CN109633026A - A kind of method that liquid chromatography-tandem mass spectrometry detects carbendazim and its metabolin - Google Patents
A kind of method that liquid chromatography-tandem mass spectrometry detects carbendazim and its metabolin Download PDFInfo
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Abstract
The invention discloses the methods of a kind of liquid chromatography-tandem mass spectrometry detection carbendazim and its metabolin, are related to edible mushroom detection technique field.It is extracted this method comprises: being mixed with acetonitrile with sample to be tested, adds NaCl, be centrifuged after mixing, supernatant is taken to be prepared into sample detection liquid after purification；The sample detection liquid injection liquid chromatography-tandem mass spectrometry instrument is drawn to be detected.This method may be implemented to the carbendazim and its metabolin 2- aminobenzimidazole, 2- hydroxybenzimidazole and benzimidazole in sample while detect.This method accuracy with higher, precision and sensitivity.
Description
Technical field
The present invention relates to edible mushroom detection technique fields, detect in particular to a kind of liquid chromatography-tandem mass spectrometry more
The method of bacterium spirit and its metabolin.
Background technique
Carbendazim is benzimidazole germicide, and absorbability is strong, wide sterilization spectrum, is mainly used for prevention and treatment by sac fungus, half
Know the multiple diseases on the crops such as field crop caused by bacterium and basidiomycetes, veterinary antibiotics.Carbendazim belongs to less toxic fungicide,
Chemical property is stablized, and degradation half life is long in the natural environment, can influence human health by food chain.Carbendazim is in plant
It is interior it is degradable be 2- aminobenzimidazole (2-AB), and 2-AB is to human skin and the toxic effect of eyes.Rouchaud et al.
In carrot, strawberry and apple other than detecting containing 2-AB, while there are also benzimidazoles, 2- aminobenzimidazole, neighbour
The toxic organic compounds such as phenylenediamine, aniline.
Premenstruum (premenstrua) investigation discovery can largely use carbendazim in the planting process of agaricus bisporus, thus research carbendazim and
The detection method of its metabolin is of great significance to the safe condition for monitoring and reinforcing agaricus bisporus.Ion pairing
Detection method mainly has UV-VIS spectrophotometry, thin-layer chromatography detection method, immuno-chemical method, gas chromatography, ion to hand over
Colour changing spectrometry, high performance liquid chromatography (HPLC) method and liquid chromatograph mass spectrography (LCMS) method etc..Using liquid chromatogram measuring kind
Carbendazim and probenazole and use superelevation phase liquid chromatography-tandem matter (UPLC-MS/MS) technology in eggplant measure in apple simultaneously
Carbendazim, probenazole and thiophanate-methyl it has been reported that still measure carbendazim and its metabolin 2- amino in edible mushroom simultaneously
There is not been reported for benzimidazole, 2- hydroxybenzimidazole and the remaining method of benzimidazole.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
The purpose of the present invention is to provide the methods of a kind of liquid chromatography-tandem mass spectrometry detection carbendazim and its metabolin.
This method may be implemented to the carbendazim and its metabolin 2- aminobenzimidazole, 2- hydroxybenzimidazole and benzo miaow in sample
Azoles detects simultaneously.
The present invention is implemented as follows:
A kind of method of liquid chromatography-tandem mass spectrometry detection carbendazim and its metabolin provided by the invention, the metabolism
Object includes 2- aminobenzimidazole, 2- hydroxybenzimidazole and benzimidazole comprising following steps:
Sample detection liquid preparation step: being mixed with sample to be tested with acetonitrile and extracted, and adds NaCl, after mixing from
The heart takes supernatant to be prepared into sample detection liquid after purification；
Liquid chromatography-tandem mass spectrometry detecting step: draw the sample detection liquid inject liquid chromatography-tandem mass spectrometry instrument into
Row detection.
Further, in some embodiments of the present invention, used in liquid chromatography-tandem mass spectrometry detecting step
Liquid phase chromatogram condition it is as follows:
Mobile phase A: methanol, Mobile phase B: the aqueous solution containing ammonium acetate and formic acid；Flow velocity: 0.4mL/min；Type of elution:
Gradient elution；Column temperature: 45 DEG C；Sample volume: 5 μ L.
