Method for rapidly identifying different producing areas of Chinese prickly ash

Abstract

The invention discloses a method for rapidly identifying different producing areas of Chinese prickly ash, and belongs to the field of natural spice identification. The method comprises the following steps: firstly, obtaining a characteristic chromatogram of volatile components in Sichuan pepper by adopting a gas chromatography-tandem mass spectrometry method, and then identifying the producing area of the Sichuan pepper according to a relative peak area proportion relation of the volatile components; the identification method disclosed by the invention is rapid, high in identification accuracy and simple in operation process.

Description

Technical Field

[0001] The present invention belongs to the field of identification of natural spices, and particularly relates to a method for rapidly identifying different producing areas of Chinese prickly ash. Background Art

[0002] As a natural spice, Chinese prickly ash has a unique fragrance and numbness, and is an indispensable condiment in Chinese cuisine cooking. It can not only add flavor to food, but also has certain medicinal value. Chinese prickly ash is widely used in hot pot, marinated dishes, etc., bringing a strong and fragrant taste and aroma to the dishes. The main types of Chinese prickly ash in China include Gansu red Chinese prickly ash, Sichuan Hanyuan tribute pepper, Shaanxi Hancheng red Chinese prickly ash, Maowen red Chinese prickly ash, southern Chinese prickly ash (Hanyuan and Yanyuan), green Chinese prickly ash (Jinyang and Zhaotong), and rattan pepper, etc. The quality of Chinese prickly ash is affected by the climate and variety differences of the producing areas, and there are large differences in flavor quality and market price. Therefore, accurately identifying red Chinese prickly ash from different producing areas is of great significance for improving the management ability of raw material quality, preventing fraud, and protecting the legitimate rights and interests of consumers and producers.

[0003] At present, there are few studies on the identification of the producing areas of Chinese prickly ash, mainly including electronic nose sensors and high performance liquid chromatography. Among them, the electronic nose sensor method mainly trains data through a machine learning classification model to obtain a Chinese prickly ash producing area recognition model. For example, a method for identifying the producing area of Chinese prickly ash is disclosed in the prior art. This method collects Chinese prickly ash samples from different regions and extracts their characteristic data, trains a Chinese prickly ash producing area recognition model using machine learning technology, and then analyzes the characteristic data of new samples through this model to predict the producing area of Chinese prickly ash. Although it can distinguish Chinese prickly ash from different producing areas, its analysis process is relatively complex, and the change of flavor during the storage of Chinese prickly ash will also affect the detection results. High performance liquid chromatography is mostly used for the quality control research of the numbness component index of Chinese prickly ash. The prior art also discloses the determination of 6 sanshool compounds in Chinese prickly ash and their producing area identification by liquid chromatography - tandem mass spectrometry. The test results of this method are extremely susceptible to the influence of the pretreatment extraction of sanshool compounds, and the actual application of distinguishing the producing areas of Chinese prickly ash has not been realized.

[0004] Therefore, when analyzing the producing area of Chinese prickly ash using the existing technical methods, there are problems such as complex processing methods, and at the same time, some key substance information may be missed, resulting in the differential components selected being unable to accurately characterize Chinese prickly ash from different producing areas, thus leading to errors in the identification results of the producing areas of Chinese prickly ash. Summary of the Invention

[0005] In view of the above - mentioned prior art, the present invention discloses a method for rapidly identifying different producing areas of Chinese prickly ash to solve the technical problems of complex operation and inaccurate discrimination of the existing methods for identifying the producing areas of Chinese prickly ash.

[0006] To achieve the above object, the technical solution adopted by the present invention is: to provide a method for rapidly identifying different producing areas of Chinese prickly ash, which comprises the following steps:

[0007] S1: Take Chinese prickly ash, and obtain the characteristic chromatogram of the volatile components of Chinese prickly ash by gas chromatography-tandem mass spectrometry; the characteristic peaks corresponding to sabinene, myrcene, D-limonene, 1,8-cineole, α-pinene and (-)-α-pinene are included in the said characteristic chromatogram.

[0008] S2: Identify the origin of Chinese prickly ash according to the numerical values of A1, A2, A3 and A4; the calculation formula of A1 is shown in Formula I, the calculation formula of A2 is shown in Formula II, the calculation formula of A3 is shown in Formula III, and the calculation formula of A4 is shown in Formula IV.

[0009]

[0010] (Percentage of relative peak area of D-limonene + Percentage of relative peak area of 1,8-cineole) × 100 Ⅲ;

[0011] Percentage of relative peak area of 1,8-cineole × 100 Ⅳ;

[0012] When A1 < 1, A3 > 45, -0.3 < A2 < 0.3, 1 < A4 < 6, the Chinese prickly ash is the red Chinese prickly ash from Wudu, Gansu.

