CN104267111A

CN104267111A - Pinellia ternate medicinal material detection method

Info

Publication number: CN104267111A
Application number: CN201410375377.5A
Authority: CN
Inventors: 宋平顺; 李波; 韩斌; 陈杰; 李登鹏; 赵建邦; 李士博; 李冬华; 张明童
Original assignee: GANSU ZHONGTIAN PHARMACEUTICAL Co Ltd
Current assignee: GANSU ZHONGTIAN PHARMACEUTICAL Co Ltd
Priority date: 2014-07-31
Filing date: 2014-07-31
Publication date: 2015-01-07

Abstract

The invention relates to a medicinal material detection method and concretely relates to a method for detecting alkaloid content and pesticide residue content of a pinellia ternate medicinal material. The method comprises alkaloid content determination: by chloroform, extracting a sample to be detected so that the extract is obtained and is used as a sample solution, preparing a contrast solution from ephedrine hydrochloride, determining a light absorption value by ultraviolet analysis and carrying out comparison calculation, and pesticide residue content determination: preparing a contrast solution based on acetonitrile protection, preparing a sample solution by acetone ultrasonic treatment, GPC gel penetration chromatogram purification and cyclohexane-ethyl acetate elution, determining content of a plurality of pesticide residues in the pinellia ternate medicinal material by a gas chromatography-mass spectrometry combined method and carrying out concentration calculation. The method provided by the invention solves the technical problem of operation complexity and limitation of the traditional physicochemical property discriminating method, has high accuracy, can be operated simply, has a low cost and has a good application prospect and economic benefits.

Description

Detection method of pinellia ternata medicinal material

Technical Field

The invention belongs to the field of quality detection of traditional Chinese medicinal materials, and particularly relates to a quality detection method of a pinellia ternata medicinal material.

Background

The rhizoma Pinelliae is dry tuber of rhizoma Pinelliae of Araceae, and is in similar spherical shape, with some slightly inclined part being long spherical shape with diameter of 1-1.5 cm; the surface is white or light yellow. The top end is provided with a sunken stem mark, and the periphery is densely covered with dotted root marks; the lower part is blunt and round and is smoother; firm, white cross section, rich powder, powder smelling irritating nose; light smell, pungent and pungent taste, numb tongue and pungent taste. Pinellia ternate has the effects of drying dampness and resolving phlegm, calming adverse-rising energy and preventing vomiting, and relieving distension and fullness and dispersing accumulation of pathogen. The traditional Chinese medicine composition is mainly used for treating symptoms such as damp-phlegm cold drink, vomit, regurgitation, cough, asthma and excessive phlegm, fullness in chest and diaphragm, phlegm syncope, headache, dizziness, insomnia, external carbuncle and swelling and the like, and is a traditional bulk medicine in China. Pinellia ternata contains various chemical components, mainly contains organic acid, alkaloid, pinellia ternata protein, volatile oil, amino acid, starch and the like. Modern researches show that the components contained in pinellia ternata have wide physiological activity, wherein the alkaloid content is closely related to the vomiting-arresting and cough-relieving effects of pinellia ternata, so the alkaloid content is often used as an important index for quality control of the pinellia ternata medicinal material.

In recent years, the market demand of pinellia ternata is continuously increased, wild resources are reduced year by year, and the artificial cultivation is slow, so that the storage amount and the yield of the pinellia ternata resources are greatly reduced. Leading to the appearance of a plurality of counterfeit products in the market, wherein the pesticide residue of a plurality of counterfeit products exceeds the standard and explodes the exterior, bringing great impact to the quality, the safety and the effectiveness of the pinellia ternata medicinal materials, and becoming the bottleneck restricting the development of the pinellia ternata series medicinal materials.

At present, the effective detection method of the quality-certified pinellia ternate is a traditional identification method of morphological characteristics and physicochemical characteristics, has certain limitations, is not enough to control the quality of the pinellia ternate on the whole, and is used as a common clinical traditional Chinese medicine, the quality of the pinellia ternate is influenced by a plurality of factors such as physicochemical indexes and large pesticide residue, so that a scientific quality detection method is needed to be established for evaluating the quality of the pinellia ternate.

