese medicine bitter orange from a fragrant garden based on a high-resolution mass spectrometry technology. The method is mainly used for quickly identifying the traditional Chinese medicine fructus aurantii and the garden balsam. The invention is mainly used for a supplementary identification method which determines the traditional Chinese medicine as bitter orange or a fragrant garden but cannot be further distinguished based on the conventional morphological and appearance identification. The method is different from the conventional morphological appearance identification, and can effectively distinguish and identify the bitter orange and the fragrant garden by adopting a high-resolution mass spectrometry technology under the condition that the conventional morphological appearance identification is difficult to distinguish or the complete morphological appearance is lost.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for distinguishing traditional Chinese medicine fructus aurantii from a fragrance garden based on a high-resolution mass spectrometry technology comprises the following steps:
s1, collecting representative fructus aurantii, fragrant garden and pomelo medicinal materials, respectively extracting by adopting alcohol reagents to obtain respective test solution, and collecting a total ion flow diagram of the obtained test solution by adopting the condition of ultra-high performance liquid chromatography combined with quadrupole time-of-flight mass spectrometry;
s2, screening characteristic components which can be distinguished from each other from the total ion flow diagram of the collected bitter orange, the fragrant garden and the pomelo to obtain the mass number of the corresponding characteristic components;
s3, identifying the compound components through literature and library searching technology according to the obtained characteristic component mass numbers and corresponding primary and secondary mass spectrograms, and obtaining the compound;
s4, establishing a method for distinguishing the traditional Chinese medicine fructus aurantii from the incense garden according to known characteristic components, sample extraction conditions and high-resolution mass spectrum conditions;
and S5, adopting the method established in S4 to the sample to be detected, simultaneously acquiring the characteristic compound reference substance and the mass spectrogram of the sample to be detected, extracting the ion flow diagram of the characteristic compound, and presenting the same molecular ion peak at the retention time consistent with the ion flow diagram of the characteristic compound reference substance.
Preferably, in the above method, in S1, the representative samples of fructus aurantii, xiangyuan and pomelo are collected in the main producing areas of the country, and the coverage area includes the areas of Jiangxi, Zhejiang, Fujian, Hunan and the like, which have certain regional representativeness. Fructus Aurantii, Citrus wilsonii Tanaka and Citrus grandis (Burm) Merr, identified as Citrus aurantium L.
Preferably, in the above method, in S1, the alcohol reagent is methanol (analytically pure); preferably, when the extraction is carried out, the addition amount of the methanol is 25ml calculated by 0.1g of the traditional Chinese medicinal materials, and the ultrasonic extraction mode is adopted for extraction for 30 min.
Preferably, in the above method, the ultrasonic conditions are 250W and 40 kHz.
Preferably, in the above method, in S1, the total ion flow diagram of fructus Aurantii, fructus Citri Limoniae, and fructus Citri Grandis and its molecular ion peak extracted at m/z305.1021 are shown in fig. 1.
Preferably, in the method, in S2, the screening process of the characteristic component is to adopt UPLC-Q-TOF high resolution mass spectrometry to collect MS/MS mass spectrometry data, introduce Agilent MPP software to perform PCA and multivariate discriminant analysis, establish discriminant models of fructus aurantii, sweet dumplings and pomelos, and screen inter-group difference components; 53 unique components of the sweet round are obtained in total (see figure 2); searching and matching are carried out by adopting a compound database of Agilent TCM library-V20-04-17, 9 compounds identified by database retrieval mass spectrum data parameter matching are selected for screening (table 1), and the mass spectrum information of hydrated oxidized decursin (the mass spectrum information of the hydrated oxidized decursin is shown in table 2, the total ion flow graph of the hydrated oxidized decursin and the molecular ion peak extracted at m/z305.1021 thereof are shown in fig. 1, and the typical mass spectrum of the hydrated oxidized decursin is shown in fig. 3) can effectively distinguish a fragrance garden and fructus aurantii, so that the mass spectrum screening method is established.
In the technical scheme, the pomelo is adopted for the purposes of reducing noise of clustering analysis, narrowing the screening range of characteristic components of the fragrance garden in the discrimination model and facilitating simplification of an experimental process.
