CN105974018B - Method based on Multifunctional cleanup column-high performance liquid chromatography detection sitotoxismus flavine - Google Patents
Method based on Multifunctional cleanup column-high performance liquid chromatography detection sitotoxismus flavine Download PDFInfo
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- CN105974018B CN105974018B CN201610302120.6A CN201610302120A CN105974018B CN 105974018 B CN105974018 B CN 105974018B CN 201610302120 A CN201610302120 A CN 201610302120A CN 105974018 B CN105974018 B CN 105974018B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
Abstract
The present invention develops a kind of based on the multifunctional purifying column purification high performance liquid chromatography detection remaining method of sitotoxismus flavine.Food samples, by multifunctional purifying column purification, take scavenging solution 5.0mL to pass through N using 80mL acetonitrile+20mL water dissolutions, ultrasonic extraction2Drying, 1.0mL water constant volumes obtain machine liquid.When the invention realizes toxoflavin residual in detection sample, good purification quantifies accurately, eliminates influence of the solvent effect to toxoflavin chromatographic behavior.Mobile phase enhances reservation of the toxoflavin in reverse-phase chromatographic column with first alcohol and water gradient elution, and toxoflavin and other chaff interferents efficiently separate when realizing sample analysis, so as to achieve the purpose that accurate quantitative analysis.The invention can effectively remove the interference such as lipid, pigment and the protein in sample during sample purification, and clean-up effect is good, and quantitative analysis accuracy is good, high sensitivity, result favorable reproducibility, the toxoflavin residue detection suitable for numerous food.
Description
Technical field
The present invention relates to technical field of food safety more particularly to one kind to be based on Multifunctional cleanup column-high performance liquid chromatography
The method that method detects sitotoxismus flavine.
Background technology
Toxoflavin (toxoflavin) (CAS:Structural formula 84-82-2) is：
It is a kind of bacteriotoxin for causing food poisoning generated by Pseudomonas cocovenenans subsp farinofermantans.Common
Contaminated food products is mainly cereal fermented product, potato product and white fungus etc..Pseudomonas cocovenenans subsp farinofermantans food poisoning is more
Summer and autumn (main 5~August) overcast and rainy moist season is happened at, causes Pseudomonas cocovenenans due to food storage is improper and quickly breeds
Growth, the edible food by its pollution can cause poisoning, show as the diseases such as epigastric discomfort, Nausea and vomiting, dizziness and general weakness
Shape seriously may occur in which hepatosplenomegaly, subcutaneous hemorrhage, blood urine and shock etc., and the death rate is up to 40~100%.For many years about coconut palm
The report that malicious pseudomonad poisoning causes a lot of death is more, poisons by food caused by being found in nineteen fifty-three fermented flour earliest, after
Find there is food poisoning caused by Pseudomonas cocovenenans throughout the country successively.Guangnan " hanging slurry cake " coconut palm poison is false within 2014
Monad food poisoning just causes more people's death, and the Liaoyang of the Spring Festival in 2015 occurs Suantangzi poisoning, doubts because of rice yeast-like fungi
Acid and 4 people of toxoflavin poisoning induced are dead.
At present, about the detection method of toxoflavin, corresponding national standard or professional standard be there is no.Recent domestic closes
In the research of sitotoxismus flavine detection technique, also it is rarely reported.
Invention content
It is an object of the invention to be directed to the deficiency of existing detection technique, a kind of side for detecting sitotoxismus flavine is provided
Method.The present invention can detect cereal fermented product and (including fermented maize face, glutinous rice flour, hang slurry cake, cornstarch, vinegar bean jelly
Deng), the sitotoxismuses flavine such as white fungus and its product, potato product (such as potato vermicelli, sweet potato starch, sweet potato starch) it is residual
It stays.
The purpose of the present invention is achieved through the following technical solutions：One kind is based on Multifunctional cleanup column-efficient liquid phase
The method that chromatography detects sitotoxismus flavine, includes the following steps：
(1) sample extraction condition：After weighing 20~25g samples and 100mL extracting solutions (+20 water of 80 acetonitrile) mixing, ultrasound
30min is extracted, takes extracting solution, 5000r/min centrifugation 5min obtain supernatant.
(2) sample purification：The supernatant 10mL that step 1 is taken to obtain crosses Multifunctional cleanup column and is purified；After purification, take
Scavenging solution 5.0mL is dried up with N2, then with 1.0mL pure water constant volumes, and machine liquid is obtained after the dissolving that is vortexed.
