CN106370758A - Chinese herbal medicine improved QuEChERS filler bag and application thereof in detection of Chinese herbal medicine pesticide residues - Google Patents
Chinese herbal medicine improved QuEChERS filler bag and application thereof in detection of Chinese herbal medicine pesticide residues Download PDFInfo
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- CN106370758A CN106370758A CN201611075247.5A CN201611075247A CN106370758A CN 106370758 A CN106370758 A CN 106370758A CN 201611075247 A CN201611075247 A CN 201611075247A CN 106370758 A CN106370758 A CN 106370758A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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Abstract
The invention provides a Chinese herbal medicine improved QuEChERS filler bag. The Chinese herbal medicine improved QuEChERS filler bag contains 1 part (by weight) of carbon nano-material, 2-15 parts (by weight) of amino functionalized adsorption material, 2-15 parts (by weight) of nonpolar functional group modified silica-gel material and 2-15 parts (by weight) of water-absorbing adsorbent, wherein the four kinds of fillers in the filler bag are mixed uniformly and are filled in a 15ml centrifugal tube. The invention further provides a method for detecting Chinese herbal medicine pesticide residues. According to the Chinese herbal medicine improved QuEChERS filler bag and the method, through using the materials of different physical and chemical properties in a mixed manner, the effect of removing interference matrixes from a detection process for pesticide residues of samples of seven species of Chinese herbal medicines, i.e., radix glycyrrhizae, radix paeoniae alba, Chinese angelica, rhubarb roots, atractylodes macrocephala, rhizoma chuanxiong and pinellia tuber is achieved; compared with the common solid-phase extraction pretreatment method, the detection time is saved by at least one half, and the consumption of the filler is only 1/4 that of a solid-phase extraction column, so that the detection cost and time cost of the samples are reduced greatly.
Description
Technical field
The invention belongs to Physico-chemical tests field and in particular to a kind of Chinese herbal medicine improved quechers filler bag and its inspection
Survey the application in pesticide made of Chinese medicinal herbs residual.
Background technology
Chinese medicine is the valuable cultural heritage of China, is Chinese nation's disease preventing and treating, rehabilitation, the rule for the treatment of producing offspring
Precious.Chinese crude drug and decoction pieces industry are the important composition departments of China's medicinal industry, are also that China's pharmaceuticals industry has independent intellectual
One of industry of property right.Meanwhile, one of main big class product of Chinese crude drug and decoction pieces or China's Chinese medicine outlet, Chinese medicine in recent years
The export trade quickly grows, now, the world's annual Chinese medicine volume of trade oneself reach 50,000,000,000 dollars, and increased with 15% speed.But
China's Chinese medicine outlet only accounts for the 3%～6% of cosmopolitian plant medicine market, and this is not corresponded with the status pole of Chinese medicine big country of China.
In recent years, the demand expanding day to natural drug for the countries in the world, especially particularly pays close attention to green medicine.Chinese medicine matter
Amount except the effective ingredient of Chinese medicine itself should stablize controlled in addition to, the Pesticide Residue in Chinese medicine has caused everybody attention,
And threaten the Health and Living quality of the people.Mostly the Chinese medicine of China is to export to state with the identity of food or food supplement
Outward, many countries and regions are by strict food standard requirement Chinese medicine in the world, as long as certain index exceeding standard is suspended sale of simultaneously without exception
Destroy.The Chinese medicine of China's export on the state such as America and Europe market, repeatedly because pesticide residues are exceeded etc., checked and detained by reason, and pesticide residues are dirty
Dye has become " bottleneck " that Chinese medicine goes to the world, has influence on the modernization of Chinese medicine, internationalization process.Therefore, Farm chemical of Chinese berbs residual is asked
One of Ti Shi China Chinese medicine research field key issue in the urgent need to address.
Chinese scholar just started the research of Chinese crude drug Pesticide Residues detection method early in 1980.Xue Jian etc. opens very early
Begin concern Chinese crude drug Pesticide Residues problem, but for pesticide residue detection method research concentrate on earliest several single
Other kinds such as the Gamma Hexaochlorocyclohexane in kind, such as organic chlorine agriculture chemicals, ddt.China's " Chinese Pharmacopoeia " (version one in 2010) advises
Determine the detection method of machine chlorine class, organic phosphates and pyrethroid pesticide totally 24 kinds of pesticide residues, indicate China's medicine
The great attention of highest code centering medical material safety, but, only to Huang in " Chinese Pharmacopoeia " (version one in 2010) text
Stilbene, Radix Glycyrrhizae, stem and leaf of Radix Ginseng total saponins and Radix Ginseng total saponinss have made organic chlorine agriculture chemicals (Gamma Hexaochlorocyclohexane, clofenotane, pentachloronitrobenzene)
The regulation of residue limits, is not particularly suited for the mensure of many pesticide residues such as multiple organochlorines, pyrethroid in Chinese crude drug.
