CN103543221A - Method for simultaneously detecting multiple mycotoxins in milk - Google Patents
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Abstract
The invention discloses a method for simultaneously detecting multiple mycotoxins in milk. The method comprises the following steps: (1) extracting the mycotoxins from milk to obtain a crude mycotoxin extract; (2) purifying and concentrating the crude mycotoxin extract; (3) carrying out gradient eluting on the concentrated mycotoxins on a chromatographic column through a mobile phase and collecting eluate; and (4) qualitatively and quantitatively detecting the collected eluate by a mass spectrometer. An efficient, sensitive and stable method is created in the invention for simultaneously detecting aflatoxin M1, ochratoxin A, zearalenone and alpha-zearalenol in milk. The linearity, sensitivity, recovery, accuracy and reproducibility of the detection method disclosed by the invention are verified in fresh milk, liquid milk and milk powder, and as shown in the verification results, the detection method disclosed by the invention is good in linear range, high in sensitivity, good in credibility and strong in stability.
Description
Technical field
The present invention relates to a kind of method that detects mycotoxin in milk, relate in particular to a kind of method that adopts Liquid Chromatography-Tandem Mass Spectrometry method simultaneously to detect aflatoxin M 1, ochratoxin A, zearalenone and α-zearalenol in milk, belong to the detection field of mycotoxin in milk.
Background technology
Milk has become the necessity of people's life, and especially infant's milk is the best substitute of breast milk, but mycotoxin has become one of main quality safety risks and assumptions of milk, serious threat human health.Mycotoxin is in milk processing, be no matter pasteurize or the high temperature sterilization mycotoxin of all cannot degrading, therefore mycotoxin can completely remain in dairy products,, in milk, mycotoxin more and more gets more and more people's extensive concerning, particularly aflatoxin M
1, ochratoxin A, zearalenone and α-zearalenol come into one's own because of its pollution level and toxicity.
At present ，Nai industry developed country has actively monitored mycotoxin contamination situation in milk, but less in Chinese relevant report, this may with lack high-throughout detection technique and have certain relation.Traditional detection method respectively has its relative merits.Enzyme linked immunosorbent assay, as the most representative method for quick now, has been widely used in mycotoxin analyzing and testing, but due to false positive and can not accurate quantification etc. drawbacks limit its further apply.Therefore, the quantitative detecting method based on technology such as thin-layered chromatography, gas chromatography, high pressure liquid chromatographies has been set up, but these methods can only detect an a kind of or class mycotoxin, can not meet monitoring and the scientific research demand of mycotoxin in modern milk industry.In recent years, Ultra Performance Liquid Chromatography tandem mass spectrum (UPLC-MS/MS) because it is highly sensitive, high selectivity and the high flux common method that become that many mycotoxins analyze, be widely used in the detection of mycotoxin in food, feed, blood plasma, urine and Chinese herbal medicine.Along with mycotoxin contamination in people's growing interest milk, in milk, many mycotoxins of UPLC-MS/MS Simultaneous Detection becomes the focus of research, but the defects such as the method existing a little less than low, credible poor, the stability of sensitivity in various degree have much room for improvement.
Summary of the invention
The object of this invention is to provide the method that detects multiple mycotoxin in milk when a kind of, the method has the advantages such as the range of linearity is good, highly sensitive, credibility is good, stability is strong.
The object of the invention is to be achieved through the following technical solutions:
A method that simultaneously detects multiple mycotoxin in milk, the method comprises the following steps:
(1) extract the mycotoxin in milk, obtain mycotoxin crude extract; (2) by concentrated after mycotoxin crude extract purifying; (3) by chromatographic column on the mycotoxin after concentrated, use eluent gradient wash-out, collect eluate; (3) eluate of collection is carried out to qualitative and quantitative detection with mass spectrometer.
