A method for identifying the origin of traditional Chinese medicine Evodia rutaecarpa based on electronic nose odor detection

Abstract

The present invention discloses a method for identifying the origin of the Chinese medicine Evodia rutaecarpa based on electronic nose odor detection, and belongs to the technical field of Chinese medicinal materials and quality analysis and detection. The powder to be detected is sampled through a headspace sampling bottle and detected by an electronic nose, and the sensor response value is obtained. W1S is used as a difference sensor and W6S is used as a reference sensor. The origin of the Chinese medicine Evodia rutaecarpa is confirmed according to the ratio of the response values ​​of W1S and W6S; when the ratio of the response values ​​of W1S and W6S is 2.4-3.1, it is sparse hair Evodia rutaecarpa, when the ratio of the response values ​​is 3.5-5.2, it is stone tiger, and when the ratio of the response values ​​is 5.8-6.5, it is Evodia rutaecarpa. The method for identifying the origin of the Chinese medicine Evodia rutaecarpa based on electronic nose odor detection provided by the present invention is fast, non-destructive, does not require complex sample pre-treatment, is simple and environmentally friendly, has low detection cost, and has intuitive results. It is suitable for batch rapid, objective and accurate judgment of the origin of the Chinese medicine Evodia rutaecarpa.

Description

Technical Field

[0001] The invention belongs to the technical field of Chinese medicinal materials and quality analysis and detection, and particularly relates to a method for identifying the origin of the Chinese medicinal material Evodia rutaecarpa based on electronic nose odor detection. Background Art

[0002] Evodia rutaecarpa Euopsis rutaecarpa (Juss.) Benth., Shihu Euodia rutaecarpa (Juss) Benth.var. Officinalis (Dode) Huang or Evodia rutaecarpa Euopsis rutaecarpa (Juss.) Benth. var. bodinieri The dried nearly mature fruit of (Dode) Huang tastes pungent and bitter, is hot in nature, and slightly toxic. It has the effects of dispelling cold and relieving pain, lowering adverse reactions and stopping vomiting, and boosting yang and stopping diarrhea. It is one of the commonly used warming medicines in clinical practice. The three types of Chinese medicines Evodia rutaecarpa collected in the pharmacopoeia have certain differences in ingredients, pharmacological effects, etc. Among them, the content of dehydroevodiamine and narcissin in Shihu is relatively high, the content of evodiamine and evodiamine in Evodia rutaecarpa is relatively high, and the content of various ingredients in sparse hair Evodia rutaecarpa is lower than that of other bases. The differences in ingredients and their contents lead to differences in drug efficacy mechanisms. Studies have shown that Shihu has better anti-inflammatory and analgesic effects, Evodia rutaecarpa has the effect of protecting gastric mucosa, and sparse hair Evodia rutaecarpa can greatly reduce gastric acid irritation. Therefore, accurately determining the origin of the Chinese medicine Evodia rutaecarpa is helpful to ensure the quality of medicinal materials and decoction pieces, accurately exert the therapeutic characteristics of Chinese medicines of different origins Evodia rutaecarpa, and ensure the safety and effectiveness of clinical medication.