At present, problem present in the domestic pesticide residue analysis in Chinese crude drug is mainly: in related research report, inspection
The traditional Chinese medicinal materials assortment surveyed does not enrich；Chinese crude drug is excessively single to the pesticide species of pesticide residue determination, negligible amounts；Due to Chinese medicine
Material base qualitative diversity and complexity, do not have a kind of general relative efficiency carries out pre-treatment to complicated Chinese crude drug substrate
Method, and do not have one kind can cover the multiclass such as organochlorine, organophosphors, pyrethroid and carbamate, Multiple Pesticides simultaneously
The detection method of residual.In terms of Chinese crude drug residue limits standard: a. standard total amount is few, covering pesticide species are very few, non-adult
System；B. standard formulation relatively lags behind, and lacks the system detectio to related pesticide residues data and monitoring；C. lack and commented with risk
Based on estimating, work out the scientific basis of Chinese crude drug Pesticide Residue standard；D. the detection method of Chinese crude drug pesticide residues falls behind,
Fail to pay close attention to international trend.
In recent years, the developed country such as European Union, the U.S., Japan and Korea S proposes very strict technology to the Chinese medicine of import and health product
Index request, the particularly control to persticide residue limit index.Japanese Kampo crude drug preparation association was on May 19th, 2005
Issued " with regard to the industry self-inspection standard of Chinese crude drug residual pesticide ", " Chinese crude drug persticide residue algoscopy " with 20 days respectively, " close
Industry self-inspection standard in Chinese medicine preparation residual pesticide " and " Chinese medicine preparation persticide residue algoscopy ", and in June, 2006
Formal execution.4 industry standards by the Radix Astragali, Radix Polygalae, Radix Glycyrrhizae, Cortex cinnamomi japonici (Ramulus Cinnamomi), Herba Asari, Fructus Corni, Folium Perillae, Fructus Jujubae, Pericarpium Citri Reticulatae, Folium Eriobotryae and
11 Chinese crude drug organic chlorine agriculture chemicals residual quantities of Cortex Moutan bring up to total bhc 0.2mg/kg, total ddt 0.2mg/kg；To contain
The trace standard of pesticide of above-mentioned 11 Chinese crude drugs and Radix Ginseng, Radix Ginseng Rubra and Folium Sennae all formulations of totally 14 traditional Chinese medicinal materials assortments all carries
Height, and determine corresponding detection method, the industry standard is formally received in the 15th edition Japanese Pharmacopoeia that in April, 2006 revises
Carry as national standard.
2006 korean foods drug administration (kfda) disclose in Chinese medicine heavy metal and residual approval standard and detection
Method.New method clear stipulaties Pesticide Residue in 30 kinds of common Chinese crude drugs for 42 kinds of pesticide, compared with Japan, Korea Spro
The standard that state this time puts into effect is more strict and concrete.Wherein to Gamma Hexaochlorocyclohexane, clofenotane, drinox, dieldrin, endrin etc. 15
Plant pesticide and worked out the unified standard being directed to all vegetalitas crude drugs, in addition also work out 27 other to indivedual crude drug kinds
The trace standard of pesticide, to limitation requirement in 21 kinds of Farm chemical of Chinese berbs residue criterions such as Semen oryzae sativae, Fructus Lycii then reference food." American Pharmacopeia-
NF " publish once every year, (usp36-nf312012 publishes, and in May, 2013 gives birth to have published the 36th edition at present
Effect)." American Pharmacopeia " of new edition includes 70 kinds of pesticide residues quantity measuring methods such as organochlorine, organophosphors, pyrethroid, limitation
Standard and computing formula, 37 kinds of the vegetable drug being related to." European Pharmacopoeia " list including drinox, Gamma Hexaochlorocyclohexane, ddt and its
Isomer, in 70 kinds of interior pesticide limitations, for unlisted pesticide in pharmacopeia, need to instruct and 90/ referring additionally to European Union 76/895
The related limitation regulation of 642 instructions.For being also NM pesticide in above-mentioned 2 instructions, its limitation can be by listed in pharmacopeia
Formula calculates.The traditional Chinese medicinal materials assortment being related in " European Pharmacopoeia " has 180 kinds.