Further, in some embodiments of the present invention, the program of gradient elution is as follows:
| Time | Mobile phase A | Mobile phase B |
| 0min | 5% | 95% |
| 0~1.0min | 95% | 5% |
| 1.0~3.0min | 95% | 5% |
| 3.0~3.6min | 5% | 95% |
| 3.6~4.0min | 5% | 95% |
I.e. in 0min, 5% (volume ratio) mobile phase A+95% (volume ratio) Mobile phase B, in 0-1min in proportion by
+ 5% Mobile phase B of up to 95% mobile phase A that edges up maintains+5% Mobile phase B of 95% mobile phase A in 1-3min, then 3-
3.6min, is gradually decrease to+95% Mobile phase B of 5% mobile phase A in proportion, and 3.6-4min maintains 5% mobile phase A+95% stream
Dynamic phase.
Further, in some embodiments of the present invention, in Mobile phase B, acetic acid ammonium concentration is 10mmol/L, first
Acid content is 0.1% (mass volume ratio).
Further, in some embodiments of the present invention, used in liquid chromatography-tandem mass spectrometry detecting step
Mass Spectrometry Conditions it is as follows:
Ionization mode: electric spray ion source (ESI) positive ion mode；Capillary voltage: 2.5kv；Ion source temperature:
150℃；Desolventizing temperature: 450 DEG C；Atomization gas flow velocity: 1000L/h；Taper hole gas velocity: 150L/h；Collision gas flow velocity: 0.11L/
h；Detection mode: MRM.
Further, in some embodiments of the present invention, MRM parameter is as shown in the table:
Data understand in table are as follows:
For the detection of carbendazim, quota ion pair is 191.9 and 159.9, orifice potential 42V, and collision energy is
20eV；Qualitative ion pair is 191.9 and 132.0, orifice potential 42V, collision energy 20eV.
For the detection of 2- aminobenzimidazole, quota ion pair 134.0 and 65.0, orifice potential 36V, collision energy
For 26eV；Qualitative ion pair is 134.0 and 80.0, orifice potential 36V, collision energy 26eV.
For the detection of 2- hydroxybenzimidazole, quota ion pair 135.0 and 107.0, orifice potential 36V, impact energy
Amount is 26eV；Qualitative ion pair is 135.0 and 91.0, orifice potential 36V, collision energy 26eV.
For the detection of benzimidazole, quota ion pair 119.0 and 39.0, orifice potential 42V, collision energy is
20eV；Qualitative ion pair is 119.0 and 92.0, orifice potential 42V, collision energy 20eV.
Further, in some embodiments of the present invention, the atomization gas is nitrogen, and the taper hole gas is nitrogen,
The collision gas is argon gas.
Further, in some embodiments of the present invention, to be measured by every 10g in sample detection liquid preparation step
Sample is corresponding to be mixed acetonitrile and the sample to be tested using the ratio of 20ml acetonitrile, through extraction of ocean eddies and ultrasonic extraction
Afterwards, NaCl is added in the corresponding ratio that 5g NaCl is added of every 10g sample, after mixing, is centrifuged after purification, takes supernatant purified
After be prepared into the sample detection liquid.
Further, in some embodiments of the present invention, the time of extraction of ocean eddies is 5-15min；Ultrasonic extraction
Time is 5-15min；The condition of centrifugation are as follows: revolving speed 3000-5000rpm, centrifugation time 5-10min.
Further, in some embodiments of the present invention, the sample to be tested is edible mushroom；
Preferably, the edible mushroom is agaricus bisporus.
