Method for identifying traditional Chinese medicine evodia rutaecarpa base based on GC-IMS characteristic odor substances

Abstract

The invention provides a method for identifying a traditional Chinese medicine evodia rutaecarpa base based on GC-IMS characteristic odor substances, which comprises the following steps: carrying out headspace GC-IMS detection on a sample, and determining that the sample is evodia rutaecarpa when the peak volume ratio of 2 (E)-hexenoic acid to dimethyl disulfide to 3-methylthio propanol to 2-methyl methoxybenzoate is 1: (1.4-2.0): (1.4-2.4): (1.7-2.6); when the ratio of the medicinal materials is 1: (0.4-0.9): (0.6-1.0): (0.6-1.2), the medicinal materials are evodia rutaecarpa or stonecrop Then, when the peak volume ratio of the cyclopentanone to the L-carvone is 5.3-5.7, determining that the evodia rutaecarpa is the evodia rutaecarpa; when the ratio is 6.2-7.6, the sample is a stone tiger. The method provided by the invention is rapid, lossless, free of complex sample pretreatment, simple, environment-friendly, low in detection cost, visual in result and suitable for rapidly, objectively and accurately judging the traditional Chinese medicine evodia base in batches.

Description

Technical Field

[0001] The invention belongs to the technical field of quality detection of Chinese medicinal materials or decoction pieces, and specifically relates to a method for identifying the origin of the Chinese medicinal material Evodia rutaecarpa. Background Art

[0002] The disclosure of this background information is intended to enhance understanding of the general background of the invention and should not necessarily be taken as an acknowledgment or any form of suggestion that this information constitutes the prior art already known to a person skilled in the art.

[0003] Fructus evodiae is a plant of the Rutaceae family. Evodia rutaecarpa (Juss.) Benth., Shihu Evodia rutaecarpa (Juss) Benth.var. Officinalis (Dode) Huang or Evodia rutaecarpa Evodia rutaecarpa (Juss.) Benth. var. bodinieri The dried nearly mature fruit of (Dode) Huang was first recorded in Shennong's Herbal Classic and listed as a medium-grade product. It is a traditional Chinese medicine commonly used in clinical practice. Evodia rutaecarpa mainly contains alkaloids, bitter elements, flavonoids and volatile oils, and has pharmacological effects such as anti-inflammatory, analgesic, anti-gastric ulcer and antiemetic. It is often used in clinical practice to treat cardiovascular diseases, digestive diseases, oral ulcers and other difficult and complicated diseases with significant efficacy. However, as a multi-origin Chinese medicine, Evodia rutaecarpa has very similar morphological characteristics, but large differences in internal quality, which is not conducive to its quality control and clinical precision medication.

[0004] The main methods for identifying the origin of the traditional Chinese medicine Evodia rutaecarpa include trait identification, microscopic identification, physical and chemical identification, and DNA molecular identification. Traditional trait identification mainly evaluates the size and color of the medicinal material, and believes that Evodia rutaecarpa with small grains and green color is the best for medicinal use. The "Compilation of Standards for Specifications and Grades of Chinese Medicinal Materials" divides Evodia rutaecarpa into two specifications, "medium flower" and "small flower", based on market circulation. The main difference is the fruit diameter, but small grains, large grains, medium flowers, and small flowers cannot be used to identify its origin. Some scholars have identified different origins of Evodia rutaecarpa through fingerprints, but this method has problems such as cumbersome sample preparation methods and detection conditions, long time consumption, high cost of reference substances and organic solvents, and certain risks and pollution of reagents. Compared with traditional identification methods, DNA molecules can provide rich information for species identification. There have been studies on molecular identification of Evodia rutaecarpa using universal DNA barcodes such as ITS, ITS2 and psbA-trnH, but they cannot fully express the genetic background of Evodia rutaecarpa plants, so the above technologies cannot accurately identify the origin of Evodia rutaecarpa. Therefore, it is urgent and necessary to establish a method for rapid and effective identification of the origin of the traditional Chinese medicine Evodia rutaecarpa.

