Fingerprint spectrum of radix euphorbiae lantu and adulterants thereof and establishment method and application thereof

Abstract

The invention discloses a method for establishing a fingerprint spectrum of radix euphorbiae lantu and a counterfeit product thereof, which comprises the following steps: respectively pulverizing and sieving radix euphorbiae lantu samples for later use, putting the radix euphorbiae lantu samples into a headspace sample injection bottle, and capping and sealing; and carrying out ultra-fast gas phase electronic nose separation detection, carrying out programmed temperature rise to obtain effective smell information of the stellera chamaejasme and the fake stellera chamaejasme, and calibrating fingerprint characteristics by using relative retention parameters so as to obtain the fingerprint spectrum. Respectively determining the types of the stellera chamaejasme samples according to relative retention parameters in the fingerprint spectrum; the invention further discloses a fingerprint spectrum of the radix euphorbiae lantu and the adulterants of the radix euphorbiae lantu, and the fingerprint spectrum of the radix euphorbiae lantu and the adulterants of the radix euphorbiae lantu provided by the invention combines visual heat map analysis and clustering analysis, so that rapid identification of the four kinds of original radix euphorbiae lantu is realized.

Description

Technical Field

[0001] The present invention relates to the field of quality control of Chinese medicinal materials, and in particular to a fingerprint spectrum of wolfsbane and its mixed and counterfeited products, and an establishment method and application thereof. Background Art

[0002] With the continuous development of my country's medical industry, the traditional Chinese medicine industry has become a national industry in my country. It is the only way for its development to promote the modernization of traditional Chinese medicine in all directions and realize the standardization of traditional Chinese medicine. The key issue in the modernization of traditional Chinese medicine lies in the quality control and evaluation of traditional Chinese medicine. It is urgent to establish a quality evaluation method based on the theoretical guidance of traditional Chinese medicine and in line with the current situation of traditional Chinese medicine. my country's traditional Chinese medicine resources are extremely rich and there are many varieties, but there are many places where traditional Chinese medicine is planted, which are widely distributed and difficult to supervise, resulting in uneven quality of medicinal materials on the market and difficulty in distinguishing between true and false. Different medicinal materials have different species and active ingredients, and their pharmacological effects and clinical efficacy are often very different. Therefore, a simple and fast method that can identify a large number of counterfeits is needed.

[0003] Wolfsbane was first recorded in Shennong's Herbal Classic and was listed as a low-grade herb. The origin of wolfsbane was confused in the herbal books of previous dynasties until the Song Dynasty, when it was clearly defined as the root of Stellera chamaejasme L., a plant of the Thymelaeaceae family. Historically, wolfsbane was used in combination with sunflower, Euphorbia fischeriana Steud., and Euphorbia ebracteolata Hayata. In the early stage of collecting wolfsbane samples, it was found that wolfsbane is roughly divided into red wolfsbane, white wolfsbane and coelenterate in the market: red wolfsbane refers to wolfsbane of the family Thymelaeaceae, with the Tibetan name Rezhage, which is now included in the 20th edition of the "Inner Mongolia Mongolian Medicine Preparation Specifications"; white wolfsbane refers to the roots of Euphorbia chamaejasme and Euphorbia cerana of the Euphorbiaceae family, which are now included in the 20th edition of the "Chinese Pharmacopoeia", among which Euphorbia cerana is more commonly used; coelenterate refers to Alocasia odora K.Koch of the family Araceae, which is commonly used in Guangdong and Guangxi, and is generally regarded as a counterfeit. Among them, the Euphorbia chamaejasme and the Daphne chamaejasme have different original plants, different properties, flavors and functions. The main active ingredients in Daphne chamaejasme are total flavonoids and furanocoumarin lactones; the main active ingredients of Euphorbia chamaejasme are terpenes, tannins, flavonoids, etc. The difference in the chemical components contained in the two also shows that there are obvious differences between wolfsbane and Euphorbia chamaejasme. Li Shizhen also pointed out the mistake of using Euphorbia cerana (Euphorbia chamaejasme) as Stellera chamaejasme (Stellera chamaejasme). Therefore, the mixing and misuse of Euphorbiaceae Stellera chamaejasme and Stellera chamaejasme should be avoided in industrial production and clinical use. In addition, studies have shown that the two Euphorbiaceae stellera chamaejasme specified in the Pharmacopoeia, Euphorbia cerana and Euphorbia cerana, not only have significant differences in chemical composition, but also show different effects in antibacterial, anti-tumor and antioxidant aspects. Therefore, the mixing of Euphorbia cerana and Stellera chamaejasme should also be avoided. However, the appearance of different origins of Stellera chamaejasme is similar, and most of them are powdered medicines, so the medicinal preparations and compatible granules cannot be identified from the appearance. Based on the problems of the numerous origins of Stellera chamaejasme decoction pieces and the impact of the clinical efficacy of the mixing of genuine and fake products, there are studies that have integrated transcriptomics and bioactivity, liquid chromatography-mass spectrometry and other technical means to achieve the origin identification of Stellera chamaejasme, but the sample pretreatment is complicated and time-consuming, and cannot meet the requirements of rapid detection and analysis of medicinal material quality. As a poisonous Chinese medicinal material, accurate authenticity identification of wolfsbane can not only ensure its effectiveness in clinical use, but also reduce the harm caused by mixing and misusing medicinal materials.

[0004] Electronic nose is a gas detection system that imitates biological olfaction, which can digitize and visualize information such as the type and content of volatile components. At present, electronic noses have been widely used in food, environment and medical fields. Since most Chinese medicines have specific odors, electronic noses are increasingly being studied in terms of the origin, processing and storage of Chinese medicines. Chinese medicine fingerprint is a method used for quality control and evaluation of Chinese medicine. It analyzes the chemical components in Chinese medicinal materials and Chinese medicine preparations through chromatographic techniques such as high-performance liquid chromatography and gas chromatography to form a representative characteristic spectrum similar to a "fingerprint". The characteristics of Chinese medicine fingerprint are its comprehensiveness, specificity and stability. It can fully reflect the various components in the complex system of Chinese medicine and has good representativeness and repeatability. Intuitive visualization heat map analysis can intuitively reflect the relevant data in the fingerprint spectrum, and then intuitively see the similarities and differences between samples; cluster analysis divides the Chinese medicine fingerprint spectrum data under study into a series of subsets to achieve clear and simplified exploratory statistical analysis research; the combination of the two can achieve the goal of quickly and accurately evaluating the quality of Chinese medicine from an overall perspective and multiple levels. This technology has the advantages of simple operation, rapid implementation, intuitive results, and concise conclusions. It has universal applicability and can be used for holistic and systematic quality evaluation research of traditional Chinese medicine. Summary of the invention

[0005] The present invention designs and develops the fingerprint spectrum of wolfsbane and its mixed and counterfeit products. The purpose of the present invention is to be able to quickly and accurately process and analyze large quantities of sample data, and accurately identify Euphorbia lunulata, Euphorbia stellera chamaejasme, the mixed product Daphne stellera chamaejasme and the counterfeit Alocasia lily.