[0013] When A1 > 1, A3 > 45, -0.3 < A2 < 0.3, A4 > 8, the Chinese prickly ash is the red Chinese prickly ash from Hancheng, Shaanxi.

[0014] When A2 > 0.4, A3 > 45, the Chinese prickly ash is the southern Chinese prickly ash from Sichuan.

[0015] When A1 < 1, -0.3 < A2 < 0.3, A3 > 45, A4 < 0.5, the Chinese prickly ash is the red Chinese prickly ash from Maowen, Sichuan.

[0016] When A3 < 35, the Chinese prickly ash is the green Chinese prickly ash or rattan pepper produced in Sichuan or Chongqing.

[0017] On the basis of the above technical solution, the present invention can also be improved as follows.

[0018] Further, the injection mode in the gas chromatography-tandem mass spectrometry is headspace injection, and the headspace parameters are as follows:

[0019] The temperature of the constant temperature furnace is 60.0 °C; the temperature of the sample flow path is 150.0 °C; the temperature of the transmission line is 150.0 °C; the constant temperature time of the sample bottle is 30.00 min.

[0020] Further, the injection port temperature in the gas chromatography-tandem mass spectrometry is 250 °C; the carrier gas flow rate is 1.2 mL / min.

[0021] Further, in gas chromatography-tandem mass spectrometry, the stationary phase of the chromatographic column is (5%-phenyl)-methyl polysiloxane, the column temperature is 50°C, and the chromatographic column temperature programming is as follows:

[0022] Step number Heating rate (℃ / min) Temperature (℃) Holding time (min) 1 / 50 3 2 15 95 1 3 2 110 1 4 4 170 1 5 8 260 3 。

[0023] Further, in gas chromatography-tandem mass spectrometry, the ion source temperature is 280°C, the mass spectrometry quadrupole temperature is 150°C, and the scanning mode is full scan mode

[0024] The beneficial effects of the present invention are as follows:

[0025] 1. The identification method in the present invention is rapid, has a high identification accuracy rate, and the operation process is simple. Specific Embodiments

[0026] The following detailed description of the specific embodiments of the present invention is made in conjunction with the examples.

[0027] The HP-5ms (30m, 0.25mm, 0.25μm) chromatographic column used in the examples was purchased from Agilent Technologies (China) Co., Ltd.

[0028] Example 1

[0029] A method for rapidly identifying Zanthoxylum bungeanum from different producing areas

[0030] Twenty-eight Zanthoxylum bungeanum samples were selected for testing. The twenty-eight Zanthoxylum bungeanum samples were blindly numbered, and the relative peak area ratios of the characteristic aroma components (sabinene, myrcene, D-limonene, 1,8-cineole, α-pinene, and (-)-α-pinene) of the blind samples were determined by gas chromatography-tandem mass spectrometry. The determination method conditions were set as follows:

[0031] ① Sample preparation and headspace injection parameter settings

[0032] 2 g of Zanthoxylum bungeanum granules with a storage time within 18 months were respectively taken into a 20 mL headspace vial, and the headspace injection parameters were set as shown in Table 1.

[0033] Table 1

[0034] Temperature of the constant temperature furnace 60.0℃ Temperature of the sample flow path 150.0℃ Temperature of the transfer line 150.0℃ Constant temperature time of the sample bottle 30.00 min

[0035] ② Gas chromatography condition settings

[0036] Install an HP-5ms (30m, 0.25mm, 0.25μm) chromatographic column. The stationary phase of this chromatographic column is (5%-phenyl)-methyl polysiloxane. Set the inlet temperature to 250°C, the carrier gas flow rate to 1.2 mL / min (constant flow rate), and the chromatographic column temperature programming is shown in Table 2.

[0037] Table 2

[0038]

[0039]

[0040] ③ Mass spectrometry condition setting

[0041] The ion source temperature is 280 °C, the mass spectrometry quadrupole temperature is 150 °C, and the scanning mode: full scan.