[0003] The main methods for identifying the origin of traditional Chinese medicine include traditional experience identification, chemical component analysis, and DNA barcoding technology. In traditional experience, according to the size of the particles of the traditional Chinese medicine Evodia rutaecarpa, there are "large particles" and "small particles". The large particles refer to Evodia rutaecarpa, while the sparse hair Evodia rutaecarpa and the stone tiger are both "small particles". Due to differences in harvest time and origin, it is difficult to identify the origin by particle size; from the color point of view, the surface of the traditional Chinese medicine Evodia rutaecarpa of different origins is dark yellow-green to brown, with a large color span, and is related to the harvest time, so it is also difficult to identify the origin by appearance color. There are other traits and microscopic identification methods, but the integrity of the characteristics of the original plants or medicinal materials of Evodia rutaecarpa is high, and the identification requires long-term experience accumulation, so it is difficult to quickly and effectively achieve the origin identification of the traditional Chinese medicine Evodia rutaecarpa. Some scholars have used fingerprints to identify different origins of Evodia rutaecarpa, but this method has problems such as cumbersome sample preparation methods and detection conditions, long time consumption, and high costs of reference materials and organic solvents. Although modern DNA technology can sequence, assemble and annotate the whole genome of the traditional Chinese medicine Evodia rutaecarpa, most test samples must use fresh medicinal plants, which are difficult to collect and difficult to accurately identify the origin. A few methods that can extract DNA from medicinal materials or decoction pieces require toxic solvents such as chloroform, which are less safe. At present, most of the traditional Chinese medicine Evodia rutaecarpa circulating in the market are in the form of medicinal materials or decoction pieces. Therefore, it is urgent and necessary to establish a method for quickly and effectively identifying different origins of traditional Chinese medicine Evodia rutaecarpa.

[0004] The Chinese medicine Evodia rutaecarpa has a strong flavor, unique aroma, and distinct odor characteristics. Electronic nose is a new method for Chinese medicine odor detection that has emerged in recent years. Its 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 Chinese medicine Evodia rutaecarpa based on electronic nose odor detection, and realizing rapid and effective identification of the origin of commercially available 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

[0005] In view of the problems in the prior art of identifying the different origins of the Chinese medicinal material Evodia rutaecarpa, which are complex to operate, costly and have poor safety, the present invention provides a method for identifying the origin of the Chinese medicinal material Evodia rutaecarpa based on electronic nose odor detection. The method does not require complicated sample pretreatment, is simple and environmentally friendly, uses fewer consumables during the identification process, and provides intuitive results. This method is of great significance for quickly identifying the origin of Evodia rutaecarpa, improving the quality control method of Evodia rutaecarpa, and ensuring accurate clinical medication.

[0006] The present invention is achieved through the following technical solutions:

[0007] A method for identifying the origins of different traditional Chinese medicines Evodia rutaecarpa based on electronic nose odor detection, wherein the powder to be detected is sampled through a headspace sampling bottle and detected by an electronic nose, and a sensor response value is obtained. W1S is used as a difference sensor and W6S is used as a reference sensor, and the origin of the traditional Chinese medicine Evodia rutaecarpa is confirmed according to the ratio of the response values ​​of W1S and W6S.

[0008] When the ratio of W1S to W6S response values ​​is 2.4-3.1, it is Evodia rutaecarpa; when the ratio is 3.5-5.2, it is Psoralea corylifolia; when the ratio is 5.8-6.5, it is Evodia rutaecarpa;

[0009] The W1S is a sensor sensitive to short-chain alkanes (methane, etc.), and the W6S is a sensor sensitive to hydrogen.

[0010] Furthermore, the electronic nose is a PEN-3 type electronic nose.

[0011] Furthermore, the parameters of the electronic nose are set as follows: sample interval 1 s, flushing time 60-120 s, zeroing time 3-5 s, pre-sampling time 3-5 s, measurement time 120 s, chamber flow 400-500 mL / min, and initial injection flow 400-500 mL / min.

[0012] Furthermore, the sampling amount of the powder to be detected is 0.5~1 g.

[0013] Furthermore, the powder to be tested is crushed before use and passed through a No. 3 sieve.