In milk, whether the extraction effect of mycotoxin successfully has decisive influence to detecting.While having scholar's mycotoxin in beverage, milk and wheat to detect, utilize formic acid or acetic acid acidified sample before extraction, this is mainly in order to improve the recovery of fumonisins, and to aflatoxin M
1, ochratoxin A, zearalenone and α-zearalenol the recovery have no significant effect.Applicable extraction agent can improve the extraction efficiency of mycotoxin in milk greatly, in sample, add methyl alcohol or acetonitrile both can also extract mycotoxin by protein precipitation, but different matrix and mycotoxin, there is difference in the extraction efficiency of methyl alcohol and acetonitrile, the present invention has compared the extraction effect that extracts solvent methanol and acetonitrile, result shows the extraction effect that be better than methyl alcohol of acetonitrile to the extraction efficiency highly significant of these four kinds of mycotoxins, therefore, the present invention preferably adopts acetonitrile as the mycotoxin extracting in solvent extraction milk.
Adopt ultrahigh pressure liquid phase chromatogram tandem mass spectrometry (UPLC-MS/MS) to detect the many mycotoxins ubiquity matrix effect in milk.Matrix effect affects signal intensity, quantitative limit and accuracy, so UPLC-MS/MS must investigate and avoid matrix effect, the emphasis that this UPLC-MS/MS detection method that has become mycotoxin is developed.And weaken or the optimum method of eliminating matrix effect impact is that sample is carried out to pre-service, pre-service can be removed chaff interference, enriched with trace sample, sample is more mated with the separation and detection technology of employing.
In trace analysis, purification and enriching step have huge effect to sensitivity.Analysis result shows, crude extract sample direct injected without purification and enrichment, Interference Peaks is more, dtr signal, because there is strong signal suppressing effect in matrix effect, so directly inject the testing requirement that extract can not meet relevant limit standard, need the mycotoxin in purification and enriched sample.The present invention has compared mycosep226 and the purification effect of HLB post to mycotoxin, result demonstration, and during the enrichment of Mycosep226 column purification, the dtr signal of OTA and α-ZOL, so that cannot accurate quantitative analysis OTA and α-ZOL.And the purification enrichment efficiency of HLB post is higher, effectively removed interfering material.Therefore, the present invention preferably adopts these four kinds of mycotoxins of aflatoxin M 1, ochratoxin A, zearalenone and α-zearalenol in HLB column purification enrich milk.
Determining that HLB post is in optimum purification enrichment milk after these four kinds of mycotoxin modes of aflatoxin M 1, ochratoxin A, zearalenone and α-zearalenol, the present invention crosses post pH value, crosses absorption and elution efficiency that the parameters such as post speed, washing volume and eluting solvent are optimized to improve mycotoxin comprising mycotoxin crude extract.
The present invention is according to 2
4+ 1 total divisor experimental design filters out Key Influential Factors.Experimental result discovery, when other parameter constant, crossing post crude extract pH and eluent is two most critical parameters that affect purifying and enrichment result.From response surface figure, can find out, mycotoxin crude extract pH value is lower, and in eluent, methanol content is higher, and signal is better.With pH (5.0 – 8.5), increase, signal suppressing effect strengthens, and the recovery reduces rapidly.Therefore, the present invention determines that it is 5.0 that mycotoxin crude extract is crossed post optimal pH, and eluent is preferably 100% methyl alcohol.Existing bibliographical information pH was lower than 6.0 o'clock, and the recovery is understood fast reducing; Crossing post crude extract pH is that 8.5 o'clock recovery are maximum, and matrix effect is minimum.The parameter that the present invention optimizes and the parameter differences of bibliographical information are larger.
After determining HLB post crude extract pH5.0 and 100% meoh eluate, the present invention has further investigated washing volume and has crossed the impact of post speed on purification enrichment effect, the present invention is by final discovery of multilevel factor design, while having served as post speed and be 1.5mL/min and washing volume 2mL, there is best concentration effect.
In the present invention, chromatographic resolution used adopts BEH C
18chromatographic column (2.1 * 50mm, 1.7 μ m), mobile phase is methyl alcohol and 0.1% ammoniacal liquor, gradient elution mycotoxin analyte;
Adopt positive and negative ion scan mode to carry out instrumental method and learn research, determine that the ion pair that abundance ratio is the highest is respectively quantitative and qualitative analysis ion for monitoring ion, adopts polyion reaction monitoring pattern to detect.