Disclosure of Invention

Therefore, the technical problem to be solved by the invention is to solve the problems of complex detection method and difficult quality control of the pinellia ternata medicinal material in the prior art, and further provide a method for simply and quickly detecting the pinellia ternata medicinal material with high accuracy.

In order to solve the technical problems, the invention is realized by the following technical scheme:

the invention provides a detection method of a pinellia ternate medicinal material, which comprises a step of measuring the content of total alkaloids and a step of measuring the pesticide residue, wherein the steps of:

a: the method for measuring the content of the total alkaloids comprises the following steps:

(1) weighing ephedrine hydrochloride 2.10mg dried at 110 deg.C of 100-; precisely measuring 1mL, 2 mL, 3mL, 4 mL and 5mL of the solutions respectively, adding water to 5mL, sequentially and precisely adding 5mL of buffer solution with the pH value of 5.40, 1mL of bromothymol blue standard solution with the volume fraction of 0.05% and 10mL of chloroform, shaking and standing until the layering is stable, and respectively taking chloroform layers of the samples for later use as standard samples;

precisely taking 5mL of deionized water, precisely adding 5mL of buffer solution with the pH value of 5.40, 1mL of bromothymol blue standard solution with the volume fraction of 0.05% and 10mL of chloroform in sequence, shaking and standing until the layering is stable, and taking a chloroform layer for later use as a blank control sample;

taking each standard sample and the blank control sample, performing ultraviolet spectrophotometry detection at the wavelength of 414nm, and drawing a standard regression equation by taking the concentration of ephedrine hydrochloride as a horizontal coordinate and the light absorption value as a vertical coordinate;

(2) accurately weighing 0.3g of powder of a medicinal material to be detected which is dried to constant weight, adding 0.5mL of concentrated ammonia water and 10mL of chloroform, carrying out cold soaking for 2-4 hours, carrying out ultrasonic extraction for 1-2 hours in an ice bath, and filtering and collecting a filtrate containing total alkaloids; washing the residue obtained by filtering with 10mL of chloroform for 3 times (4, 3 and 3mL respectively), filtering, mixing filtrates, recovering chloroform layer at 80 deg.C, and evaporating to obtain sample extract;

precisely adding 5mL of buffer solution with pH of 5.40, 1mL of bromothymol blue solution with volume fraction of 0.05% and 5mL of water into a separating funnel in sequence, and mixing; precisely measuring 10mL of chloroform for 3 times, respectively 4 mL, 3mL and 3mL, sequentially transferring the extract of the standby test sample into the separating funnel, shaking and standing until the layering is stable, and taking a chloroform layer as the test sample;

taking the blank control sample in the step (1) as a control, carrying out ultraviolet spectrophotometry detection at the wavelength of 414nm, measuring the absorbance of the sample, and calculating the content of total alkaloids in the test sample;

b: the determination of the pesticide residue comprises the following steps:

(1) accurately weighing a proper amount of triphenyl phosphate, and adding acetone to prepare a solution containing 100 mu g of triphenyl phosphate per 1ml as an internal standard stock solution;

precisely measuring 1ml of each pesticide reference product storage solution and 1ml of the internal standard storage solution respectively, and adding acetone to a constant volume of 100ml to serve as a mixed reference product storage solution; precisely measuring appropriate amount, adding acetonitrile to constant volume to obtain 20-1000ng/ml solutions with different concentrations, and using as mixed reference solution;

dissolving appropriate amount of ribonolactone in acetonitrile to obtain a solution containing 20mg of ribonolactone per 1ml, dissolving appropriate amount of sorbitol in water to obtain a solution containing 10mg of sorbitol per 1 ml; precisely measuring the ribonolactone and sorbitol solution respectively by 1ml, mixing uniformly, adding acetonitrile to constant volume to 10ml, and using the mixture as an analysis protective agent;