[0006] The present invention also designs and develops a method for establishing the fingerprint spectrum of wolfsbane and its mixed and counterfeit products. The purpose of the present invention is to establish an identification method that can quickly and accurately process and analyze large quantities of sample data, and accurately identify Euphorbia lunulata, Euphorbia stellera, mixed product Daphne stellera and counterfeit Alocasia lily.

[0007] The present invention also designs and develops the application of the fingerprint spectrum of wolfsbane and its mixed products in the rapid identification of wolfsbane and its mixed products.

[0008] The technical solution provided by the present invention is:

[0009] The method for establishing the fingerprint spectrum of wolfsbane and its mixed products comprises:

[0010] Take the wolfberry chamaejasme samples and grind them into powder, sieve them for later use, put them into headspace injection bottles, and seal them with a cap;

[0011] Through ultra-fast gas phase electronic nose separation and detection, programmed temperature is performed to obtain effective odor information of wolfsbane of different origins and its counterfeits, and fingerprint features are calibrated with relative retention parameters to obtain the fingerprint spectrum;

[0012] Determine the types of the wolfberry samples according to the relative retention parameters in the fingerprints;

[0013] Wherein, the wolfsbane samples include Euphorbia cerasifera, Euphorbia chamaejasme, Stellera chamaejasme and Alocasia odora; and

[0014] The one with peaks 5, 8, 13 and 24 is Euphorbia lunulata; the one with peaks 4, 8, 9, 11 and 17 is Euphorbia stellariae; the one with peaks 4, 7, 8, 9, 11, 13 and 17 is Stellera chamaejasme; the one with peaks 5 and 17 is Alocasia lily.

[0015] Preferably, the fingerprint spectrum obtained by using a non-polar MXT-5 chromatographic column has 24 common fingerprint peaks, and the relative retention parameters are:

[0016] Peak 1: 0.90; Peak 2 is the reference peak: 1.00; Peak 3: 1.06; Peak 4: 1.10; Peak 5: 1.11; Peak 6: 1.19; Peak 7: 1.27; Peak 8: 1.28; Peak 9: 1.38; Peak 10: 1.40; Peak 11: 1.48; Peak 12: 1.70; Peak 13: 2.01; Peak 14: 2.10; Peak 15: 2.21; Peak 16: 2.35; Peak 17: 2.42; Peak 18: 2.56; Peak 19: 2.57; Peak 20: 2.99; Peak 21: 3.09; Peak 22: 3.18; Peak 23: 3.80; Peak 24: 4.25.

[0017] Preferably, the fingerprint spectrum obtained by using the weakly polar MXT-1701 chromatographic column has 24 common fingerprint peaks, and the relative retention parameters are:

[0018] Peak 1: 0.99; Peak 2 is the reference peak: 1.00; Peak 3: 0.97; Peak 4: 1.07; Peak 5: 0.97; Peak 6: 1.07; Peak 7: 1.15; Peak 8: 1.52; Peak 9: 1.25; Peak 10: 1.25; Peak 11: 1.44; Peak 12: 1.64; Peak 13: 1.64; Peak 14: 1.82; Peak 15: 1.83; Peak 16: 2.04; Peak 17: 2.06; Peak 18: 2.06; Peak 19: 2.10; Peak 20: 2.57; Peak 21: 2.69; Peak 22: 2.51; Peak 23: 3.23; Peak 24: 3.49.

[0019] Preferably, the programmed temperature includes:

[0020] At 0.7℃·s -1 The heating rate is raised to 80°C and lasts for 0s;

[0021] At 2℃·s -1 The heating rate was raised to 250°C and continued for 10 seconds;

[0022] At 2℃·s -1 The temperature was raised to 251°C at a rate of 10 s.

[0023] Preferably, the parameter optimization conditions in the ultra-fast gas phase electronic nose separation detection process are:

[0024] The shaking time was 20 min, the shaking temperature was 70 °C, the injection volume was 3000 μL, and the injection speed was 125 μL·s -1 , injection port temperature was 200°C, injection duration was 29 s, and rotation speed was 500 r·min -1 The initial temperature of the trap was 40 °C and the flow rate of the trap was 10 mL min -1 , trapping duration was 34 s, trap final temperature was 250 °C, initial column temperature was 50 °C, acquisition time was 150 s, detector temperature was 260 °C, and FID gain was 12.

[0025] Preferably, the relative peak areas of Euphorbia lunatum in the fingerprint are: Peak 1: 0.48; Peak 2 is the reference peak: 1.00; Peak 3: 0.47; Peak 4: 0.00; Peak 5: 0.79; Peak 6: 0.14; Peak 7: 0.00; Peak 8: 0.39; Peak 9: 0.00; Peak 10: 0.07; Peak 11: 0.00; Peak 12: 0.40; Peak 13: 1.60; Peak 14: 0.56; Peak 15: 1.03; Peak 16: 0.32; Peak 17: 0.00; Peak 18: 0.15; Peak 19: 0.25; Peak 20: 0.17; Peak 21: 0.15; Peak 22: 0.19; Peak 23: 0.14; Peak 24: 0.05;

[0026] The relative peak areas of Euphorbia chamaejasme in the fingerprint are as follows: Peak 1: 3.56; Peak 2 is a reference peak: 1.00; Peak 3: 2.89; Peak 4: 1.16; Peak 5: 0.00; Peak 6: 0.41; Peak 7: 0.00; Peak 8: 0.32; Peak 9: 0.97; Peak 10: 0.53; Peak 11: 0.27; Peak 12: Peak: 1.01; Peak 13: 0.00; Peak 14: 0.36; Peak 15: 0.08; Peak 16: 0.37; Peak 17: 0.37; Peak 18: 0.02; Peak 19: 0.06; Peak 20: 0.14; Peak 21: 0.02; Peak 22: 0.07; Peak 23: 0.06; Peak 24: 0.00;

[0027] The relative peak areas of Stellera chamaejasme in the fingerprint are as follows: Peak 1: 0.65; Peak 2 is a reference peak: 1.00; Peak 3: 0.53; Peak 4: 0.16; Peak 5: 0.00; Peak 6: 0.21; Peak 7: 0.14; Peak 8: 0.08; Peak 9: 0.16; Peak 10: 0.12; Peak 11: 0.06; Peak 12: : 0.28; Peak 13: 0.02; Peak 14: 0.26; Peak 15: 0.30; Peak 16: 0.07; Peak 17: 0.13; Peak 18: 0.03; Peak 19: 0.03; Peak 20: 0.11; Peak 21: 0.03; Peak 22: 0.04; Peak 23: 0.05; Peak 24: 0.00; and

[0028] The relative peak areas of calla lily in the fingerprint are: peak 1: 0.27; peak 2 is the reference peak: 1.00; peak 3: 0.11; peak 4: 0.00; peak 5: 0.05; peak 6: 0.06; peak 7: 0.00; peak 8: 0.00; peak 9: 0.00; peak 10: 0.05; peak 11: 0.00; peak 12: 0.00; peak 13: 0.00; peak 14: 0.00; peak 15: 0.00; peak 16: 0.00; peak 17: 0.00; peak 18: 0.00; peak 19: 0.01; peak 20: 0.01; peak 21: 0.01; peak 22: 0.01 : 0.13; Peak 13: 0.00; Peak 14: 0.05; Peak 15: 0.05; Peak 16: 0.06; Peak 17: 0.02; Peak 18: 0.02; Peak 19: 0.02; Peak 20: 0.05; Peak 21: 0.01; Peak 22: 0.02; Peak 23: 0.05; Peak 24: 0.00.

