CN104897767A - Method for rapidly detecting chlorpyrifos in honey by using neutral desorption-extractive electrospray ionization mass spectrometry - Google Patents
Method for rapidly detecting chlorpyrifos in honey by using neutral desorption-extractive electrospray ionization mass spectrometry Download PDFInfo
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Abstract
The invention belongs to the technical field of detection and discloses a method for directly detecting chlorpyrifos in honey by using neutral desorption-extractive electrospray ionization mass spectrometry. The method comprises the following steps: (1) preparing labeled honey; (2) detecting selection of a chlorpyrifos extraction agent and a neutral desorption agent by using neutral desorption-extractive electrospray ionization mass spectrometry; and (3) selecting three-level characteristic fragment ions m/z296 of m/z352 to perform quantitative analysis, thereby obtaining the amount of chlorpyrifos in honey. According to the method disclosed by the invention, a to-be-detected sample does not need to be pretreated, the chlorpyrifos in honey is rapidly detected and identified, and the defects such as complex operating steps and high time consumption in the existing analysis technology are improved.
Description
Technical field
The invention belongs to detection technique field, particularly the detection method of the dead tick of honey poisoning.
Background technology
Chlopyrifos is a kind of widely used high-efficiency broad spectrum organophosphorus pesticide, both can kill mite, can do again health deinsectization medicine, be mainly used in the prevention and control of plant diseases, pest control of the various crop such as vegetables fruit tree, cotton, but larger to the threat of nectariferous plant.Toxicologic study shows, chlopyrifos has the effect significantly suppressing cholinesterase activity, produces and poisons, and have certain teratogenesis to the central nervous system of mouse.In honey, the analysis and research of organophosphorus pesticide show, residual the exceed standard phenomenon ubiquity of chlopyrifos in honey.China is the first in the world bee-keeping big country, is also that bee product is produced and big export country.Along with the raising of living standards of the people and the fast development of foreign trade, the chlopyrifos residue in honey has become the primary factor affecting China's honey outlet, the national food security of serious harm and expanding economy.
At present, conventional chlopyrifos detection method has enzyme-linked immunosorbent assay, high performance liquid chromatography, Liquid Chromatography/Mass Spectrometry, gas chromatography mass spectrometry method etc.These methods generally all need complicated sample pretreatment process, have complex operation step, the defect such as time-consuming, bring much inconvenience to the detection of the dead tick of honey poisoning.
Summary of the invention
The object of this invention is to provide a kind of method dead tick of honey poisoning being remained to direct-detection newly.The present invention, without the need under the condition of sample pretreatment, directly detects fast to the chlopyrifos in honey.The present invention adopts the thtee-stage shiplock fragment of chlopyrifos to carry out quantitative test, avoids false positive, improves the accuracy detected.
Detection method of the present invention carries out the detection of containing chlopyrifos honey sample.
Technical solution of the present invention is as follows:
A method for neutral desorb-dead tick of electron spray extraction MALDI-MS direct-detection honey poisoning, comprises the steps:
(1) mark-on honey preparation: take testing sample honey, stand-by;
Mark-on honey is prepared: parallel several parts take heavy without chlopyrifos honey with testing sample honey etc., add the chlopyrifos solution of gradient concentration respectively, stir, one-tenth mark-on honey, stand-by;
Testing sample honey and mark-on honey are all sealed 65 DEG C of water-bath 5min with preservative film; Treat honey cool to room temperature, detect;
(2) neutral desorb-electron spray extraction MALDI-MS detects: ND-EESI-MS is set to positive ion detecting pattern, Mass Spectrometer Method sweep limit is m/z 50 ~ 400; With methanol aqueous solution for neutral desorb reagent; Ionization voltage 3.5kV; Ion transfer tube temperature is 300 DEG C; Atomization gas is nitrogen, and pressure is 1.0MPa; Extractant formic acid: methyl alcohol: water volume ratio 1:2:2, flow velocity is 4 μ L/min;
During collision induced dissociation experiment, chlopyrifos parent ion m/z 352 width is set to 1.2Da, collision energy 30%, and collision duration is 30ms; Secondary m/z 324 ion width is set to 1.4Da, and collision energy is 15%, and collision duration is 30ms, using three grades of m/z 296 as quota ion;
Other parameter adopts LTQ-MS system Automatic Optimal; Spraying solvent channel and horizontal plane angle are 30 °, and solvent spray mouth and mass spectrum mouth distance are 0.5cm; For ensureing that sample molecule carries out colliding and reacting with reagent ion to greatest extent, two spray channel angles keep 60 °, and sample nozzle and mass spectrum entrance distance are 0.5cm;
(3) judgement of chlopyrifos whether is contained: if having m/z 296 ion signal peak in three grades of fragments of m/z 352, in interpret sample, have chlopyrifos;
Three grades of fragments characteristic ion m/z 296 of m/z 352 are selected to carry out quantitative test, with the dead tick concentration of mark-on honey poisoning for horizontal ordinate, with the absolute signal strengths of m/z 296 for ordinate drawing standard curve, draw the concentration of the dead tick of testing sample honey poisoning according to typical curve.
