Method for identifying drying process of rhizoma polygonati product or powder raw material

Abstract

According to the method for identifying the drying process of the polygonatum sibiricum product or the powder raw material, when a compound shown in a formula (I) and / or a formula (II) is detected in the polygonatum sibiricum product or the powder raw material through a GCMS technology, the drying mode of the polygonatum sibiricum product or the powder raw material is freeze drying; when the compound shown in the formula (III) is detected, the drying mode of the rhizoma polygonati product or the powder raw material is infrared drying. The compound shown in the formula (I) and / or the compound shown in the formula (II) and the compound shown in the formula (III) serve as markers for distinguishing the raw materials of the rhizoma polygonati product as infrared drying, effective identification of the drying process of the rhizoma polygonati product is achieved, the detection method is simple and easy to implement, and detection of the markers can be achieved through conventional pretreatment and detection methods. The detected polygonatum sibiricum products can be but not limited to solid, pasty and liquid samples; the detected polygonatum types comprise polygonatum cyrtonema, polygonatum kingianum, polygonatum kingianum and related hybrid varieties.

Description

Technical Field

[0001] The present invention belongs to the technical field of drying method identification, and particularly relates to a method for identifying the drying process of polygonatum products or powder raw materials. Background Technique

[0002] Polygonatum is the rhizome of a perennial herb of the genus Polygonatum in the family Liliaceae and is included in the Chinese Pharmacopoeia 2020 Edition. The harvesting period of polygonatum is short, and the water content is high, making it prone to mildew or rot. Therefore, it is crucial to promptly adopt an appropriate drying method for treatment.

[0003] Various drying methods can significantly affect the color attributes, sensory characteristics, internal chemical components, and biological activities of foods. In recent decades, the main drying techniques for traditional Chinese medicines have included hot air drying, freeze drying, infrared drying, vacuum drying, and microwave drying, etc. Various drying methods mainly rely on experimental equipment. Due to their high maturity and strong applicability, the above-mentioned classical drying techniques have always been the focus of laboratory research and large-scale applications. Among them, hot air drying, freeze drying, infrared drying, vacuum drying, and microwave drying have been the five most studied drying methods since 2000. The advantages of these methods mainly lie in improving the drying speed and the overall quality of products. Freeze drying is highly regarded because it can retain chemical composition and physical properties to the greatest extent. However, due to its high cost, it has not been widely adopted. Infrared drying technology is favored because of its uniform heating and low pollution risk.

[0004] The quality of polygonatum products or powder raw materials varies due to different drying methods. However, there is currently no detection method for evaluating the drying process of polygonatum products or powder raw materials. Therefore, it is of great significance to provide a method that can effectively identify whether polygonatum products or powder raw materials are freeze-dried or infrared-dried. Summary of the Invention

[0005] Aiming at the problems existing in the above background technique, the purpose of the present invention is to provide a method for identifying the drying process of polygonatum products or powder raw materials. This method uses a gas chromatography-mass spectrometry (GC-MS) instrument for detection, with characteristic chemical components as identification markers, and can effectively identify polygonatum raw materials and their products prepared by freeze-drying process and infrared-drying process. Specifically, it is achieved through the following technical solutions:

[0006] A method for identifying the drying process of polygonatum products or powder raw materials. When the compound shown in formula (I) and / or the compound shown in formula (II) is detected in the polygonatum product or powder raw material, then the drying method of the polygonatum product or powder raw material is freeze drying; when the compound shown in formula (III) is detected in the polygonatum product or powder raw material, then the drying method of the polygonatum product or powder raw material is infrared drying;

[0007]

[0008]

[0009] Furthermore, the following treatments are carried out before GC-MS detection:

[0010] 1) When the polygonatum raw material and its products are solid, first grind the polygonatum sample to obtain a powder sample, weigh the powder sample and put it into a glass headspace vial, and preheat it in a metal bath heater; insert the DVB / CAR / PDMS extraction head of solid-phase microextraction into the gas chromatography injection port for aging, then insert it into the headspace vial for adsorption, take out the extraction head and insert it into the gas chromatography injection port for desorption analysis;

[0011] 2) When the polygonatum raw material and its products are paste-like, take the polygonatum sample, add chloroform and extract it by ultrasonic, filter it with filter paper and concentrate it to dryness, add chloroform to dissolve it, and finally filter it through a microporous membrane into a sample bottle;

[0012] 3) When the polygonatum raw material and its products are liquid, concentrate it to dryness, add chloroform to dissolve it, and finally filter it through a microporous membrane into a sample bottle.

[0013] Furthermore, in step 1), the particle size of the powder is 10 - 200 mesh, the aging temperature is 260 °C, the aging time is 5 min, the adsorption temperature is 40 °C, and the adsorption time is 40 min.