The invention has the following advantages:
The present invention measures carbendazim and its metabolin 2- ammonia in agaricus bisporus using liquid chromatography-tandem mass spectrometry technology simultaneously
The method of base benzimidazole, 2- hydroxybenzimidazole and benzimidazole residual quantity, it is easy to operate, quick, it is qualitative, quantitative accurately
It leans on, high sensitivity, can satisfy while detecting carbendazim in edible mushroom such as agaricus bisporus and its major metabolite residual quantity
It is required that.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is total ion chromatogram (TIC, the Total Ions of 0.010mg/L carbendazim and its metabolin
Chromatograph)。
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
Liquid chromatography-tandem mass spectrometry provided in this embodiment detection carbendazim and its metabolin, that is, 2- aminobenzimidazole,
The method of 2- hydroxybenzimidazole and benzimidazole is as follows:
1.1 instruments and reagent
Liquid chromatography-tandem mass spectrometry instrument (electric spray ion source, Waters, US), BEH C18 chromatographic column (1.7 μm,
2.1mm*100mm) (Waters, US), MX-F vortex mixer (Chinese DRAGONLAB company), 5415D centrifuge (beauty
Eppendorf company, state), anhydrous MgSO4, C18 and PSA cleanser, 0.22 μm of organic filter membrane (company is composed by middle Guoan).
(purity >=98% is purchased from for carbendazim, 2- aminobenzimidazole, 2- hydroxybenzimidazole and benzimidazole standard items
German Dr.Ehrenstorfer company), acetonitrile and methanol (chromatographically pure, United States Merck company)；Formic acid and ammonium acetate (chromatographically pure,
United States Merck company)；Use for laboratory water is level-one water.
The configuration of 1.2 standard reserving solutions
Carbendazim, 2- aminobenzimidazole, 2- hydroxybenzimidazole and benzimidazole standard items are accurately weighed, it is molten with acetonitrile
Solution is configured to the standard reserving solution that mass concentration is 1000mg/L.
1.3 instrument condition
1.3.1 liquid phase chromatogram condition
Mobile phase A is methanol, and Mobile phase B is the aqueous solution of ammonium acetate and 0.1% formic acid containing 10mmol/L；Flow velocity:
0.4mL/min；Gradient elution program is as follows:
| Time | Mobile phase A | Mobile phase B |
| 0min | 5% | 95% |
| 0~1.0min | 95% | 5% |
| 1.0~3.0min | 95% | 5% |
| 3.0~3.6min | 5% | 95% |
| 3.6~4.0min | 5% | 95% |
。
Column temperature: 45 DEG C；Sample volume: 5 μ L.
1.3.2. Mass Spectrometry Conditions
Electric spray ion source (ESI) positive ion mode；Capillary voltage: 2.5kv；Ion source temperature: 150 DEG C；Desolventizing
Temperature: 450 DEG C, atomization gas (nitrogen) flow velocity: 1000L/h；Taper hole gas (nitrogen) flow velocity: 150L/h；Collision gas (argon gas) flow velocity:
0.11L/h；Detection mode: MRM.
MRM parameter is as shown in table 1 below:
Table 1
1.3.3. sample treatment
It extracts: accurately weighing 10g sample such as agaricus bisporus sample, after being placed in 50mL plastic centrifuge tube, 20mL is added
Acetonitrile, extraction of ocean eddies 10min, ultrasonic extraction 10min add 5g NaCl to shake up, and 4000rpm is centrifuged 5min, and supernatant is spare.
Purification: Aspirate supernatant about 1.5mL is in advance added with the 2mL of anhydrous magnesium sulfate 150mg, C1850mg and PSA50mg
Purified that (purification run can refer to application number 2018113298977, entitled to reduce matrix effect in plastic centrifuge tube
It is a kind of to be carried out for the solid-phase extraction device of alkene oxime amine purification and the Chinese invention patent application of alkene oxime amine detection method),
5min is centrifuged in 8000rpm after vortex mixing 30s.Supernatant 0.5mL is taken, level-one water (H is added2O) 0.5mL is mixed, and crosses 0.22 μm
Liquid chromatography tandom mass spectrometry determination is carried out after filter membrane.