The invention has the beneficial effects as follows: (1) detection limit is lower, 1.64ng/mL is limited to detecting of the dead tick of honey poisoning.(2) adopt three grades of signals as quantifiable signal, avoid false positive.(3) the inventive method adopts formic acid: methyl alcohol: neutral desorb is carried out in water (1:2:2) spraying, and desorption efficiency is high, improves the intensity of echo signal.(4) in-situ study of honey is achieved, without the need to carrying out pre-service to sample.(5) application of the direct honey pollutant monitoring technology fast of realization is made to become possibility, for the sustainable development of honey industry lays the foundation.
Accompanying drawing explanation
Fig. 1 is the ND-EESI Experimental equipment of the inventive method.
Fig. 2 is the MS of chlopyrifos of the present invention (100ng/mL)
nspectrogram, in figure, (a) is chlopyrifos methanol solution first mass spectrometric figure, and (b) is chlopyrifos methanol solution tandem mass spectrum figure, c () is mark-on honey chlopyrifos first mass spectrometric figure, (d) is mark-on honey chlopyrifos tandem mass spectrum figure.
Fig. 3 is that the present invention to spray in reagent Optimal Experimental m/z 296 CID signal intensity with the changing trend diagram of electron spray extractant, in figure, (1) is for different organic solvents is as extractant, (2) for variable concentrations formic acid methanol solution is as extractant, (3) A-D is respectively 20% formic acid+80% methyl alcohol; 20% formic acid+40% methyl alcohol+40% acetone; 20% formic acid+40% methyl alcohol+40% ethyl acetate; 20% formic acid+40% methyl alcohol+40% water.
Fig. 4 is m/z 296 signal strength map under the different neutral strippant of the present invention.
Fig. 5 is the optimization figure affecting chlopyrifos mass spectrum behavior condition in the present invention, in figure, a optimization figure that () is electron spray voltage, b optimization figure that () is extractant flow velocity, c optimization figure that () is atomization gas pressure, d optimization figure that () is desorb air pressure, the optimization figure that (e) is ion transfer tube temperature.
Fig. 6 is the working curve of variable concentrations mark-on honey.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
The LTQ mono-XL Linear ion trap mass spectrometer that the mass spectrometer that example of the present invention uses is Finnigan company of the U.S., data handling system is the XCalibur data handling system of Finnigan company of the U.S..
Neutral desorption apparatus and EESI ion gun, developed voluntarily by Jiangxi Province's mass spectrum science and instrument key lab; Precision electronic balance (METTLERTOLEDO).Methyl alcohol (chromatographically pure, SKCHEM work is with LS); Chlopyrifos standard items (purity is 99%, Aladdin Reagent Company); The LTQ-XL Linear ion trap mass spectrometer that the mass spectrometer that example of the present invention uses is Finnigan company of the U.S., data handling system is the Xcalibur data handling system of Finnigan company of the U.S..
Embodiment 1
This experiment uses the ND-EESI-MS method shown in Fig. 1 to test chlopyrifos honey solution (100ng/mL),
(1) chlopyrifos standard solution: the appropriate chlopyrifos standard items of precise, are dissolved in methyl alcohol, is made into the chlopyrifos standard solution that concentration is 2mg/mL, keeps in Dark Place in-3 DEG C.Get 100 μ L 2mg/mL chlopyrifos standard solution, be diluted to 4mL with ultrapure water, concentration is 50 μ g/mL.
(2) mark-on honey chlopyrifos solution: graduated cylinder is placed in analytical balance, peeling zero, getting 9.9mL honey by graduated cylinder correct amount, weigh, is 13.96232g.Then respectively each 10mL conical flask is placed in analytical balance, peeling zero, takes 13.96g honey respectively.Seal 65 DEG C of water-bath 5min with preservative film after weighing, measuring 100 μ L 50 μ g/mL dilutions in respectively filling in the conical flask of honey, stirring.Treat honey cool to room temperature, carry out Mass Spectrometer Method.