[0014] Furthermore, the GC-MS detection conditions are as follows:

[0015] DB-Wax chromatographic column (30 m × 0.25 mm, 0.25 μm), the carrier gas is helium, the flow rate is 1.0 mL / min, the injection port temperature is 260 °C, the temperature programming: the initial temperature is 50 °C, hold for 1 min, then increase the temperature at a rate of 5 °C / min to 220 °C, hold for 1 min, and then increase the temperature at a rate of 8 °C / min to 280 °C, hold for 3 min;

[0016] Mass spectrometry conditions: the ion source temperature is 230 °C, the quadrupole temperature is 200 °C, the interface temperature is 280 °C, the mass scanning range is m / z 30 - 550, and the qualitative library is NIST2020.

[0017] The compounds shown in formula (I) and / or the compounds shown in formula (II) of the present invention are used as markers for freeze-drying of raw materials for distinguishing Polygonatum products, and the compounds shown in formula (III) are used as markers for infrared drying of raw materials for distinguishing Polygonatum products, so as to effectively identify the drying process of Polygonatum products. The detection method is simple and easy to operate, and the detection of markers can be achieved by conventional pretreatment and gas chromatography-mass spectrometry. The detected Polygonatum products can be, but are not limited to, solid states (such as medicinal materials, decoction pieces, tablets, capsules, etc.), paste states (such as extracts, medicated ointments, etc.), and liquid samples (such as beverages, oral liquids, etc.); the detected types of Polygonatum include Polygonatum cyrtonema Hua, Polygonatum serratum (Wang et al.) Hoo & Tsai, Polygonatum sibiricum Redoute and related hybrid varieties. Description of the Drawings

[0018] Figure 1 It is the total ion current chromatogram of GC-MS of the Polygonatum sample prepared by freeze-drying;

[0019] Figure 2 It is the total ion current chromatogram of GC-MS of the Polygonatum sample prepared by infrared drying;

[0020] Figure 3 It is the total ion current chromatogram of GC-MS of the Polygonatum sample prepared by hot air drying;

[0021] Figure 4 It is the total ion current chromatogram of GC-MS of the Polygonatum sample prepared by microwave drying;

[0022] Figure 5 It is the total ion current chromatogram of GC-MS of the Polygonatum sample prepared by vacuum drying;

[0023] Figure 6 It is the secondary mass spectrum of the compound shown in formula (I);

[0024] Figure 7 It is the secondary mass spectrum of the compound shown in formula (II);

[0025] Figure 8 It is the secondary mass spectrum of the compound shown in formula (III). Detailed Embodiments

[0026] The present invention will be further described below with specific embodiments.

[0027] The experimental methods used in the following embodiments are all conventional methods unless otherwise specified.

[0028] The materials, reagents, etc. used in the following embodiments can be obtained from commercial channels unless otherwise specified.

[0029] Example 1

[0030] 1. Preparation of Materials and Samples

[0031] Fresh polygonatum rhizome was collected from Lishui, Zhejiang in November 2024 and identified as the tuberous root of the polygonatum plant of the Liliaceae family. After each sample was immediately washed, the surface of the sample was wiped with absorbent paper and evenly divided into five parts: for freeze-drying, infrared drying, hot air drying, microwave drying, and vacuum drying respectively.

[0032] Freeze-drying: First, the sample to be dried was placed in a -80°C freezer for pre-freezing for 2 hours, and then the sample was placed in a vacuum freeze-dryer (fd-1a-50, Shanghai Leewen Scientific Instrument Co., Ltd, Shanghai, China) with a vacuum pressure of 6.0 Pa and a cold trap temperature of -50°C for drying.

[0033] Microwave drying: The sample was placed in a microwave dryer (COWB-4L, Jiangyin Microwave Energy System Equipment Co., Ltd, Jiangsu, China) with a microwave operating frequency of 2450 MHz, a rated input power of 3200 W, and a relative humidity of 4.00 ± 0.50%.

[0034] Infrared drying: During the drying process, the sample to be dried was placed on the tray of an infrared dryer (WS70-1, Hangzhou Qiwei Instrument) at a position 10 cm away from the infrared heat source. The instrument is equipped with two infrared bulbs, each with a power of 275 W and an insulation resistance of 10 MΩ. The total power of the dryer is 550 W, and the relative humidity is 4.00 ± 0.50%.

[0035] Hot air drying: The sample to be dried was evenly placed in a hot air dryer (DHG-9140A, Shanghai Jinghongexperiment Equipment Co., Ltd, Shanghai, China). The instrument parameters were set as a temperature of 50°C, a wind speed of 0.5 m / s, a relative humidity of 6.00 ± 0.50%, and the working power of the instrument was 1600 W.

[0036] Vacuum drying: After the polygonatum sample was evenly placed in a vacuum oven (DZF-6090, Shanghai Aogum Instrument Manufacturing Co., Ltd, Shanghai, China), the vacuum pump was turned on. After the relative pressure reached 0.085 MPa, the vacuum was stopped, the drying temperature was set at 50°C, and the power of the instrument was 1400 W.

