CN108760929A - A method of detection 8 kinds of mycotoxins of FRUCTUS CITRI SARCODACTYLIS - Google Patents
A method of detection 8 kinds of mycotoxins of FRUCTUS CITRI SARCODACTYLIS Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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 discloses a kind of methods measuring 8 kinds of mycotoxins of FRUCTUS CITRI SARCODACTYLIS, the present invention measures 8 kinds of mycotoxins (ochratoxin A, zearalenone, fumonisin B1, sterigmatocystin, aflatoxin B1, aflatoxin B 2, aflatoxin G 1, aflatoxin G 2) simultaneously in a system, it is detached using Thermo Hypersil GOLD chromatographic columns, using 0.1% formic acid water-formic acid acetonitrile as mobile phase；Using electron spray ionisation pattern, negative ions scan simultaneously.The result shows that 8 kinds of fungimycin relationships in the range of linearity of the present invention couple are good；For detection limit between 0.16~5ng/mL, the rate of recovery under basic, normal, high three kinds of pitch-based spheres is 79.0~112.8%, and uses Internal standard.Matrix effect of the present invention is little on the influence of the testing result of mycotoxin, accuracy is high, precision is good, specificity is strong, simple and efficient, and the multicomponent that can be used for mycotoxin in Chinese medicine measures.
Description
Technical field
The present invention relates to a kind of methods of 8 kinds of mycotoxins in measurement FRUCTUS CITRI SARCODACTYLIS, belong to field of traditional Chinese medicine detection.
Background technology
Fingered citron be Rutaceae citrus plant (Citrus medica L.var.sarcodactylisSwingle) at
Ripe fruit, main product also have cultivation in Guangdong, in Fujian, Sichuan, zhejiang and other places area.Wherein, wanted from Zhaoqing Guangdong, height, Deqing,
The fingered citron on the ground such as Yunan is known as " FRUCTUS CITRI SARCODACTYLIS ", is Guangdong tunnel product.FRUCTUS CITRI SARCODACTYLIS not only can be as medicinal material, it may also be used for infuses
Tea is steep in wine, or even can also make delicacies, has effects that strengthening the spleen and stomach, relaxing tendons and activating collaterals, regulating qi-flowing for eliminating phlegm.On May 31st, 2016,
The first batch of legislative Protection south of the Five Ridges, Guangdong traditional Chinese medicinal materials assortment is born, and FRUCTUS CITRI SARCODACTYLIS is selected in the first batch one of 8 kinds of Chinese medicines, it is seen that FRUCTUS CITRI SARCODACTYLIS
As Guangdong authentic medicinal herbs, there is own strategic significance in " wide medicine " orients towards the whole country popularization.
Due to the damp and hot subtropical climate in Guangdong, Chinese medicine is easy in processes such as plantation, acquisition, storage, processing by fungi
Pollution, to generate a variety of mycotoxins, seriously affects the quality and drug safety of Chinese medicine.Currently, true in grain, food
Bacterium and its endotoxin contamination are in widespread attention, and propose prevention and control measure, regulation and limit standard.In order to ensure Chinese medicine
Drug safety improves quality standard, and it is extremely urgent to build a kind of method that can detect a variety of mycotoxins in Chinese medicine simultaneously.
Invention content
The purpose of the present invention is to provide a kind of methods measuring 8 kinds of mycotoxins of FRUCTUS CITRI SARCODACTYLIS.
The technical solution used in the present invention is：
A method of measuring 8 kinds of mycotoxins of FRUCTUS CITRI SARCODACTYLIS, which is characterized in that include the following steps：
The preparation of one, solution
Mix the preparation of inner mark solution：Use acetontrile13C34-FB1、13C20-OTA、13C18These three interior targets of-ZEN are mixed
Close inner mark solution；
The preparation of test solution：By the finely ground mixing of FRUCTUS CITRI SARCODACTYLIS sample, add methyl alcohol-formic acid-water, is added13C17- AFB1 and
Mixed inner mark solution mixing, ultrasonic centrifugal treating, Aspirate supernatant are dried up in 35~42 DEG C of nitrogen, and methanol aqueous solution redissolves, filtering
Film obtains test solution；
It is prepared by reference substance solution：Prepare the OTA of various concentration with methanol, acetonitrile prepare FB1, ZEN of various concentration, ST,
AFB1, AFB2, AFG1, AFG2 mixed standard solution obtain pair of serial various concentration according to the preparation method of test solution
According to product solution；
Two, are measured
The test solution of above-mentioned preparation and reference substance solution are subjected to LC-MS/MS detections.