Result as shown in Figure 2, chlopyrifos at ND-EESI ion gun, under positive ion mode, m/z 352 chlopyrifos [C
9h
11cl
3nO
3pS]
+during Tandem Mass Spectrometry Analysis, fragmention has m/z 324, m/z 296, m/z 278.They are respectively m/z 352 and lose 1 (-C
2h
5), 2 (-C
2h
5), 2 (-C
2h
5) and an one's share of expenses for a joint undertaking H
2o.Again CID is done to m/z 324, m/z 296, confirm above scission fragments further, all consistent with the fragments characteristic in document.For guaranteeing experimental reliability, adopt EESI-MS to carry out MS/MS mass spectrum check analysis to 100ng/mL chlopyrifos standard solution, result shows, chlopyrifos ND-EESI-MS
nspectrogram and its EESI-MS
nspectrogram fits like a glove.Therefore, if signal peak m/z 352 can be detected in actual sample, and in MS/MS spectrogram, observe principal character ion m/z 324 and m/z 296, then can judge in this sample containing chlopyrifos.
For getting rid of false positive when detecting, three grades of fragments characteristic quasi-molecular ions m/z 296 are adopted to be echo signal, for improving its signal intensity, the optimization of spraying reagent has been carried out in this experiment, with the chlopyrifos mark-on honey of 100ng/mL for experimental subjects, with the response intensity of three grades of mass signal m/z 296 for standard, carry out the Optimal Experimental of water, methyl alcohol, ethanol, ethyl acetate, propyl alcohol, butanols, benzene and P-xylene, acetonitrile and acetone, as shown in Fig. 3 (1).Through groping in a large number, adopt the methyl alcohol of different formic acid volume fraction as three grades of characteristic ion m/z 296 signal intensities of chlopyrifos under extractant, find that acid adding has extraordinary effect, result is as shown in Fig. 3 (2), be presented at 20% formic acid methanol solution as spraying reagent, three grades of fragments characteristic m/z 296 signal intensities of the dead tick of honey poisoning are the strongest, but the maximal acid concentration that mass spectrometer can allow is 20%, can not increase acid concentration more for this reason.For exploring reagent of better spraying, adopt 20% formic acid+80% methyl alcohol; 20% formic acid+40% methyl alcohol+40% acetone; 20% formic acid+40% methyl alcohol+40% ethyl acetate; 20% formic acid+40% methyl alcohol+40% water is as electron spray reagent, and result shows, and 20% formic acid+40% methyl alcohol+40% water effect is best, as Fig. 3 (3).Therefore, the extractant of this experiment is 20% formic acid+40% methyl alcohol+40% water mixed solution.
This experiment has been carried out neutral strippant and has been explored, with 20% formic acid+40% methyl alcohol+40% water for electron spray extractant, successively by 90% methyl alcohol+10% water, 80% methyl alcohol+20% water, 60% methyl alcohol+40% water, 40% methyl alcohol+60% water, 20% methyl alcohol+80% water, 100% water is that strippant detects chlopyrifos thtee-stage shiplock characterising mass spectrometry fragment m/z 296 signal intensity, and result as shown in Figure 4.
The exploration of ion gun condition has been carried out in this experiment, according to the mass spectrum behavior of chlopyrifos standard solution, in the positive-ion mode, all the mass spectrum response signal intensity of selection chlopyrifos thtee-stage shiplock characterising mass spectrometry fragment m/z 296 represents the detection efficiency to chlopyrifos molecule.As shown in Fig. 5 (a), during voltage too little (being less than 1.5kV), signal intensity is lower, along with increasing of voltage, Target Signal Strength raises rapidly, when voltage too large (being greater than 3.5kV), signal intensity decreases on the contrary, reaches best when 3.5kV; As shown in Fig. 5 (b), the extraction efficiency of electron spray solvent flow rate when 4 μ L/min is maximum; As shown in Fig. 5 (c), experiment shows, along with the increase of atomization pressure, Target Signal Strength also increases thereupon, when air pressure exceedes certain value (being greater than 1.0MPa), major part ion can be buried in oblivion at mass spectrum mouth edge, and Target Signal Strength also can significantly decline, and reaches best when 1MPa; As shown in Fig. 5 (d), when desorb air pressure is 1.2MPa, signal is the strongest, and desorption efficiency is the highest; As shown in Fig. 5 (e), temperature is from 100 DEG C ~ 300 DEG C, and Target Signal Strength raises rapidly, but after temperature is greater than 300 DEG C, signal intensity reduces gradually, and therefore, experimental selection ion transfer tube temperature is 300 DEG C.