[0029] The fingerprint spectrum of wolfsbane and its mixed products is established using the establishment method.

[0030] Preferably, the fingerprint spectrum obtained by using a non-polar MXT-5 chromatographic column has 24 common fingerprint peaks, and the relative retention parameters are:

[0031] Peak 1: 0.90; Peak 2 is the reference peak: 1.00; Peak 3: 1.06; Peak 4: 1.10; Peak 5: 1.11; Peak 6: 1.19; Peak 7: 1.27; Peak 8: 1.28; Peak 9: 1.38; Peak 10: 1.40; Peak 11: 1.48; Peak 12: 1.70; Peak 13: 2.01; Peak 14: 2.10; Peak 15: 2.21; Peak 16: 2.35; Peak 17: 2.42; Peak 18: 2.56; Peak 19: 2.57; Peak 20: 2.99; Peak 21: 3.09; Peak 22: 3.18; Peak 23: 3.80; Peak 24: 4.25; or

[0032] The fingerprint spectrum using the weakly polar MXT-1701 chromatographic column has 24 common fingerprint peaks, and the relative retention parameters are:

[0033] Peak 1: 0.99; Peak 2 is the reference peak: 1.00; Peak 3: 0.97; Peak 4: 1.07; Peak 5: 0.97; Peak 6: 1.07; Peak 7: 1.15; Peak 8: 1.52; Peak 9: 1.25; Peak 10: 1.25; Peak 11: 1.44; Peak 12: 1.64; Peak 13: 1.64; Peak 14: 1.82; Peak 15: 1.83; Peak 16: 2.04; Peak 17: 2.06; Peak 18: 2.06; Peak 19: 2.10; Peak 20: 2.57; Peak 21: 2.69; Peak 22: 2.51; Peak 23: 3.23; Peak 24: 3.49.

[0034] Preferably, the relative peak areas of Euphorbia lunatum in the fingerprint are: Peak 1: 0.48; Peak 2 is the reference peak: 1.00; Peak 3: 0.47; Peak 4: 0.00; Peak 5: 0.79; Peak 6: 0.14; Peak 7: 0.00; Peak 8: 0.39; Peak 9: 0.00; Peak 10: 0.07; Peak 11: 0.00; Peak 12: 0.40; Peak 13: 1.60; Peak 14: 0.56; Peak 15: 1.03; Peak 16: 0.32; Peak 17: 0.00; Peak 18: 0.15; Peak 19: 0.25; Peak 20: 0.17; Peak 21: 0.15; Peak 22: 0.19; Peak 23: 0.14; Peak 24: 0.05;

[0035] The relative peak areas of Euphorbia chamaejasme in the fingerprint are as follows: Peak 1: 3.56; Peak 2 is a reference peak: 1.00; Peak 3: 2.89; Peak 4: 1.16; Peak 5: 0.00; Peak 6: 0.41; Peak 7: 0.00; Peak 8: 0.32; Peak 9: 0.97; Peak 10: 0.53; Peak 11: 0.27; Peak 12: Peak: 1.01; Peak 13: 0.00; Peak 14: 0.36; Peak 15: 0.08; Peak 16: 0.37; Peak 17: 0.37; Peak 18: 0.02; Peak 19: 0.06; Peak 20: 0.14; Peak 21: 0.02; Peak 22: 0.07; Peak 23: 0.06; Peak 24: 0.00;

[0036] The relative peak areas of Stellera chamaejasme in the fingerprint are as follows: Peak 1: 0.65; Peak 2 is a reference peak: 1.00; Peak 3: 0.53; Peak 4: 0.16; Peak 5: 0.00; Peak 6: 0.21; Peak 7: 0.14; Peak 8: 0.08; Peak 9: 0.16; Peak 10: 0.12; Peak 11: 0.06; Peak 12: : 0.28; Peak 13: 0.02; Peak 14: 0.26; Peak 15: 0.30; Peak 16: 0.07; Peak 17: 0.13; Peak 18: 0.03; Peak 19: 0.03; Peak 20: 0.11; Peak 21: 0.03; Peak 22: 0.04; Peak 23: 0.05; Peak 24: 0.00; and

[0037] The relative peak areas of calla lily in the fingerprint are: peak 1: 0.27; peak 2 is the reference peak: 1.00; peak 3: 0.11; peak 4: 0.00; peak 5: 0.05; peak 6: 0.06; peak 7: 0.00; peak 8: 0.00; peak 9: 0.00; peak 10: 0.05; peak 11: 0.00; peak 12: 0.00; peak 13: 0.00; peak 14: 0.00; peak 15: 0.00; peak 16: 0.00; peak 17: 0.00; peak 18: 0.00; peak 19: 0.01; peak 20: 0.01; peak 21: 0.01; peak 22: 0.01 : 0.13; Peak 13: 0.00; Peak 14: 0.05; Peak 15: 0.05; Peak 16: 0.06; Peak 17: 0.02; Peak 18: 0.02; Peak 19: 0.02; Peak 20: 0.05; Peak 21: 0.01; Peak 22: 0.02; Peak 23: 0.05; Peak 24: 0.00.

[0038] The fingerprint spectrum of wolfsbane and its mixed products is used in identifying wolfsbane and its mixed products, and the fingerprint spectrum is used.

