CN103940921B - A kind of liquid chromatography-tandem mass of Microcystin - Google Patents
A kind of liquid chromatography-tandem mass of Microcystin Download PDFInfo
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- CN103940921B CN103940921B CN201410011060.3A CN201410011060A CN103940921B CN 103940921 B CN103940921 B CN 103940921B CN 201410011060 A CN201410011060 A CN 201410011060A CN 103940921 B CN103940921 B CN 103940921B
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Abstract
The invention discloses a kind of liquid chromatography-tandem mass of Microcystin, comprise the following steps: (1) sample pre-treatments; (2) enrichment and purification; (3) LC-MS/MS detects.Method of the present invention is easy and simple to handle, qualitative, quantitative ability is comparatively strong, can be used as the reliable method detecting quality and assessment food safety risk.
Description
Technical field
The present invention relates to a kind of liquid chromatography-tandem mass of Microcystin, belong to instrument detection technique field.
Background technology
Algae health food is a kind of is principal ingredient primarily of algae one-celled plants powder, add a small amount of excipient or simple be the health food that raw material is made with algae powder.Edible algae main at present take spirulina as representative.Spirulina contains rich in protein, mineral matter (calcium, iron, zinc, phosphorus, magnesium and iodine etc.), vitamin (B1, B2, B12, C, E, K etc.) and beta carotene, gamma-linoleic acid, chlorophyll and the various amino acid useful to health.
Cultivating spirulina by manual method is the major way producing algae health food at present, and toxigenic microcystic aeruginosa, Microcystis viridis, Hui Shi Microcystis aeruginosa and quiver algae, anabena etc. all can belong to blue-green algae with spirulina.Theoretically, the growth of producing malicious blue-green algae can be controlled under strict condition of culture.But because the algae slurry of current domestic spirulina manufacturing enterprise is cultivated, gathered in the crops under open environment, in process of production, culturing pool and spirulina slurry are all very likely subject to the pollution of producing malicious blue-green algae, the malicious blue-green algae of product has been gathered in the crops while results spirulina slurry, can not remove completely due to the wash-out starched spirulina and produce malicious blue-green algae, and will pollution algae health food by producing Microcystin that malicious blue-green algae produces, thus serious harm be caused to human health.
Microcystin take liver as target organ, can impel the growth of tumour cell, is one of the strongest liver cancer promoter found up to now.The primary hepatic carcinoma incidence of disease of China some areas is high relevant with local resident's Long Term Contact Microcystin.Microcystin is class ring-type seven peptide compounds, and find that there is about 60 kinds of isomeride at present, kind common in China's eutrophication water is MC-LR and MC-RR, and wherein MC-RR is the most common, and MC-LR toxicity is maximum.
At present about the extraction of Microcystin and detection method also many, also the method for useful liquid chromatography-tandem mass spectrometry detects, but in detection method before, the pre-treatment step Toxic extraction of sample is incomplete, and has other impurity to disturb.Especially for algae sample, current existing pre-treating method is very limited for the removal of pigment, causes in Mass Spectrometer Method, occur comparatively significantly matrix effect, thus reduces detection sensitivity and accuracy.In addition, because Microcystin has polypeptide class formation, in its molecular structure, there is hydroxyl and amino isopolarity group, very easily generate [M+H]
+with [M+2H]
2+ion.
Set up the detection method of Microcystin in a kind of algae health food of fast and reliable, to the security ensureing algae health food, promote the technological innovation of manufacturing enterprise, improve domestic algae health food quality and class, ensure that the people's is healthy significant.
