CN106546672B - A kind of residue analysis method of polyoxin on ginseng - Google Patents
A kind of residue analysis method of polyoxin on ginseng Download PDFInfo
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Abstract
The invention provides a kind of residue analysis method of polyoxin on ginseng, residue analysis method of kind of the polyoxin on ginseng is established, the polyoxin remained in sample is extracted with the aqueous solution homogeneous containing formic acid, is crossed after film, liquid chromatography mass mass spectrum（HPLCMS‑MS）Detection, the standard curve of correction, quantified by external standard method are set up using the vehicle solution without agricultural chemicals to be measured.The simple organic reagent used of pre-treatment is less, and the rate of recovery meets residues of pesticides criterion calls, and method meets the requirement of current environmental protection.And the degree of accuracy of detection method, precision meet the technical requirements of retention analysis, detection lower bound reaches domestic and international technical regulation and limit standard requirement.Average recovery rate of the present invention is 74.6%~94.7%, average relative standard's deviation（RSD）For 1.3%~7.8%, detection limit is less than 0.06mg/kg, with easy to operate, quick, sensitivity is high, characteristic is strong, the accurate advantage of reproducible, qualitative, quantitative.
Description
Technical field
It is to existing residue analysis method the invention provides a kind of residue analysis method of polyoxin on ginseng
Improvement, belong to Chinese herbal medicine chemical analysis technology field.
Background technology
Polyoxin be by doctor Lang of Japan Chemical research institute Suzuki three et al. in 1963 from Kumamoto county Su Jun mills
Soil in a kind of actinomyces for isolating, be a kind of broad spectrum activity antimicrobial fungicides, with uptake and translocation effect.Nineteen eighty-two
Rise to go into operation in China and apply, be mainly used in preventing and treating wheat powdery mildew, black fleck disease of ginseng, Alternaria alternate, cucumber downy mildew is melon
Droop, rice sheath blight disease, alternaria leaf spot of apple, strawberry and grape grey mould, a variety of fungal diseases such as the withered sheath disease of forest.Its
Mechanism of action is unique, can interfere with the biosynthesis of cell membrane chitin, the ascus of cell membrane is constituted by matrix of chitin
Some fungies of Gammaproteobacteria, Basidiomycetes and deuteromycetes, germ tube, mycelium contact meeting local bulkiness after medicament, rupture, overflowed carefully
Intracellular inclusion, causes germ dead, so as to reach that bactericidal is acted on.
As classical bactericide, polyoxin series bactericidal agent since the advent of the world is fast in countries in the world pesticide market portion
Speed expands, extensive use.As people are environmentally safe and concern of food security, all kinds of agricultural chemicals are in surrounding medium and various works
Method for detecting residue in thing turns into pesticide field study hotspot.Therefore, the sterilization of polyoxin class how is efficiently and rapidly determined
Method for detecting residue in agent surrounding medium and various crops also turns into the hot issue of the medicament.However, due to medicament itself
Feature, although also having residue analysis method of the document report on such agricultural chemicals in the surrounding mediums such as soil both at home and abroad, such as
Turn into pesticide science worker for many years one using the residue limits in C18 reverse-phase chromatographic columns and Diode Array Detector product and medicinal material
The problem of straight effort is solved.In recent years, my device, high performance liquid chromatography, Capillary Electrophoresis-electrogenerated chemiluminescence method (CE-ECL)
Deng, but these methods are applied to that the generally existing rate of recovery in ginseng matrix is low, and the phenomenon such as poor reproducibility does not possess reference, because
This, the determination of residual amount of polyoxin series bactericidal agent turns into the difficult point during current residual is analyzed in ginseng.Polyoxin series bactericidal agent
As a kind of bactericide of high-efficiency broad spectrum, it is widely used in the agricultural production processes such as veterinary antibiotics, medicinal material, it is how efficiently quick
It is determined in crop, fruit state in ginseng production process, ginseng agricultural university amount uses polyoxin series bactericidal agent preventing and treating black fleck disease of ginseng
Etc. disease, in order to avoid polyoxin turns into the technology barriers of external limitation China ginseng outlet, and the outlet of China's ginseng is solved
Fallen into a passive position in polyoxin residue problem situation, for polyoxin series bactericidal agent, successfully filter out one it is simple to operate,
The rate of recovery is high, the residue analysis method of favorable reproducibility is imperative.The foundation of this residue analysis method can not only make China
The residual detection technique level of ginseng agriculture, standard and external Complete Synchronization, while can also avoid meeting with foreign countries in ginseng exit procedure
Green barrier.