(2) precisely weighing 10g of medicinal material fine powder to be measured, adding 1g of sodium chloride, uniformly mixing, precisely adding 100ml of acetone, carrying out ice bath ultrasonic treatment for 30 minutes, centrifuging, quickly transferring supernatant into a conical bottle with a plug containing 1g of anhydrous sodium sulfate, and standing for 30 minutes; then, precisely measuring 60ml of the solution, concentrating the solution under reduced pressure to be nearly dry, and adding a solvent with the volume ratio of 1:1, dissolving a sample in cyclohexane-ethyl acetate solution, fixing the volume to 10ml, filtering, taking filtrate, purifying by GPC gel permeation chromatography, and performing gel permeation chromatography on the filtrate in a volume ratio of 1: eluting with cyclohexane-ethyl acetate solution of 1 as mobile phase, collecting eluate, transferring into KD bottle, and concentrating under reduced pressure to near dryness;

adding the mixture into the sample in a volume ratio of 1: dissolving 5ml of the ethyl acetate-acetone mixed solution of 1, transferring the dissolved solution to a graphite carbon-amino mixed solid phase extraction column, and mixing the dissolved solution with the volume ratio of 1: eluting with 15ml of ethyl acetate-acetone mixed solution of 1, collecting eluent, blowing nitrogen to near dryness, adding 5 mu l of internal standard stock solution, adding acetonitrile to constant volume to 1ml, and using the volume as a test solution;

(3) precisely measuring 400 mu L of each of the mixed reference substance solution and the test substance solution with each concentration, respectively adding 100 mu L of the analysis protective agent, uniformly mixing, precisely absorbing 1 mu L of the analysis protective agent, and performing gas chromatography-mass spectrometry combined instrument measurement; wherein,

the gas chromatographic analysis conditions are as follows: taking an elastic quartz capillary column DB17ms with the specification of 30m multiplied by 0.25mm multiplied by 0.25um, taking high-purity helium as a carrier gas, the column flow rate is 1.3ml/min, the sample injection amount is 1 mu l, adopting high-pressure non-split-flow sample injection, setting the temperature of a sample injection port to be 230 ℃, and specifically adopting a temperature rise program as follows: the initial temperature was 60 ℃, ramped to 120 ℃ at 30 ℃/min, ramped to 200 ℃ at 10 ℃/min, ramped to 230 ℃ at 2 ℃/min, ramped to 300 ℃ at 30 ℃/min, and held for 7 minutes;

the EI source mass spectrometry conditions are as follows: the electron energy is set to 70eV, the ion source temperature is 230 ℃, and the interface temperature is 250 ℃.

In the determination of the pesticide residue, the GPC gel permeation chromatography purification step specifically comprises the following conditions: the filler is Bio-Beads S-X3200-400 meshes, the purification column is 2.5mm multiplied by 40cm, the specific elution parameters are purification and impurity removal 900S, the target object is collected for 1200S, and the column is cleaned for 300S.

In the determination of the pesticide residue, the pesticide reference substance comprises dichlorvos, methamidophos, acephate, tetrachloronitrobenzene, hexachlorobenzene, alpha-hexachlorocyclohexane, beta-hexachlorocyclohexane, gamma-hexachlorocyclohexane, omethoate, diazinon, pentachloronitrobenzene, monocrotophos, disulfoton, phosphamidol I, dimethoate, heptachlor, pentachloroaniline, chlorothalonil, methyl chlorpyrifos, aldrin, captan, phosphamidoII, methyl parathion, methyl pyrimidylphenyl sulfide, metalaxyl, triadimefon, chlorpyrifos, malathion, fenitrothion, parathion, pendimethalin, cis-epoxy heptachlor, trans-epoxy heptachlor, triadimenol A, triadimenol B, trans-chlordane, cis-endosulfan, cis-chlordane, trans-endosulfan, PP ' -DDE, PP ' -DDD, ddT, PP ' -DDT, Dieldrin, methidathion, endrin, ethion, triphenyl phosphate, bifenthrin, endosulfate, iprodione, fenpropathrin, dicofol, cyhalothrin, methoxyddt, dicofol, vothion, permethrin 1, permethrin 2, cypermethrin, fenvalerate, deltamethrin.

In the determination of the content of the total alkaloids, the buffer solution is a citric acid-sodium citrate buffer solution with pH of 5.40.

Further, in the measurement of the content of the total alkaloids, the particle size of the medicinal material to be detected is 180-2000 μm.

Furthermore, in the determination of the pesticide residue, the particle size of the drug to be tested is 180-2000 μm.