[0039] The beneficial effects of the present invention are:

[0040] 1. The fingerprint of the wolfberry and its mixed and counterfeit products provided by the present invention adopts an intuitive and visualized heat map analysis combined with cluster analysis, thereby realizing the rapid identification of four original wolfberry, and realizing the multi-level, systematic rapid analysis and identification research of genuine Euphorbia lunae and Euphorbia chamaejasme, mixed product Daphne chamaejasme and genuine wolfberry (including Euphorbia lunae and Euphorbia chamaejasme), counterfeit Alocasia odora and genuine wolfberry (including Euphorbia lunae and Euphorbia chamaejasme), mixed product Daphne chamaejasme and counterfeit Alocasia odora, and analyzing and evaluating the wolfberry base from the perspective of overall odor components;

[0041] 2. The method for establishing the fingerprint of wolfsbane and its mixed products provided by the present invention can realize the rapid distinction of wolfsbane samples of different origins, among which variables 20 (lauric aldehyde), 15 ((+)-limonene), 16 (3,6-nonadienal), 14 (3-octanone), and 6 (trans-1,2-dichloroethylene) are key odor difference markers for distinguishing wolfsbane of different origins. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1a The odor fingerprints of 48 batches of different-origin wolfberry described in the present invention (the chromatographic column is a non-polar MXT-5 chromatographic column, in the figure, "EE" represents Euphorbia lunulata, "EF" represents Euphorbia chamaejasme, "SC" represents the common mixed product of wolfberry, Stellera chamaejasme, and "AO" represents the common fake product of wolfberry, Alocasia rapa);

[0043] Figure 1b The odor fingerprints of 48 batches of different-origin wolfberry of the present invention (the chromatographic column is a weakly polar MXT-1701 chromatographic column, in the figure, "EE" represents Euphorbia lunulata, "EF" represents Euphorbia chamaejasme, "SC" represents the common mixed product of wolfberry, Stellera chamaejasme, and "AO" represents the common fake product of wolfberry, Alocasia odorata);

[0044] Figure 2 This is a comparison diagram of the odor fingerprints of different origins of stellera chamaejasme of the present invention;

[0045] Figure 3 It is a heat map and cluster analysis result diagram of 48 batches of different original wolfsbane described in the present invention (in the figure, "EE" represents Euphorbia lunulata, "EF" represents Euphorbia chamaejasme, "SC" represents the common mixed product of wolfsbane, Stellera chamaejasme, "AO" represents the common fake product of wolfsbane, Alocasia chamaejasme, and CP represents the odor peak);

[0046] Figure 4 The PCA analysis result diagram of 48 batches of Stellera chamaejasme of different origins described in the present invention;

[0047] Figure 5 This is a graph showing the results of the permutation test of 48 batches of Stellera chamaejasme of different origins according to the present invention;

[0048] Figure 6 VIP diagrams of 48 batches of Stellera chamaejasme with different origins described in the present invention. DETAILED DESCRIPTION

[0049] The present invention is further described in detail below in conjunction with the accompanying drawings so that those skilled in the art can implement the invention with reference to the description.

[0050] The present invention provides a method for establishing a fingerprint spectrum of Stellera chamaejasme and its mixed and counterfeited products, characterized by comprising:

[0051] Take the wolfberry chamaejasme samples and grind them into powder, sieve them for later use, put them into headspace injection bottles, and seal them with a cap;

[0052] Through ultra-fast gas phase electronic nose separation and detection, programmed temperature is performed to obtain effective odor information of wolfsbane of different origins and its counterfeits, and fingerprint features are calibrated with relative retention parameters to obtain the fingerprint spectrum;

[0053] The types of Stellera chamaejasme samples were determined according to the relative retention parameters in the fingerprints;

[0054] Among them, the wolfsbane samples include Euphorbia lunulata, Euphorbia chamaejasme, Stellera chamaejasme and Alocasia odora; and

[0055] The one with peaks 5, 8, 13 and 24 is Euphorbia lunulata; the one with peaks 4, 8, 9, 11 and 17 is Euphorbia stellariae; the one with peaks 4, 7, 8, 9, 11, 13 and 17 is Stellera chamaejasme; the one with peaks 5 and 17 is Alocasia lily.

[0056] In another embodiment, the fingerprint spectrum obtained by using a non-polar MXT-5 chromatographic column has 24 common fingerprint peaks, and the relative retention parameters are:

[0057] Peak 1: 0.90; Peak 2 is the reference peak: 1.00; Peak 3: 1.06; Peak 4: 1.10; Peak 5: 1.11; Peak 6: 1.19; Peak 7: 1.27; Peak 8: 1.28; Peak 9: 1.38; Peak 10: 1.40; Peak 11: 1.48; Peak 12: 1.70; Peak 13: 2.01; Peak 14: 2.10; Peak 15: 2.21; Peak 16: 2.35; Peak 17: 2.42; Peak 18: 2.56; Peak 19: 2.57; Peak 20: 2.99; Peak 21: 3.09; Peak 22: 3.18; Peak 23: 3.80; Peak 24: 4.25.

[0058] In another embodiment, the fingerprint spectrum obtained by using a weakly polar MXT-1701 chromatographic column has 24 common fingerprint peaks, and the relative retention parameters are:

[0059] Peak 1: 0.99; Peak 2 is the reference peak: 1.00; Peak 3: 0.97; Peak 4: 1.07; Peak 5: 0.97; Peak 6: 1.07; Peak 7: 1.15; Peak 8: 1.52; Peak 9: 1.25; Peak 10: 1.25; Peak 11: 1.44; Peak 12: 1.64; Peak 13: 1.64; Peak 14: 1.82; Peak 15: 1.83; Peak 16: 2.04; Peak 17: 2.06; Peak 18: 2.06; Peak 19: 2.10; Peak 20: 2.57; Peak 21: 2.69; Peak 22: 2.51; Peak 23: 3.23; Peak 24: 3.49.

[0060] In another embodiment, the parameter optimization conditions in the ultra-fast gas phase electronic nose separation detection process are:

[0061] The shaking time was 20 min, the shaking temperature was 70 °C, the injection volume was 3000 μL, and the injection speed was 125 μL·s -1 , injection port temperature was 200°C, injection duration was 29 s, and rotation speed was 500 r·min -1 The initial temperature of the trap was 40 °C and the flow rate of the trap was 10 mL min -1 , trap duration was 34 s, trap final temperature was 250 °C, initial column temperature was 50 °C, acquisition time was 150 s, detector temperature was 260 °C, and FID gain was 12;

[0062] The temperature program includes: 0.7℃·s -1 The temperature was raised to 80°C at a rate of 2°C·s -1 The temperature was raised to 250°C at a rate of 2°C·s -1 The temperature was raised to 251°C at a rate of 10 s.