The content of the invention：
The invention discloses a kind of residue analysis method of polyoxin on ginseng, this method is mainly used in determining people
The method of the polyoxin content remained in the complex matrices Chinese medicine such as ginseng, American Ginseng, method has stronger reappearance, reclaims
Rate can reach more than 80%.
A kind of residue analysis method of the polyoxin of the present invention on ginseng, comprises the following steps：
1st, polyoxin B is extracted with aqueous formic acid in sample：
(1) fresh ginseng：Weigh fresh ginseng sample 5.0g to be put into beaker, add 0.3% aqueous formic acid 20mL, adjust pH
Scope 2-5, is homogenized about 2min, suction filtration is depressurized in the Buchner funnel for be covered with filter aid, and filtrate is all collected in tool plug graduated cylinder
In, portion filtrate is taken in centrifuge tube, and 12000rpm centrifugation 5min cross 0.22 μm of filter membrane, treat that liquid chromatograph-mass spectrometer is examined
Survey；
(2) ginseng dry powder：Ginseng dry powder sample 5.0g is weighed in conical flask with stopper, 0.3% aqueous formic acid is added
20mL, adjusts pH scope 2-5, mechanical shaking extraction 1h, suction filtration is depressurized in the Buchner funnel for be covered with filter aid, and filtrate is all collected
In tool plug graduated cylinder, portion filtrate is taken in centrifuge tube, and 12000rpm centrifugation 5min cross 0.22 μm of filter membrane, treat liquid chromatogram-matter
Compose combined instrument detection；
2nd, analysis test：
(1) instrument condition：
Chromatographic column：Agilent Zorbax RRHD Eclipse Plus C18 3.0×100mm 1.8μm；
Mobile phase：Ammonium acetate 2.5mmol/L+0.05% aqueous formic acids: methanol elution gradient；
Gradient elution program：
Flow velocity：0.3mL/min；
Column temperature：30℃；
Sample size：10μl.
(2) mass spectral analysis condition：
Ionize source module：Electro-spray ionization；
Ionize source polarity：Positive ion mode (ESI+)；
Scan mode：Multiple-reaction monitoring (MRM)；
Atomization gas：Nitrogen；
Atomization gas pressure：45psi；
Capillary voltage：4000V；
Dry temperature degree：400℃；
Dry gas stream speed：12L/min；
Polyoxin：Quota ion：508.1/490.1；
Qualitative ion：508.1/366；
Fragmentation voltage in source：120V；
Collision gas energy：508.1/490.1(10V)；
508.1/366(20V)。
3rd, standard curve, quantified by external standard method polyoxin B are set up with matrix；
(1) the foundation of standard curve：
Polyoxin standard items 0.0345g accurately is weighed, 10ml is settled to 10% methanol aqueous solution, is configured to
1000mg/kg standard mother liquor, then this standard mother liquor is diluted to 0.05,0.1,0.2,0.5,1.0, the mark of 2.0mg/kg series
Quasi- solution, is determined according to above-mentioned liquid-phase condition, and the μ l of sample size 5 obtain polyoxin B MRM spectrograms 1, is sat using sample introduction concentration to be horizontal
Mark, peak area is ordinate, draws standard curve, linear regression equation is Y=12216x-149.29, and coefficient correlation is r=
0.9994, it the results are shown in Table 1
The standard curve of the polyoxin B of table 1
(2) minimum detection limit：
Under these conditions, the limit of identification of polyoxin B is 1.05 × 10-1ng。
(3) concentration limit
Tested according to TIANZHU XINGNAO Capsul, polyoxin is dry in soil, plant, fresh ginseng and ginseng under above-mentioned instrument condition
Concentration limit in powder is 0.2mg/kg.
(4) relative retention time
Relative retention time of the polyoxin B on liquid chromatograph-mass spectrometer is 1.69min or so.