The method of the invention determines the authenticity and quality of the pinellia ternate medicinal material by measuring the content of total alkaloids in the pinellia ternate medicinal material and detecting the pesticide residue of the pinellia ternate medicinal material. And the content of the total alkaloids is determined by an ultraviolet spectrophotometer detection method, and the method is accurate, simple and feasible. The method detects the residual pesticide amount of the medicinal materials in a gas chromatography-mass spectrometry combined mode, has high detection accuracy and simple and quick method, can effectively detect common pesticide types in the pinellia ternata medicinal materials at one time through specific screening of detection conditions, and has better accuracy and practical effect.

Drawings

In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific examples thereof and with the accompanying drawings, in which:

FIG. 1 is a gas chromatogram (full scan) of a pesticide standard in the description of the present invention;

FIG. 2 is a gas chromatogram (0-10 minute scan) of a pesticide standard in the description of the present invention;

FIG. 3 is a gas chromatogram of a pesticide standard in the description of the present invention (10-20 min full scan);

FIG. 4 is a gas chromatogram (20-40 min full scan) of a pesticide standard in the description of the present invention.

Detailed Description

Example 1 measurement of Total Alkaloids

1 Instrument and reagent

1.1 Instrument UV-1601 visible ultraviolet spectrophotometer (Shimadzu, Japan); KQSOB ultrasonic cleaner (ultrasonic instruments ltd, kunshan); a pH meter model mettler-toledo filter 320.

1.2 reagent ephedrine hydrochloride reference substance (China food and drug testing research institute batch No. 0714-; bromthymol blue standard solution and citric acid-sodium citrate buffer solution (pH is 5.40). Other reagents were analytically pure.

1.3 test drugs

The production areas of the medicinal materials are as follows: gansu Tianshui wild (not peeled), Gansu Tianshui wild pinellia ternate, Gansu Tianshui 1, Gansu Tianshui 2, Gansu Tianshui 3, Gansu xi he 1, Gansu xi he 2, Gansu xi he 3, Gansu Wudu, Gansu Hui county, Yunnan, Guizhou, Jiangxi and Hubei.

2. Experimental methods

2.1 control solution preparation and Linear relationship examination 2.10mg of ephedrine hydrochloride dried to constant weight at 105 deg.C was weighed and placed in a 100mL volumetric flask, water was added to the scale, and the mixture was shaken to obtain a solution containing 21.0. mu.g of ephedrine hydrochloride per 1 mL. Precisely measuring 1mL, 2 mL, 3mL, 4 mL and 5mL of the above solvent solutions, respectively adding water to 5mL, adding 5mL of buffer solution with pH value of 5.40, sequentially and precisely adding 1mL of 0.05% bromothymol blue standard solution and 10mL of chloroform, shaking for 1min, standing for layering, standing for 1 hr, and respectively taking chloroform layers for later use. A blank control solution was prepared by the same method using 5mL of deionized water. The chloroform solution was measured at 414nm of Boehringer's concentration and the absorbance was plotted on the abscissa and the regression equation was found to be 0.087C-0.0967, 0.9990 (n: 3). The ephedrine hydrochloride solution shows a good linear relationship at 2.10-10.50 mu g/mL.

2.2 preparation of test solution 0.160g of powder dried to constant weight (sieved by a three-sieve) is precisely weighed, 0.5mL of concentrated ammonia water and 10mL of chloroform are added, after cold soaking for 3 hours, ultrasonic extraction is carried out for 1 hour in ice bath, filtration is carried out, residues are washed and filtered by 10mL of chloroform for 3 times (4, 3 and 3mL), filtrates are combined, chloroform is recovered at 80 ℃ and evaporated to dryness, a separating funnel is taken, 5mL of bromothymol blue solvent with pH value of 5.40 buffer solution 5mL0.05 percent and 5mL of water are precisely added in sequence, 10mL of chloroform is precisely weighed and then transferred into the separating funnel for shaking for 1min, and after 1 hour, the chloroform layer is separated and then the absorbance is measured at the wavelength of 414 nm.

2.3 the test solution and the blank control solution were taken, and the absorbance at the wavelength of 414nm was measured, and the content was calculated as (%) C.times.10-6/(W.times.dilution factor). times.100% and as (%) 1/10, the results are shown in Table 1.

TABLE 1 Total alkaloid determination (%)

The content of the carbon dioxide is determined to be not less than 0.020% by actual measurement.