TABLE 1 search and identification table for spectrum library of different compounds of the present invention
Preferably, in the above method, in S1, the ultra high performance liquid chromatography adopts the following conditions:
chromatographic conditions are as follows: a chromatographic column: agilent SB C18(100 mm. times.2.1 mm, 1.8 μm) column; column temperature: 30 ℃; flow rate: 0.4 ml/min; performing detection by binary gradient elution, wherein a mobile phase A is acetonitrile, and a mobile phase B is 0.1% formic acid aqueous solution; in the 0-7 min period, the total volume of the mobile phase is 100%, the volume of the mobile phase A is increased from 15% to 25%, and the volume of the mobile phase B is decreased from 85% to 75%; in the 7 th-8 th min, the volume of the mobile phase A is gradually increased from 25% to 40%, and the volume of the mobile phase B is gradually decreased from 75% to 60%; at 8-10 min, the volume of the mobile phase A is gradually increased from 40% to 45%, and the volume of the mobile phase B is gradually decreased from 60% to 55%; in 10-13 min, the volume of the mobile phase A is gradually increased from 45% to 60%, and the volume of the mobile phase B is gradually decreased from 55% to 40%; and at 13-15 min, the volume of the mobile phase A is decreased from 60% to 15%, and the volume of the mobile phase B is increased from 40% to 85%. .
Preferably, in the above method, in S1, the quadrupole time-of-flight mass spectrometry adopts the following conditions:
an ion source: electrospray ionization (ESI); positive ion scan mode: electrospray voltage: 5500V; ion source temperature: 550 ℃; air curtain air: 35 psi; atomizing: 55 psi; auxiliary gas: 55 psi; de-clustering voltage: 60V; collision voltage: 35V; the scanning mode is primary mass spectrum full scanning and secondary mass spectrum full scanning, and the scanning range is 100-1500 m/z; reference ion m/z: 121.0480, and 922.0098.
Preferably, in the above method, in S3, performing library search matching with the mass spectrometry software traditional Chinese medicine database according to the retention time, the primary accurate mass number and the secondary mass spectrum of the test sample, and identifying the characteristic compound;
preferably, in the above method, in S3, the characteristic compound is hydrated oxypeucedanin(Oxypeucedanin hydrate), a characteristic component of a garden, with a molecular weight of 304.29 Da; MS (Mass Spectrometry)1(m/z)305.1021[M+H]+；MS2(m/z)203.0345[M+H]+、147.0437[M+H]+(ii) a A typical mass spectrum of oxypeucyanin hydrate is shown in FIG. 3.
Preferably, in the above method, in S4, the method for identifying the quality product of fructus aurantii is as follows: the ion flow chromatogram of the test sample extracted by mass-to-charge ratio (m/z)305.1021 should not have a chromatographic peak corresponding to the reference, if the corresponding chromatographic peak is present, the corresponding secondary mass spectrum should not be consistent with the reference.
TABLE 2 Mass Spectrometry information Table of oxypeucyanin hydrate of the invention
A method for distinguishing traditional Chinese medicine fructus aurantii from a fragrance garden based on a high-resolution mass spectrometry technology comprises the following steps:
(1) preparation of a reference solution: taking a proper amount of the characteristic component of the hydrated oxypeucedanin, precisely weighing, and adding an alcohol reagent for dissolving to obtain a reference substance solution;
(2) preparing a test solution: taking a test sample medicinal material, precisely weighing, and extracting with an alcohol reagent to obtain a test sample solution;
(3) and (3) determination: respectively acquiring total ion flow diagrams of the reference solution and the test solution by adopting ultra-high performance liquid chromatography combined quadrupole time-of-flight mass spectrometry, and respectively extracting a primary mass spectrogram and/or a secondary mass spectrogram;
(4) and (4) judging a result: if the primary mass spectrogram of the test sample solution extracted by the mass-to-charge ratio (m/z)305.1021 does not have a chromatographic peak corresponding to the primary mass spectrogram of the reference sample solution extracted by the same mass-to-charge ratio, the test sample is a normal product of fructus Aurantii;
on the contrary, if the primary mass spectrogram of the test solution extracted by the mass-to-charge ratio (m/z)305.1021 shows chromatographic peaks corresponding to the primary mass spectrogram of the reference solution extracted by the same mass-to-charge ratio, if the secondary mass spectrograms of the test solution extracted by the mass-to-charge ratios (m/z)203.0345 and 147.0437 do not show chromatographic peaks corresponding to the secondary mass spectrograms of the reference solution extracted by the same mass-to-charge ratio, the test solution is the quality product of fructus aurantii;
on the contrary, if the secondary mass spectrograms of the test solution extracted by the mass-to-charge ratios (m/z)203.0345 and 147.0437 have chromatographic peaks respectively corresponding to the secondary mass spectrograms of the reference solution extracted by the same mass-to-charge ratios, the test solution is a fragrance garden adulteration.