In sum, lack the method that can simultaneously detect 322 kinds of pesticide residues in Chinese herbal medicine at present, therefore, in stepping up
The Detection Technologies of Pesticide Residues research work in medicine, improves China's Chinese medicine quality safety criterion and detection technique level extremely further
Close important.Research work is in line with international standards, the international competitiveness to lifting China tcm product, promotes the development meaning of Chinese Medicine Industry
Justice is great.
Content of the invention
In view of this, the first object of the present invention is to provide a kind of Chinese herbal medicine improved quechers filler bag, by such as
Lower filler composition: carbon nanomaterial, the adsorbing material of aminofunctional, the silica gel material of non-polar functional group's modification, water absorption
Adsorbent.
Preferably, in the improved quechers filler bag of Chinese herbal medicine of the present invention, the ratio of described filler is: 1 weight
The silicon that amount part carbon nanomaterial, the adsorbing material of 2-15 weight portion aminofunctional, 2-15 weight portion non-polar functional group modify
Glue material, 2-15 weight portion hydroscopicity adsorbent；Preferably, four kinds of filler mix homogeneously in described filler bag, are seated in 15ml
In centrifuge tube.
Preferably, in the improved quechers filler bag of Chinese herbal medicine of the present invention, described carbon nanomaterial is selected from single
Any one or two kinds of wall carbon nano tube, multi-walled carbon nano-tubes and double-walled carbon nano-tube material；Preferably, described carbon nanometer material
In 2nm-50nm, specific surface area is 5-50m to the size of material2/ g, average pore size is
Preferably, in the improved quechers filler bag of Chinese herbal medicine of the present invention, the absorption of described aminofunctional
Material is selected from any one or a few in amino bonded silica gel, polyamino bonded silica gel and amination polyethylene divinylbenzene；
The size of the adsorbing material of described aminofunctional is 20 μm -100 μm, and specific surface area is 300-800m2/ g, average pore size
For
Preferably, in the improved quechers filler bag of Chinese herbal medicine of the present invention, described non-polar functional group modifies
Silica gel material be selected from octadecyl functional group bonded silica gel, in phenyl functional group's bonded silica gel and Yi Ji functional group bonded silica gel
One or more；The silica gel material size that described non-polar functional group modifies is 20 μm -100 μm, and specific surface area is
300-800m2/ g, average pore size isPhosphorus content is 10%-20% weight.
Preferably, in the improved quechers filler bag of Chinese herbal medicine of the present invention, described hydroscopicity adsorbent is no
Color orthorhombic system crystals.
Preferably, in the improved quechers filler bag of Chinese herbal medicine of the present invention, described material with carbon element is received for many walls carbon
Rice material, the size of described multi-wall carbon nano-tube material is 10nm-20nm, and specific surface area is 10m2/ g, average pore size isDescribed aminofunctional adsorbing material is polyamino bonded silica gel psa；The silica gel material that described non-polar functional group modifies
Expect for octadecyl functional group bonded silica gel c18；Described hydroscopicity adsorbent is mgso4；It is highly preferred that in of the present invention
In medical herbs improved quechers filler bag, described multi-walled carbon nano-tubes (nano card): polyamino bonded silica gel (psa): ten
Eight alkyl functionals group's bonded silica gel (c18): the weight of anhydrous magnesium sulfate ratio is for 2:15:15:15.
Another object of the present invention is to providing a kind of method of detection Chinese herbal medicine residual pesticide, comprise the following steps:
1) Chinese herbal medicine sample pulverizer is pulverized；
2) by step 1) the Chinese herbal medicine sample of gained carries out water immersion, solvent extraction, centrifugation, obtains supernatant；
3) use quechers filler bag detecting step 2 as improved in said herbal medicine) gained supernatant, vibrate, from
The heart, takes supernatant liquid filtering film, obtains testing sample；
4) by step 3) testing sample that obtains measures through gc-q-tof/ms, carries data base using instrument, to Chinese herbal medicine
The pesticide of middle residual carries out examination.
Preferably, of the present invention detection Chinese herbal medicine residual pesticide method in, described step 1) Chinese herbal medicine be sweet
Grass, the Radix Paeoniae Alba, Radix Angelicae Sinensis, Radix Et Rhizoma Rhei, the Rhizoma Atractylodis Macrocephalae, Rhizoma Chuanxiong or the Rhizoma Pinelliae.
Preferably, of the present invention detection Chinese herbal medicine residual pesticide method in, described step 2) in water soak side
Method soaks sample 30min for ultra-pure water.