[0014] Beneficial Effects

[0015] The method for identifying the origin of the traditional Chinese medicine Evodia rutaecarpa based on electronic nose odor detection provided by the present invention is rapid, non-destructive, does not require complicated sample pretreatment, is simple and environmentally friendly, has low detection cost, and produces intuitive results. It is suitable for rapid, objective and accurate batch determination of the origin of the traditional Chinese medicine Evodia rutaecarpa. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is the OPLS-DA analysis diagram of different origin Chinese medicine Evodia rutaecarpa;

[0017] Figure 2 This is the Permutation verification analysis diagram of different origin Chinese medicine Evodia rutaecarpa;

[0018] Figure 3 This is the projection diagram of the importance of 10 sensor variables of different origin Chinese medicine Evodia rutaecarpa;

[0019] Figure 4 OPLS-DA analysis diagram to verify the electronic nose's ability to identify Evodia rutaecarpa from different Chinese medicinal materials. DETAILED DESCRIPTION

[0020] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only to further illustrate the features and advantages of the present invention, rather than to limit the present invention.

[0021] 1. Instruments and samples

[0022] Instrument model: PEN-3 electronic nose, which consists of 10 sensors, namely W1C, W5S, W3C, W6S, W5C, W1S, W1W, W2S, W2W, and W3S. The response characteristics of each sensor of the PEN-3 electronic nose are shown in Table 1 below:

[0023] Table 1 Response characteristics of each sensor of PEN-3 electronic nose

[0024] sensor Performance Description W1C Aromatic ingredients, benzene W5S High sensitivity, very sensitive to nitrogen oxides W3C Ammonia, sensitive to aromatic ingredients W6S Mainly selective for hydrogen W5C Alkane aromatic components W1S Sensitive to short-chain alkanes such as methane W1W Sensitive to inorganic sulfides W2S Sensitive to alcohols, ethers, aldehydes and ketones W2W Aromatic ingredients, sensitive to organic sulfides W3S Sensitive to alkanes, long chain alkanes .

[0025] The sources of the Chinese medicine Evodia rutaecarpa are shown in Table 2 below:

[0026] Table 2 Information on samples of traditional Chinese medicine Evodia rutaecarpa

[0027] Sample No. Evodia rutaecarpa Specification Origin SM1 Evodia rutaecarpa Medicinal Materials Jiangxi SM2 Evodia rutaecarpa Medicinal Materials Jiangxi SM3 Evodia rutaecarpa Medicinal Materials Hunan SM4 Evodia rutaecarpa Pieces Jiangxi SM Verification Evodia rutaecarpa Medicinal Materials Jiangxi SH1 Stone Tiger Pieces Zhejiang SH2 Stone Tiger Pieces Jiangxi SH3 Stone Tiger Pieces Zhejiang SH4 Stone Tiger Pieces Zhejiang SH Verification Stone Tiger Pieces Zhejiang ZY1 Evodia rutaecarpa Pieces Sichuan ZY2 Evodia rutaecarpa Pieces Sichuan ZY3 Evodia rutaecarpa Pieces Sichuan ZY4 Evodia rutaecarpa Pieces Guizhou ZY Verification Evodia rutaecarpa Pieces Sichuan .

[0028] Example 1

[0029] (1) Crush the 12 batches of Chinese medicine Evodia rutaecarpa samples (SM1, SM2, SM3, SM4, SH1, SH2, SH3, SH4, ZY1, ZY2, ZY3, ZY4) respectively, pass through a No. 3 sieve, weigh 0.5 g of the powder, put it into a headspace sample bottle, tighten the bottle cap, seal it with a sealing film, and place it at room temperature for 15 min;

[0030] (2) The electronic nose sampling needle was inserted into the headspace sample bottle, and a needle connected to an activated carbon filter was inserted at a position 2 cm deeper than the sampling needle. The parameters of the electronic nose were set as follows: sampling interval 1 s, flushing time 120 s, zeroing time 5 s, pre-sampling time 5 s, measurement time 120 s, chamber flow 500 mL / min, and initial injection flow 500 mL / min. Ten sensor response values ​​were obtained. The sensor response values ​​of 12 batches of different origin Chinese medicine Evodia rutaecarpa are shown in Table 3:

[0031] Table 3 Sensor response values ​​of different origin Chinese herbal medicines Evodia rutaecarpa