[0005] The smell of most traditional Chinese medicines is closely related to their origin and quality. The smell of traditional Chinese medicines with different origins, origins and processing methods can reflect the differences in their volatile components. Therefore, the smell of traditional Chinese medicine is one of the important criteria for quality evaluation. Gas chromatography-ion mobility mass spectrometry (GC-IMS) is a new method for the detection of the smell of traditional Chinese medicines that has emerged in recent years. GC-IMS detection does not require complex sample pretreatment, the method is simple and environmentally friendly, the consumables used in the identification process are few, and the results are intuitive. Therefore, exploring and establishing a method for identifying the origin of the traditional Chinese medicine Evodia rutaecarpa based on GC-IMS odor detection, and realizing rapid, effective and accurate identification of the origin of Evodia rutaecarpa medicinal materials or decoction pieces, is of great significance to improving the quality control method of Evodia rutaecarpa and promoting clinical precision medicine use. Summary of the invention

[0006] In view of the problem that it is difficult and complicated to identify the origin of the traditional Chinese medicine Evodia rutaecarpa in the prior art, the present invention provides a method for identifying the origin of the traditional Chinese medicine Evodia rutaecarpa based on GC-IMS characteristic odor substances. The method does not require complicated sample pretreatment, is simple and environmentally friendly, uses fewer consumables in the identification process, and the results are intuitive.

[0007] To achieve the above purpose, the present invention adopts the following technical solution.

[0008] A method for identifying the origin of the traditional Chinese medicine Evodia rutaecarpa based on GC-IMS characteristic odor substances, comprising the following steps: (1) The powder of the medicinal material or decoction piece of Evodia rutaecarpa to be tested is tested by gas chromatography-ion mobility spectrometry through headspace injection to obtain a characteristic fingerprint spectrum; (2) Obtain the peak volumes of 2(E)-hexenoic acid, dimethyl disulfide, 3-methylthiopropanol, and methyl 2-methoxybenzoate, and make the following judgments: When the ratio of the peak volumes of 2(E)-hexenoic acid, dimethyl disulfide, 3-methylthiopropanol and methyl 2-methoxybenzoate was 1:(1.4-2.0):(1.4-2.4):(1.7-2.6), the origin was determined to be Evodia rutaecarpa; When the ratio of the peak volumes of 2(E)-hexenoic acid, dimethyl disulfide, 3-methylthiopropanol and methyl 2-methoxybenzoate is 1:(0.4-0.9):(0.6-1.0):(0.6-1.2), the origin is determined to be Evodia rutaecarpa or Evodia sparsely hairy; (3) When the origin is Evodia rutaecarpa or Evodia rutaecarpa, further obtain the peak volumes of cyclopentanone and L-carvone and make the following judgment: When the ratio of the peak volumes of cyclopentanone and L-carvone is 5.3-5.7, the origin is determined to be Evodia rutaecarpa; when the ratio is 6.2-7.6, the origin is determined to be Lycopodiella cernua.

[0009] Furthermore, the headspace operation steps include: weighing 0.5-1 g of the powder of the Evodia rutaecarpa sample to be tested, placing it in a headspace injection bottle, incubating it at 80° C. for 15 min, and then injecting the headspace sample.

[0010] Furthermore, the conditions of the gas chromatography-ion mobility mass spectrometry are as follows: the chromatographic column is MXT-5, 30 m, ID: 0.53 mm, df: 1.0 μm; the chromatographic column temperature is 60°C; the carrier gas / drift gas: N 2 ; IMS temperature: 45℃; in automatic headspace sampling unit, injection volume: 200 μL; incubation time: 15 min; incubation temperature: 80℃; injection needle temperature: 85℃; incubation speed: 500 rpm; The gas chromatography conditions were as follows: E1 drift gas volume flow rate was 75 mL / min; E2 gas phase carrier gas volume flow rate: 0-2min, 2 mL / min; 2-10 min, 2-10 mL / min; 10-20 min, 10-100 mL / min; 20-25 min, 100-150 mL / min; 25-40 min, 150 mL / min.