Sensitivity testing result shows, adopt the present invention to detect, the LOD of four kinds of mycotoxins and LOQ scope are respectively 0.001 – 0.005 μ g/kg and 0.003 – 0.015 μ g/kg, meet the requirement of limiting the quantity of that the various countries such as China, European Union and the U.S. are detected mycotoxin in milk completely.
In different mark-on levels and milk substrate, the monitoring method recovery of the present invention is 87.0%-109%, and relative standard deviation is 3.4%-9.9%, and this shows that detection method precision of the present invention is higher.The inventive method is in three varying levels and matrix, and relative standard deviation and reappearance are all lower than 10%, and this shows that detection method of the present invention possesses higher stability.
The present invention has set up a kind of aflatoxin M in milk that detects efficient, sensitive, stable time
1, ochratoxin A, zearalenone and α-zearalenol Ultra Performance Liquid Chromatography tandem mass spectrometry.Take 0.1% ammoniacal liquor and methyl alcohol as mobile phase carries out gradient elution, utilize BEH C
18chromatographic column just can separated these the four kinds of mycotoxins of success in 2min.Detection method of the present invention is verified respectively in fresh milk, liquid milk and milk powder, and linearity, sensitivity, the recovery, accuracy and reappearance all prove that the detection method range of linearity of the present invention is good, highly sensitive, credibility is good, stability is strong.
Accompanying drawing explanation
The selectivity ion flow graph of Fig. 1 0.025 μ g/kg mixed standard solution under multiple-reaction monitoring pattern.
The recovery of the different mycotoxin extraction agents of Fig. 2: methyl alcohol and acetonitrile milk sample mark-on concentration 0.025 μ g/kg.
The result of the milk sample direct injected of Fig. 3 mark-on 0.025 μ g/kg.
The milk sample of Fig. 4 mark-on 0.025 μ g/kg is crossed the purification effect of HLB post to mycotoxin.
The milk sample of Fig. 5 mark-on 0.025 μ g/kg is crossed the purification effect of mycosep226 post to mycotoxin.
Fig. 6 AFM
1cross post factorial effect by the Pareto diagram that subtracts order and arrange.
Fig. 7 AFM
1response surface figure; Washing volume 2mL, Solid-Phase Extraction flow velocity 0.5mL/min.Embodiment
By the following example, embodiments of the present invention will be more specifically described, it should be understood that described embodiment is only exemplary, does not form any restriction to scope of the present invention.It will be understood by those skilled in the art that lower without departing from the spirit and scope of the present invention and can the details of technical solution of the present invention and form be modified or be replaced, but these modifications or replacement all fall into protection scope of the present invention.1. experimental apparatus and reagent
1.1 main experimental apparatuss
The main experimental apparatus of table 1
1.2 standard items and main agents
Table 2 standard items and main agents
The preparation of 1.3 mycotoxin standard solution
Each mycotoxin standard reserving solution of 50mg/L: take each mycotoxin standard items of 5mg and be dissolved in respectively in 100ml methyl alcohol.The middle mixed standard solution of 500 μ g/L: draw each storing solution of 1mL in 100mL volumetric flask, mix by methanol constant volume.5 μ g/L hybrid standard storing solutions: in the middle of drawing 1mL, mixed standard solution is in 100mL volumetric flask, and methanol constant volume mixes.Working fluid methyl alcohol: water (50:50, V/V) dilution hybrid standard storing solution preparation.The freezing preservation at-20 ℃ of storing solution and intermediate standard mixed liquor, working fluid is 4 ℃ of preservations.
2 chromatographic conditions
Chromatographic resolution adopts ACQUITY
bEH C
18column chromatography post (2.1 * 50mm, 1.7 μ m) is separated under 400 μ L/min flow velocitys.Mobile phase is A(0.1% ammoniacal liquor) and B(methyl alcohol).Mobile phase A linear change gradient is in time: 0min, 90%; 2.0min, 10%; 2.1min, 90%; 4.0min, 90%.Chromatogram column temperature is 40 ℃, sampling volume 5 μ L.