Preferably, of the present invention detection Chinese herbal medicine residual pesticide method in, described step 2) described in solvent carry
The method taking is using acetonitrile, methanol, acetone, n-hexane, 1% acetic acid acetonitrile and 1% acetic acid acetonitrile-acetate buffer system
One or more extract；It is highly preferred that described step 2) in Extraction solvent be 1% acetic acid acetonitrile-sodium acetate buffer, and
Sodium chloride, anhydrous magnesium sulfate one or two；It is highly preferred that described step 2) in Extraction solvent be 1% acetic acid acetonitrile-second
Sour sodium buffer, with sodium chloride.
Preferably, in the method for detection Chinese herbal medicine residual pesticide of the present invention, described extracting mode includes vortex and carries
Take, supersound extraction or mechanical shaking extraction；It is highly preferred that described extracting mode is mechanical shaking extraction.
Preferably, of the present invention detection Chinese herbal medicine residual pesticide method in, described step 2) described in medium-height grass
Medicine sample with the amount ratio of Extraction solvent, buffer salt is: 1g:1ml～10ml:0.1g～1g.
Preferably, of the present invention detection Chinese herbal medicine residual pesticide method in, step 3) described in Chinese herbal medicine improve
Quechers filler be selected from SWCN, multi-walled carbon nano-tubes, double-walled carbon nano-tube material, amino bonded silica gel, many
Amino bonded silica gel and amination polyethylene divinylbenzene, octadecyl functional group bonded silica gel, phenyl functional group's bonded silica
Any one or a few in glue, Yi Ji functional group bonded silica gel and anhydrous magnesium sulfate；Preferably, in detection of the present invention
In the method for medical herbs residual pesticide, the improved quechers filler of described Chinese herbal medicine is multi-walled carbon nano-tubes (nano card), many
Amino bonded silica gel (psa), octadecyl functional group bonded silica gel (c18), anhydrous magnesium sulfate；Most preferably, Chinese herbal medicine
The ratio of quechers filler is multi-walled carbon nano-tubes (nano card), polyamino bonded silica gel (psa), octadecyl sense
Group's bonded silica gel (c18), the weight ratio of anhydrous magnesium sulfate are for 2:15:15:15.
From the foregoing, it will be observed that the Chinese herbal medicine of the present invention improved quechers filler bag and with the improved quechers of Chinese herbal medicine
Filler bag, as the basis of sample pre-treatments, the method for detecting Chinese herbal medicine residual pesticide, at least has the advantage that
1) the Chinese herbal medicine improved quechers filler bag, being related in the present invention is by the material to different physicochemical properties
Being used in mixed way of material, has reached removal Radix Glycyrrhizae, the Radix Paeoniae Alba, Radix Angelicae Sinensis, Radix Et Rhizoma Rhei, the Rhizoma Atractylodis Macrocephalae, Rhizoma Chuanxiong and seven kinds of Chinese herbal medicine sample pesticide of the Rhizoma Pinelliae
The effect of the interference substrate in residuals detection process, more common Solid-Phase Extraction pre-treating method not only saves at least one
Half detection time, and amount of filler is only the 1/4 of solid-phase extraction column, and the testing cost greatling save sample became with the time
This.
2) multiple agricultures in the larger conventional Chinese herbal medicine of the export volume such as Radix Glycyrrhizae, the Radix Paeoniae Alba, Radix Angelicae Sinensis, Radix Et Rhizoma Rhei, the Rhizoma Atractylodis Macrocephalae, Rhizoma Chuanxiong, Rhizoma Pinelliae
The detection method of medicine residual is through the improved quechers filler arriving of optimization design and pre-treating method, it is possible to obtain preferably
Clean-up effect, and the preferable response rate can be obtained, can accomplish to 322 kinds of pesticide residues in Chinese herbal medicine, disposable extract
Purify, single injected sampling detects, compared with traditional solid phase extraction method and gc-ms/ms detection method, can save and detect into
Originally, work efficiency hundreds times are improved.
Specific embodiment
Further technical scheme is illustrated it should be understood that being only this below below by way of specific embodiment
Bright exemplary illustration, is not limited to the protection domain of the claims in the present invention.
Embodiment 1: Chinese herbal medicine improved quechers filler bag detection example 1
The present embodiment is used for Chinese herbal medicine improved quechers filler bag and the detection medium-height grass medicinal herb grower that the present invention provides is described
The sample-pretreating method of medicine residue and detection method.
The present embodiment is with the Chinese herbal medicine Rhizoma Atractylodis Macrocephalae as testing sample:
(1) the Chinese herbal medicine Rhizoma Atractylodis Macrocephalae is produced in Yunnan, and size-reduced machine is pulverized, and labelling is indicated in sealing.