Example 2 measurement of residual amount of pesticide

1 Instrument and reagent

1.1 Instrument-Clarus 600 gas chromatography-mass spectrometer (PE company, USA), HS10260D ultrasonic extractor (Kunshan ultrasonic Instrument Co., Ltd.), RE-52A rotary evaporator (Shanghai Yangrong Biochemical apparatus factory).

1.2 reagent of dichlorvos, methamidophos, acephate, tetrachloronitrobenzene, hexachlorobenzene, alpha-hexachloro, beta-hexachloro, gamma-hexachloro, omethoate, diazinon, pentachloronitrobenzene, monocrotophos, fonofos, phosphamidol, dimethoate, heptachlor, pentachloranilide, chlorothalonil, chlorpyrifos-methyl, aldrin, captan, phosphamidol II, methyl parathion, pirimiphos-methyl, pentachlorophenyl sulfide, metalaxyl, triadimefon, chlorpyrifos, malathion, fenitrothion, parathion, pendimethalin, cis epoxy heptachlor, trans epoxy heptachlor, triadimenol A, triadimenol B, trans-chlordane, cis-chlordane, trans-endosulfan, PP '-DDE, PP' -DDD, OP '-DDT, PP' -DDT, dieldrin, promaphos, isothiophos, 64 kinds of pesticide reference substance storage solutions such as ethion, triphenyl phosphate, bifenthrin, endosulfan, iprodione, fenpropathrin, dicofol, cyhalothrin, methoxy DDT, dicofol, vofenthion, permethrin 1, permethrin 2, cypermethrin, fenvalerate, deltamethrin and the like are provided by China food and drug testing research institute.

Triphenyl phosphate, acetone, acetonitrile, cyclohexane and ethyl acetate are imported pesticide residue grade; ribonolactone, sorbitol, sodium chloride and anhydrous sodium sulfate are superior pure.

1.3 the samples, rhizoma Pinelliae and other genuine lot samples, are purchased from the producing area or from Lanzhou Huanghe medicinal material market as raw medicinal materials.

2 methods and results

2.1 gas chromatography analysis conditions elastic quartz capillary column (30m × 0.25mm × 0.25um) DB17ms, high purity helium as carrier gas, and column flow rate of 1.3 ml/min; the injection port temperature is 230 ℃, the injection amount is 1 mu l, and high-pressure non-split injection is carried out. Temperature rising procedure: the initial temperature is 60 deg.C, 30 deg.C/min to 120 deg.C, 10 deg.C/min to 200 deg.C, 2 deg.C/min to 230 deg.C, 30 deg.C/min to 300 deg.C, and is maintained for 7 min.

Mass spectrometry (EI source) measurement conditions: 70eV, the ion source temperature 230 ℃ and the interface temperature 250 ℃. The SIM conditions are shown in Table 2, and the detection results are shown in FIGS. 1, 2, 3 and 4.

TABLE 2 GC-MS detection index and SIM determination conditions

2.2 preparation of internal standard stock solution A proper amount of triphenyl phosphate is precisely weighed, and acetone is added to prepare a solution containing 100 mug of acetone per 1ml, thus obtaining the product.

2.3 preparation of Mixed reference solutions 1ml of each stock solution of pesticide reference and 1ml of stock solution of internal standard were measured precisely, placed in a 100ml measuring flask, diluted to the scale with acetone, shaken up to give a stock solution of mixed reference (1. mu.g/ml). Respectively and precisely measuring appropriate amount, and adding acetonitrile to prepare 20-1000ng/ml mixed reference substance solutions with different concentration series.

Formulation of analytical protectants: taking a proper amount of ribonolactone, adding acetonitrile to dissolve the ribonolactone, and preparing a solution containing 20mg of ribonolactone per 1 ml; in addition, a proper amount of sorbitol is taken, and water is added for dissolving to prepare a solution containing 10mg of sorbitol per 1 ml. Precisely measuring the ribonolactone and sorbitol solutions by 1ml respectively, adding into the same 10ml measuring flask, diluting with acetonitrile to scale, and shaking.