(5) TIANZHU XINGNAO Capsul and relative standard deviation：
Using fresh ginseng and ginseng dry powder as matrix, addition polyoxin B be 0.2,1, tri- levels of 5mg/kg, be repeated 5 times,
According to step 1 and the step 2 assay method rate of recovery, 2-3 is the results are shown in Table, typical MRM spectrograms are shown in Fig. 2-4.Polyoxin is in fresh people
Average recovery rate difference 74.7~94.7% and 74.6~86.0% in ginseng and ginseng dry powder, the coefficient of variation is respectively 1.3~
4.2% and 4.6~7.8%.
4th, result is calculated
The residual quantity of sample Pesticides is counted with mass fraction w, and numerical value is represented with milligrams per kilogram (mg/kg), by formula (1)
Calculate：
In formula：
The residual quantity mass fraction of w --- sample Pesticides, unit is milligrams per kilogram (mg/kg)；
ρ s --- sample solution mass concentration, unit is milligrams per liter (mg/L)；
V0 --- the final constant volume of sample solution, unit is milliliter (ml)；
M --- sample mass, unit is gram (g)；
Result of calculation retains 2 significant digits effective digital.
The TIANZHU XINGNAO Capsul of polyoxin in the fresh ginseng of table 2
The TIANZHU XINGNAO Capsul of polyoxin in the ginseng dry powder of table 3
The positive effect of the present invention is：Residue analysis method of kind of the polyoxin on ginseng is established, with containing formic acid
Aqueous solution homogeneous extract the polyoxin that remains in sample, cross after film, liquid chromatography mass-mass spectrum (HPLCMS-MS) detection,
The standard curve of correction, quantified by external standard method are set up using the vehicle solution without agricultural chemicals to be measured.Have used in pre-treatment is simple
Machine reagent is less, and the rate of recovery meets residues of pesticides criterion calls, and method meets the requirement of current environmental protection.And detection method
The degree of accuracy, precision meet the technical requirements of retention analysis, detection lower bound reaches that domestic and international technical regulation and limit standard will
Ask.Average recovery rate of the present invention is 74.6%~94.7%, and average relative standard's deviation (RSD) is 1.3%~7.8%, detection
Limit is less than 0.06mg/kg, with easy to operate, quick, sensitivity is high, characteristic is strong, reproducible, qualitative, quantitative is accurately excellent
Point.
Brief description of the drawings：
Fig. 1 is polyoxin B MRM spectrograms；
Fig. 2 is ginseng blank spectrogram；
Fig. 3 is that ginseng adds spectrogram；
Fig. 4 is ginseng sample spectra figure.
Fig. 5：Plant not acid adding pitch-based sphere 1mg/kg spectrograms；
Fig. 6：Plant acid adding pitch-based sphere 1mg/kg spectrograms；
Fig. 7：Soil not acid adding pitch-based sphere 1mg/kg spectrograms；
Fig. 8：Soil:Acid adding pitch-based sphere 1mg/kg spectrograms；
Fig. 9：Fresh ginseng not acid adding pitch-based sphere 5mg/kg spectrograms；
Figure 10：Fresh ginseng acid adding pitch-based sphere 5mg/kg spectrograms；
Figure 11：Dry ginseng's not acid adding pitch-based sphere 5mg/kg spectrograms；
Figure 12：Dry ginseng's acid adding pitch-based sphere 5mg/kg spectrograms.
Embodiment：
The two of three rooms in Tonghua, Jilin Province fair An County Yulin town Zhu Xian villages and Jilin Province Baishan Fusong County Songjianghe Area town
Year two places residue test result, 10% Wettable polyoxin powder, 100~150mg/kg of dosage (amount of formulation 666.7~
1000 times of liquid), in black fleck disease of ginseng initial stage (high more than the 15cm of ginseng plant) application method：Cauline leaf spray-on process.Harvest time ginseng
The residual quantity of polyoxin is 0.201~0.404mg/kg in plant；The residual quantity of polyoxin is 0.234 in harvest time soil
~1.109mg/kg；The residual quantity of polyoxin is respectively less than 0.2mg/kg in harvest time fresh ginseng；It is many in harvest time ginseng dry powder
The residual quantity of antimycin is respectively less than 0.2mg/kg.