Further, the preparation process of the test solution is：
The finely ground mixing of 0.50~1.50g FRUCTUS CITRI SARCODACTYLIS samples is weighed, 3~4mL methyl alcohol-formic acids-water is added, is added 1~5uL's13C17- AFB1 and mixed inner mark solution mixing, ultrasonic centrifugal treating are drawn 1~2mL supernatants and are dried up in 35~42 DEG C of nitrogen, added
Enter the redissolution of 250~750 μ L methanol-water solutions, filter membrane obtains test solution.
Further, the preparation process of the reference substance solution is：
It weighs the common mixing of OTA, ZEN, FB1, ST, AFB1, AFG1, AFB2, AFG2 and is diluted to standard intermediate fluid, draw mark
Quasi- intermediate fluid with acetontrile go out concentration be respectively 100ng/mL, 500ng/mL, 500ng/mL, 500ng/mL, 100ng/mL,
The mixed reference substance solution of 100ng/mL, 33ng/mL and 33ng/mL take the mixed standard solution 1mL of various concentration, press respectively
According to the preparation method of test solution, the reference substance solution of serial various concentration is obtained.
Further, in the preparation of the test solution, the volume ratio of formic acid-methanol-water is 1:75~80:15~
25。
Further, in the preparation of the test solution,13C17- AFB1 and mixed internal standard C volume ratios are 1:1~4.
Further, in the preparation of the test solution, the condition of centrifugation is 3~5 DEG C, 8000~12000r/
Min, centrifugation time are 8~13min.
Further, in the preparation of the test solution, supernatant:Methanol:The volume ratio of water is 7~13:2~6:
1。
Further, in LC-MS/MS continuous modes, the program of the gradient elution is：
Wherein the mobile phase A of liquid chromatogram is 0.1~0.3% aqueous formic acid；Mobile phase B is 0.1~0.3% formic acid second
Nitrile.
Further, the MS testing conditions are：Use electric spray ion source；Source parameters is：Collide atmospheric pressure：
9psi；Gas curtain atmospheric pressure：40psi；Using negative ions while scan pattern；550 DEG C of ion source temperature.
Further, the MS detection parameters are as shown in the table：
* is quota ion in table.
Further, in detection process, blank sample control group is also set up, blank sample control group removes and is not added with FRUCTUS CITRI SARCODACTYLIS sample
Outside product, remaining operation is the same as the operation of test solution.
The beneficial effects of the invention are as follows：
The present invention is using the Common fungi toxin in FRUCTUS CITRI SARCODACTYLIS as research object, it is intended to probe into out the Chinese medicine of a set of high throughput
The detection method of middle mycotoxin.Simple and quick, high sensitivity of the invention, detection limit is good, is measured simultaneously in the same system
Five class mycotoxins of FRUCTUS CITRI SARCODACTYLIS, and use Internal standard, it is effective to eliminate matrix effect with the wide of ensuring method
General property, reliability and applicability provide effective technological means to the quality safety of FRUCTUS CITRI SARCODACTYLIS on the market.
Description of the drawings
Fig. 1 is addition ochratoxin A, fumonisin B1, sterigmatocystin, Gibberella zeae alkene in blank test sample
The total ion current of eight kinds of ingredients such as ketone, aflatoxin B1, aflatoxin B 2, aflatoxin G 1 and aflatoxin G 2
Figure.
Fig. 2 is the total ion current figure of blank test sample.
Fig. 3 is the MRM figures of eight kinds of mycotoxins.
Fig. 4 is the MRM figures of four kinds of Isotopic Internal Standards.