In the above technical solution, in the step (2), the sample to be tested is a suspected sample of fructus aurantii or a fragrant garden that cannot be identified based on conventional morphological and appearance identification.
The application of hydrated oxypeucedanin in distinguishing traditional Chinese medicine fructus aurantii from a garden based on a high-resolution mass spectrometry technology.
The basic principle of the invention is as follows:
with the rapid development of mass spectrometry technology, ultra-high performance liquid chromatography-quadrupole time of flight mass spectrometry (UPLC-Q-TOF-MS) has the advantages of high analysis speed, high sensitivity and resolution and simultaneous determination of multiple components, and has remarkable advantages in separation and analysis of endogenous components in a near-source Chinese medicament and a complex compound patent medicament matrix.
According to the situation, the invention establishes a special identification method of the traditional Chinese medicine-characteristic components, develops a method for distinguishing the traditional Chinese medicine fructus aurantii from the fragrant garden based on an ultra-high performance liquid phase quadrupole time-of-flight mass spectrometry technology, can effectively solve the problem that the traditional Chinese medicine fructus aurantii and the fragrant garden are difficult to distinguish in actual work, and provides a technical method and a basis for fighting the illegal action of faking the traditional Chinese medicine fructus aurantii as a fake product in the fragrant garden.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention develops a method for distinguishing traditional Chinese medicine fructus aurantii from a garden based on an ultra-high performance liquid phase quadrupole time-of-flight mass spectrometry technology, establishes a special distinguishing method of 'traditional Chinese medicine-characteristic components', finds a characteristic compound capable of distinguishing fructus aurantii from the garden, namely Oxypeucedanin hydrate, and can quickly and effectively distinguish the fructus aurantii from the garden;
(2) the method adopts an empirical identification method based on morphological appearance, which is different from the conventional method of bitter orange and fragrant garden, so that subjective fault tolerance is avoided, the specificity of the method is enhanced, the problem that the traditional Chinese medicine bitter orange and the fragrant garden are difficult to distinguish in actual work can be effectively solved, and a technical method and a basis are provided for fighting the illegal behavior that the fragrant garden counterfeit goods falsify as the traditional Chinese medicine bitter orange.
Drawings
FIG. 1 is a total ion flow diagram of bitter orange, sweet round, pomelo and hydrated oxypeucedanin of the present invention (A. bitter orange total ion flow diagram; C. sweet round total ion flow diagram; E. pomelo total ion flow diagram; G. hydrated oxypeucedanin total ion flow diagram) and its molecular ion peak extracted at m/z305.1021 (B. bitter orange molecular ion peak; D. sweet round molecular ion peak; F. pomelo molecular ion peak; H. hydrated oxypeucedanin molecular ion peak);
FIG. 2 is a graph of Wen's differential compound for bitter orange, sweet round and grapefruit of the present invention;
FIG. 3 is a typical mass spectrum of oxypeucyanin hydrate of the invention;
FIG. 4 shows the mass spectrum screening results of Baoxing Chinese patent drug preparation of example 1 of the present invention (A. total ion flow diagram of test sample; B. primary mass spectrum (m/z 305.1021) extracted from test sample; C. secondary mass spectrum (m/z 203.0345) extracted from test sample; D. secondary mass spectrum (m/z 147.0437) extracted from test sample; E. total ion flow diagram of negative sample; F. primary mass spectrum (m/z 305.1021) extracted from negative sample; G. secondary mass spectrum (m/z 203.0345) extracted from negative sample; H. secondary mass spectrum (m/z 147.0437) extracted from negative sample; I. total ion flow diagram of control sample; J. primary mass spectrum (m/z 305.1021) extracted from control sample; K. secondary mass spectrum (m/z 203.0345) extracted from control sample; L. secondary mass spectrum (m/z 147.0437) extracted from control sample; wherein, the test sample is Baoxinning Chinese patent medicine preparation to be tested, the negative sample is fructus aurantii quality product and Baoxinning Chinese patent medicine preparation, and the reference sample is hydrated oxypeucedanin. )
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description and accompanying drawings. It is to be understood that these examples are for further illustration of the invention and are not intended to limit the scope of the invention. In addition, it should be understood that the invention is not limited to the above-described embodiments, but is capable of various modifications and changes within the scope of the invention.