Embodiment 1：The measure of polyoxin in ginseng plant
Weigh ginseng Plant samples 5.0g to be put into beaker, add 0.3% aqueous formic acid 20mL, adjust pH scope 2-5,
About 2min is homogenized, suction filtration is depressurized in the Buchner funnel for be covered with filter aid, filtrate is all collected in tool plug graduated cylinder, drawing section
Divide filtrate in centrifuge tube, 12000rpm centrifugation 5min cross 0.22 μm of filter membrane, treat that liquid chromatograph-mass spectrometer is detected, MRM
Spectrogram is shown in Fig. 5-Fig. 6, can be seen that the rate of recovery is significantly improved after acid adding from Fig. 5, Fig. 6.
The measurement result of polyoxin in the ginseng plant of embodiment 1
Embodiment 2：The measure of polyoxin in ginseng soil
Soil sample 5.0g is weighed in conical flask with stopper, 0.3% aqueous formic acid 20mL is added, pH scope 2-5, vibration is adjusted
1h is extracted, suction filtration is depressurized in the Buchner funnel for be covered with filter aid, filtrate is all collected in tool plug graduated cylinder, is drawn part and filter
Liquid is in centrifuge tube, and 12000rpm centrifugation 5min cross 0.22 μm of filter membrane, treat that liquid chromatograph-mass spectrometer is detected, MRM spectrograms
See Fig. 7-Fig. 8, can be seen that the rate of recovery is significantly improved after acid adding from Fig. 7, Fig. 8.
The measurement result of polyoxin in the soil of embodiment 2
Embodiment 3：The measure of polyoxin in fresh ginseng
Weigh fresh ginseng sample 5.0g to be put into beaker, add 0.3% aqueous formic acid 20mL, regulation pH scopes 2-5 is even
About 2min is starched, suction filtration is depressurized in the Buchner funnel for be covered with filter aid, filtrate is all collected in tool plug graduated cylinder, draws part
Filtrate is in centrifuge tube, and 12000rpm centrifugation 5min cross 0.22 μm of filter membrane, treat that liquid chromatograph-mass spectrometer is detected, MRM spectrums
Figure is shown in Fig. 9-Figure 10, can be seen that the rate of recovery is significantly improved after acid adding from Fig. 9, Figure 10.
The measurement result of polyoxin in the soil of embodiment 2
Embodiment 4：The measure of polyoxin in ginseng dry powder
Ginseng dry powder sample 5.0g is weighed in conical flask with stopper, 0.3% aqueous formic acid 20mL is added, pH scopes are adjusted
2-5, mechanical shaking extraction 1h, depressurizes suction filtration in the Buchner funnel for be covered with filter aid, filtrate is all collected in tool plug graduated cylinder, inhaled
Portion filtrate is taken in centrifuge tube, 12000rpm centrifugation 5min cross 0.22 μm of filter membrane, treat that liquid chromatograph-mass spectrometer is detected,
MRM spectrograms are shown in figure, and 11- Figure 12 can be seen that the rate of recovery is significantly improved after acid adding from Figure 11, Figure 12..
The measurement result of polyoxin in the ginseng dry powder of embodiment 4
Claims (1)
1. a kind of residue analysis method of polyoxin B on ginseng, comprises the following steps：
1) polyoxin B is extracted with aqueous formic acid in sample：
(1) fresh ginseng：
Fresh ginseng sample 5.0g is weighed, 0.3% aqueous formic acid 20mL is added, pH scope 2-5 are adjusted, about 2min is homogenized, in paving
Suction filtration is depressurized in the Buchner funnel for having filter aid, after filtrate is all collected, portion filtrate 12000rpm centrifugation 5min, mistake is drawn
0.22 μm of filter membrane, treats that liquid chromatograph-mass spectrometer is detected；
(2) ginseng dry powder：
Ginseng dry powder sample 5.0g is weighed, 0.3% aqueous formic acid 20mL is added, pH scope 2-5, mechanical shaking extraction 1h is adjusted,
Suction filtration is depressurized in the Buchner funnel for being covered with filter aid, after filtrate is all collected, portion filtrate 12000rpm centrifugation 5min are drawn,
0.22 μm of filter membrane is crossed, treats that liquid chromatograph-mass spectrometer is detected；
2) analysis test：
(1) instrument condition：