Summary of the invention
Technical matters to be solved by this invention is: the liquid chromatography-tandem mass providing a kind of easy and simple to handle, Microcystin that qualitative, quantitative ability is stronger
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A liquid chromatography-tandem mass for Microcystin, comprises the following steps:
(1) sample pre-treatments
Accurately take through the algae health products 1.0g pulverized, homogeneous is crossed, extract toxin with 10mL60% methanol aqueous solution, 200rpm shaking table concussion 60min, more ultrasonic process 30min, less than the 20 DEG C centrifugal 10min of 8000rpm, get supernatant;
Supernatant pH value to 4.0 is regulated with 2mol/L formic acid, standing 3h can be observed to occur a large amount of flocculent deposit in solution, less than the 20 DEG C centrifugal 10min of 8000rpm, obtain light yellow supernatant or water white transparency liquid, add weak aqua ammonia in solution and pH value is adjusted to 7.0, add ultrapure water subsequently and be accurately settled to 30mL, now obtain comparatively pure crude extract;
(2) enrichment and purification
First with 10mL methyl alcohol and 10mL ultrapure water activation C18 solid-phase extraction column, reactivation process flow control is at 1-2 drop/sec, get 15mL crude extract injection C18 solid-phase extraction column and carry out enrichment, flow control is at 1 drop/sec, then more respectively with 20% and 30% methanol aqueous solution each 10mL drip washing C18 solid-phase extraction column, to remove impurity, last with 5mL70% methanol aqueous solution (containing 0.05% formic acid) wash-out Microcystin, nitrogen blows near dry, be settled to 0.5mL with 50% acetonitrile solution, treat that liquid chromatography-tandem mass spectrometry (LC-MS/MS) detects;
Solid-phase extraction column can play good enrichment, clean-up effect, and the multiplex methanol-eluted fractions of bibliographical information, the recovery is better.In the present invention, when using pure methyl alcohol as eluent, find that the MC-LR recovery is better, and the recovery of MC-RR is extremely low.Again carry out recovery experiment add the formic acid of 0.05% concentration in methyl alcohol after, find that the recovery of MC-RR is significantly improved.
(3) LC-MS/MS detects
Liquid-phase condition Waters Atlantis dC18 chromatographic column (2.1mm × 150mm, 5 μm), column temperature 30 DEG C; Sample size 20 μ L; Mobile phase A is water (containing 0.05% formic acid, 5mmol/L ammonium formate), and B is 95% acetonitrile (containing 0.05% formic acid, 5mmol/L ammonium formate); Condition of gradient elution is in table 1:
Table 1 condition of gradient elution
Mass Spectrometry Conditions Ionization mode is electro-spray ionization holotype (ESI+); Multiple-reaction monitoring pattern (MRM); Collision atmospheric pressure (CAD): 8; Gas curtain atmospheric pressure (CUR): 15; Electron spray voltage (IS): 5000V; Ion source temperature (TEM): 600 DEG C.
Multiple-reaction monitoring ion pair and the mass spectrum correlation parameter of compound are as shown in table 2.
The multiple-reaction monitoring ion pair of table 2 compound and mass spectrum correlation parameter table
* be quota ion
When liquid chromatography-mass spectrography detects, due to the impact of matrix effect, cause the effect of target compound generation ion enhancer or inhibitor, adopt and do not obtain matrix blank solution preparation gradient hybrid standard product solution (0 containing target determinand, 0.1,0.2,0.5,1.0,2.0,5.0 μ g/kg).Condition measures according to the above analysis, with peak area to concentration linear regression.Redeterminate after exceeding the sample needs dilution of the range of linearity.
Table 3 typical curve and linear relationship
In sample, the retention time of Microcystin chromatographic peak is compared with the retention time of respective standard chromatographic peak, and variation range should within ± 2.5%.The signal to noise ratio (S/N ratio) at the reconstructed ion chromatogram peak of the qualitative ion of Microcystin should be more than or equal to 3(S/N >=3), the signal to noise ratio (S/N ratio) at the reconstructed ion chromatogram peak of quota ion should be more than or equal to 10(S/N >=10).The detect and track of MC-LR and MC-RR is all 0.1 μ g/kg.