[0032] Sample name W1C W5S W3C W6S W5C W1S W1W W2S W2W W3S SM1 0.95 8.62 1.00 0.97 0.96 2.34 16.60 1.38 3.86 0.99 SM2 0.88 10.18 0.96 0.96 0.92 3.02 20.91 1.53 4.83 0.98 SM3 0.90 14.34 0.97 0.98 0.92 2.64 27.37 1.45 5.34 0.99 SM4 0.87 14.63 0.94 0.96 0.88 3.02 31.58 1.55 6.68 0.98 SH1 0.81 12.69 0.88 0.97 0.82 4.97 29.84 2.04 5.93 1.00 SH2 0.91 8.71 0.96 0.95 0.92 3.52 20.45 1.66 4.93 0.99 SH3 0.92 9.21 0.97 0.94 0.94 3.31 19.84 1.59 5.01 0.99 SH4 0.78 19.49 0.85 0.96 0.78 4.95 39.84 2.07 7.01 0.99 ZY1 0.65 35.83 0.75 1.03 0.64 6.00 68.22 2.42 8.04 1.00 ZY2 0.65 23.61 0.75 1.02 0.65 6.28 62.36 2.48 7.76 1.00 ZY3 0.63 22.16 0.73 1.02 0.62 6.58 66.20 2.56 8.07 1.00 ZY4 0.65 21.83 0.75 1.01 0.65 6.52 60.73 2.59 7.88 1.00 .

[0033] (3) Intuitive analysis

[0034] As shown in Table 3, the response values ​​of the electronic nose sensors W6S and W3S of different origin Chinese medicinal materials Evodia rutaecarpa are relatively stable and can be selected as reference sensors. However, the response values ​​of the electronic nose sensors W5S, W1W and W1S of different origin Chinese medicinal materials Evodia rutaecarpa are quite different. Among them, the sensor response values ​​of Evodia rutaecarpa and the other two origins (Evodia rutaecarpa sparse hair and Evodia rutaecarpa sparse hair) are quite different. Further analysis found that the response values ​​of the electronic nose sensor W1S of the three origin Chinese medicinal materials Evodia rutaecarpa sparse hair hair and Evodia rutaecarpa sparse hair hair are significantly different.

[0035] (4) Partial least squares discriminant analysis

[0036] OPLS-DA analysis was performed with the response values ​​of the 10 sensors of the electronic nose as variables. The results are as follows: Figure 1 As shown in the figure, the three kinds of original Chinese medicinal materials Evodia rutaecarpa are clustered into one category respectively, with high distinction and obvious differences, indicating that there are differences in smell among the three. Therefore, the original Chinese medicinal materials Evodia rutaecarpa can be identified by smell.

[0037] (5) Screening of differential odor marker sensors

[0038] The Permutation model of the traditional Chinese medicine Evodia rutaecarpa with different origins was verified, and the number of tests was set to 200. The model R on the left 2 and Q 2 The values ​​are lower than the right side, indicating that there is no overfitting. Figure 2 The variable importance projection value (VIP) can be used to screen important difference variables. The larger the value, the greater the contribution of the variable to the model classification ability. The variable importance projection diagram of 10 sensors of different original Chinese medicine Evodia rutaecarpa is shown in Figure 3 As shown, according to VIP>1, W1W, W5S, and W1S were screened out as differential odor sensors of three original Chinese medicinal materials Evodia rutaecarpa, and this result was consistent with the intuitive analysis.

[0039] Based on the above analysis, considering the complexity of the odor differences between different batches and different origins of the Chinese herbal medicine Evodia rutaecarpa, a relatively stable ratio of different sensor response values ​​was selected as the basis for differentiation. Therefore, W6S was selected as the reference sensor. Because there were large differences in the W1S sensor response values ​​of the three origins of Evodia rutaecarpa, W1S was selected as the difference sensor. By calculation, it was determined that when the ratio of W1S to W6S was 2.4~3.1, it was Evodia rutaecarpa; when the ratio was 3.5~5.2, it was Evodia rutaecarpa; when the ratio was 5.8~6.5, it was Evodia rutaecarpa. When the above ratio requirements were met, the origin of the Chinese herbal medicine Evodia rutaecarpa could be determined.