Specific implementation mode
With reference to embodiment, the invention will be further described.
Instrument and reagent：
(1) instrument：LC-MS instrument：AB Sciex Triple Quad 5500；Chromatographic column：Thermo Hypersil
GOLD (1.9 μm, 100 × 2.1mm) is reverse phase C18Liquid-phase chromatographic column；High speed low temperature centrifugal machine：Thermo Fisher
ScientificX1R；Turbine mixer：TalboysTalbous；
Pure water meter：MILLIPORE Mili-Q Advantage A10；Balance：Sartorius BS323S, METTLER
MS205DU；Nitrogen evaporator：ANPEL DC-24；The multi-functional oscillator of speed governing：Changzhou Ao Hua Instrument Ltd. HY-2A；Number
Control ultrasonic washing instrument：KQ-500DE, Kunshan Ultrasonic Instruments Co., Ltd..
(2) reagent：Methanol：Chromatographically pure；Acetonitrile：Chromatographically pure；Formic acid：Chromatographically pure；Table 1 is reference substance information.
1 reference substance of table
Embodiment 1
One, solution is prepared：
1) preparation of inner mark solution is mixed：
Precision draws 1.0mL's13C34-FB1、13C20-OTA、13C18- ZEN titers remove in 10mL volumetric flasks13C34-
Except FB1 methanol dilutions, with dilution in acetonitrile to graduation mark, mixing.Obtain a concentration of 2.55 μ g/mL's13C34-FB1、
A concentration of 1.00 μ g/mL's13C20- OTA's and a concentration of 2.51 μ g/mL13C18The standard internal standard intermediate fluid of-ZEN.Cause13C17-
The mother liquid concentration of AFB1 titers is relatively low (0.503 μ g/mL), is used as independent internal standard.
Precision draws 1.0mL13C34-FB1、1.6mL 13C20-OTA、1.6mL 13C18- ZEN standard internal standard intermediate fluids, altogether
With being placed in 10ml volumetric flasks, with dilution in acetonitrile to graduation mark to get to simultaneously containing 0.4 μ g/mL13C34-FB1、0.1μg/mL13C20-OTA、0.4μg/mL 13C18The mixed internal standard of-ZEN；
2) preparation of test solution：
Precision weighs 1.00g (being accurate to 0.01g) FRUCTUS CITRI SARCODACTYLIS powder sample and is placed in 10ml plastic centrifuge tubes, and 4mL is added
Methyl alcohol-formic acid-water (volume ratio 79：1：20), shaking makes powder be uniformly dispersed, 5 μ L's of addition13C17- AFB1 and 100 μ L
Mixed internal standard, vortex mixing, ultrasonic extraction 30min centrifuges 10min under the conditions of 4 DEG C, 10000r/min.Accurately pipette supernatant
Liquid 1mL is placed in 2mL plastic centrifuge tubes, is blown to using nitrogen at 40 DEG C close dry, and 500 μ L methanol-waters are added, and (volume ratio is
80：20) residue is redissolved, abundant vortex mixing makes residue dissolve.Organic filter membrane that 0.22 μm of liquid filtration will finally be redissolved, obtains confession
Test sample solution.
3) preparation of blank control group：In addition to being not added with FRUCTUS CITRI SARCODACTYLIS sample, remaining operating procedure such as (2), blank pair obtained
According to group.
4) prepared by reference substance solution：
Precision weighs ochratoxin A (OTA), zearalenone (ZEN), fumonisin B1 (FB1), aspergillus versicolor poison
Plain (ST), aflatoxin B1 (AFB1), aflatoxin B 2 (AFB2), aflatoxin G 1 (AFG1), aflatoxin G 2
(AFG2) each 1.0mL is in 10mL volumetric flasks, and in addition to FB1 is using methanol dilution constant volume, remaining is with acetonitrile dissolving, constant volume.?
To a concentration of 1.0 μ g/mL of OTA, a concentration of 5.0 μ g/mL of ZEN, a concentration of 5.0 μ g/mL of FB1, a concentration of 5.0 μ g/mL of ST, Huang
The concentration of the mixed mark (B1, B2, G1, G2) of aspertoxin is respectively the standard of 100ng/mL, 33ng/mL, 100ng/mL, 33ng/mL
Intermediate fluid.