Example 1
Identification of a kindergarten drug in a baoxinning Chinese patent medicine preparation (earlier identification has confirmed that a formula in the baoxinning Chinese patent medicine preparation contains bitter orange drug or kindergarten drug but cannot be further distinguished):
1.1 chromatographic conditions
A chromatographic column: agilent SB C18(100 mm. times.2.1 mm, 1.8 μm) column; column temperature: 30 ℃; flow rate: 0.4 ml/min; binary gradient elution was used (mobile phase a was acetonitrile and mobile phase B was 0.1% formic acid in water): 0-7 min, 15% → 25% A, 85% → 75% B; 7-8 min, 25% → 40% A, 75% → 60% B; 8-10 min, 40% → 45% A, 60% → 55% B; 10-13 min, 45% → 60% A, 55% → 40% B; 13-15 min, 60% → 15% A, 40% → 85% B.
1.2 Mass Spectrometry conditions
An ion source: electrospray ionization (ESI); positive ion scan mode: electrospray voltage: 5500V; ion source temperature: 550 ℃; air curtain air: 35 psi; atomizing: 55 psi; auxiliary gas: 55 psi; de-clustering voltage: 60V; collision voltage: 35V; the scanning mode is primary mass spectrum full scanning (MS) and secondary mass spectrum full scanning (MS/MS), and the scanning range is 100-1500 m/z; reference ion m/z: 121.0480, and 922.0098.
1.3 preparation of control solutions
Taking a proper amount of the hydrated oxypeucedanin reference substance, precisely weighing, and adding methanol to prepare a solution containing 2 mug of the hydrated oxypeucedanin per 1ml, thus obtaining the reference substance solution.
1.4 preparation of negative sample solution
Taking a negative sample, namely a fructus aurantii quality product, adding Baoxinning Chinese patent medicine preparation powder of about 0.1g, precisely weighing, placing in a conical flask with a plug, precisely adding 25ml of methanol, weighing, carrying out ultrasonic treatment (250W, 40kHz) for 30min, cooling, weighing again, supplementing the weight loss by using methanol, shaking up, filtering, and taking a subsequent filtrate to obtain a negative sample solution.
1.5 preparation of test solutions
Taking a test sample, namely about 0.1g of Baoxinning Chinese patent medicine preparation powder to be tested, precisely weighing, placing in a conical flask with a plug, precisely adding 25ml of methanol, weighing, carrying out ultrasonic treatment (250W, 40kHz) for 30min, cooling, weighing again, supplementing the weight loss by using methanol, shaking up, filtering, and taking a subsequent filtrate to obtain a test sample solution.
1.6 assay method
Precisely absorbing 2 mu l of the control solution, 1-2 mu l of the negative sample solution and 1-2 mu l of the test solution respectively, injecting the solutions into a liquid chromatography-mass spectrometer (Agilent 1290-UPLC and Agilent 6545Q-TOF) for measurement, and recording a primary mass spectrum and a secondary mass spectrum.