(2) weigh the Rhizoma Atractylodis Macrocephalae sample (being accurate to 0.01g) of 5g step (1), in 50ml centrifuge tube, add 10ml water, leaching
Bubble 30min, adds 10ml 1% acetic acid acetonitrile-sodium acetate buffer solution, adds 1g sodium chloride, and agitator vibrates 5min,
It is centrifuged 5min under 10000r/min, take supernatant 5ml.
By the 5ml supernatant addition of step (2), containing Chinese herbal medicine improved quechers filler, (Chinese herbal medicine is improved
Quechers filler: multi-walled carbon nano-tubes (nano card) 20mg, polyamino bonded silica gel (psa) 100mg, octadecyl official
Bonded silica gel (c18) 150mg, anhydrous magnesium sulfate 150mg can be rolled into a ball) 15ml centrifuge tube in, mix, agitator vibrate 3min,
It is centrifuged 5min under 10000r/min.
(3) step (3) supernatant 4.5ml spin concentration in 40 DEG C of water-baths is taken to be dried to close, concentrated solution is placed in nitrogen
Under dry up, add 0.5ml normal hexane mix, after 0.2 μm of membrane filtration, obtain testing sample solution, through gc-q-tof/ms
Measure.
(4) gc-q-tof/ms operating condition:
Chromatographic condition: chromatographic column: vf-1701ms (30m × 0.25mm × 0.25um) (j＆w scientific, folsom,
ca)；Chromatographic column heating schedule: 40 DEG C of holding 1min, then it is warming up to 130 DEG C with 30 DEG C/min, then be warming up to 5 DEG C/min
250 DEG C, subsequently it is warming up to 300 DEG C with 10 DEG C/min, keeps 5min, then be cooled to 280 DEG C with 10 DEG C/min, keep 2min；Carry
Gas: helium, purity 99.999%；Flow velocity: 1.2ml/min；Injector temperature: 290 DEG C；Sample size 2 μ l；Input mode: no
Split sampling, solvent delay 6min.
Mass Spectrometry Conditions: Mass Spectrometry Conditions: ion source: ei (electron impact ionization source)；Ion source temperature: 280 DEG C, electron bombardment
Source energy: 70ev；Gas phase-mass spectrometer interface temperature: 290 DEG C；Scan mode: carry out tof pattern in the way of 5 spectrograms per second complete
Scanning, mass number scope 50～600amu..
(5) data base that foundation instrument carries is inclined to obtaining numerical value retrieval by header, search argument retention time in step (5)
Difference is defined to ± 0.5min, and accurate mass deviation is defined to ± 100ppm, detects at least three fragment ions, and according to every kind ofization
The measured value of each key element of compound and the deviation of theoretical value in built data base, provide retrieval matching score value, retrieval coupling automatically
The compound of score value ＞ 60, that is, confirm detection target compound.
(6) determine that detection pesticide 2- phenylphenol and Furadan in the Chinese herbal medicine Rhizoma Atractylodis Macrocephalae are produced in this Yunnan by above method.
Embodiment 2: Chinese herbal medicine improved quechers filler bag detection example 2
With the Chinese herbal medicine Rhizoma Atractylodis Macrocephalae as testing sample, detection method, with embodiment 1, differs only in change sample to the present embodiment
Source and filler bag, concrete grammar is as follows:
(1) the Chinese herbal medicine Rhizoma Atractylodis Macrocephalae is produced in Jiangxi, and size-reduced machine is pulverized, and labelling is indicated in sealing.
(2) weigh the Rhizoma Atractylodis Macrocephalae sample (being accurate to 0.01g) of 5g step (1), in 50ml centrifuge tube, add 10ml water, leaching
Bubble 30min, adds 10ml 1% acetic acid acetonitrile-sodium acetate buffer solution, adds 1g sodium chloride, and agitator vibrates 5min,
It is centrifuged 5min under 10000r/min, take supernatant 5ml.
(3) supernatant of step (2) is added in the 15ml centrifuge tube containing Chinese herbal medicine improved quechers filler,
(Chinese herbal medicine improved quechers filler includes: multi-walled carbon nano-tubes (nano card) 20mg, polyamino bonded silica gel (psa)
150mg, octadecyl functional group bonded silica gel (c18) 200mg, anhydrous magnesium sulfate 150mg), mix, agitator vibrates 3min,
It is centrifuged 5min under 10000r/min.
(4) take step (3) supernatant 4.5ml in 40 DEG C of water-baths spin concentration to closely dry, concentrated solution is placed in and blows under nitrogen
Dry, add the normal hexane of 0.5ml to mix, after 0.2 μm of membrane filtration, obtain testing sample solution, survey through gc-q-tof/ms
Fixed.