Method of the present invention is easy and simple to handle, qualitative, quantitative ability is comparatively strong, can make the reliable method detecting algae health products quality and assessment food safety risk.This method removes pigment and floccus by regulating the means such as pH, greatly reduces the matrix effect of sample on mass spectrum; In mass spectrum mrm parameter, this method adopts MC-LR band doubly charged [M+2H]
2+498 molions, as parent ion, use band unicharged [M+H] than in other patented claims
+995 molions have higher detection sensitivity as mothers and sons.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is [M+H] of MC-LR
+for the fragment ion spectrogram that parent ion produces.
Fig. 2 is [M+2H] of MC-LR
2+for the fragment ion spectrogram that parent ion produces.
Fig. 3 is that MC-LR is with [M+H]
+ion, as in parent ion situation, determines two pairs of ion pairs, 995.8/135.1 and 995.8/509.5.
Fig. 4 is that MC-LR is with [M+2H]
2+ion, as in parent ion situation, determines two couples of ion pair 498.4/135.1 and 498.4/861.5.
Fig. 5 is the second order ms figure of MC-LR.
Fig. 6 is the second order ms figure of MC-RR.
Fig. 7 is MC-LR and MC-RR total ion current figure.
Embodiment
The selection of embodiment 1 parent ion
The many employings of existing MC-LR Mass Spectrometry detection method [M+H]
+ion is as parent ion, and the present invention compares [M+H] of MC-LR
+with [M+2H]
2+the response of secondary fragment ion, result shows [M+2H] of MC-LR
2+the secondary ion fragment that ion can meet with a response stronger as parent ion, the present invention finally selects [M+2H]
2+ion is as MC-LR parent ion, and its Mass Spectrometer Method sensitivity is apparently higher than existing detection method.[M+2H] of the two positive charge of parent ion select tape of MC-LR
2+ion.
Fig. 1 is [M+H] of MC-LR
+for the fragment ion spectrogram that parent ion produces, Fig. 2 is [M+2H] of MC-LR
2+for the fragment ion spectrogram that parent ion produces, after mass spectrometry parameters is optimized, again carry out secondary fragment scanning, find [M+2H] of MC-LR
2+the secondary ion fragment that ion can meet with a response stronger as parent ion.
Fig. 3 is that MC-LR is with [M+H]
+ion, as in parent ion situation, determines two pairs of ion pairs, 995.8/135.1 and 995.8/509.5; Fig. 4 is that MC-LR is with [M+2H]
2+ion, as in parent ion situation, determines two couples of ion pair 498.4/135.1 and 498.4/861.5.After MRM optimization and ion gun optimization are carried out respectively to above two class ion pairs, under respective optimal conditions, liquid chromatography-tandem mass spectrometry detection is carried out to the MC-LR standard items of same concentrations, by the comparative analysis to mass spectrogram, find that MC-LR is with [M+2H]
2+ion has stronger response as the two pairs of ion pairs determined in parent ion situation, and sensitivity is higher.
Embodiment 2 sample pre-treatments condition
Sample pre-treatments
The present invention is based on algae sample, and the matrix of algae sample is more complicated than the matrix of water sample, and pre-treatment is more complicated.
Accurately take through the algae health products 1.0g pulverized, homogeneous is crossed, extract toxin with 10mL60% methanol aqueous solution, 200rpm shaking table concussion 60min, more ultrasonic process 30min, less than the 20 DEG C centrifugal 10min of 8000rpm, get supernatant.
Supernatant pH value to 4.0 is regulated with 2mol/L formic acid, standing 3h can be observed to occur a large amount of flocculent deposit in solution, less than the 20 DEG C centrifugal 10min of 8000rpm, obtain light yellow supernatant or water white transparency liquid, add weak aqua ammonia in solution and pH value is adjusted to 7.0, add ultrapure water subsequently and be accurately settled to 30mL, now obtain comparatively pure crude extract.