[0063] In another embodiment, the relative peak areas of Euphorbia lunatum in the fingerprint are: Peak 1: 0.48; Peak 2 is a reference peak: 1.00; Peak 3: 0.47; Peak 4: 0.00; Peak 5: 0.79; Peak 6: 0.14; Peak 7: 0.00; Peak 8: 0.39; Peak 9: 0.00; Peak 10: 0.07; Peak 11: 0.00 ; Peak 12: 0.40; Peak 13: 1.60; Peak 14: 0.56; Peak 15: 1.03; Peak 16: 0.32; Peak 17: 0.00; Peak 18: 0.15; Peak 19: 0.25; Peak 20: 0.17; Peak 21: 0.15; Peak 22: 0.19; Peak 23: 0.14; Peak 24: 0.05;

[0064] The relative peak areas of Euphorbia chamaejasme in the fingerprint are: Peak 1: 3.56; Peak 2 is the reference peak: 1.00; Peak 3: 2.89; Peak 4: 1.16; Peak 5: 0.00; Peak 6: 0.41; Peak 7: 0.00; Peak 8: 0.32; Peak 9: 0.97; Peak 10: 0.53; Peak 11: 0.27; Peak 12: : 1.01; Peak 13: 0.00; Peak 14: 0.36; Peak 15: 0.08; Peak 16: 0.37; Peak 17: 0.37; Peak 18: 0.02; Peak 19: 0.06; Peak 20: 0.14; Peak 21: 0.02; Peak 22: 0.07; Peak 23: 0.06; Peak 24: 0.00;

[0065] The relative peak areas of Stellera chamaejasme in the fingerprint are: Peak 1: 0.65; Peak 2 is the reference peak: 1.00; Peak 3: 0.53; Peak 4: 0.16; Peak 5: 0.00; Peak 6: 0.21; Peak 7: 0.14; Peak 8: 0.08; Peak 9: 0.16; Peak 10: 0.12; Peak 11: 0.06; Peak 12: : 0.28; Peak 13: 0.02; Peak 14: 0.26; Peak 15: 0.30; Peak 16: 0.07; Peak 17: 0.13; Peak 18: 0.03; Peak 19: 0.03; Peak 20: 0.11; Peak 21: 0.03; Peak 22: 0.04; Peak 23: 0.05; Peak 24: 0.00;

[0066] The relative peak areas of Alocasia odora in the fingerprint are: Peak 1: 0.27; Peak 2 is the reference peak: 1.00; Peak 3: 0.11; Peak 4: 0.00; Peak 5: 0.05; Peak 6: 0.06; Peak 7: 0.00; Peak 8: 0.00; Peak 9: 0.00; Peak 10: 0.05; Peak 11: 0.00; Peak 12: 0.13; Peak 13: 0.00; Peak 14: 0.05; Peak 15: 0.05; Peak 16: 0.06; Peak 17: 0.02; Peak 18: 0.02; Peak 19: 0.02; Peak 20: 0.05; Peak 21: 0.01; Peak 22: 0.02; Peak 23: 0.05; Peak 24: 0.00.

[0067] The present invention also provides a fingerprint spectrum of wolfsbane and its mixed products. The fingerprint spectrum obtained by using a non-polar MXT-5 chromatographic column has 24 common fingerprint peaks, and the relative retention parameters are:

[0068] Peak 1: 0.90; Peak 2 is the reference peak: 1.00; Peak 3: 1.06; Peak 4: 1.10; Peak 5: 1.11; Peak 6: 1.19; Peak 7: 1.27; Peak 8: 1.28; Peak 9: 1.38; Peak 10: 1.40; Peak 11: 1.48; Peak 12: 1.70; Peak 13: 2.01; Peak 14: 2.10; Peak 15: 2.21; Peak 16: 2.35; Peak 17: 2.42; Peak 18: 2.56; Peak 19: 2.57; Peak 20: 2.99; Peak 21: 3.09; Peak 22: 3.18; Peak 23: 3.80; Peak 24: 4.25; or

[0069] The fingerprint spectrum using the weakly polar MXT-1701 chromatographic column has 24 common fingerprint peaks, and the relative retention parameters are:

[0070] Peak 1: 0.99; Peak 2 is the reference peak: 1.00; Peak 3: 0.97; Peak 4: 1.07; Peak 5: 0.97; Peak 6: 1.07; Peak 7: 1.15; Peak 8: 1.52; Peak 9: 1.25; Peak 10: 1.25; Peak 11: 1.44; Peak 12: 1.64; Peak 13: 1.64; Peak 14: 1.82; Peak 15: 1.83; Peak 16: 2.04; Peak 17: 2.06; Peak 18: 2.06; Peak 19: 2.10; Peak 20: 2.57; Peak 21: 2.69; Peak 22: 2.51; Peak 23: 3.23; Peak 24: 3.49.

[0071] In another embodiment, the relative peak areas of Euphorbia lunatum in the fingerprint are: Peak 1: 0.48; Peak 2 is a reference peak: 1.00; Peak 3: 0.47; Peak 4: 0.00; Peak 5: 0.79; Peak 6: 0.14; Peak 7: 0.00; Peak 8: 0.39; Peak 9: 0.00; Peak 10: 0.07; Peak 11: 0.00 ; Peak 12: 0.40; Peak 13: 1.60; Peak 14: 0.56; Peak 15: 1.03; Peak 16: 0.32; Peak 17: 0.00; Peak 18: 0.15; Peak 19: 0.25; Peak 20: 0.17; Peak 21: 0.15; Peak 22: 0.19; Peak 23: 0.14; Peak 24: 0.05;

[0072] The relative peak areas of Euphorbia chamaejasme in the fingerprint are: Peak 1: 3.56; Peak 2 is the reference peak: 1.00; Peak 3: 2.89; Peak 4: 1.16; Peak 5: 0.00; Peak 6: 0.41; Peak 7: 0.00; Peak 8: 0.32; Peak 9: 0.97; Peak 10: 0.53; Peak 11: 0.27; Peak 12: : 1.01; Peak 13: 0.00; Peak 14: 0.36; Peak 15: 0.08; Peak 16: 0.37; Peak 17: 0.37; Peak 18: 0.02; Peak 19: 0.06; Peak 20: 0.14; Peak 21: 0.02; Peak 22: 0.07; Peak 23: 0.06; Peak 24: 0.00;

[0073] The relative peak areas of Stellera chamaejasme in the fingerprint are: Peak 1: 0.65; Peak 2 is the reference peak: 1.00; Peak 3: 0.53; Peak 4: 0.16; Peak 5: 0.00; Peak 6: 0.21; Peak 7: 0.14; Peak 8: 0.08; Peak 9: 0.16; Peak 10: 0.12; Peak 11: 0.06; Peak 12: : 0.28; Peak 13: 0.02; Peak 14: 0.26; Peak 15: 0.30; Peak 16: 0.07; Peak 17: 0.13; Peak 18: 0.03; Peak 19: 0.03; Peak 20: 0.11; Peak 21: 0.03; Peak 22: 0.04; Peak 23: 0.05; Peak 24: 0.00;

[0074] The relative peak areas of Alocasia odora in the fingerprint are: Peak 1: 0.27; Peak 2 is the reference peak: 1.00; Peak 3: 0.11; Peak 4: 0.00; Peak 5: 0.05; Peak 6: 0.06; Peak 7: 0.00; Peak 8: 0.00; Peak 9: 0.00; Peak 10: 0.05; Peak 11: 0.00; Peak 12: 0.13; Peak 13: 0.00; Peak 14: 0.05; Peak 15: 0.05; Peak 16: 0.06; Peak 17: 0.02; Peak 18: 0.02; Peak 19: 0.02; Peak 20: 0.05; Peak 21: 0.01; Peak 22: 0.02; Peak 23: 0.05; Peak 24: 0.00.