1.7 determination of results
If the primary mass spectrogram of the test sample solution extracted by the mass-to-charge ratio (m/z)305.1021 does not have a chromatographic peak corresponding to the primary mass spectrogram of the reference sample solution extracted by the same mass-to-charge ratio, the test sample is not mixed with a fake Xiangyuan feed and is a qualified medicine, namely the test sample is a bitter orange genuine product fed Baoxinning Chinese patent medicine preparation;
on the contrary, if a chromatographic peak corresponding to the primary mass spectrum of the reference solution extracted with the same mass-to-charge ratio (m/z)305.1021 appears in the primary mass spectrum of the test solution extracted with the mass-to-charge ratio, as other components (i.e. isomers) with the same molecular weight as that of the hydrated oxypeucedanin may exist in different varieties of fructus aurantii, in order to eliminate the matrix interference, the judgment needs to be further carried out through the secondary mass spectrum;
further, if the secondary mass spectrograms of the test sample solution extracted by the mass-to-charge ratios (m/z)203.0345 and 147.0437 do not have chromatographic peaks respectively corresponding to the secondary mass spectrograms of the reference sample solution extracted by the same mass-to-charge ratio, the test sample is not mixed with a fake incense garden for feeding and is a qualified medicine, namely the test sample is a fructus aurantii quality product fed Baoxinning Chinese patent medicine preparation;
on the contrary, if the secondary mass spectrograms of the test solution extracted by the mass-to-charge ratios (m/z)203.0345 and 147.0437 respectively correspond to the secondary mass spectrograms of the reference solution extracted by the same mass-to-charge ratios, the test solution is adulterated in the fragrant garden to be fed, and the test solution is an unqualified medicine, namely the test solution is a traditional Chinese medicine preparation prepared by adulterating bitter orange in the fragrant garden to be fed with baoxinning.
As can be seen from F and J in fig. 4, since the primary mass spectrum extracted from the negative sample with the mass-to-charge ratio (m/z)305.1021 does not have a chromatographic peak corresponding to the primary mass spectrum extracted from the control hydrated oxypeucedanin with the mass-to-charge ratio (m/z)305.1021, the negative sample does not contain the hydrated oxypeucedanin, and thus the negative sample is not mixed with the pseudo-flavor garden ingredient and is a qualified drug, i.e., the negative sample is the fructus aurantii quality ingredient baoxinning Chinese patent drug preparation.
It can be seen from B, C, D and J, K, L in fig. 4 that, since the first mass spectrum extracted from the test solution at the mass-to-charge ratio (m/z)305.1021 shows the chromatographic peak corresponding to the first mass spectrum extracted from the reference hydrated oxypeucedanin at the mass-to-charge ratio (m/z)305.1021, and the second mass spectrum extracted from the test solution at the mass-to-charge ratios (m/z)203.0345 and 147.0437 shows the chromatographic peaks corresponding to the second mass spectra extracted from the reference hydrated oxypeucedanin at the mass-to-charge ratios (m/z)203.0345 and 147.0437, respectively, it indicates that the test product contains hydrated oxypeucedanin, and thus it indicates that the test product is mixed with pseudo-flavor garden feed and is an unqualified drug, i.e., the test product is a bitter orange mixed with pseudo-flavor garden baoxinning preparation.
The above description is not intended to limit the invention, nor is the invention limited to the examples set forth above. Those skilled in the art should also appreciate that they may make various changes, modifications, additions and substitutions within the spirit and scope of the invention.
Claims (8)
1. A method for distinguishing traditional Chinese medicine fructus aurantii from a fragrance garden based on a high-resolution mass spectrometry technology is characterized by comprising the following steps:
(1) preparation of a control solution: taking a proper amount of the characteristic component of the hydrated oxypeucedanin, precisely weighing, and adding an alcohol reagent for dissolving to obtain a reference substance solution;
(2) preparing a test solution: precisely weighing the test sample medicinal material, and dissolving with alcohol reagent to obtain test sample solution;
(3) and (3) determination: respectively acquiring total ion flow diagrams of the reference solution and the test solution by adopting ultra-high performance liquid chromatography combined quadrupole time-of-flight mass spectrometry, and respectively extracting a primary mass spectrogram and/or a secondary mass spectrogram;
(4) and (4) judging a result: if the first-order mass spectrum of the test solution extracted by the mass-to-charge ratio (m/z)305.1021 does not have a chromatographic peak corresponding to the first-order mass spectrum of the reference solution extracted by the same mass-to-charge ratio, the test sample is the fructus aurantii quality product;
on the contrary, if the primary mass spectrogram of the test solution extracted by the mass-to-charge ratio (m/z)305.1021 shows chromatographic peaks corresponding to the primary mass spectrogram of the reference solution extracted by the same mass-to-charge ratio, if the secondary mass spectrograms of the test solution extracted by the mass-to-charge ratios (m/z)203.0345 and 147.0437 do not show chromatographic peaks corresponding to the secondary mass spectrograms of the reference solution extracted by the same mass-to-charge ratio, the test solution is the quality product of fructus aurantii;
on the contrary, if the secondary mass spectrograms of the test solution extracted by the mass-to-charge ratios (m/z)203.0345 and 147.0437 have chromatographic peaks respectively corresponding to the secondary mass spectrograms of the reference solution extracted by the same mass-to-charge ratios, the test solution is a fragrance garden adulteration.