Enrichment and purification
First with 10mL methyl alcohol and 10mL ultrapure water activation C18 solid-phase extraction column, reactivation process flow control is at 1-2 drop/sec, get 15mL crude extract injection C18 solid-phase extraction column and carry out enrichment, flow control is at 1 drop/sec, then more respectively with 20% and 30% methanol aqueous solution each 10mL drip washing C18 solid-phase extraction column, to remove impurity, last with 5mL70% methanol aqueous solution (containing 0.05% formic acid) wash-out Microcystin, nitrogen blows near dry, be settled to 0.5mL with 50% acetonitrile solution, treat that liquid chromatography-tandem mass spectrometry (LC-MS/MS) detects.
This method removes pigment and floccus by regulating the means such as pH, greatly reduces the matrix effect of sample on mass spectrum.
The determination of embodiment 3LC-MS/MS testing conditions
As illustrated in figs. 5-7, according to relevant regulations in No. 657/2002/EECth, CAC and EU resolution, select two pairs of ions to carry out MRM monitoring can meet, the simultaneously selection of daughter ion mainly considers that wherein parent ion and daughter ion are chosen according to the mass spectrogram of often kind of compound and architectural characteristic, and it is less to analyze mesostroma interference at actual sample.Determine the molion of various material, then respectively with the molion of various compound for parent ion, full scan is carried out to its daughter ion and chooses that abundance is comparatively strong, two pairs of less daughter ions of interference are qualitative ion, as shown in Figure 1-2, the ion flow graph of the two pairs of ions finally determined as shown in Figure 3 for MC-LR and MC-RR second order ms figure.Finally optimize various mass spectrometry parameters with multiple-reaction monitoring (MRM) positive ion mode.
LC-MS/MS testing conditions:
Liquid-phase condition Waters Atlantis dC18 chromatographic column (2.1mm × 150mm, 5 μm), column temperature 30 DEG C; Sample size 20 μ L; Mobile phase A is water (containing 0.05% formic acid, 5mmol/L ammonium formate), and B is 95% acetonitrile (containing 0.05% formic acid, 5mmol/L ammonium formate); Gradient elution;
Mass Spectrometry Conditions Ionization mode is electro-spray ionization holotype (ESI+); Multiple-reaction monitoring pattern (MRM); Collision atmospheric pressure (CAD): 8; Gas curtain atmospheric pressure (CUR): 15; Electron spray voltage (IS): 5000V; Ion source temperature (TEM): 600 DEG C.
Embodiment 4 recovery is tested
(1) sample adds:
Get the interpolation that blank algae health products sample carries out three levels, the Pitch-based sphere of MC-LR and MC-RR toxin is all 0.1 μ g/kg, 1.0 μ g/kg, 5.0 μ g/kg, each level do 6 parallel.
(2) sample pre-treatments
Accurately take the algae health products 1.0g having added toxin, extract toxin with 10mL60% methanol aqueous solution, 200rpm shaking table concussion 60min, more ultrasonic process 30min, less than the 20 DEG C centrifugal 10min of 8000rpm, get supernatant.
Regulate supernatant pH value to 4.0 with 2mol/L formic acid, leave standstill 3h, less than the 20 DEG C centrifugal 10min of 8000rpm, add weak aqua ammonia and pH value are adjusted to 7.0, add ultrapure water subsequently and be accurately settled to 30mL.
(3) enrichment and purification
First with 10mL methyl alcohol and 10mL ultrapure water activation C18 solid-phase extraction column, reactivation process flow control is at 1-2 drop/sec, get 15mL crude extract injection C18 solid-phase extraction column and carry out enrichment, flow control is at 1 drop/sec, then more respectively with 20% and 30% methanol aqueous solution each 10mL drip washing C18 solid-phase extraction column, last with 5mL70% methanol aqueous solution (containing 0.05% formic acid) wash-out Microcystin, nitrogen blows near dry, be settled to 0.5mL with 50% acetonitrile solution, treat that liquid chromatography-tandem mass spectrometry (LC-MS/MS) detects.