(5) gc-q-tof/ms operating condition:
Chromatographic condition: chromatographic column: vf-1701ms (30m × 0.25mm × 0.25um) (j＆w scientific, folsom,
ca)；Chromatographic column heating schedule: 40 DEG C of holding 1min, then it is warming up to 130 DEG C with 30 DEG C/min, then be warming up to 5 DEG C/min
250 DEG C, subsequently it is warming up to 300 DEG C with 10 DEG C/min, keeps 5min, then be cooled to 280 DEG C with 10 DEG C/min, keep 2min；Carry
Gas: helium, purity 99.999%；Flow velocity: 1.2ml/min；Injector temperature: 290 DEG C；Sample size 2 μ l；Input mode: no
Split sampling, solvent delay 6min.
Mass Spectrometry Conditions: Mass Spectrometry Conditions: ion source: ei (electron impact ionization source)；Ion source temperature: 280 DEG C, electron bombardment
Source energy: 70ev；Gas phase-mass spectrometer interface temperature: 290 DEG C；Scan mode: carry out tof pattern in the way of 5 spectrograms per second complete
Scanning, mass number scope 50～600amu..
(6) data base that foundation instrument carries is inclined to obtaining data retrieval by header, search argument retention time in step (5)
Difference is defined to ± 0.5min, and accurate mass deviation is defined to ± 100ppm, detects at least three fragment ions, and according to every kind ofization
The measured value of each key element of compound and the deviation of theoretical value in built data base, provide retrieval matching score value, retrieval coupling automatically
The compound of score value ＞ 60, that is, confirm detection target compound.
(7) determine that detection pesticide Elacron and meta-tolyl-N-methylcarbamate (MTMC) in the Chinese herbal medicine Rhizoma Atractylodis Macrocephalae are produced in this Jiangxi by above method.
Embodiment 3: Chinese herbal medicine improved quechers filler bag detection example 3
With the Chinese herbal medicine Rhizoma Atractylodis Macrocephalae as testing sample, detection method, with embodiment 1, differs only in change sample to the present embodiment
Source, concrete grammar is as follows:
The present embodiment is with the Chinese herbal medicine Rhizoma Atractylodis Macrocephalae as testing sample:
(1) the Chinese herbal medicine Rhizoma Atractylodis Macrocephalae is produced in Gansu, and size-reduced machine is pulverized, and labelling is indicated in sealing.
(2) weigh the Rhizoma Atractylodis Macrocephalae sample (being accurate to 0.01g) of 5g step (1), in 50ml centrifuge tube, add 10ml water, leaching
Bubble 30min, adds 10ml% acetic acid acetonitrile-sodium acetate buffer solution, adds 1g sodium chloride, and agitator vibrates 5min,
It is centrifuged 5min under 10000r/min, take supernatant 5ml.
(3) supernatant of step (2) is added in the 15ml centrifuge tube containing Chinese herbal medicine improved quechers filler,
(Chinese herbal medicine improved quechers filler includes: multi-walled carbon nano-tubes (nano card) 30mg, polyamino bonded silica gel (psa)
150mg, octadecyl functional group bonded silica gel (c18) 150mg, anhydrous magnesium sulfate 150mg), mix, agitator vibrates 3min,
It is centrifuged 5min under 10000r/min.
(4) take step (3) supernatant 4.5ml in 40 DEG C of water-baths spin concentration to closely dry, concentrated solution is placed in and blows under nitrogen
Dry, add the normal hexane of 0.5ml to mix, after 0.2 μm of membrane filtration, obtain testing sample solution, survey through gc-q-tof/ms
Fixed.
(5) gc-q-tof/ms operating condition:
Chromatographic condition: chromatographic column: vf-1701ms (30m × 0.25mm × 0.25um) (j＆w scientific, folsom,
ca)；Chromatographic column heating schedule: 40 DEG C of holding 1min, then it is warming up to 130 DEG C with 30 DEG C/min, then be warming up to 5 DEG C/min
250 DEG C, subsequently it is warming up to 300 DEG C with 10 DEG C/min, keeps 5min, then be cooled to 280 DEG C with 10 DEG C/min, keep 2min；Carry
Gas: helium, purity 99.999%；Flow velocity: 1.2ml/min；Injector temperature: 290 DEG C；Sample size 2 μ l；Input mode: no
Split sampling, solvent delay 6min.