Experimental example
In the edible mushroom (button mushroom) addition concentration be respectively 10 μ g/kg, 50 μ g/kg and 100 μ g/kg carbendazim,
2- aminobenzimidazole, 2- hydroxybenzimidazole and benzimidazole are placed 24 hours, are detected using 1 detection method of embodiment, often
6 parallel determinations of a level calculate, and the results are shown in Table 2 and Fig. 1, the rate of recovery (measured value/addition of carbendazim and its metabolite
Value * 100%) it is 92.1%~99.5%, relative standard deviation (RSD) is 2.1%~5.1%.Test the rate of recovery and opposite mark
Quasi- deviation can satisfy analysis method requirement.
Table 2
It can be seen from the results above that detection method provided in an embodiment of the present invention, can quickly detect it is more in edible mushroom
Bacterium spirit and its metabolite, that is, 2- aminobenzimidazole, 2- hydroxybenzimidazole and benzimidazole, can meet more bacterium in edible mushroom
The trace detection analysis of spirit and its metabolite.The detection method has very high accuracy (rate of recovery > 92.1%), precision
(after liquid chromatography tandem mass spectrometry analysis, sensitivity is below 3.0 μ for degree (relative standard deviation < 5.1%) and sensitivity
G/kg while), and it is easy to operate, meet carbendazim and its metabolite detection and sample pre-treatments in domestic and international edible mushroom
Requirement.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method of liquid chromatography-tandem mass spectrometry detection carbendazim and its metabolin, the metabolin includes 2- aminobenzene
And imidazoles, 2- hydroxybenzimidazole and benzimidazole, which is characterized in that it includes the following steps:
Sample detection liquid preparation step: being mixed with sample to be tested with acetonitrile and extracted, and is added NaCl, is centrifuged after mixing, only
Supernatant is taken to be prepared into sample detection liquid after change；
Liquid chromatography-tandem mass spectrometry detecting step: it draws the sample detection liquid injection liquid chromatography-tandem mass spectrometry instrument and is examined
It surveys.
2. used the method according to claim 1, wherein in liquid chromatography-tandem mass spectrometry detecting step
Liquid phase chromatogram condition is as follows:
Mobile phase A: methanol, Mobile phase B: the aqueous solution containing ammonium acetate and formic acid；Flow velocity: 0.4mL/min；Type of elution: gradient
Elution；Column temperature: 45 DEG C；Sample volume: 5 μ L.
3. according to the method described in claim 2, it is characterized in that, the program of gradient elution is as shown in the table:
。
4. according to the method described in claim 2, it is characterized in that, acetic acid ammonium concentration is 10mmol/L, first in Mobile phase B
Acid content is 0.1%.
5. method according to claim 1-4, which is characterized in that in liquid chromatography-tandem mass spectrometry detecting step
In, Mass Spectrometry Conditions used are as follows:
Ionization mode: electric spray ion source positive ion mode；Capillary voltage: 2.5kv；Ion source temperature: 150 DEG C；Precipitation
Agent temperature: 450 DEG C；Atomization gas flow velocity: 1000L/h；Taper hole gas velocity: 150L/h；Collision gas flow velocity: 0.11L/h；Detection side
Formula: MRM.
6. according to the method described in claim 5, it is characterized in that, MRM parameter is as shown in the table:
7. according to the method described in claim 5, the taper hole gas is nitrogen, institute it is characterized in that, the atomization gas is nitrogen
Stating collision gas is argon gas.
8. method according to claim 1-4, which is characterized in that in sample detection liquid preparation step, by every
10g sample to be tested is corresponding to be mixed acetonitrile and the sample to be tested using the ratio of 20ml acetonitrile, through extraction of ocean eddies and is surpassed
After sound extracts, NaCl is added in the corresponding ratio that 5g NaCl is added of every 10g sample, after mixing, centrifugation takes supernatant purified
After be prepared into the sample detection liquid.
9. according to the method described in claim 8, it is characterized in that, the time of extraction of ocean eddies is 5-15min；Ultrasonic extraction when
Between be 5-15min；The condition of centrifugation are as follows: revolving speed 3000-5000rpm, centrifugation time 5-10min.
10. method according to claim 1-4, which is characterized in that the sample to be tested is edible mushroom.
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