The accurate each 1.0mL of OTA, ZEN, FB1, ST standard intermediate fluid that draws is made into OTA in 10mL volumetric flasks with acetonitrile
The mixed reference substance solution for being 500ng/mL for 100ng/mL, ZEN 500ng/mL, FB1 500ng/mL, ST takes mixing to mark
Quasi- solution 1ml obtains the reference substance solution of serial various concentration according to the preparation method of step (2) test solution.
Two, are measured
The test solution of above-mentioned preparation and reference substance solution are subjected to LC-MS/MS measurement
Standard curve is prepared and the range of linearity
1) it is appropriate that reference substance solution prepared by the present invention is drawn respectively, with vehicle solution (negative control, by FRUCTUS CITRI SARCODACTYLIS
The preparation of sample test solution and upper machine testing) dilution be prepared into series standard solution：The concentration gradient of AFB1, AFG1, OTA
Respectively：1.0,2.0,5.0,10,25,50,100ng/mL；The concentration gradient of AFB2, AFG2 is respectively：0.3,0.6, 1.5,
3.0,7.5,15,30ng/mL；The concentration gradient of FB1, ST is respectively：5.0,10,25,50,125,250ng/mL；ZEN's is dense
Spending gradient is：5.0,10,25,50,125,250,500ng/mL.Wherein, every part of reference substance solution contains13C20- OTA is
5.0ng/mL、13C18- ZEN be 50ng/mL,13C34- FB1 be 20ng/mL,13C17- AFB1 is 2.5ng/mL.
2) the accurate mixed standard solution for measuring various concentration.Chromatography-mass spectroscopy condition detection according to the invention, with target
The chromatographic peak peak area external standard of mycotoxin is ordinate with internal standard ratio (Y), and sample introduction concentration (X, ng/mL) is abscissa, is painted
Producing linear regression equation (is shown in Table 2).Using standard curve minimum point as reference, with characteristic ion signal-to-noise ratio S/N>3 is corresponding dense
Degree is detection limit concentration, and the linear equation obtained, the range of linearity, related coefficient, detection limit are shown in Table 2.
The different mycotoxin regression equations of table 2, the range of linearity, correlation coefficient r, detection limit LOD
The operation of liquid phase systems chromatography detection and corresponding conditional parameter:
Chromatographic column：Chromatographic column is reverse phase C18Liquid-phase chromatographic column (with octadecylsilane chemically bonded silica (ODS) for filler)；
Flow velocity 0.3mL/min；Sample size：5μL；Column temperature：40℃；Mobile phase：A：0.1% aqueous formic acid；B phases：0.1% formic acid second
Nitrile.Gradient elution program is shown in Table 3.
3 Liquid Chromatography-Tandem Mass Spectrometry elution program of table
(2) Mass Spectrometry Conditions
Electro-spray ionization source (ESI), capillary voltage positive ion mode are 5500V, and negative ion mode is -4500V.From
Component parameter is shown in Table 4, and each compound mass spectrometry parameters are shown in Table 5.
4 source parameters of table
5 Mass Spectrometer Method mycotoxin parameter of table
Note：* quota ion
Qualitative determination：Test solution and reference substance are measured according to the high performance liquid chromatography-tandem mass condition of embodiment 1
Solution, if the mass chromatography peak retention time of detection is consistent with standard sample, and the test sample spectrogram after background correction
In, the relative abundance of each qualitative ion is compared with the reference substance solution spectrogram obtained under the close similarity condition of concentration, error amount
The data being subject in table 6 then can determine that there are corresponding measured objects in sample.