Mass Spectrometry Conditions: Mass Spectrometry Conditions: ion source: ei (electron impact ionization source)；Ion source temperature: 280 DEG C, electron bombardment
Source energy: 70ev；Gas phase-mass spectrometer interface temperature: 290 DEG C；Scan mode: carry out tof pattern in the way of 5 spectrograms per second complete
Scanning, mass number scope 50～600amu..
(6) data base carrying according to instrument to acquisition information retrieval by header in step (5), search argument retention time is inclined
Difference is defined to ± 0.5min, and accurate mass deviation is defined to ± 100ppm, detects at least three fragment ions, and according to every kind ofization
The measured value of each key element of compound and the deviation of theoretical value in built data base, provide retrieval matching score value, retrieval coupling automatically
The compound of score value ＞ 60, that is, confirm detection target compound.
(7) determine that detection pesticide tolelofos-methyl, triapenthenol in the Chinese herbal medicine Rhizoma Atractylodis Macrocephalae are produced in this Gansu by above method.
Embodiment 4: Chinese herbal medicine improved quechers filler bag detection example 4
With the Chinese herbal medicine Rhizoma Atractylodis Macrocephalae as testing sample, detection method, with embodiment 1, differs only in change sample to the present embodiment
Source, concrete grammar is as follows:
The present embodiment is with the Chinese herbal medicine Rhizoma Atractylodis Macrocephalae as testing sample:
(1) the Chinese herbal medicine Rhizoma Atractylodis Macrocephalae is produced in Hebei, and size-reduced machine is pulverized, and labelling is indicated in sealing.
(2) weigh the Rhizoma Atractylodis Macrocephalae sample (being accurate to 0.01g) of 5g step (1), in 50ml centrifuge tube, add 10ml water, leaching
Bubble 30min, adds 10ml acetonitrile, adds 1g sodium chloride, 4g anhydrous magnesium sulfate, agitator vibrates 5min, under 10000r/min
Centrifugation 5min, takes supernatant 5ml.
(3) supernatant of step (2) is added in the 15ml centrifuge tube containing Chinese herbal medicine improved quechers filler,
(Chinese herbal medicine improved quechers filler includes: multi-walled carbon nano-tubes (nano card) 20mg, polyamino bonded silica gel (psa)
150mg, octadecyl functional group bonded silica gel (c18) 150mg, anhydrous magnesium sulfate 150mg), mix, agitator vibrates 3min,
It is centrifuged 5min under 10000r/min.
(4) take step (3) supernatant 4.5ml in 40 DEG C of water-baths spin concentration to closely dry, concentrated solution is placed in and blows under nitrogen
Dry, add the normal hexane of 0.5ml to mix, after 0.2 μm of membrane filtration, obtain testing sample solution, survey through gc-q-tof/ms
Fixed.
(5) gc-q-tof/ms operating condition:
Chromatographic condition: chromatographic column: vf-1701ms (30m × 0.25mm × 0.25um) (j＆w scientific, folsom,
ca)；Chromatographic column heating schedule: 40 DEG C of holding 1min, then it is warming up to 130 DEG C with 30 DEG C/min, then be warming up to 5 DEG C/min
250 DEG C, subsequently it is warming up to 300 DEG C with 10 DEG C/min, keeps 5min, then be cooled to 280 DEG C with 10 DEG C/min, keep 2min；Carry
Gas: helium, purity 99.999%；Flow velocity: 1.2ml/min；Injector temperature: 290 DEG C；Sample size 2 μ l；Input mode: no
Split sampling, solvent delay 6min.
Mass Spectrometry Conditions: Mass Spectrometry Conditions: ion source: ei (electron impact ionization source)；Ion source temperature: 280 DEG C, electron bombardment
Source energy: 70ev；Gas phase-mass spectrometer interface temperature: 290 DEG C；Scan mode: carry out tof pattern in the way of 5 spectrograms per second complete
Scanning, mass number scope 50～600amu..
(6) data base carrying according to instrument to acquisition information retrieval by header in step (5), search argument retention time is inclined
Difference is defined to ± 0.5min, and accurate mass deviation is defined to ± 100ppm, detects at least three fragment ions, and according to every kind ofization
The measured value of each key element of compound and the deviation of theoretical value in built data base, provide retrieval matching score value, retrieval coupling automatically
The compound of score value ＞ 60, that is, confirm detection target compound.
(7) determine this Hebei to produce in the Chinese herbal medicine Rhizoma Atractylodis Macrocephalae by above method and detect pesticide suffer, cyphenothrin, pleasure
Spirit.