[0011] The present invention has the following advantages: The present invention detected 86 volatile odor substances in different origin Chinese medicine Evodia rutaecarpa by GC-IMS spectrum analysis of three origin Chinese medicines Evodia rutaecarpa. Combining characteristic fingerprint spectrum with VIP analysis and screening, it was determined that there were three characteristic odor substances that can be used to distinguish Evodia rutaecarpa from the other two origin Chinese medicines Evodia rutaecarpa (Evodia sparse hair and Evodia rutaecarpa sparse hair and Evodia rutaecarpa sparse hair), and one non-characteristic odor substance; one characteristic odor substance that can be used to distinguish Evodia rutaecarpa sparse hair and Evodia rutaecarpa sparse hair and one non-characteristic odor. The identification of different origin Chinese medicines Evodia rutaecarpa sparse hair and Evodia rutaecarpa sparse hair can be achieved through the ratio range of characteristic and non-characteristic odor substances, and the result is highly accurate, which can provide a new idea for identifying different origin Chinese medicines Evodia rutaecarpa sparse hair or decoction pieces based on characteristic odor substances.

[0012] The method for identifying the origin of the traditional Chinese medicine Evodia rutaecarpa based on GC-IMS characteristic odor substances provided by the present invention adopts the ratio of characteristic odor substances and non-characteristic odor substances, which can realize the identification of three origins, and the measurement result is more accurate; the method of the present invention is fast, non-destructive, does not require complicated sample pretreatment, the method is simple, environmentally friendly, has low detection cost, and the result is intuitive, and is suitable for batch fast, objective and accurate judgment of the origin of the traditional Chinese medicine Evodia rutaecarpa. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 The GC-IMS three-dimensional spectra of different origin Chinese medicine Evodia rutaecarpa; Figure 2 This is the GC-IMS two-dimensional top view of Evodia rutaecarpa of different origins; Figure 3 GC-IMS differential spectrograms of Evodiae Fructus from different origins Figure 4 GC-IMS characteristic fingerprint spectra of Evodiae Fructus from different origins Figure 5 OPLS-DA permutation test analysis chart of Evodiae Fructus and Evodiae Fructus from another two origins Figure 6 VIP analysis chart of Evodiae Fructus and Evodiae Fructus from another two origins Figure 7 OPLS-DA permutation test analysis chart of Evodiae Fructus inermis and Evodiae rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang Figure 8 VIP analysis chart of Evodiae Fructus inermis and Evodiae rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang Figure 9 GC-IMS three-dimensional spectrograms of verification samples of Evodiae Fructus from different origins Figure 10 GC-IMS two-dimensional top view of verification samples of Evodiae Fructus from different origins Figure 11 GC-IMS differential spectrograms of verification samples of Evodiae Fructus from different origins Figure 12 GC-IMS characteristic fingerprint spectra of verification samples of Evodiae Fructus from different origins Specific embodiments

[0014] The present invention will be further described below in conjunction with embodiments and drawings, but the present invention is not limited by the following embodiments.

[0015] Embodiment 1 Establishment and verification of the method (1) Method establishment Collect Evodiae Fructus of traditional Chinese medicine from different origins, and the sources are shown in Table 1.

[0016] Table 1 Information of Evodiae Fructus samples Precisely weigh 0.5 g of each of the powders of Evodiae Fructus inermis (SM1, SM2, SM3, and SM4), Evodiae rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang (SH1, SH2, SH3, and BZ4), and Evodiae Fructus (ZY1, ZY2, ZY3, and ZY4) in Table 1, place them in 20 mL headspace vials respectively, incubate at 80 °C for 15 min and then inject the samples, and determine them by GC-IMS; The conditions of the above GC-IMS are as follows: the chromatographic column is MXT-5, 30 m, ID: 0.53 mm, df: 1.0 μm; the column temperature is 60 °C; the carrier gas / drift gas: N 2; IMS temperature: 45 °C; In the automatic headspace injection unit, injection volume: 200 μL; Incubation time: 15 min; Incubation temperature: 80 °C; Syringe temperature: 85 °C; Incubation rotation speed: 500 rpm; Gas chromatography conditions: The drift gas volume flow rate of E1 is 75 mL / min; The gas carrier volume flow rate of E2: 0 - 2 min, 2 mL / min; 2 - 10 min, 2 - 10 mL / min; 10 - 20 min, 10 - 100 mL / min; 20 - 25 min, 100 - 150 mL / min; 25 - 40 min, 150 mL / min.