(3) chromatographiccondition：The upper machine liquid that step 2 is obtained passes through quarternary low pressure or binary height equipped with DAD detectors
Pressure liquid chromatography system carries out chromatography, chromatographic column：ODS reverse-phase chromatographic columns (such as ODS C18), 250*4.6mm, 5 μm；Stream
Dynamic phase is：Methanol and water gradient elution, volume ratio for (0~10min, 7：93；10.1~20min, 98：2；20.1~27min,
7:93)；Sample size：20μL；Flow velocity：1.0mL/min；Column temperature：30℃.Detection wavelength：258nm.
(4) qualitative analysis of samples：The retention time and characteristic light spectrogram obtained according to step 3 chromatography, with standard specimen
Retention time and characteristic light spectrogram are compared, if the two is coincide, show containing toxoflavin.
(5) sample amounts are analyzed：Standard specimen is prepared：Toxoflavin is dissolved in water, it is respectively 0.05,0.1,0.2 to be configured to concentration,
0.4,1.0,2.0,5.0,10.0 μ g/mL series standards use liquid.Peak area is responded as ordinate using standard specimen, standard specimen is a concentration of
Abscissa (μ g/mL) draws calibration curve.According to the response peak area that step 3 chromatography obtains, using external standard method, to sample
Toxoflavin content carries out quantitative analysis in product.
Further, the concentration is respectively 0.05,0.1,0.2,0.4,1.0,2.0,5.0,10.0 μ g/mL series standards
It is as follows using the preparation method of liquid：0.0100g toxoflavins standard items are weighed in 10mL volumetric flasks, after methanol dissolving, are settled to
Scale is configured to 1.0mg/mL standard mother liquors.It is positioned in -18 DEG C of refrigerators, can preserve 3 months.Before use, take out holding chamber
Wen Hou, taking 200 μ L standards mother liquors, water is settled to scale, shakes up in 10mL volumetric flasks, is configured to the centre of 20.0 μ g/ml and makes
Use liquid.It takes respectively among 25 μ L, 50 μ L, 100 μ L, 200 μ L, 500 μ L, 1.0mL using liquid and 50 μ L, 100 μ L standard mother liquors
In 10mL volumetric flasks, water is settled to scale.
Further, the detection food (including fermented maize face, glutinous rice flour, hangs slurry cake, corn for cereal fermented product
Starch, vinegar bean jelly etc.), white fungus and its product, potato product (such as potato vermicelli, sweet potato starch, sweet potato starch) etc..
The invention has the advantages that it disclosure satisfy that detection will using a kind of detection efficiency height, clean-up effect and the rate of recovery
The solid phase extraction techniques asked by optimizing extraction conditions in pretreatment process (Extraction solvent and extraction time), select 80% second
Extracts reagent of the nitrile water (volume ratio) as toxoflavin in sample, ultrasonic extraction 30min realize the abundant of object toxoflavin
Extraction, reduces highly polar impurity component (pigment, fat and other interfering components etc.) and toxoflavin is done in chromatography
It disturbs.In addition, the present invention improves chromatographic condition, establishing effectively realizes using first alcohol and water gradient elution as mobile phase
The separation of target analytes toxoflavin and other interfering components during sample detection.The present invention is in actually detected, Solid Free extraction
Pillar activates and elution step, and detection efficiency is high, good purification, high sensitivity, application easy to spread, and suitable for a variety of foods
Toxoflavin retention analysis in product sample.
Description of the drawings
Fig. 1 is calibration curve (Y=142529.9x+12501.41, the R of standard specimen2=0.9998, R=0.9999)；
Fig. 2 is toxoflavin standard specimen chromatogram (retention time 10.785min)；
Fig. 3 is toxoflavin spectrogram；
Fig. 4 is the chromatogram of 80% methanol water dissolution toxoflavin；
Fig. 5 is the chromatogram that 90% methanol dissolves toxoflavin；
Fig. 6 is the chromatogram that 100% methanol dissolves toxoflavin；
Fig. 7 is fermented maize face sample chromatogram figure (feminine gender)；
Fig. 8 is fermented maize face sample spectrum diagram (corresponding retention time is 10.331min)；
The chromatogram (crossing column purification) that Fig. 9 is the methanol-water of volume fraction 70% when being Extraction solvent；
The chromatogram (crossing column purification) that Figure 10 is the ethanol water of volume fraction 70% when being Extraction solvent；
The chromatogram (crossing column purification) that Figure 11 is the acetonitrile water of volume fraction 70% when being Extraction solvent；
The chromatogram (but column purification) that Figure 12 is the acetonitrile water of volume fraction 80% when being Extraction solvent；
The chromatogram (crossing column purification) that Figure 13 is the acetonitrile water of volume fraction 80% when being Extraction solvent；
Figure 14 is the fermented maize complexion spectrogram that pitch-based sphere is 0.1mg/kg；
Figure 15 is the fermented maize complexion spectrogram that pitch-based sphere is 0.5mg/kg；
Figure 16 is the fermented maize complexion spectrogram that pitch-based sphere is 1.5mg/kg；
Specific embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1：Draw the calibration curve of response peak area-toxoflavin concentration.