The experiment of mark-on chlopyrifos is carried out, to determine the range of linearity and the detection limit of this method according to above-mentioned experimental technique.Owing to detecting in real time in honey sample, in order to get rid of the false positive of signal, three grades of fragments characteristic ion m/z 296 of experimental selection m/z 352 carry out quantitative test, deduct corresponding blank background simultaneously.The standard model of each concentration measures 6 times, with the absolute signal strengths mean value of m/z 296 and corresponding chlopyrifos concentration curve plotting, as shown in Figure 6.Experiment shows, within the scope of chlopyrifos concentration 100 ~ 1000ng/mL, ionic strength and concentration have good linear relationship, and equation of linear regression is y=2.444x-63.76, R
2=0.997.According to LOD=c3 σ/S, S/N=3, c are the concentration of standard items, and σ is standard deviation, and S is net phase induction signal average strength), calculate this method and 1.64ng/mL is limited to detecting of mark-on honey.
Embodiment 2
A method for neutral desorb-dead tick of electron spray extraction MALDI-MS direct-detection honey poisoning, comprises the steps:
(1) mark-on honey preparation: take testing sample honey, stand-by;
Mark-on honey is prepared: parallel several parts take heavy without chlopyrifos honey with testing sample honey etc., add the chlopyrifos solution of gradient concentration respectively, stir, one-tenth mark-on honey, stand-by;
Testing sample honey and mark-on honey are all sealed 65 DEG C of water-bath 5min with preservative film; Treat honey cool to room temperature, detect;
(2) neutral desorb-electron spray extraction MALDI-MS detects: ND-EESI-MS is set to positive ion detecting pattern, Mass Spectrometer Method sweep limit is m/z 50 ~ 400; With methanol aqueous solution for neutral desorb reagent; Ionization voltage 3.5kV; Ion transfer tube temperature is 300 DEG C; Atomization gas is nitrogen, and pressure is 1.0MPa; Extractant formic acid: methyl alcohol: water volume ratio 1:2:2, flow velocity is 4 μ L/min;
During collision induced dissociation experiment, chlopyrifos parent ion m/z 352 width is set to 1.2Da, collision energy 30%, and collision duration is 30ms; Secondary m/z 324 ion width is set to 1.4Da, and collision energy is 15%, and collision duration is 30ms, using three grades of m/z 296 as quota ion;
Other parameter adopts LTQ-MS system Automatic Optimal; Spraying solvent channel and horizontal plane angle are 30 °, and solvent spray mouth and mass spectrum mouth distance are 0.5cm; For ensureing that sample molecule carries out colliding and reacting with reagent ion to greatest extent, two spray channel angles keep 60 °, and sample nozzle and mass spectrum entrance distance are 0.5cm;
(3) judgement of chlopyrifos whether is contained: if having m/z 296 ion signal peak in three grades of fragments of m/z 352, in interpret sample, have chlopyrifos.
Three grades of fragments characteristic ion m/z 296 of m/z 352 are selected to carry out quantitative test, with the dead tick concentration of mark-on honey poisoning for horizontal ordinate, with the absolute signal strengths of m/z 296 for ordinate drawing standard curve, draw the concentration of the dead tick of testing sample honey poisoning according to typical curve.
Embodiment 3
(1) take commercially available honey 13.96g in 10mL conical flask, preservative film seals 65 DEG C of water-bath 5min; Treat honey cool to room temperature, detect;
(2) neutral desorb-electron spray extraction MALDI-MS detects: ND-EESI-MS is set to positive ion detecting pattern, Mass Spectrometer Method sweep limit is m/z 50 ~ 400; With methyl alcohol: water volume ratio 1:1 is neutral desorb spraying reagent; Ionization voltage 3.5kV; Ion transfer tube temperature is 300 DEG C; Atomization gas is nitrogen, and pressure is 1.0MPa; Extractant formic acid: methyl alcohol: water volume ratio 1:2:2, flow velocity is 4 μ L/min;
During collision induced dissociation experiment, chlopyrifos parent ion m/z 352 width is set to 1.2Da, collision energy 30%, and collision duration is 30ms; Secondary m/z 324 ion width is set to 1.4Da, and collision energy is 15%, and collision duration is 30ms, using three grades of m/z 296 as quota ion;
Other parameter adopts LTQ-MS system Automatic Optimal; Spraying solvent channel and horizontal plane angle are 30 °, and solvent spray mouth and mass spectrum mouth distance are 0.5cm; For ensureing that sample molecule carries out colliding and reacting with reagent ion to greatest extent, two spray channel angles keep 60 °, and sample nozzle and mass spectrum entrance distance are 0.5cm;
(3) judgement of chlopyrifos whether is contained: if having m/z 296 ion signal peak in three grades of fragments of m/z 352, chlopyrifos has been described.