[0017] (2) Visual analysis Use the Reporter plug-in built in VOCal software to directly compare the differences in volatile odor substances of Evodia rutaecarpa (Juss.) Benth. with three origins. The GC-IMS three-dimensional spectrograms of Evodia rutaecarpa var. bodinieri (SM1, SM2, SM3, and SM4), Evodia rutaecarpa var. officinalis (SH1, SH2, SH3, and SH4), and Evodia rutaecarpa (ZY1, ZY2, ZY3, ZY4) are as Figure 1 shown. One peak in the three-dimensional spectrogram represents one substance. Red represents high concentration, and white represents low concentration.

[0018] The two-dimensional top views of Evodia rutaecarpa var. bodinieri (SM1, SM2, SM3, SM4), Evodia rutaecarpa var. officinalis (SH1, SH2, SH3, SH4), and Evodia rutaecarpa (ZY1, ZY2, ZY3, ZY4) are as Figure 2 shown. The abscissa is the ion migration time, the vertical line at the starting end is the reaction ion peak (RIP peak) after normalization, the ordinate is the retention time of gas chromatography, and each point on both sides of the RIP represents a volatile organic compound. The color indicates the concentration of the organic compound, and the darker the color, the greater the concentration.

[0019] The GC-IMS difference spectrograms of volatile odor substances of Evodia rutaecarpa var. bodinieri (SM1, SM2, SM3, SM4), Evodia rutaecarpa var. officinalis (SH1, SH2, SH3, SH4), and Evodia rutaecarpa (ZY1, ZY2, ZY3, ZY4) are as Figure 3 shown. Taking the spectrogram of Evodia rutaecarpa var. bodinieri SM1 as the reference, if the volatile organic compounds are the same, the background after subtraction is white. Red indicates that the concentration of this substance is higher than the reference, and blue represents that the concentration of this substance is lower than the reference. It can be Figures 1-3 seen that the differences in volatile substances between Evodia rutaecarpa and the other two origins of Evodia rutaecarpa (Evodia rutaecarpa var. bodinieri, Evodia rutaecarpa var. officinalis) are relatively obvious, while the overall differences between Evodia rutaecarpa var. bodinieri and Evodia rutaecarpa var. officinalis are relatively small.

[0020] (3) Fingerprint analysis The Gallery Plot plug-in was used to compare the formed characteristic fingerprint spectra, analyze the differential odor substances, and the GC-IMS characteristic fingerprint spectra of Evodia rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang (SM1, SM2, SM3, SM4), Evodia rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang (SH1, SH2, SH3, SH4), and Evodia rutaecarpa (Juss.) Benth. (ZY1, ZY2, ZY3, ZY4) are as follows Figure 4 shown; each row in the figure represents all the signal peaks selected in a sample, and each column represents the signal peaks of the same volatile organic compound in different samples; the color represents the concentration of the substance, and the darker the red color, the greater the concentration. The NIST database and IMS database built into the software were used for qualitative analysis of volatile organic compounds, and a total of 86 volatile organic compounds were detected, mainly including acids, aldehydes, ketones, alcohols, ethers, esters, etc. The peak volumes of dimethyl disulfide, 1-Propanol, 3-(methylthio), and Methyl 2-methoxybenzoate in Evodia rutaecarpa (Juss.) Benth. are relatively large, while the peak volumes of the above components in the other two original Evodia rutaecarpa (Evodia rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang, Evodia rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang) are relatively small and numerically close. Therefore, the above three components can be used as characteristic odor substances to identify Evodia rutaecarpa (Juss.) Benth. from the other two original Evodia rutaecarpa (Evodia rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang, Evodia rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang). The peak volume differences of cyclopentanone in samples of Evodia rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang and Evodia rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang are relatively large and can be used as characteristic odor substances to identify the two, as shown in Table 2 and Table 3