The above is only the preferred embodiment of the present invention it is noted that ordinary skill people for the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of improved quechers filler bag of Chinese herbal medicine is it is characterised in that described Chinese herbal medicine improved quechers filler
Bag be made up of following filler: carbon nanomaterial, the adsorbing material of aminofunctional, non-polar functional group modify silica gel material,
Hydroscopicity adsorbent.
2. the improved quechers filler bag of Chinese herbal medicine according to claim 1 is it is characterised in that the weight of described filler
Ratio is for silica gel material that 1 part of carbon nanomaterial, the adsorbing material of 2-15 part aminofunctional, 2-15 part non-polar functional group modify
Material, 2-15 part hydroscopicity adsorbent；Preferably, four kinds of filler mix homogeneously in described filler bag, are seated in 15ml centrifuge tube.
3. the improved quechers filler bag of Chinese herbal medicine according to claim 1 is it is characterised in that described carbon nanomaterial
Any one or two kinds selected from SWCN, multi-walled carbon nano-tubes and double-walled carbon nano-tube material；Preferably, described carbon
In 2nm-50nm, specific surface area is 5-50m to the size of nano material2/ g, average pore size is
4. the improved quechers filler bag of Chinese herbal medicine according to claim 1 it is characterised in that: described aminofunctional
Adsorbing material be selected from amino bonded silica gel, in polyamino bonded silica gel and amination polyethylene divinylbenzene any one or
Several；The size of the adsorbing material of described aminofunctional is 20 μm -100 μm, and specific surface area is 300-800m2/ g, puts down
All apertures are
5. the improved quechers filler bag of Chinese herbal medicine according to claim 1 it is characterised in that: described nonpolar sense
The silica gel material that group modifies is selected from octadecyl functional group bonded silica gel, phenyl functional group's bonded silica gel and Yi Ji functional group bonding
One or more of silica gel；The silica gel material size that described non-polar functional group modifies is 20 μm -100 μm, specific surface
Amass as 300-800m2/ g, average pore size isPhosphorus content is 10%-20% weight.
6. the improved quechers filler bag of Chinese herbal medicine according to claim 1 it is characterised in that: described water absorption absorption
Agent is colourless orthorhombic system crystals.
7. the improved quechers of the Chinese herbal medicine according to claim 1～6 any one filler bag it is characterised in that: institute
Stating material with carbon element is multi-wall carbon nano-tube material, and the size of described multi-wall carbon nano-tube material is 10nm-20nm, and specific surface area is
10m2/ g, average pore size isDescribed aminofunctional adsorbing material is polyamino bonded silica gel psa；Described nonpolar official
It is octadecyl functional group bonded silica gel c18 that the silica gel material modified can be rolled into a ball；Described hydroscopicity adsorbent is mgso4.
8. a kind of method of detection Chinese herbal medicine residual pesticide, comprises the following steps:
1) Chinese herbal medicine sample pulverizer is pulverized；
2) by step 1) the Chinese herbal medicine sample of gained carries out water immersion, solvent extraction, centrifugation, obtains supernatant；
3) using the Chinese herbal medicine improved quechers filler bag detecting step 2 as described in any one of claim 1～7) gained
Supernatant, vibration, centrifugation, take supernatant liquid filtering film, obtain testing sample；
4) by step 3) testing sample that obtains measures through gc-q-tof/ms, carries data base using instrument, to residual in Chinese herbal medicine
The pesticide staying carries out examination.
9. method according to claim 8 is it is characterised in that described step 1) in Chinese herbal medicine be Radix Glycyrrhizae, the Radix Paeoniae Alba, when
Return, Radix Et Rhizoma Rhei, the Rhizoma Atractylodis Macrocephalae, Rhizoma Chuanxiong or the Rhizoma Pinelliae.
10. method according to claim 8 is it is characterised in that described step 2) in the method soaked of water be ultrapure water logging
Bubble sample 30min；The method of described solvent extraction is using acetonitrile, methanol, acetone, n-hexane, 1% acetic acid acetonitrile and 1% second
One or more extractions of sour acetonitrile-acetate buffer system；Described extracting mode includes extraction of ocean eddies, supersound extraction or vibration
Extract；
Preferably, described step 2) in Extraction solvent be 1% acetic acid acetonitrile-sodium acetate buffer, and sodium chloride, anhydrous sulfur
Sour magnesium one or two；It is highly preferred that described step 2) in Extraction solvent be 1% acetic acid acetonitrile-sodium acetate buffer, with
Sodium chloride；
Preferably, described step 2) described in Chinese herbal medicine sample with the amount ratio of Extraction solvent, buffer salt be: 1g:1ml～
10ml:0.1g～1g.
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Application publication date: 20170201 |