2. The method for distinguishing the traditional Chinese medicine fructus aurantii from the fragrant garden based on the high-resolution mass spectrometry technology as claimed in claim 1, wherein in the step (1), the characteristic component screening process is to adopt UPLC-Q-TOF high-resolution mass spectrometry to collect MS/MS mass spectrometry data, introduce Agilent MPP software to perform PCA and multivariate discriminant analysis, establish discriminant models of fructus aurantii, fragrant round and pomelo, and screen interclass difference components; 53 unique components of the sweet dumplings are obtained; selecting 9 compounds identified by database retrieval mass spectrum data parameter matching, screening, and verifying by combining a comparison quality spectrogram to find that the hydrated oxypeucedanin can effectively distinguish the garden and the bitter orange to be a unique component of the sweet dumpling, thereby establishing a mass spectrum screening method.
3. The method for distinguishing fructus aurantii from a garden balsam which is a traditional Chinese medicine based on the high-resolution mass spectrometry technology as claimed in claim 1, wherein in the step (1), the alcohol reagent is methanol; adding the methanol to prepare a solution containing 2 micrograms per 1ml, thus obtaining the reference substance solution.
4. The method according to claim 1, wherein in the step (2), the alcohol reagent is methanol; when the dissolution is carried out, the addition amount of the methanol is 25ml calculated by 0.1g of the traditional Chinese medicinal materials, and ultrasonic treatment is adopted for 30 min.
5. The method for distinguishing the traditional Chinese medicine fructus aurantii from the garden on the basis of the high-resolution mass spectrometry technology as claimed in claim 1, wherein in the step (3), 2 μ l of the control solution and 1-2 μ l of the test solution are respectively and precisely absorbed, injected into a liquid chromatography-mass spectrometer for measurement, and a primary mass spectrum and/or a secondary mass spectrum are/is recorded.
6. The method for distinguishing the traditional Chinese medicine fructus aurantii from the fragrant garden based on the high-resolution mass spectrometry technology as claimed in claim 1, wherein in the step (3), the ultra-high performance liquid chromatography adopts the following conditions:
chromatographic conditions are as follows: a chromatographic column: agilent SB C18(100 mm. times.2.1 mm, 1.8 μm) column; column temperature: 30 ℃; flow rate: 0.4 ml/min; binary gradient elution is adopted, wherein a mobile phase A is acetonitrile, and a mobile phase B is 0.1% formic acid aqueous solution; based on the total volume of the mobile phase as 100%, in 0-7 min, the volume of the mobile phase A is increased from 15% to 25%, and the volume of the mobile phase B is decreased from 85% to 75%; in the 7 th-8 th min, the volume of the mobile phase A is gradually increased from 25% to 40%, and the volume of the mobile phase B is gradually decreased from 75% to 60%; at 8-10 min, the volume of the mobile phase A is gradually increased from 40% to 45%, and the volume of the mobile phase B is gradually decreased from 60% to 55%; in 10-13 min, the volume of the mobile phase A is gradually increased from 45% to 60%, and the volume of the mobile phase B is gradually decreased from 55% to 40%; and at 13-15 min, the volume of the mobile phase A is decreased from 60% to 15%, and the volume of the mobile phase B is increased from 40% to 85%.
7. The method for distinguishing the traditional Chinese medicine fructus aurantii from the fragrant garden based on the high-resolution mass spectrometry technology as claimed in claim 1, wherein in the step (3), the quadrupole time-of-flight mass spectrometry adopts the following conditions:
an ion source: electrospray ionization (ESI); positive ion scan mode: electrospray voltage: 5500V; ion source temperature: 550 ℃; air curtain air: 35 psi; atomizing: 55 psi; auxiliary gas: 55 psi; de-clustering voltage: 60V; collision voltage: 35V; the scanning mode is primary mass spectrum full scanning and secondary mass spectrum full scanning, and the scanning range is 100-1500 m/z; reference ion m/z: 121.0480, and 922.0098.
8. The application of hydrated oxypeucedanin in distinguishing traditional Chinese medicine fructus aurantii from a garden based on a high-resolution mass spectrometry technology.
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