The mensuration of sample Chlorpyrifos content: gathered by this device in three grades of fragments of m/z 352 in honey sample and have m/z 296 ion signal peak, obtain its signal strength data, these data are substituted into formula: y=2.444x-63.76, calculates the content (concentration unit is ng/mL) of sample Chlorpyrifos.
To 50 and 500ng/mL chlopyrifos honey solution replicate determination 6 times, calculated by typical curve, the recovery is respectively 82.02% and 109.28%, and precision (RSD) is respectively 4.02% and 4.34%.
Claims (2)
1. a method for neutral desorb-dead tick of electron spray extraction MALDI-MS direct-detection honey poisoning, is characterized in that comprising the steps:
(1) mark-on honey preparation: take testing sample honey, stand-by;
Mark-on honey is prepared: parallel several parts take heavy without chlopyrifos honey with testing sample honey etc., add the chlopyrifos solution of gradient concentration respectively, stir, one-tenth mark-on honey, stand-by;
Testing sample honey and mark-on honey are all sealed 65 DEG C of water-bath 5min with preservative film; Treat honey cool to room temperature, detect;
(2) neutral desorb-electron spray extraction MALDI-MS detects: ND-EESI-MS is set to positive ion detecting pattern, Mass Spectrometer Method sweep limit is m/z 50 ~ 400; With methanol aqueous solution for neutral desorb reagent; With formic acid methanol aqueous solution for electron spray extraction agent; Ionization voltage 3.5kV; Ion transfer tube temperature is 300 DEG C; Atomization gas is nitrogen, and pressure is 1.0MPa; Electron spray extraction agent flow velocity is 4 μ L/min;
During collision induced dissociation experiment, chlopyrifos parent ion m/z 352 width is set to 1.2Da, collision energy 30%, and collision duration is 30ms; Secondary m/z 324 ion width is set to 1.4Da, and collision energy is 15%, and collision duration is 30ms, using three grades of m/z 296 as quota ion;
Other parameter adopts LTQ-MS system Automatic Optimal; Spraying solvent channel and horizontal plane angle are 30 °, and solvent spray mouth and mass spectrum mouth distance are 0.5cm; For ensureing that sample molecule carries out colliding and reacting with reagent ion to greatest extent, two spray channel angles keep 60 °, and sample nozzle and mass spectrum entrance distance are 0.5cm;
(3) judgement of chlopyrifos whether is contained: if having m/z 296 ion signal peak in three grades of fragments of m/z 352, in interpret sample, have chlopyrifos;
Three grades of fragments characteristic ion m/z 296 of m/z 352 are selected to carry out quantitative test, with the dead tick concentration of mark-on honey poisoning for horizontal ordinate, with the absolute signal strengths of m/z 296 for ordinate drawing standard curve, per sample, the signal intensity of three grades of fragments characteristic ion m/z 296 of m/z 352 substitutes into the concentration that typical curve formula draws the dead tick of testing sample honey poisoning.
2. method according to claim 1, is characterized in that with methyl alcohol: water volume ratio 1:1 is neutral desorb reagent; With formic acid: methyl alcohol: water volume ratio 1:2:2 is electron spray extraction agent.
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| CN105445360A (en) * | 2015-11-30 | 2016-03-30 | 南昌大学 | Method for quickly detecting dichlorvos in honey through ND-EESI-MS (neutral desorption-extractive electrospray ionization-mass spectrography) |
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| CN105606693A (en) * | 2016-03-15 | 2016-05-25 | 南昌大学 | Method for directly detecting five chemical pollutants in propolis through extractive electrospray ionization mass spectrum |
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| CN106596698A (en) * | 2016-11-10 | 2017-04-26 | 南昌大学 | Method for distinguishing freshness of lotus seeds by using direct IMS (imaging mass spectrometry) technology |
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