(4) LC-MS/MS detects
Liquid-phase condition Waters Atlantis dC18 chromatographic column (2.1mm × 150mm, 5 μm), column temperature 30 DEG C; Sample size 20 μ L; Mobile phase A is water (containing 0.05% formic acid, 5mmol/L ammonium formate), and B is 95% acetonitrile (containing 0.05% formic acid, 5mmol/L ammonium formate); Condition of gradient elution is in table 1:
Table 1 condition of gradient elution
Mass Spectrometry Conditions Ionization mode is electro-spray ionization holotype (ESI+); Multiple-reaction monitoring pattern (MRM); Collision atmospheric pressure (CAD): 8; Gas curtain atmospheric pressure (CUR): 15; Electron spray voltage (IS): 5000V; Ion source temperature (TEM): 600 DEG C.
Multiple-reaction monitoring ion pair and the mass spectrum correlation parameter of compound are as shown in table 2.
The multiple-reaction monitoring ion pair of table 2 compound and mass spectrum correlation parameter table
* be quota ion
Experimental result shows, and the recovery of this experimental technique is 91.4% ~ 99.6%, and the coefficient of variation is 1.2% ~ 6.3%.
Embodiment 5
At 2 kinds of health-care spinulina foods that stochastic buying 2 domestic enterprises in supermarket produce, one is tablet, and one is capsule.Tablet samples adopts homogenizer to carry out pulverizing homogeneous, and capsule product removes outer capsule, gets internal helicoid algae powder.This method is utilized to carry out the detection of Microcystin to 2 kinds of products.
(1) sample pre-treatments
Accurately take Powdered spirulina sample 1.0g, extract toxin with 10mL60% methanol aqueous solution, 200rpm shaking table concussion 60min, more ultrasonic process 30min, less than the 20 DEG C centrifugal 10min of 8000rpm, get supernatant.
Regulate supernatant pH value to 4.0 with 2mol/L formic acid, leave standstill 3h, less than the 20 DEG C centrifugal 10min of 8000rpm, add weak aqua ammonia and pH value are adjusted to 7.0, add ultrapure water subsequently and be accurately settled to 30mL.
Get blank spirulina powder and carry out interpolation recovery experiment, MC-LR, MC-RR toxin adds water product and is all 1.0 μ g/kg, and pre-treating method is identical with sample method.
(2) enrichment and purification
First with 10mL methyl alcohol and 10mL ultrapure water activation C18 solid-phase extraction column, reactivation process flow control is at 1-2 drop/sec, get 15mL crude extract injection C18 solid-phase extraction column and carry out enrichment, flow control is at 1 drop/sec, then more respectively with 20% and 30% methanol aqueous solution each 10mL drip washing C18 solid-phase extraction column, last with 5mL70% methanol aqueous solution (containing 0.05% formic acid) wash-out Microcystin, nitrogen blows near dry, be settled to 0.5mL with 50% acetonitrile solution, treat that liquid chromatography-tandem mass spectrometry (LC-MS/MS) detects.
(3) LC-MS/MS detects
Liquid-phase condition Waters Atlantis dC18 chromatographic column (2.1mm × 150mm, 5 μm), column temperature 30 DEG C; Sample size 20 μ L; Mobile phase A is water (containing 0.05% formic acid, 5mmol/L ammonium formate), and B is 95% acetonitrile (containing 0.05% formic acid, 5mmol/L ammonium formate); Condition of gradient elution sees the following form:
Table condition of gradient elution
Mass Spectrometry Conditions Ionization mode is electro-spray ionization holotype (ESI+); Multiple-reaction monitoring pattern (MRM); Collision atmospheric pressure (CAD): 8; Gas curtain atmospheric pressure (CUR): 15; Electron spray voltage (IS): 5000V; Ion source temperature (TEM): 600 DEG C.
Multiple-reaction monitoring ion pair and the mass spectrum correlation parameter of compound are as shown in the table.
The multiple-reaction monitoring ion pair of table compound and mass spectrum correlation parameter table
* be quota ion
(4) testing result
The recovery of method is: MC-LR is 92.5%, MC-RR is 97.1%.