[0037] The samples dried by the above different methods were ground to 100 meshes, 2.000 g was weighed and placed in a 15 mL glass headspace vial, and placed in a metal bath heater for preheating; the DVB / CAR / PDMS extraction head of solid-phase microextraction was inserted into the gas chromatography injection port and aged at 260°C for 5 min, then inserted into the headspace vial, adsorbed at 60°C for 15 min, and the extraction head was taken out and inserted into the gas chromatography injection port for desorption analysis.

[0038] 2. GC-MS Analysis and Detection

[0039] The gas chromatography conditions are as follows: DB-Wax chromatographic column (30m×0.25mm, 0.25μm), the carrier gas is helium, the flow rate is 1.0mL / min, the inlet temperature is 260°C, and the temperature programming: the initial temperature is 50°C, held for 1min, then heated at a rate of 5°C / min to 220°C, held for 1min, and then heated at a rate of 8°C / min to 280°C, held for 3min.

[0040] The mass spectrometry conditions are as follows: the ion source temperature is 230°C, the quadrupole temperature is 200°C, the interface temperature is 280°C, the mass scanning range is m / z 30 - 550, and the qualitative library is NIST2020.

[0041] Figures 1 - 5 Total ion chromatograms of high-resolution mass spectrometry of Polygonatum sibiricum samples prepared by freeze-drying, infrared drying, hot air drying, microwave drying, and vacuum drying, respectively;

[0042] Figure 6 It is the ion fragmentation pattern of formula (Ⅰ); Figure 7 It is the ion fragmentation pattern of formula (Ⅱ); Figure 8 It is the ion fragmentation pattern of formula (Ⅲ).

[0043] From Figures 1 - 5 it can be seen that there are significant differences in Polygonatum sibiricum samples prepared by different drying methods.

[0044] The high-resolution MS / MS data of the compound of formula (Ⅰ) are 41, 68, 95, 109, 137, 152, the retention time is 11.815min, and it can be identified as 2-methoxy-3-(1-methylethyl)-Pyrazine by comparing with the database NIST.

[0045] The high-resolution MS / MS data of the compound of formula (Ⅱ) are 30, 44, 71, 149, 311, 357, 390, 420, 447, 450, 494, the retention time is 2.207min, and it can be identified as 7,7'-dinitro-Spiro[9,9']difluorene-2,2'-dicarboxylic acid by comparing with the database NIST. The high-resolution MS / MS data of the compound of formula (Ⅲ) are 41, 55, 69, 109, 137, 152, the retention time is 11.66min, and it can be identified as 3,6-Dimethyl-2,3,3a,4,5,7a-hexahydrobenzofuran by comparing with the database NIST.

Claims

1. A method for identifying the drying process of polygonatum products or powder raw materials, characterized in that: When the compound represented by formula (I) and / or the compound represented by formula (II) is detected in the polygonatum product or powder raw material by GCMS, the drying method of the polygonatum product or powder raw material is freeze drying; when the compound represented by formula (III) is detected in the polygonatum product or powder raw material, the drying method of the polygonatum product or powder raw material is infrared drying; 2. The method for identifying the drying process of polygonatum sibiricum products or powder raw materials according to claim 1, characterized in that: The following treatments were performed before GC-MS detection: 1) When the polygonatum raw material and its product are solid, first grind the polygonatum sample to obtain a powder sample, weigh the powder sample and put it into a glass headspace bottle, and place it in a metal bath heater for preheating; insert the DVB / CAR / PDMS extraction head of the solid phase microextraction into the gas chromatography injection port for aging, then insert it into the headspace bottle for adsorption, take out the extraction head and insert it into the gas chromatography injection port for desorption analysis; 2) When the raw material of polygonatum and its product are in a paste state, take a polygonatum sample, add chloroform to perform ultrasonic extraction, filter and concentrate to dryness, add chloroform to dissolve, and finally filter to a sample bottle through a microporous filter membrane; 3) When the polygonatum raw material and its product are liquid, they are concentrated to dryness, dissolved in chloroform, and finally filtered through a microporous filter membrane into a sample bottle.

3. A method for identifying the drying process of polygonatum products or powder raw materials as claimed in claim 2, characterized in that: In step 1), the particle size of the powder is 10-200 mesh, the aging temperature is 260° C., the aging time is 5 min, the adsorption temperature is 40° C., and the adsorption time is 40 min.

4. A method for identifying the drying process of polygonatum products or powder raw materials as claimed in claim 2, characterized in that: The GC-MS detection conditions are: DB-Wax column (30m×0.25mm, 0.25μm), helium as carrier gas, flow rate 1.0mL / min, injection port temperature 260℃, heating program: initial temperature 50℃, hold for 1min, then increase to 220℃ at a rate of 5℃ / min, hold for 1min, then increase to 280℃ at a rate of 8℃ / min, hold for 3min; Mass spectrometry conditions: ion source temperature 230 °C, quadrupole temperature 200 °C, interface temperature 280 °C, mass scanning range m / z 30-550, qualitative library NIST2020.

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