2.4 preparation of test solution 10g of test fine powder was weighed precisely and placed in a 100ml conical flask, 1g of sodium chloride was added, 100ml of acetone was added precisely, ultrasonic treatment was performed in an ice bath for 30 minutes, centrifugation was performed, and the supernatant was transferred rapidly into a conical flask with a stopper containing 1g of anhydrous sodium sulfate and placed for 30 minutes. Precisely measuring 60ml, concentrating under reduced pressure to near dryness, adding a small amount of cyclohexane: dissolving a sample by using an ethyl acetate (1:1) solution, quantitatively diluting the sample to 10ml, uniformly mixing, filtering, purifying the filtrate by using Gel Permeation Chromatography (GPC), injecting 5ml, (GPC main parameters: packing Bio-Beads S-X3200-400 meshes, purifying columns 2.5mm multiplied by 40cm, elution parameters: pre run900S, main run1200S and tail run300S), and purifying the filtrate by using cyclohexane: eluting with ethyl acetate (1:1) as mobile phase, collecting eluate, transferring into KD bottle, and concentrating under reduced pressure to near dryness.

2.5 purifying the sample solution, adding 5ml of ethyl acetate-acetone (1:1) mixed solution for dissolving, quantitatively transferring the dissolved solution to a graphite carbon (500mg) -amino (500mg) mixed solid phase extraction column, eluting by using 15ml of ethyl acetate-acetone (1:1) mixed solution, collecting eluent, blowing nitrogen to the column to be dry, adding acetonitrile into residues for dissolving, adding 5 mu l of internal standard stock solution, and fixing the volume of acetonitrile to 1ml to obtain the product.

2.6 methodological validation

2.6.1 precision test 1. mu.L of the diluted mixed standard solution was precisely aspirated, the sample introduction was repeated 5 times, and the RSD value was calculated, the calculation results are shown in Table 3.

Precision test of table 364 pesticides

2.6.2 sample application recovery test A certain amount of mixed standard solution was added to the samples, 3 samples with 3 addition levels were extracted and tested by the selected method, and the recovery of various pesticides in the samples was calculated by background subtraction, the results are shown in Table 4.

Sample application recovery test for 464 pesticides in table

2.6.3 detection limit determination the minimum amount of components detected was determined by diluting the pesticide standard solution to different concentrations, and the results are shown in Table 5.

Detection limits of 564 pesticides in table

2.6.4 Linear relationship the pesticide standard solutions were diluted to different concentrations and the linear range of the components was determined and the results are shown in Table 6.

TABLE 664 Linear equations for pesticides

2.7 the determination method comprises precisely measuring 400 μ L of each of the mixed reference solution and the test solution, adding 100 μ L of the analysis protective agent, mixing, precisely sucking 1 μ L of the mixture, injecting into a gas chromatography-mass spectrometer, measuring, and calculating to obtain the results shown in Table 7.

TABLE 7 pinellia Ternata pesticide residue test results report (mg/kg)

TABLE 7 report (mg/kg) of the results of the detection of pesticide residues in pinellia ternata (Table continuation)

3, analysis of measurement results:

3.1 results of pesticide residue determination, the pesticide residue was detected in 14 batches of samples, the detection rate was 100%, and the current situation of pesticide residue in pinellia ternata was relatively common. Relates to 20 different pesticides of organochlorine, organophosphorus and pyrethroid. The specific pesticide residues are fenpropathrin, cyhalothrin, trans-permethrin, cis-permethrin, triadimefon, methyl parathion, malathion, parathion, methamidophos, pentachloroanilide, chlorothalonil, flufenthion, trichlorfon, dichlorvos, acephate, tetrachloronitrobenzene, phosmet, phosphamidon, chlorpyrifos-methyl and metalaxyl.

3.2 the residue number of the pesticide in the pinellia tuber medicinal materials is different, 1 pesticide residue is detected in a few varieties, and 2-3 pesticide residues are mostly detected. The causes of pesticide residue in the traditional Chinese medicinal materials are complicated due to the influences of factors such as environment, planting technology, processing and storage.

3.3 the banned pesticides of 5 kinds including methyl parathion, methamidophos, fonofos and phosphamidon which are forbidden to use in the production of Chinese traditional medicine GAP are detected in pinellia tuber. Among other detected pesticides, triadimefon, metalaxyl, chlorothalonil fungicides, chlorpyrifos-methyl, dichlorvos, acephate, malathion, and vothion insecticides, and trichlorfon acaricides are all pesticides which can be used in production.