(1) 0.0100g toxoflavins standard items are weighed in 10mL volumetric flasks, after methanol dissolving, scale is settled to, is configured to
1.0mg/mL standard mother liquors.It is positioned in -18 DEG C of refrigerators, can preserve 3 months.Before use, after taking out placement room temperature, 200 μ are taken
For L standards mother liquor in 10mL volumetric flasks, water is settled to scale, shakes up, and the centre for being configured to 20.0 μ g/ml uses liquid.It takes respectively
Using liquid and 50 μ L among 25 μ L, 50 μ L, 100 μ L, 200 μ L, 500 μ L, 1.0mL, 100 μ L standards mother liquors are in 10mL capacity
In, water is settled to scale.It is respectively 0.05,0.1,0.2,0.4,1.0,2.0,5.0,10.0 μ g/ml series marks to be configured to concentration
Standard uses liquid.
Meanwhile constant volume solution is optimized in the part, and it is right to compare different volumes score methanol-water (0~100%)
The influence of toxoflavin chromatographic behavior.It was found that the methanol aqueous solution (Fig. 4) of volume fraction 80%, 90% methanol aqueous solution (Fig. 5),
100% methanol (Fig. 6) is more significant to the adverse effect of toxoflavin chromatographic behavior in chromatography.Methanol volume in constant volume solution
During more than 80% score, in chromatography, toxoflavin chromatographic peak profile is into two bifurcated peaks.From structural analysis, toxoflavin is
Middle polarity compound, solvent effect is strong, using highly polar water as constant volume solvent can eliminate the solvent effect of toxoflavin so as to
Form sharp symmetrical chromatographic peak.Due to (pH under toxoflavin acid condition<When 2) it is unstable, this study portion is in mobile phase item
Do not use organic acid in part and constant volume solution.
(2) peak area is responded as ordinate using standard specimen, a concentration of abscissa of standard specimen (μ g/mL) draws calibration curve.Such as
Shown in Fig. 1.Retention time is as shown in Fig. 2, characteristic light spectrogram is as shown in Figure 3.
Embodiment 2：The present embodiment detects the toxoflavin in fermented maize face by the following method：
(1) sample extraction condition：After weighing 20~25g samples and 100mL extracting solutions (+20 water of 80 acetonitrile) mixing, ultrasound
30min is extracted, takes extracting solution, 5000r/min centrifugation 5min obtain supernatant.
(2) sample purification：The supernatant 10mL that step 1 is taken to obtain crosses Multifunctional cleanup column and is purified；After purification, take
Scavenging solution 5.0mL N2Drying, then with 1.0mL pure water constant volumes, machine liquid is obtained after the dissolving that is vortexed.
(3) chromatographiccondition：The upper machine liquid that step 2 is obtained passes through quarternary low pressure or binary height equipped with DAD detectors
Pressure liquid chromatography system carries out chromatography, chromatographic column：ODS reverse-phase chromatographic columns (such as ODS C18), 250*4.6mm, 5 μm；Stream
Dynamic phase is：Methanol and water gradient elution ((0~10min, 7：93；10.1~20min, 98：2；20.1~27min, 7:93)；Into
Sample amount：20μL；Flow velocity：1.0mL/min；Column temperature：30℃.Detection wavelength：258nm.
The semiconvection is moved phase condition and is optimized, and compares when a certain proportion of acetic acid is added in mobile phase to malicious yellow
The influence that plain color spectrum retains.Acetic acid belongs to highly polar organic acid, and adding in acetic acid in mobile phase is equivalent to the polarity for enhancing mobile phase,
So as to reduce retention time of the toxoflavin in reverse-phase chromatographic column, it is unfavorable for toxoflavin and interfering compound during sample analysis
Separation.This part uses first alcohol and water gradient elution mobile phase, is conducive to middle polarity compound toxoflavin and other interferenceization
Efficiently separating for object is closed, so as to achieve the purpose that accurate quantitative analysis.
(4) qualitative analysis of samples：According to step 3 chromatography, obtained retention time as described in Figure 7, characteristic light spectrogram
As shown in figure 8, found after being compared with the retention time (Fig. 2) and characteristic light spectrogram (Fig. 3) of the standard specimen of the acquisition of embodiment 1,
The characteristic light spectrogram (Fig. 3) of the fermentation rice and flour characteristic light spectrogram (Fig. 8) detected in the present embodiment and standard specimen is misfitted, and shows to be free of
There is toxoflavin.