[0042] The determination results by gas chromatography - tandem mass spectrometry are shown in Table 3, and then the origin of Zanthoxylum bungeanum is identified according to the numerical values of A1, A2, A3 and A4; among them, the calculation formula of A1 is shown in Formula I, the calculation formula of A2 is shown in Formula II, the calculation formula of A3 is shown in Formula III, and the calculation formula of A4 is shown in Formula IV;

[0043]

[0044] (Relative peak area ratio of D - limonene + Relative peak area ratio of 1,8 - cineole) × 100 Ⅲ;

[0045] Relative peak area ratio of 1,8 - cineole × 100 Ⅳ;

[0046] When A1 < 1, A3 > 45, - 0.3 < A2 < 0.3, 1 < A4 < 6, the origin of Zanthoxylum bungeanum is Gansu (Wudu red Zanthoxylum bungeanum in Gansu); when A1 > 1, A3 > 45, - 0.3 < A2 < 0.3, A4 > 8, the origin of Zanthoxylum bungeanum is Hancheng in Shaanxi (Hancheng red Zanthoxylum bungeanum in Shaanxi); when A2 > 0.4, A3 > 45, the origin of Zanthoxylum bungeanum is Sichuan (Southern Sichuan Zanthoxylum bungeanum); when A1 < 1, - 0.3 < A2 < 0.3, A3 > 45, A4 < 0.5, the origin of Zanthoxylum bungeanum is Sichuan (Maowen red Zanthoxylum bungeanum); when A3 < 35, the origin of Zanthoxylum bungeanum is Sichuan or Chongqing (green Zanthoxylum bungeanum and rattan pepper); the obtained identification results are shown in Table 4.

[0047] Table 3 Relative peak area ratio of characteristic aroma components (%)

[0048]

[0049]

[0050] Table 4 Sample identification results

[0051]

[0052]

[0053] According to the results in Table 4, the accuracy rate of identifying the origin of unknown Zanthoxylum bungeanum samples by this method can reach 100%.

[0054] Although the specific embodiments of the present invention have been described in detail in conjunction with the embodiments, it should not be construed as a limitation on the scope of protection of this patent. Within the scope described in the claims, various modifications and variations that can be made by those skilled in the art without creative efforts still fall within the scope of protection of this patent.

Claims

1. A method for rapidly identifying different origins of Zanthoxylum bungeanum, characterized in that: It includes the following steps: S1: Take Chinese prickly ash, and obtain the characteristic chromatogram of the volatile components of Chinese prickly ash by gas chromatography-tandem mass spectrometry; the characteristic peaks corresponding to sabinene, myrcene, D-limonene, 1,8-cineole, α-pinene and (-)-α-pinene are included in the characteristic chromatogram; S2: Identify the origin of Chinese prickly ash according to the numerical values of A1, A2, A3 and A4; the calculation formula of A1 is shown in Formula I, the calculation formula of A2 is shown in Formula II, the calculation formula of A3 is shown in Formula III, and the calculation formula of A4 is shown in Formula IV; (Relative peak area ratio of D-limonene + relative peak area ratio of 1,8-cineole) × 100 Ⅲ; Relative peak area ratio of 1,8-cineole × 100 Ⅳ; When A1 < 1, A3 > 45, -0.3 < A2 < 0.3, 1 < A4 < 6, the Chinese prickly ash is the red Chinese prickly ash from Wudu, Gansu; When A1 > 1, A3 > 45, -0.3 < A2 < 0.3, A4 > 8, the Chinese prickly ash is the red Chinese prickly ash from Hancheng, Shaanxi; When A2 > 0.4, A3 > 45, the Chinese prickly ash is the southern Chinese prickly ash from Sichuan; When A1 < 1, -0.3 < A2 < 0.3, A3 > 45, A4 < 0.5, the Chinese prickly ash is the red Chinese prickly ash from Mao County, Sichuan; When A3 < 35, the origin of the Chinese prickly ash is the green Chinese prickly ash or rattan pepper from Sichuan or Chongqing.

2. The method for rapidly identifying different origins of Zanthoxylum bungeanum according to claim 1, wherein: The injection method in gas chromatography-tandem mass spectrometry is headspace injection, and the headspace parameters are as follows: The temperature of the constant temperature furnace is 60.0 °C; the temperature of the sample flow path is 150.0 °C; the temperature of the transmission line is 150.0 °C; the constant temperature time of the sample bottle is 30.00 min.

3. The method for rapidly identifying different origins of Zanthoxylum bungeanum according to claim 1, wherein: The injection port temperature in gas chromatography-tandem mass spectrometry is 250 °C; the carrier gas flow rate is 1.2 mL / min.

4. The method for rapidly identifying different origins of Zanthoxylum bungeanum according to claim 1, characterized in that: The stationary phase of the chromatographic column in gas chromatography-tandem mass spectrometry is (5%-phenyl)-methylpolysiloxane, the column temperature is 50 °C, and the chromatographic column temperature programming is as follows: 。 5. The method for rapidly identifying different origins of Zanthoxylum bungeanum according to claim 1, characterized in that: The ion source temperature in gas chromatography-tandem mass spectrometry is 280 °C, the mass spectrometry quadrupole temperature is 150 °C, and the scanning mode is full scan mode.

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