Chromatographic column：Agilent Zorbax RRHD Eclipse Plus C18 3.0×100mm 1.8μm；
Mobile phase：Ammonium acetate 2.5mmol/L+0.05% aqueous formic acids: methanol elution gradient；
Gradient elution program：
Flow velocity：0.3mL/min；Column temperature：30℃；Sample size：10μl；
(2) mass spectral analysis condition：
Ionize source module：Electro-spray ionization；
Ionize source polarity：Positive ion mode (ESI+)；
Scan mode：Multiple-reaction monitoring (MRM)；
Atomization gas：Nitrogen；
Atomization gas pressure：45psi；
Capillary voltage：4000V；
Dry temperature degree：400℃；
Dry gas stream speed：12L/min；
Polyoxin B：Quota ion：508.1/490.1；Qualitative ion：508.1/366；Fragmentation voltage in source：120V；Collision
Gas energy：508.1/490.1 it is 10V；508.1/366 is 20V；
3) standard curve, quantified by external standard method polyoxin B are set up with matrix；
(1) the foundation of standard curve：
Polyoxin B standard items 0.0345g accurately is weighed, 10ml is settled to 10% methanol aqueous solution, is configured to 1000mg/kg
Standard mother liquor, then this standard mother liquor is diluted to 0.05,0.1,0.2,0.5,1.0, the standard liquid of 2.0mg/kg series, press
Determined according to above-mentioned liquid-phase condition, the μ l of sample size 5 obtain chromatogram, using sample introduction concentration as abscissa, peak area is ordinate, is painted
Standard curve processed, linear regression equation is Y=12216x-149.29, and coefficient correlation is r=0.9994；
(2) minimum detection limit：
Under these conditions, the limit of identification of polyoxin B is 1.05 × 10-1ng；
(3) concentration limit
Tested according to TIANZHU XINGNAO Capsul, polyoxin B is in soil, plant, fresh ginseng and ginseng dry powder under above-mentioned instrument condition
In concentration limit be 0.2mg/kg；
(4) relative retention time
Relative retention time of the polyoxin B on liquid chromatograph-mass spectrometer is 1.69min；
(5) TIANZHU XINGNAO Capsul and relative standard deviation：
Using fresh ginseng and ginseng dry powder as matrix, addition polyoxin B be 0.2,1, tri- levels of 5mg/kg, be repeated 5 times, according to
Above-mentioned pre-treating method and instrument condition the assay method rate of recovery；Polyoxin B averagely returning in fresh ginseng and ginseng dry powder
Yield difference 74.7~94.7% and 74.6~86.0%, the coefficient of variation is respectively 1.3~4.2% and 4.6~7.8%；
4) result is calculated
The residual quantity of sample Pesticides is counted with mass fraction w, and numerical value is represented with milligrams per kilogram (mg/kg), based on formula (1)
Calculate：
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In formula：
The residual quantity mass fraction of w --- sample Pesticides, unit is milligrams per kilogram (mg/kg)；
ρ s --- sample solution mass concentration, unit is milligrams per liter (mg/L)；
V0 --- the final constant volume of sample solution, unit is milliliter (ml)；
M --- sample mass, unit is gram (g)；
Result of calculation retains 2 significant digits effective digital.
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| CN107153101B (en) * | 2017-04-24 | 2020-11-24 | 上海市农业科学院 | Detection method of plant-derived feed polyoxin |
| CN109001328A (en) * | 2018-08-17 | 2018-12-14 | 山东省农业科学院农业质量标准与检测技术研究所 | A kind of LC-MS/MS detection method of polyoxin B |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103776929A (en) * | 2014-01-23 | 2014-05-07 | 陕西绿盾生物制品有限责任公司 | Method for detecting polyoxins B by high performance liquid chromatography method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103776929A (en) * | 2014-01-23 | 2014-05-07 | 陕西绿盾生物制品有限责任公司 | Method for detecting polyoxins B by high performance liquid chromatography method |
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| Microbiological assay for quantitative determination of polyoxin B;Li Sun等;《Process Biochemistry》;2009;第44卷;第361-364页 * |
| Residual Efficacy of Fungicides for Controlling Brown Patch on Creeping Bentgrass Fairways;John P. Daniels等;《Plant Disease》;201312;第97卷(第12期);第1620-1625页 * |
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