[0075] The present invention also provides application of the fingerprint spectrum of wolfsbane and its mixed and counterfeit products in identifying wolfsbane and its mixed and counterfeit products.

[0076] Example

[0077] 1. Materials and instruments: Heracles II ultrafast gas phase electronic nose (BT125D; Alpha MOS, France); Zhicheng constant temperature culture oscillator (ZWY-103D; Shanghai Zhicheng Analytical Instrument Manufacturing Co., Ltd.); 1 / 10,000 balance (FA2004; Shanghai Sunny Hengping Scientific Instrument Co., Ltd.). 48 batches of wolfsbane medicinal materials were collected from 16 provinces including Anhui, Northeast China, Gansu, and Guangdong. The source information is shown in Table 1. Its origin was identified by Professor Dou Zhiying of the School of Traditional Chinese Medicine of Tianjin University of Traditional Chinese Medicine; nC6~nC 16 n-Alkane standard solution (batch number: 563121, RESTEK, USA) and experimental water were purchased from Watsons.

[0078] Table 1 Information of different batches of Stellera chamaejasme samples

[0079]

[0080] 2. Establishment Method

[0081] (1) Sample preparation: Powder the 48 batches of Stellera chamaejasme samples mentioned above, pass them through a No. 4 pharmacopoeia sieve, and set aside. Accurately weigh 0.5 g of the medicinal powder, place them in 20 mL headspace injection bottles, seal them with a cap, and inject them three times in parallel.

[0082] (2) Heracles II ultrafast gas phase electronic nose instrument conditions: The Heracles II ultrafast gas phase electronic nose is equipped with two chromatographic columns: one is a non-polar MXT-5 chromatographic column, and the other is a weakly polar MXT-1701 chromatographic column. After the sample is separated by the two chromatographic columns working in parallel, the separated substances are detected using a hydrogen flame ionization detector (FID). The specific analysis condition parameters are shown in Table 2, thereby obtaining effective odor information of wolfsbane of different origins and its counterfeits.

[0083] Table 2 Ultrafast gas phase electronic nose analysis conditions

[0084]

[0085] (3) Data analysis:

[0086] The chromatographic conditions under the item "Heracles II ultrafast gas phase electronic nose instrument conditions" were used to analyze 48 batches of medicinal materials. After deducting the blank sample, the spectral information of the four original Stellera chamaejasme slices was obtained. The obtained spectral information was imported into the Origin 64 drawing software to draw the odor fingerprint of two chromatographic columns with different polarities. The 24 odor peaks with good separation effect (peak area ≥ 500, retention index ≥ 85) from different original Stellera chamaejasme were used as research peak indicators, and their peak area and retention time information were obtained. The Hitlop Pro biomedical visualization platform (https: / / hiplot.com.cn / home / index.html) was used to perform heat map and cluster analysis on the samples. The odor information of the different origin stellera chamaejasme samples was qualitatively characterized using normal alkane standard solutions (nC6 to nC16), and the retention times of the 24 odor peaks were calibrated to the Kovats retention index (RI) (the electronic nose comes with software that can calibrate the retention time (RT) to the Kovats retention index (RI), which is a method of calibrating the retention parameters of unknown compounds to those of a series of normal alkanes (such as nC6 to nC16) under the same conditions. 16) retention parameters are compared and a relative value obtained through calculation. The retention index reflects the retention behavior of unknown compounds on the chromatographic column and is only used for the qualitative analysis of compounds. Generally, the larger the retention index, the greater the possibility of the compound being qualitatively identified. Therefore, the retention index of the qualitative compound finally selected in this embodiment is greater than ≥85), and the qualitative analysis is performed on it using the Arochembase database and Alphasoftv12.44 software. The OPLS-DA model of different original wolfsbane was established using SIMCAP14.1 software.

[0087] 3. Implementation results

[0088] In this embodiment, the Chinese medicine wolfsbane is used as a model, and cluster analysis combined with Chinese medicine fingerprint data technology is used to quickly identify wolfsbane of different origins and their mixed and counterfeit products. The "Ward.D2" algorithm is selected, and the Euclidean distance is used as the measurement. After the data is standardized, a content clustering heat map is drawn.

[0089] As shown in Figures 1 and 2, the fingerprints show that the odor components of the four types of wolfsbane are significantly different, which directly reflects the chemical reasons why different types of wolfsbane cannot be mixed as one substance.

[0090] like Figure 3 As shown, the heat map on the right can intuitively reflect the content differences of multiple components, and the cluster map on the left can reflect the regular information of the chromatographic fingerprint of traditional Chinese medicine. From the heat map analysis, it can be intuitively seen that there are certain differences in the content of chemical components of the four original wolfsbane, which intuitively reflects the chemical reasons why different original wolfsbane cannot be regarded as a mixed substance; from the cluster pedigree diagram, it can be seen that the mixed product Daphne chamaejasme is clustered into a small category, the fake Calla lily is clustered into a small category, and the two small categories are clustered into a large category; the Euphorbia chamaejasme, Euphorbia lunae and Euphorbia chamaejasme of the Euphorbiaceae family specified in the Pharmacopoeia are each clustered into a large category, and there is no overlap with fakes and mixed products, which realizes the rapid identification of the four original wolfsbane, and realizes the distinction between genuine Euphorbia lunae and Euphorbia chamaejasme, mixed product Daphne chamaejasme and genuine wolfsbane (including Euphorbia lunae and Euphorbia chamaejasme), fake Calla lily and genuine wolfsbane (including Euphorbia lunae and Euphorbia chamaejasme), and mixed product Daphne chamaejasme and fake Calla lily.

[0091] As shown in Tables 3 and 4, using normal alkane standard solution (nC6~nC 16) The retention time of the chromatographic peaks of the odor of different origins of Stellera chamaejasme was calibrated to the Kovats retention index (RI), and the odor peaks were qualitatively analyzed using the Arochembase database and Alphasoftv12.44 software to obtain the possible compounds and their sensory description information as well as the relative retention parameters and relative peak areas of the common peaks of different origins of Stellera chamaejasme. The origin of the Chinese medicine Stellera chamaejasme was identified based on the common peaks: the common peaks of peaks 5, 8, 13, and 24 were Euphorbia lunae; the common peaks of peaks 4, 8, 9, 11, and 17 were Euphorbia chamaejasme; the common peaks of peaks 4, 7, 8, 9, 11, 13, and 17 were Stellera chamaejasme; the common peaks of peaks 5 and 17 were Alocasia chamaejasme. Among them, peak 24 (tridecylbenzene) is the unique odor peak of Euphorbia lunaejasme, and peak 7 (2,2-dichloropropane) is the unique odor peak of Stellera chamaejasme. These two odor peaks are the key odor components for distinguishing Euphorbia lunaejasme and Stellera chamaejasme.