[0021] Table 2 Characteristic and non-characteristic odor substances and peak volumes for differentiating Evodia rutaecarpa (Juss.) Benth. from the other two original Evodia rutaecarpa Table 3 Characteristic and non-characteristic odor substances and peak volumes for differentiating Evodia rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang and Evodia rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang Taking the ratio range between the selected characteristic odor substances as the definition criterion, no matter which one of the three characteristic odor substances is used as the benchmark, there is partial overlap in the ratio ranges between the characteristic odor substances of the three original Evodia rutaecarpa, and the identification of the original cannot be completed, as shown in Table 4

[0022] Table 4 Ratio ranges with the ratio range between characteristic odor substances as the definition criterion Based on this, it is necessary to introduce other substances to complete the identification of the origin of Evodiae Fructus. Among the three origin traditional Chinese medicines of Evodiae Fructus, compared with other volatile components, the peak volume of 2(E)-hexenoic acid has a relatively small difference and can be selected as a non-characteristic odor substance. Simply from the peak volume of cyclopentanone, the differential component in samples of E. rutaecarpa var. bodinieri and E. rutaecarpa var. officinalis, the Evodiae Fructus of the two origins can be distinguished according to different peak volume ranges. However, considering that the peak volume is affected by factors such as the testing time and the batch of the tested samples, to improve the accuracy and reliability of the obtained results, when distinguishing E. rutaecarpa var. bodinieri and E. rutaecarpa var. officinalis, non-characteristic odor substances of E. rutaecarpa var. bodinieri and E. rutaecarpa var. officinalis are also searched for, and the ratio range of characteristic odor substances to non-characteristic odor substances is used for origin differentiation. The peak volumes of l-carvone in samples of E. rutaecarpa var. bodinieri and E. rutaecarpa var. officinalis are small and the numerical differences are small, which can be selected as non-characteristic odor substances, as shown in Table 2 and Table 3.

[0023] To verify the rationality of the selected characteristic and non-characteristic odor substances, using Simca 14.1 software, with the GC-IMS peak volume information of the three origin Evodiae Fructus as variables, setting the Evodiae Fructus samples as group "1", and the samples of E. rutaecarpa var. bodinieri and E. rutaecarpa var. officinalis as group "2", orthogonal partial least squares discriminant analysis (OPLS-DA) is carried out, and permutation test is used for model verification, and variable importance projection analysis is carried out. The larger the VIP value, the greater the contribution to distinguishing Evodiae Fructus from the other two origin Evodiae Fructus (E. rutaecarpa var. bodinieri, E. rutaecarpa var. officinalis). The model verification diagram and VIP diagram are shown in Figure 5 、 Figure 6 。 It can be seen that the established model is reliable. According to the VIP scores of the odor substances, characteristic odor substances are searched for among the odor substances with VIP value ≥ 1.3, and non-characteristic odor substances are searched for among the odor substances with VIP ≤ 0.5. Through screening, it is determined that dimethyl disulfide, 3-methylthiopropanol and methyl 2-methoxybenzoate are selected as the characteristic odor substances for distinguishing Evodiae Fructus from the other two origin Evodiae Fructus (E. rutaecarpa var. bodinieri, E. rutaecarpa var. officinalis), and 2(E)-hexenoic acid is selected as the non-characteristic odor substance for distinguishing Evodiae Fructus from the other two origin Evodiae Fructus (E. rutaecarpa var. bodinieri, E. rutaecarpa var. officinalis). Further, with the GC-IMS peak volume information of E. rutaecarpa var. bodinieri and E. rutaecarpa var. officinalis as variables, setting the E. rutaecarpa var. bodinieri samples as group "1", and the E. rutaecarpa var. officinalis samples as group "2", VIP analysis is carried out, and the model verification and VIP diagram are shown in Figure 7 、 Figure 8。It can be seen that the established model is reliable. Similarly, according to the VIP scores of odor substances, characteristic odor substances are searched among odor substances with VIP values ≥ 1.3, and non-characteristic odor substances are searched among odor substances with VIP ≤ 0.5. Through screening, cyclopentanone is determined to be the characteristic odor substance for distinguishing Evodia rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang from Evodia rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang, and (-)-carvone is determined to be the non-characteristic odor substance for distinguishing Evodia rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang from Evodia rutaecarpa (Juss.) Benth. var. officinalis (Dode). Through screening by VIP values, it can be considered reasonable to use dimethyl disulfide, 3-(methylthio)-1-propanol, and methyl 2-methoxybenzoate as characteristic odor substances for identifying Evodia rutaecarpa and the other two original Evodia rutaecarpa (Evodia rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang, Evodia rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang), and 2(E)-hexenoic acid as a non-characteristic odor substance; and it is reasonable to use cyclopentanone as the characteristic odor substance for identifying Evodia rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang from Evodia rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang, and (-)-carvone as a non-characteristic odor substance.