Chromatographic column connects the mass spectrometer (TQS that is equipped with electric spray ion source
tM, Micromass, Manchester, UK), desolventizing gas and taper hole gas are nitrogen, and collision gas is argon gas.
3 sample pretreatments
Take 2.0g(and be accurate to 0.1mg) homogenized milk in 15mL centrifuge tube, add 8mL acetonitrile, vortex 2min(Vortex-Genie2, Scientific Industries, USA), ultrasonic 30min (KQ-500DE, China).Potpourri is centrifugal 10min under 10000r/min rotating speed.Get whole supernatants.
At 50 ℃, nitrogen blows and is concentrated into 2mL, and concentrate mixes with 4mL water, mixes, and with PBS solution, adjusts crude extract to pH5.0 ± 0.2.This crude extract is crossed the (activation: 3mL methyl alcohol → 3mL water), then wash HLB post with 2mL water and 4mL methyl alcohol respectively, collect meoh eluate, 50 ℃ of nitrogen blow near dry of HLB post with 0.5mL/min speed.Separately get the direct Mycosep226 of mistake of the supernatant column purification enrichment of decile, collect efflux.With 500 μ L methanol aqueous solutions (50:50, V/V), redissolve, cross 0.22 μ m filter membrane, treat machine.Employing external standard method is quantitative.
Experimental example 1 mass spectrum condition optimizing
By syringe pump by standard solution sample introduction, negative ions pattern (ESI
+and ESI-) lower full scan, selects ion that relative abundance of ions is the highest as parent ion.Although OTA can be at ESI
+under pattern, detect, ESI-pattern has been selected in this research, because have higher sensitivity and stability in this pattern.Because ionizing efficiency in corresponding modes is higher, ZON and α-ZOL selects negative ion mode, AFM
1select positive ion mode.In single injected sampling detects, negative ions pattern is changed automatically by both positive and negative polarity converter.The best parent ion of four kinds of mycotoxins and ionization pattern are in Table 3.
Table 3 mothers and sons ion and mass spectrum parameter
Note: mark *'s is quota ion.
Note：Asterisk(*)indicates?quantitative?ion.
Under many reaction patterns, optimize collision energy and taper hole voltage, find two daughter ions that abundance is the highest respectively as quantitative and qualitative ion.Because the structure of ZON and α-ZOL is similar with parent ion, can not be completely separated in chromatographic resolution.But ZON and α-ZOL two feature daughter ions under multiple-reaction monitoring pattern are respectively 316.8>174.8,316.8>130.8 and 318.8>275.0,318.8>160.0, can make a distinction completely, not interfere with each other (Fig. 1).Best daughter ion, collision energy and taper hole voltage are in Table 3.
The selection of experimental example 2 mycotoxin extraction agents
The mycotoxin extraction effect that extracts solvent methanol and acetonitrile has been compared in this experiment, and result shows to adopt acetonitrile as extracting the extraction efficiency higher (Fig. 2) of solvent to four kinds of mycotoxins (aflatoxin M 1, ochratoxin A, zearalenone and α-zearalenol).
Recovery R(%) be the ratio of mark-on sample concentration and concentration of standard solution, according to formula below, calculate:
R(%)=(mark-on sample signal-not mark-on sample signal) * 100/ standard solution signal
The optimization of experimental example 3 mycotoxin crude extract purification conditions
The selection of 1 purifying pillar
In trace analysis, purification and enriching step have huge effect to sensitivity.Result shows, mycotoxin crude extract sample direct injected without purification and enrichment, Interference Peaks is more, dtr signal, because there is strong signal suppressing effect (Fig. 3) in matrix effect, so directly inject the testing requirement that mycotoxin extract can not meet relevant limit standard, need the mycotoxin crude extract in purification and enriched sample.