[0040] Example 2

[0041] Three batches of different origin Chinese herbal medicine Evodia rutaecarpa (SM verification, SH verification, ZY verification) were selected for electronic nose testing (the processing method of Chinese herbal medicine Evodia rutaecarpa and the electronic nose detection method and parameters were the same as those in step (1) of Example 1). The response values ​​of 10 sensors are shown in Table 4. The response values ​​of 15 batches of Chinese herbal medicine Evodia rutaecarpa sensors including the verification samples were analyzed by OPLS-DA. The results are shown in Table 4. Figure 4 As shown, the results show that the three batches of verification samples and their corresponding original traditional Chinese medicine Evodia rutaecarpa samples are clustered into one category. The W1S and W6S ratios were calculated, and the SM verification ratio was 3.0; the SH verification ratio was 3.6; and the ZY verification ratio was 6.1. The three original Evodia rutaecarpa were all within the established ratio range, indicating that the method was stable and reliable.

[0042] Table 4 Sensor response values ​​of different origin Chinese herbal medicine Evodia rutaecarpa verification samples

[0043] W1C W5S W3C W6S W5C W1S W1W W2S W2W W3S SH Verification 0.91 10.37 0.96 0.94 0.92 3.52 22.32 1.64 5.27 0.99 SM Verification 0.88 11.28 0.96 0.97 0.91 2.94 22.38 1.50 4.68 0.98 ZY Verification 0.66 26.78 0.77 1.00 0.68 6.17 57.84 2.56 8.96 1.00 .

[0044] The present invention detects the odor of the Chinese medicinal herb Evodia rutaecarpa with different origins through an electronic nose, finds that there are differences in the response values ​​of the electronic nose W1W, W5S and W1S sensors of the Chinese medicinal herb Evodia rutaecarpa with different origins, combines the ratio definition range with the reference sensor, finds that the W1S sensor has a more obvious ratio definition range of the Chinese medicinal herb Evodia rutaecarpa with different origins, thereby effectively identifying the origin of the Chinese medicinal herb Evodia rutaecarpa through the response value ratio range of the difference sensor and the reference sensor. The method involves simple parameters, intuitive results and high accuracy, and is suitable for quickly identifying the origin of the medicinal material or decoction pieces of Evodia rutaecarpa.

Claims

1. A method for identifying the origin of the Chinese medicine Evodia rutaecarpa based on electronic nose odor detection, characterized in that: The powder to be tested is sampled through a headspace sampling bottle and tested with an electronic nose to obtain the sensor response value. W1S is used as the difference sensor and W6S is used as the reference sensor. The origin of the traditional Chinese medicine Evodia rutaecarpa is confirmed according to the ratio of the response values ​​of W1S and W6S. When the ratio of W1S to W6S response values ​​is 2.4-3.1, it is Evodia rutaecarpa; when the ratio is 3.5-5.2, it is Psoralea corylifolia; when the ratio is 5.8-6.5, it is Evodia rutaecarpa; The electronic nose is a PEN-3 type electronic nose, W1S is a sensor sensitive to short-chain alkanes, and W6S is a sensor sensitive to hydrogen; The sampling amount of the powder to be tested is 0.5-1 g; the powder to be tested is crushed before use and passed through a No. 3 sieve.

2. The method for identifying the origin of the Chinese medicine Evodia rutaecarpa based on electronic nose odor detection according to claim 1, characterized in that: The parameters of the electronic nose were set as follows: sample interval 1 s, flushing time 60-120 s, zeroing time 3-5 s, pre-sampling time 3-5 s, measurement time 120 s, chamber flow 400-500 mL / min, and initial injection flow 400-500 mL / min.

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