[0024] The method for judging the origin of traditional Chinese medicine Evodia rutaecarpa based on the peak volume ratio range of characteristic odor substances and non-characteristic odor substances in Evodia rutaecarpa with different origins is as follows: when the peak volume of the sample to be tested satisfies 2(E)-hexenoic acid:dimethyl disulfide:3-(methylthio)-1-propanol:methyl 2-methoxybenzoate = 1:(1.4 - 2.0):(1.4 - 2.4):(1.7 - 2.6), it is Evodia rutaecarpa; when the peak volume of the sample to be tested satisfies 2(E)-hexenoic acid:dimethyl disulfide:3-(methylthio)-1-propanol:methyl 2-methoxybenzoate = 1:(0.4 - 0.9):(0.6 - 1.0):(0.6 - 1.2), it is Evodia rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang or Evodia rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang.

[0025] If the sample to be tested is determined to be Evodia rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang or Evodia rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang, further origin identification is carried out through the peak volume ratio range of cyclopentanone and (-)-carvone. When the peak volume ratio range of cyclopentanone and (-)-carvone is 5.3 - 5.7, it is Evodia rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang, and when the ratio range is 6.2 - 7.6, it is Evodia rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang.

[0026] Example 2 Practical application of the detection method Samples of Evodia rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang (SM verification), Evodia rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang (SH verification), and Evodia rutaecarpa (ZY verification) in Table 1 were taken respectively and detected according to the detection method and detection conditions in Example 1 (1).

[0027] (1) Visual analysis The three-dimensional GC-IMS spectra of Evodia rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang (SM verification), Evodia rutaecarpa (Juss.) Benth. var. officinalis (Dode) Huang (SH verification), and Evodia rutaecarpa (ZY verification) are as Figure 9 shown, and the two-dimensional top view of volatile odor substances is as Figure 10 shown, and the GC-IMS difference spectrum of volatile odor substances is as Figure 11As shown, it can be seen that the differences in volatile odor substances in Evodia rutaecarpa and the verification samples of the other two origins (Evodia rutaecarpa var. bodinieri and Evodia rutaecarpa var. officinalis) are relatively obvious, while the overall differences in the verification samples of Evodia rutaecarpa var. bodinieri and Evodia rutaecarpa var. officinalis are relatively small. The verification samples (SM verification, SH verification, ZY verification) have little difference from the corresponding origin samples in Example 1.

[0028] (2)Fingerprint analysis The Gallery Plot plug-in was used to compare the formed characteristic fingerprint. The GC-IMS characteristic fingerprints of the verification samples (SM verification, SH verification, ZY verification) of Evodia rutaecarpa with three origins are as Figure 12 shown. The peak volumes of characteristic and non-characteristic odor substances in the verification samples (SM verification, SH verification, ZY verification) of Evodia rutaecarpa with three origins are shown in Table 5 and Table 6.