The range of the qualitative ion relative abundance deviation of 6 sample of table
Quantitative determination：By high performance liquid chromatography-tandem mass condition, it is molten that precision measures standard series prepared by the present invention
5 μ L of liquid inject liquid chromatography-mass spectrography/mass spectrograph, with the chromatographic peak peak area external standard of targeted fungal toxin and internal standard ratio (Y)
For ordinate, sample introduction concentration (X, ng/mL) is abscissa, draws equation of linear regression.And Isotopically labelled internal standard is pressed,13C34- FB1 as FB1 internal standard substance,13C20- OTA as OTA internal standard substance,13C18Internal standard compounds of-the ZEN as ZEN
Matter,13C17Internal standard substances of-the AFB1 as AFB1, AFB2, AFG1, AFG2 and ST, result of calculation need to deduct blank value.It is got the bid
The Liquid Chromatography-Tandem Mass Spectrometry figure of quasi- solution is referring to Fig. 3~Fig. 4.Wherein, it in test sample mass spectrogram, should must not detect and reference substance
The retention time of chromatographic peak, the mass-to-charge ratio of selected each qualitative ion, relative abundance are than consistent mass spectra peak.
The detection result of embodiment is further analyzed below.
1. matrix effect
The present invention evaluates the matrix effect of FRUCTUS CITRI SARCODACTYLIS using mark-on method after extraction.Qualitative point can not only be carried out
Analysis, and the influence value (SSE) of matrix effect can be gone out with quantitative analysis.Respectively with methanol-water (volume ratio 80：And sample 20)
Matrix solution is diluted to the working solution of gradient of concentration within the scope of linear, and standard curve, sample base are established by internal standard method
The slope of matter solution standard curve and the matrix effect that the slope ratio of blank solvent standard curve is the sample.Sample substrate is molten
The standard curve of liquid is shown in Table 7, and the standard curve of blank solution is shown in Table 8.Compare slope, SSE can be calculated by following equation
Value：
8 kinds of mycotoxin regression equations, the range of linearity, correlation coefficient rs in 7 matrix solution of table
8 kinds of mycotoxin regression equations, the range of linearity, correlation coefficient rs in 8 blank solution of table
The SSE result of calculations of 8 kinds of mycotoxins are as follows in FRUCTUS CITRI SARCODACTYLIS：AFB1 is 101.5%；AFB2 is 84.0%；AFG1
It is 99.0%；AFG2 is 102.0%；FB1 is 119.8%；OTA is 106.6%；ST is 163.0%；ZEN is 107.0%.When
SSE values are when between 80%~120%, it is believed that the matrix effect in FRUCTUS CITRI SARCODACTYLIS influences not the testing result of mycotoxin
Greatly.From result as it can be seen that when using internal standard method carry out 8 kinds of mycotoxins while quantitatively detect when, except the testing result of ST have compared with
Except big matrix effect influences, the SSE values of remaining 7 kinds of mycotoxin are meeting range substantially.
2. accuracy
Suitable standard solution intermediate fluid and inner mark solution are accurately drawn, is operated according to method prepared by test sample so that
The final concentration of eight kinds of mycotoxins is respectively (basic, normal, high three is horizontal) AFB1, AFG1, OTA：5,10,25ng/mL；AFB2,
AFG2：1.5,3.0,7.5ng/mL；FB1,ST,ZEN：25,50,125ng/mL.Each addition concentration carry out respectively 3 times it is parallel
Experiment.The design, average recovery rate result and relative standard deviation for adding three kinds of concentration levels are as shown in table 9.
As a result, it has been found that ochratoxin A, zearalenone, fumonisin B1, sterigmatocystin, aflatoxin
Between 79.0~112.8%, relative standard is inclined for B1, aflatoxin B 2, aflatoxin G 1,2 rate of recovery of aflatoxin G
Poor (RSD%) between 0.10~9.69%, accuracy is good.