3.4 other pesticides and residual limit. The analysis is carried out by adopting the maximum pesticide residue limit regulation in the national standard GB2763-2005 food, although the pesticide residue limit regulation is detected, the pesticide residue limit regulation does not exceed the food residue standard: fenpropathrin, cyhalothrin, malathion, methamidophos, chlorothalonil, dichlorvos, acephate, fonofos, phosphamidon, and metalaxyl.

Exceeding the food residue standard: methyl parathion (0.1 mg/kg of grains and 0.02mg/kg of vegetables and fruits) exceeds 5 times, parathion (0.1 mg/kg of grains and 0.01mg/kg of vegetables and fruits) exceeds 5-60 times, triazolone (0.5 mg/kg of rice and 0.05mg/kg of vegetables) exceeds 11 times, fluocinofos (0.1 mg/kg of oil products and 1mg/kg of vegetables) exceeds 20-200 times, dicoforsone (2 mg/kg of fruits) exceeds 5 times, and chlorpyrifos-methyl (5 mg/kg of grains and products, 5mg/kg of oil products and 5mg/kg of vegetables) exceeds 1.4 times.

In conclusion, the pesticide detection rate of 14 batches of pinellia ternata samples is 100%, 5 forbidden pesticides are detected in the samples, the standard exceeding rate is 41% for 7 batches of samples.

3.5 according to the measurement result, the pesticide prohibited in the production of the Chinese medicinal material GAP and the pesticide allowed to be used in the production and easy to exceed the standard are recommended to be checked in a limited way. The limited inspection of methyl parathion, phoxim, methamidophos, fonofos and phosphamidoorganophosphorus pesticides prohibited in the production of Chinese medicinal material GAP is carried out.

It should be understood that the above examples and experimental examples are only examples for clearly illustrating the present invention, and are not intended to limit the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims

1. A detection method of pinellia ternata medicinal material is characterized by comprising the following steps of measuring the content of total alkaloids and measuring the pesticide residue, wherein,

b: the determination of the pesticide residue comprises the following steps:

2. The method for detecting pinellia ternata medicinal material according to claim 1, wherein in the determination of pesticide residue, the GPC gel permeation chromatography purification step specifically comprises the following conditions: the filler is Bio-Beads S-X3200-400 meshes, the purification column is 2.5mm multiplied by 40cm, the specific elution parameters are purification and impurity removal 900S, the target object is collected for 1200S, and the column is cleaned for 300S.

3. The method for detecting pinellia ternata medicinal material according to claim 1 or 2, wherein in the determination of pesticide residue, the pesticide reference substance comprises dichlorvos, methamidophos, acephate, tetrachloronitrobenzene, hexachlorobenzene, alpha-hexachlorocyclohexane, beta-hexachlorocyclohexane, gamma-hexachlorocyclohexane, omethoate, diazinon, quintozene, monocrotophos, fonofos, phosphamidol, dimethoate, heptachlor, pentachloranilide, chlorothalonil, chlorpyrifos-methyl, aldrin, captan, phosphamidol II, methyl parathion, pirimiphos-methyl, pentachlorophenyl sulfide-methyl, metalaxyl, triadimefon, chlorpyrifos, malathion, fenitrothion, parathion, pendimethalin, cis-epoxy heptachlor, trans-epoxy heptachlor, triadimenol A, triadimenol B, trans-chlordane, cis-form endosulfan, cis-form chlordane, and chlordane, Trans-endosulfan, PP '-DDE, PP' -DDD, OP '-DDT, PP' -DDT, dieldrin, methidathion, endrin, ethion, triphenyl phosphate, bifenthrin, endosulfan, iprodione, fenpropathrin, dicofol, cyhalothrin, methoxyDDT, dicofol, vothiofos, permethrin 1, permethrin 2, cypermethrin, fenvalerate, deltamethrin.

4. The method for detecting pinellia ternata Thunb medicinal material according to any one of claims 1 to 3, wherein the buffer solution is a citric acid-sodium citrate buffer solution with pH of 5.40 in the determination of the total alkaloid content.

5. The method for detecting pinellia ternata Thunb medicinal material according to any one of claims 1 to 4, wherein the particle size of the medicinal material to be detected in the determination of the total alkaloid content is 180-2000 μm.

6. The method for detecting pinellia ternata Thunb medicinal material according to any one of claims 1 to 4, wherein in the determination of the pesticide residue, the particle size of the medicinal material to be detected is 180-2000 μm.