This experiment is Oasis HLB post (60mg, 3cm relatively
3) and Mycosep226 post to the purification of mycotoxin crude extract and refining effect to select more suitable decontaminating column.Experimental result shows, the purification enrichment efficiency of HLB post is higher, has effectively removed interfering material (Fig. 4), and during Mycosep226 column purification enrichment mycotoxin crude extract, the dtr signal of OTA and α-ZOL, so that cannot accurate quantitative analysis OTA and α-ZOL (Fig. 5).Therefore, HLB post is applicable to the purification enrichment of these four kinds of mycotoxin extracts in milk.
The optimization of 2 purification conditions
After obtaining the preliminary recovery, this experiment was further optimized the parameter of HLB post to improve absorption and the elution efficiency of analyte, and the parameter of the described HLB of mistake post comprised post pH value, crosses post speed, washing volume and eluting solvent.
According to 2
4+ 1 total divisor experimental design filters out Key Influential Factors, test parameters is designed to: mycotoxin is crossed post crude extract pH value (SPE pH:5-8.5), cross post speed S(SPE speed:0.5-1.5mL/min), washing volume V(Wash volume:2-6mL), eluting solvent E(Eluating solution:0%-100% acetonitrile/methanol solution), in minimum and the highest parameter level, test respectively.Test is applied to the blank milk sample of mark-on 25ng/kg, evaluates the most critical influence factor (table 4) of purification effect according to corresponding peak area.
Fig. 6 be AFM1 cross post factorial effect by the Pareto diagram that subtracts order and arrange, the length of every is proportional to standardization effect, can estimate the impact of each factor pair result according to standard error.HLB post factorial effect significant difference in 95% fiducial interval excessively corresponding to pillar that surpasses horizontal line.This figure shows that, when other parameter constant, crossing post crude extract pH value and eluent is two most critical parameters that affect result.The response surface of the first order modeling of the data of two most critical factors and correspondence thereof as shown in Figure 7.From response surface figure, can find out, crude extract pH value is lower, and in eluent, methanol content is higher, and signal is better; With pH value (5.0 – 8.5), increase, signal suppressing effect strengthens, and the recovery reduces rapidly.Therefore, this experiment determined that post crude extract optimal pH was 5.0, and the best group of eluting solvent becomes 100% methyl alcohol.
Determining that HLB post crude extract optimal pH was 5.0 and after best eluting solvent is 100% methyl alcohol, this experiment is further screened optimum washing volume and is crossed post speed by Optimal Experimental; Adopt multilevel factor design, cross post speed three level: 0.5mL/min, 1.0mL/min, 1.5mL/min, washing volume three horizontal 2mL, 4mL and 6mL, utilize 0.025 μ g/kg mark-on sample to carry out random sequence test.Optimum results is in Table 5; While crossing post speed and be 1.5mL/min and washing volume 2mL, respective peaks area is maximum, than other, crosses post speed and washing volume, and peak area has notable difference.Test findings explanation, than other parameter, served as HLB post crude extract pH value and be 5.0, eluting solvent is 100% methyl alcohol, cross post speed is can obtain best technique effect to the purifying of mycotoxin, enrichment under 1.5mL/min and the washing volume condition that is 2mL.
Table 42
4+ 1 total divisor test design and respective area (N=6) thereof
The optimization (N=6) of table 5 rate of extraction and washing volume
The sensitivity of experimental example 4 detection methods of the present invention, precision and stability checking
1 sensitivity checking
Chromatographic resolution adopts ACQUITY
bEH C
18column chromatography post (2.1 * 50mm, 1.7 μ m) is separated under 400 μ L/min flow velocitys.Mobile phase is A(0.1% ammoniacal liquor) and B(methyl alcohol).Mobile phase A linear change gradient is in time: 0min, 90%; 2.0min, 10%; 2.1min, 90%; 4.0min, 90%.Chromatogram column temperature is 40 ℃, sampling volume 5 μ L.Chromatographic column connects the mass spectrometer (TQS that is equipped with electric spray ion source
tM, Micromass, Manchester, UK), desolventizing gas and taper hole gas are nitrogen, and collision gas is argon gas, and mass spectrum parameter is in Table 3.