[0092] Table 3 Possible odor information of different origins of Stellera chamaejasme

[0093]

[0094] Table 4 Relative retention parameters and relative peak areas of common peaks of different origins of Stellera chamaejasme

[0095]

[0096] like Figure 4 , 5 , 6, in order to further analyze and obtain the odor difference markers, the peak area of ​​24 common odor peaks was used as the variable, and the OPLS-DA model of different origins of Stellera chamaejasme was established using SIMCA P14.1 software. 2 Y is 0.941, Q 2 is 0.93, indicating that the model can be used to quickly distinguish different origins of Stellera chamaejasme. After 200 permutation tests, R 2 The intercept is 0.0905, Q 2 The intercept is -0.359, Q 2 The intersection point of the regression line and the vertical axis is less than 0, indicating that the model is not overfitted and is valid. The results of obtaining VIP values ​​show that among the 24 odor components, 5 odor components have VIP values ​​greater than 1.0. It is speculated that variables 20 (lauric aldehyde), 15 ((+)-limonene), 16 (3,6-nonadienal), 14 (3-octanone), and 6 (trans-1,2-dichloroethylene) are key odor difference markers for distinguishing different origins of stellera chamaejasme.

[0097] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes, and they can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and the illustrations shown and described herein.

Claims

1. A method for establishing the fingerprint spectrum of wolfsbane and its mixed products, characterized in that: include: Take the wolfberry chamaejasme samples and grind them into powder, sieve them for later use, put them into headspace injection bottles, and seal them with a cap; Through ultra-fast gas phase electronic nose separation and detection, programmed temperature is performed to obtain effective odor information of wolfsbane of different origins and its counterfeits, and fingerprint features are calibrated with relative retention parameters to obtain the fingerprint spectrum; Determine the types of the wolfberry samples according to the relative retention parameters in the fingerprints; Wherein, the wolfsbane samples include Euphorbia cerana, Euphorbia chamaejasme, Stellera chamaejasme and Alocasia odora; as well as The one with peaks 5, 8, 13 and 24 is Euphorbia lunulata; the one with peaks 4, 8, 9, 11 and 17 is Euphorbia stellariae; the one with peaks 4, 7, 8, 9, 11, 13 and 17 is Stellera chamaejasme; the one with peaks 5 and 17 is Alocasia lily.

2. The method for establishing the fingerprint spectrum of Stellera chamaejasme and its mixed and counterfeited products as claimed in claim 1, characterized in that: The fingerprint spectrum obtained by using the non-polar MXT-5 chromatographic column has 24 common fingerprint peaks, and the relative retention parameters are: Peak 1: 0.90; Peak 2 is the reference peak: 1.00; Peak 3: 1.06; Peak 4: 1.10; Peak 5: 1.11; Peak 6: 1.19; Peak 7: 1.27; Peak 8: 1.28; Peak 9: 1.38; Peak 10: 1.40; Peak 11: 1.48; Peak 12: 1.70; Peak 13: 2.01; Peak 14: 2.10; Peak 15: 2.21; Peak 16: 2.35; Peak 17: 2.42; Peak 18: 2.56; Peak 19: 2.57; Peak 20: 2.99; Peak 21: 3.09; Peak 22: 3.18; Peak 23: 3.80; Peak 24: 4.

25.

3. The method for establishing the fingerprint spectrum of Stellera chamaejasme and its mixed and counterfeited products as claimed in claim 1, characterized in that: The fingerprint spectrum obtained by using the weakly polar MXT-1701 chromatographic column has 24 common fingerprint peaks, and the relative retention parameters are: Peak 1: 0.99; Peak 2 is the reference peak: 1.00; Peak 3: 0.97; Peak 4: 1.07; Peak 5: 0.97; Peak 6: 1.07; Peak 7: 1.15; Peak 8: 1.52; Peak 9: 1.25; Peak 10: 1.25; Peak 11: 1.44; Peak 12: 1.64; Peak 13: 1.64; Peak 14: 1.82; Peak 15: 1.83; Peak 16: 2.04; Peak 17: 2.06; Peak 18: 2.06; Peak 19: 2.10; Peak 20: 2.57; Peak 21: 2.69; Peak 22: 2.51; Peak 23: 3.23; Peak 24: 3.

49.

4. The method for establishing the fingerprint of Stellera chamaejasme and its mixed and counterfeited products as claimed in claim 2 or 3, characterized in that: The temperature program includes: At 0.7℃·s -1 The heating rate is raised to 80°C and lasts for 0s; At 2℃·s -1 The heating rate was raised to 250°C and continued for 10 seconds; At 2℃·s -1 The temperature was raised to 251°C at a rate of 10 s.

5. The method for establishing the fingerprint spectrum of Stellera chamaejasme and its mixed products as claimed in claim 4, characterized in that: The parameter optimization conditions during ultra-fast gas phase electronic nose separation and detection are: The shaking time was 20 min, the shaking temperature was 70 °C, the injection volume was 3000 μL, and the injection speed was 125 μL·s -1 , injection port temperature was 200°C, injection duration was 29 s, and rotation speed was 500 r·min -1 The initial temperature of the trap was 40 °C and the flow rate of the trap was 10 mL min -1 , trapping duration was 34 s, trap final temperature was 250 °C, initial column temperature was 50 °C, acquisition time was 150 s, detector temperature was 260 °C, and FID gain was 12.