98 kinds of mycotoxin rate of recovery of table and relative standard deviation
3. precision
Precision test has withinday precision experiment and day to day precision to test two methods, and withinday precision can be investigated
Same reagent, same standard curve, on the same day in, the repeatability of measurement result；Day to day precision can investigate instrument, reagent,
The difference that the minor change that environmental condition is occurred is brought.It is tested herein with withinday precision, investigates method designed by this paper
Reproducibility.Prepare FRUCTUS CITRI SARCODACTYLIS anima solution, be added into this part of anima solution a concentration of 100ng/mL AFB1,
AFG1, OTA, AFB2, AFG2 of a concentration of 33ng/mL, FB1, ZEN, ST of a concentration of 500ng/mL form a kind of mixing mark
Quasi- liquid, continuous sample introduction 6 times can obtain an accurate value, as a result as shown in Table 10, the precision standard of eight kinds of ingredients every time
Deviation illustrates that the precision of this method is good within 10%.
The precision of 10 8 kinds of mycotoxins of table
4. specificity
Fig. 1 is the total ion current figure that eight kinds of ingredients are added in blank test sample, and Fig. 2 is the total ion current of blank test sample
Figure, as seen from the figure, blank test sample is not interfered by impurity, and specificity of the present invention is good.
In conclusion the assay method of the present invention may be implemented to detect a variety of mycotoxins simultaneously and still have highly sensitive
It spends, greatly improve detection flux, be effectively improved peak type, improve reproducibility.Moreover, combining Internal standard so that
It measures more accurate.The result shows that the linear relationship of mycotoxin is good, related coefficient is high, and adds at basic, normal, high three kinds
Between adding the rate of recovery under level to be 79.0~112.8%, detection limit is between 0.16~5ng/mL.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of method measuring 8 kinds of mycotoxins of FRUCTUS CITRI SARCODACTYLIS, which is characterized in that include the following steps：
The preparation of one, solution
Mix the preparation of inner mark solution：Use acetontrile13C34-FB1、13C20-OTA、13C18In these three interior target mixing of-ZEN
Mark solution；
The preparation of test solution：By the finely ground mixing of FRUCTUS CITRI SARCODACTYLIS sample, add methyl alcohol-formic acid-water, is added13C17- AFB1 and mixed internal standard
Solution mixing, ultrasonic centrifugal treating, Aspirate supernatant are dried up in 35~42 DEG C of nitrogen, and methanol aqueous solution redissolves, and filter membrane obtains confession
Test sample solution；
It is prepared by reference substance solution：Prepare the OTA of various concentration with methanol, acetonitrile prepare FB1, ZEN of various concentration, ST, AFB1,
AFB2, AFG1, AFG2 mixed standard solution obtain the reference substance of serial various concentration according to the preparation method of test solution
Solution；
Two, are measured
The test solution of above-mentioned preparation and reference substance solution are subjected to LC-MS/MS detections.
2. according to the method described in claim 1, it is characterized in that, the preparation process of the test solution is：
The finely ground mixing of 0.50~1.50g FRUCTUS CITRI SARCODACTYLIS samples is weighed, 3~4mL methyl alcohol-formic acids-water is added, is added 1~5uL's13C17-
AFB1 and mixed inner mark solution mixing, ultrasonic centrifugal treating are drawn 1~2mL supernatants and are dried up in 35~42 DEG C of nitrogen, be added 250
~750 μ L methanol-water solutions redissolve, and filter membrane obtains test solution.
3. according to the method described in claim 1, it is characterized in that, the preparation process of the reference substance solution is：
It weighs the common mixing of OTA, ZEN, FB1, ST, AFB1, AFG1, AFB2, AFG2 and is diluted to standard intermediate fluid, in absorption standard
It is respectively 100ng/mL, 500ng/mL, 500ng/mL, 500ng/mL, 100ng/mL, 100ng/ that interstitial fluid goes out concentration with acetontrile
The mixed reference substance solution of mL, 33ng/mL and 33ng/mL take the mixed standard solution 1mL of various concentration respectively, according to for examination
The preparation method of product solution obtains the reference substance solution of serial various concentration.
4. according to the method described in claim 2, it is characterized in that, in the preparation of the test solution, formic acid-methanol-
The volume ratio of water is 1:75~80:15~25.
5. according to the method described in claim 2, it is characterized in that, in the preparation of the test solution,13C17- AFB1 and
Mixed internal standard C volume ratios are 1:1~4.