Detection limit (LOD) and quantitative limit (LOQ) are during according to 0.025 μ g/kg concentration level, and signal to noise ratio (S/N ratio) is more than or equal to the snr computation of 3 times (LOD) and 10 times (LOQ), the results are shown in Table 6.The LOD of four kinds of mycotoxins and LOQ scope are respectively 0.001 – 0.005 μ g/kg and 0.003 – 0.015 μ g/kg, meet the limit the quantity of requirements of various countries to mycotoxin in milk such as China, European Union and the U.S. completely.
2 precision and stability confirmatory experiment
Chromatographic resolution adopts ACQUITY
bEH C
18column chromatography post (2.1 * 50mm, 1.7 μ m) is separated under 400 μ L/min flow velocitys.Mobile phase is A(0.1% ammoniacal liquor) and B(methyl alcohol).Mobile phase A linear change gradient is in time: 0min, 90%; 2.0min, 10%; 2.1min, 90%; 4.0min, 90%.Chromatogram column temperature is 40 ℃, sampling volume 5 μ L.Chromatographic column connects the mass spectrometer (TQS that is equipped with electric spray ion source
tM, Micromass, Manchester, UK), desolventizing gas and taper hole gas are nitrogen, and collision gas is argon gas, and mass spectrum parameter is in Table 3.
By mark-on 0.025,0.1 in three kinds of different milk substrates and 0.5 μ g/kg mycotoxin, in different mark-on levels and milk substrate, the recovery is 87.0%-109%, and relative standard deviation is 3.4%-9.9%(table 6), this shows that detection method precision of the present invention is higher.Detection method of the present invention in three varying levels and matrix, relative standard deviation (RSDr) and reappearance (RSD
r) all lower than 10%, this shows that detection method of the present invention possesses higher stability.
Table 6 detection method sensitivity of the present invention, relative standard deviation (RSDr) and reappearance (RSD
r) the result
1R ± SD represents the recovery ± standard deviation.
2 represent that the repeat number of each each concentration of sample is 6.
Claims (10)
1. detect a method for multiple mycotoxin in milk simultaneously, it is characterized in that, the method comprises the following steps: (1) extracts the mycotoxin in milk, obtains mycotoxin crude extract; (2) by mycotoxin crude extract purifying, concentrated; (3) by chromatographic column on the mycotoxin after concentrated, use eluent gradient wash-out, collect eluate; (3) eluate of collection is carried out to qualitative and quantitative detection with mass spectrometer.
2. it is characterized in that in accordance with the method for claim 1: use acetonitrile as the mycotoxin extracting in solvent extraction milk.
3. it is characterized in that in accordance with the method for claim 1: mycotoxin crude extract is crossed to solid-phase extraction column HLB post and carry out purifying, concentrated.
4. in accordance with the method for claim 3, it is characterized in that: mycotoxin crude extract pH value is adjusted to the rear upper solid-phase extraction column HLB post of 5.0 – 8.5, after washing, uses again eluent wash-out, collect eluent.
5. it is characterized in that in accordance with the method for claim 4: after mycotoxin crude extract pH value is adjusted to 5.0, go up again solid-phase extraction column HLB post.
6. it is characterized in that in accordance with the method for claim 5: described eluent is 100% methyl alcohol.
7. according to the method described in claim 3 or 4, it is characterized in that: mycotoxin crude extract is crossed to solid-phase extraction column HLB post according to the post speed of crossing of 0.5-1.5mL/min; Preferably, mycotoxin crude extract is crossed to solid-phase extraction column HLB post according to the post speed of crossing of 1.5mL/min.
8. in accordance with the method for claim 4, it is characterized in that: washing volume is 2-6mL, is preferably 2mL.
9. it is characterized in that in accordance with the method for claim 1: chromatographic resolution adopts BEH C
18chromatographic column, mobile phase is methyl alcohol and 0.1% ammoniacal liquor, gradient elution mycotoxin analyte.
10. it is characterized in that in accordance with the method for claim 1: described mycotoxin is aflatoxin M
1, ochratoxin A, zearalenone and α-zearalenol.
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