6. The method for establishing the fingerprint spectrum of Stellera chamaejasme and its mixed and counterfeited products as claimed in claim 5, characterized in that: The relative peak areas of Euphorbia lunatum in the fingerprint are: Peak 1: 0.48; Peak 2 is the reference peak: 1.00; Peak 3: 0.47; Peak 4: 0.00; Peak 5: 0.79; Peak 6: 0.14; Peak 7: 0.00; Peak 8: 0.39; Peak 9: 0.00; Peak 10: 0.07; Peak 11: 0.00; Peak 12: 0.40; Peak 13: 1.60; Peak 14: 0.56; Peak 15: 1.03; Peak 16: 0.32; Peak 17: 0.00; Peak 18: 0.15; Peak 19: 0.25; Peak 20: 0.17; Peak 21: 0.15; Peak 22: 0.19; Peak 23: 0.14; Peak 24: 0.05; The relative peak areas of Euphorbia chamaejasme in the fingerprint spectrum are: Peak 1: 3.56; Peak 2 is a reference peak: 1.00; Peak 3: 2.89; Peak 4: 1.16; Peak 5: 0.00; Peak 6: 0.41; Peak 7: 0.00; Peak 8: 0.32; Peak 9: 0.97; Peak 10: 0.53; Peak 11: 0.27; Peak 12: 1.01; Peak 13: 0.00; Peak 14: 0.36; Peak 15: 0.08; Peak 16: 0.37; Peak 17: 0.37; Peak 18: 0.02; Peak 19: 0.06; Peak 20: 0.14; Peak 21: 0.02; Peak 22: 0.07; Peak 23: 0.06; Peak 24: 0.00; The relative peak areas of Stellera chamaejasme in the fingerprint are as follows: Peak 1: 0.65; Peak 2 is a reference peak: 1.00; Peak 3: 0.53; Peak 4: 0.16; Peak 5: 0.00; Peak 6: 0.21; Peak 7: 0.14; Peak 8: 0.08; Peak 9: 0.16; Peak 10: 0.12; Peak 11: 0.06; Peak 12: : 0.28; Peak 13: 0.02; Peak 14: 0.26; Peak 15: 0.30; Peak 16: 0.07; Peak 17: 0.13; Peak 18: 0.03; Peak 19: 0.03; Peak 20: 0.11; Peak 21: 0.03; Peak 22: 0.04; Peak 23: 0.05; Peak 24: 0.00; and The relative peak areas of Alocasia odora in the fingerprint are: Peak 1: 0.27; Peak 2 is the reference peak: 1.00; Peak 3: 0.11; Peak 4: 0.00; Peak 5: 0.05; Peak 6: 0.06; Peak 7: 0.00; Peak 8: 0.00; Peak 9: 0.00; Peak 10: 0.05; Peak 11: 0.00; Peak 12: 0.13; Peak No. 13: 0.00; Peak No. 14: 0.05; Peak No. 15: 0.05; Peak No. 16: 0.06; Peak No. 17: 0.02; Peak No. 18: 0.02; Peak No. 19: 0.02; Peak No. 20: 0.05; Peak No. 21: 0.01; Peak No. 22: 0.02; Peak No. 23: 0.05; Peak No. 24: 0.

00.

7. The fingerprint of wolfsbane and its mixed products is characterized by: The method according to any one of claims 1 to 6 is used to establish the method.

8. The fingerprint of Stellera chamaejasme and its mixed products as claimed in claim 7, characterized in that: The fingerprint spectrum obtained by using the non-polar MXT-5 chromatographic column has 24 common fingerprint peaks, and the relative retention parameters are: Peak 1: 0.90; Peak 2 is the reference peak: 1.00; Peak 3: 1.06; Peak 4: 1.10; Peak 5: 1.11; Peak 6: 1.19; Peak 7: 1.27; Peak 8: 1.28; Peak 9: 1.38; Peak 10: 1.40; Peak 11: 1.48; Peak 12: 1.70; Peak 13: 2.01; Peak 14: 2.10; Peak 15: 2.21; Peak 16: 2.35; Peak 17: 2.42; Peak 18: 2.56; Peak 19: 2.57; Peak 20: 2.99; Peak 21: 3.09; Peak 22: 3.18; Peak 23: 3.80; Peak 24: 4.25; or The fingerprint spectrum using the weakly polar MXT-1701 chromatographic column has 24 common fingerprint peaks, and the relative retention parameters are: Peak 1: 0.99; Peak 2 is the reference peak: 1.00; Peak 3: 0.97; Peak 4: 1.07; Peak 5: 0.97; Peak 6: 1.07; Peak 7: 1.15; Peak 8: 1.52; Peak 9: 1.25; Peak 10: 1.25; Peak 11: 1.44; Peak 12: 1.64; Peak 13: 1.64; Peak 14: 1.82; Peak 15: 1.83; Peak 16: 2.04; Peak 17: 2.06; Peak 18: 2.06; Peak 19: 2.10; Peak 20: 2.57; Peak 21: 2.69; Peak 22: 2.51; Peak 23: 3.23; Peak 24: 3.

49.

9. The fingerprint of Stellera chamaejasme and its mixed products as claimed in claim 7, characterized in that: The relative peak areas of Euphorbia lunatum in the fingerprint are: Peak 1: 0.48; Peak 2 is the reference peak: 1.00; Peak 3: 0.47; Peak 4: 0.00; Peak 5: 0.79; Peak 6: 0.14; Peak 7: 0.00; Peak 8: 0.39; Peak 9: 0.00; Peak 10: 0.07; Peak 11: 0.00; Peak 12: 0.40; Peak 13: 1.60; Peak 14: 0.56; Peak 15: 1.03; Peak 16: 0.32; Peak 17: 0.00; Peak 18: 0.15; Peak 19: 0.25; Peak 20: 0.17; Peak 21: 0.15; Peak 22: 0.19; Peak 23: 0.14; Peak 24: 0.05; The relative peak areas of Euphorbia chamaejasme in the fingerprint spectrum are: Peak 1: 3.56; Peak 2 is a reference peak: 1.00; Peak 3: 2.89; Peak 4: 1.16; Peak 5: 0.00; Peak 6: 0.41; Peak 7: 0.00; Peak 8: 0.32; Peak 9: 0.97; Peak 10: 0.53; Peak 11: 0.27; Peak 12: 1.01; Peak 13: 0.00; Peak 14: 0.36; Peak 15: 0.08; Peak 16: 0.37; Peak 17: 0.37; Peak 18: 0.02; Peak 19: 0.06; Peak 20: 0.14; Peak 21: 0.02; Peak 22: 0.07; Peak 23: 0.06; Peak 24: 0.00; The relative peak areas of Stellera chamaejasme in the fingerprint are as follows: Peak 1: 0.65; Peak 2 is a reference peak: 1.00; Peak 3: 0.53; Peak 4: 0.16; Peak 5: 0.00; Peak 6: 0.21; Peak 7: 0.14; Peak 8: 0.08; Peak 9: 0.16; Peak 10: 0.12; Peak 11: 0.06; Peak 12: : 0.28; Peak 13: 0.02; Peak 14: 0.26; Peak 15: 0.30; Peak 16: 0.07; Peak 17: 0.13; Peak 18: 0.03; Peak 19: 0.03; Peak 20: 0.11; Peak 21: 0.03; Peak 22: 0.04; Peak 23: 0.05; Peak 24: 0.00; and The relative peak areas of Alocasia odora in the fingerprint are: Peak 1: 0.27; Peak 2 is the reference peak: 1.00; Peak 3: 0.11; Peak 4: 0.00; Peak 5: 0.05; Peak 6: 0.06; Peak 7: 0.00; Peak 8: 0.00; Peak 9: 0.00; Peak 10: 0.05; Peak 11: 0.00; Peak 12: 0.13; Peak No. 13: 0.00; Peak No. 14: 0.05; Peak No. 15: 0.05; Peak No. 16: 0.06; Peak No. 17: 0.02; Peak No. 18: 0.02; Peak No. 19: 0.02; Peak No. 20: 0.05; Peak No. 21: 0.01; Peak No. 22: 0.02; Peak No. 23: 0.05; Peak No. 24: 0.

00.

10. Application of the fingerprint spectrum of wolfsbane and its mixed products in identifying wolfsbane and its mixed products, characterized in that: Use of a fingerprint as described in any one of claims 7 to 9.

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