6. according to the method described in claim 2, it is characterized in that, in the preparation of the test solution, the condition of centrifugation
For 3~5 DEG C, 8000~12000r/min, centrifugation time is 8~13min.
7. according to the method described in claim 1, it is characterized in that, in LC-MS/MS continuous modes, the gradient elution
Program is：
Wherein the mobile phase A of liquid chromatogram is 0.1~0.3% aqueous formic acid, and Mobile phase B is 0.1~0.3% formic acid acetonitrile.
8. according to the method described in claim 1, it is characterized in that, the MS testing conditions are：Use electric spray ion source；
Source parameters is：Collide atmospheric pressure：9psi；Gas curtain atmospheric pressure：40psi；Negative ions while scan pattern；Ion source temperature
550℃。
9. according to the method described in claim 1, it is characterized in that, the MS detection parameters are as shown in the table：
* is quota ion in table.
10. according to the method described in claim 1, it is characterized in that, in detection process, blank sample control group is also set up, it is empty
White sample controls group is in addition to being not added with FRUCTUS CITRI SARCODACTYLIS sample, remaining operation is the same as the operation of test solution.
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| CN109385488A (en) * | 2018-12-25 | 2019-02-26 | 广州中医药大学(广州中医药研究院) | Multiple PCR primer, method and the kit of Chinese medicine pollution three classes Toxigenic fungi are detected simultaneously |
| CN109557230A (en) * | 2018-12-07 | 2019-04-02 | 云南省烟草质量监督检测站 | A method of three classes dithiocarbamate residual quantity in measurement tobacco |
| CN109828072A (en) * | 2019-02-21 | 2019-05-31 | 安徽润安信科检测科技有限公司 | A kind of method that ultra performance liquid chromatography-triple quadrupole bar tandem mass spectrometer detects 16 kinds of biotoxins in liquor-making raw material simultaneously |
| CN111912916A (en) * | 2020-07-14 | 2020-11-10 | 成都中医药大学 | Method for measuring content of index components in fingered citron preparation |
| CN112362796A (en) * | 2020-10-21 | 2021-02-12 | 中国食品药品检定研究院 | Method for detecting biotoxin in bee pollen and application thereof |
| CN112461973A (en) * | 2020-11-23 | 2021-03-09 | 山东省葡萄研究院 | Novel method for detecting ochratoxin A in red wine based on hexafluorobutanol as extractant |
| CN113390992A (en) * | 2021-06-15 | 2021-09-14 | 浙江海正药业股份有限公司 | Method for analyzing and detecting trace aflatoxin in water-soluble fermented medicine |
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| CN109385488A (en) * | 2018-12-25 | 2019-02-26 | 广州中医药大学(广州中医药研究院) | Multiple PCR primer, method and the kit of Chinese medicine pollution three classes Toxigenic fungi are detected simultaneously |
| CN109385488B (en) * | 2018-12-25 | 2021-11-12 | 广州中医药大学(广州中医药研究院) | Multiplex PCR (polymerase chain reaction) primer, method and kit for simultaneously detecting three kinds of toxigenic fungi polluted by traditional Chinese medicinal materials |
| CN109828072A (en) * | 2019-02-21 | 2019-05-31 | 安徽润安信科检测科技有限公司 | A kind of method that ultra performance liquid chromatography-triple quadrupole bar tandem mass spectrometer detects 16 kinds of biotoxins in liquor-making raw material simultaneously |
| CN111912916A (en) * | 2020-07-14 | 2020-11-10 | 成都中医药大学 | Method for measuring content of index components in fingered citron preparation |
| CN112362796A (en) * | 2020-10-21 | 2021-02-12 | 中国食品药品检定研究院 | Method for detecting biotoxin in bee pollen and application thereof |
| CN112461973A (en) * | 2020-11-23 | 2021-03-09 | 山东省葡萄研究院 | Novel method for detecting ochratoxin A in red wine based on hexafluorobutanol as extractant |
| CN113390992A (en) * | 2021-06-15 | 2021-09-14 | 浙江海正药业股份有限公司 | Method for analyzing and detecting trace aflatoxin in water-soluble fermented medicine |
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