[0029] Table 5 Peak volumes of characteristic and non-characteristic odor substances for distinguishing Evodia rutaecarpa from the other two origins of Evodia rutaecarpa in the verification samples Table 6 Peak volumes of characteristic and non-characteristic odor substances for distinguishing Evodia rutaecarpa var. bodinieri and Evodia rutaecarpa var. officinalis in the verification samples Calculation found that: 1) For the ZY verification sample, 2(E)-hexenoic acid: dimethyl disulfide: 3-methylthiopropanol: methyl 2-methoxybenzoate = 1:1.6:1.7:1.7, which is determined to be Evodia rutaecarpa; for the SM verification sample, 2(E)-hexenoic acid: dimethyl disulfide: 3-methylthiopropanol: methyl 2-methoxybenzoate = 1:0.6:0.8:0.7; for the SH verification sample, 2(E)-hexenoic acid: dimethyl disulfide: 3-methylthiopropanol: methyl 2-methoxybenzoate = 1:0.6:0.8:1.1, and the two are Evodia rutaecarpa var. bodinieri or Evodia rutaecarpa var. officinalis; 2) The ratio of cyclopentanone to levomenol in the SM verification sample is 5.6, which is determined to be Evodia rutaecarpa var. bodinieri; the ratio of cyclopentanone to levomenol in the SH verification sample is 7.1, which is determined to be Evodia rutaecarpa var. officinalis. The sample verification shows that the method for identifying the origin of traditional Chinese medicine Evodia rutaecarpa based on the ratio range of peak volumes of GC-IMS characteristic and non-characteristic odor substances in the present invention is accurate and feasible.

[0030] The above are only the embodiments of the present application and are not used to limit the present application. For those skilled in the art, various changes and modifications can be made to the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included within the scope of the claims of the present application.

Claims

1. A method for identifying the origin of the Chinese medicine Evodia rutaecarpa based on GC-IMS characteristic odor substances, characterized in that: The following steps are involved: (1) The powder of the medicinal material or decoction piece of Evodia rutaecarpa to be tested is tested by gas chromatography-ion mobility spectrometry through headspace injection to obtain a characteristic fingerprint spectrum; (2) Obtain the peak volumes of 2(E)-hexenoic acid, dimethyl disulfide, 3-methylthiopropanol, and methyl 2-methoxybenzoate, and make the following judgments: When the peak volume ratio of 2(E)-hexenoic acid, dimethyl disulfide, 3-methylthiopropanol and methyl 2-methoxybenzoate is 1:(1.4-2.0):(1.4-2.4):(1.7-2.6), the origin is determined to be Evodia rutaecarpa Euopsis rutaecarpa (Juss.) Benth.; When the peak volume ratio of 2(E)-hexenoic acid, dimethyl disulfide, 3-methylthiopropanol and methyl 2-methoxybenzoate is 1:(0.4-0.9):(0.6-1.0):(0.6-1.2), the origin is determined to be Evodia rutaecarpa Euopsis rutaecarpa (Juss.) Benth. var. bodinieri (Dode) Huang or Shi Hu Euopsis rutaecarpa (Juss) Benth.var. Officinalis (Dode) Huang; (3) When the origin is Evodia rutaecarpa or Evodia rutaecarpa, further obtain the peak volumes of cyclopentanone and L-carvone and make the following judgment: When the ratio of the peak volumes of cyclopentanone and L-carvone is 5.3-5.7, the origin is determined to be Evodia rutaecarpa; when the ratio is 6.2-7.6, the origin is determined to be Lycopodiella cernua.

2. The method according to claim 1, characterized in that The headspace operation steps include: weighing 0.5-1 g of the powder of the Evodia rutaecarpa sample to be tested, placing it in a headspace injection bottle, incubating it at 80°C for 15 min, and then injecting the headspace sample.

3. The method according to claim 1, characterized in that The conditions of the gas chromatography-ion mobility mass spectrometry are as follows: the chromatographic column is MXT-5, 30 m, ID: 0.53 mm, df: 1.0 μm; the chromatographic column temperature is 60°C; the carrier gas / drift gas is N2; the IMS temperature is 45°C; in the automatic headspace injection unit, the injection volume is 200 μL; the incubation time is 15 min; the incubation temperature is 80°C; the injection needle temperature is 85°C; the incubation speed is 500 rpm; The gas chromatography conditions were as follows: E1 drift gas volume flow rate was 75 mL / min; E2 gas phase carrier gas volume flow rate: 0-2 min, 2 mL / min; 2-10 min, 2-10 mL / min; 10-20 min, 10-100 mL / min; 20-25 min, 100-150 mL / min; 25-40 min, 150 mL / min.

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