After the testing result of sample is corrected by the recovery, obtain final testing result: in tablet health-care spinulina food, MC-LR content is 0.52 μ g/kg, MC-RR content is 12.6 μ g/kg, and in capsule health-care spinulina food, MC-LR content is 0.23 μ g/kg, and MC-RR content is 27.1 μ g/kg.
Claims (4)
1. a liquid chromatography-tandem mass for Microcystin, is characterized in that, comprises the following steps:
(1) sample pre-treatments
Accurately take through algae health products 1.0 g pulverized, homogeneous is crossed, extract toxin with 10 mL 60 % methanol aqueous solutions, 200 rpm shaking tables shake 60 min, more ultrasonic process 30 min, and less than 20 DEG C centrifugal 10 min of 8000 rpm, get supernatant;
Regulate supernatant pH value to 4.0, leave standstill 3 h to can be observed in solution, to occur a large amount of flocculent deposit, less than 20 DEG C centrifugal 10 min of 8000 rpm, obtain light yellow supernatant or water white transparency liquid, add weak aqua ammonia in solution and pH value is adjusted to 6.8-7.2, add ultrapure water subsequently and be accurately settled to 30 mL, now obtain comparatively pure crude extract;
(2) enrichment and purification
First with 10 mL methyl alcohol and 10 mL ultrapure waters activation C18 solid-phase extraction column, reactivation process flow control is at 1-2 drop/sec, get 15 mL crude extracts injection C18 solid-phase extraction columns and carry out enrichment, flow control is at 1 drop/sec, then more respectively with 20 % and each 10 mL drip washing C18 solid-phase extraction columns of 30 % methanol aqueous solutions, to remove impurity, last with 5 mL 70 % methanol aqueous solution wash-out Microcystins, 70 % methanol aqueous solutions wash the formic acid containing 0.05 %, nitrogen blows near dry, 0.5 mL is settled to 50 % acetonitrile solutions, treat that liquid chromatography-tandem mass spectrometry (LC-MS/MS) detects,
(3) LC-MS/MS detects
Liquid-phase condition Waters Atlantis dC18 chromatographic column, 2.1 mm × 150 mm, 5 μm, column temperature 30 DEG C; Sample size 20 μ L; Mobile phase A is water, containing 0.05% formic acid, and 5 mmol/L ammonium formates, B is 95 % acetonitriles, containing 0.05% formic acid, 5 mmol/L ammonium formates; Gradient elution;
Mass Spectrometry Conditions Ionization mode is electro-spray ionization holotype (ESI+); Multiple-reaction monitoring pattern (MRM); Collision atmospheric pressure (CAD): 8; Gas curtain atmospheric pressure (CUR): 15; Electron spray voltage (IS): 5000 V; Ion source temperature (TEM): 600 DEG C.
2. the liquid chromatography-tandem mass of Microcystin according to claim 1, is characterized in that, adds weak aqua ammonia pH value is adjusted to 7.0 in step (1) solution.
3. the liquid chromatography-tandem mass of Microcystin according to claim 1, is characterized in that, regulates supernatant pH value to 4.0 in step (1) with 2 mol/L formic acid.
4. the liquid chromatography-tandem mass of Microcystin according to claim 1, is characterized in that, with [M+2H] in step (3)
2+ion is as parent ion.
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| CN106279359A (en) * | 2016-08-11 | 2017-01-04 | 中国水稻研究所 | A kind of method preparing five kinds of ustilaginoidea virens toxin |
| CN107389825B (en) * | 2017-08-11 | 2020-07-07 | 浙江省食品药品检验研究院 | Method for determining algae toxins in water based on full-automatic online solid-phase extraction-ultra-high performance liquid chromatography-linear ion trap tandem mass spectrometry |
| CN113447581A (en) * | 2021-06-23 | 2021-09-28 | 中国食品药品检定研究院 | Method for detecting microcystin in algae food and raw materials for producing algae food |
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