Embodiment 3：The present embodiment in example 2, while prepares the positive by adding in toxoflavin standard items in maize flour
Fermented maize face sample is a, and is detected with same procedure.Wherein in step 1, extracts reagent is tried in this part
It tests, has selected methanol-water (Fig. 9), 70% ethanol water (Figure 10) and the 70% acetonitrile water (Figure 11) of equal volume score 70%, examined
Examine influence of the different organic solvents to extraction efficiency and the influence to multifunctional purifying column purification, recovering effect.Wherein, difference has
Influence of the solvent to extraction efficiency by positive corn fermentation face it is extracted after, take respectively 3.0ml extracting solutions direct N2 dryings,
Machine is analyzed in water dissolution, and the rate of recovery brought so as to exclude column purification influences.In addition, extracting section liquid is respectively taken respectively by more
Function purifies column purification, further investigates purification, the rate of recovery of different solvents.Concrete outcome is shown in Table 1.By attached drawing 9,
10,11 and table 1 as can be seen that equal volume score under, the extraction efficiency of acetonitrile and the purification of Multifunctional cleanup column, recovering effect
Better than methanol and ethyl alcohol.
The toxoflavin content (being represented with peak area) that 1 different solvents of table measure when extracting
| Organic solvent volume score | 70% methanol-water | 70% ethanol water | 70% acetonitrile water |
| Peak area (but column) | 82047 | 73708 | 97234 |
| Peak area (crosses column) | 42664 | 31957 | 60285 |
| Rate of recovery % | 52.0 | 43.4 | 62.0 |
Embodiment 4：The present embodiment in embodiment 3, while has studied step 1 in different volumes score acetonitrile water to extraction
The influence of efficiency.Fermented maize face has selected 10%~100% acetonitrile water, passes through ultrasonic extraction 30min, after centrifugation, difference
3.0mL extracting solutions are taken through N2Drying, 1.0ml water constant volume post analysis.The results are shown in Table 2.It was found that Extraction solvent acetonitrile volume point
Extraction efficiency highest (Figure 12) when number is 80%, and during through multifunctional purifying column purification, clean-up effect and the best (figure of the rate of recovery
, therefore Extraction solvent of the 80% acetonitrile water of this experimental selection as this part 13).
The toxoflavin content (being represented with peak area) that the different acetonitrile volume fractions of table 2 measure when extracting
Remarks：ND expressions do not detect
Embodiment 5：The present embodiment in embodiment 3, while has studied step 1 the ultrasonic extraction time to extraction efficiency
It influences.Using positive fermented maize face, using 80% acetonitrile water as Extraction solvent, ultrasonic time 0min, 5min have been selected,
10min, 20min, 30min, 40min by being combined with step 2 multifunctional purifying column purification, analyze the ultrasonic extraction time
Influence.It was found that effective extraction of target analytes toxoflavin can be realized during ultrasonic extraction 30min.Concrete outcome is shown in Table 3 institutes
Show.
Influence (with peak area represented) of the 3 ultrasonic extraction time of table to toxoflavin extraction efficiency
Embodiment 6：The present embodiment is separately added into 0.05mg/kg (Figure 14), 0.5mg/ in the fermented maize face of embodiment 2
Kg (Figure 15) and 1.5mg/kg (Figure 16) toxoflavin, and be detected with same procedure, each concentration of adding uses parallel determination 6
Part sample investigates the detection limit of the different recovery of standard addition for adding concentration, precision and this method.
According to the response peak area that chromatography obtains, using external standard method, with reference to Fig. 1, to toxoflavin content in sample into
Row quantitative analysis, measures that the results are shown in Table 4.This method rate of recovery is more than 78%, and precision is less than 3%.Through repeatedly weighing
Repetition measurement finds that this method accuracy is high, and stability is good surely, is limited to detection of the signal-to-noise ratio (S/N) not less than 3 calculating this method
0.1mg/kg。
The different pitch-based sphere rate of recovery and precision measure (n=6) in 4 fermented maize face of table
| Pitch-based sphere/mg/kg | Measure content/mg/kg | The rate of recovery/% | RSD/% |
| 0.1 | 0.078 | 78 | 3.5 |
| 0.5 | 0.44 | 88 | 1.9 |
| 1.5 | 1.22 | 81 | 2.3 |
Claims (3)
- A kind of 1. method based on Multifunctional cleanup column-high performance liquid chromatography detection sitotoxismus flavine, which is characterized in that Include the following steps：（1）Sample extraction condition：20 ~ 25 g samples are weighed, is mixed in and is extracted by 100 mL that 80mL acetonitriles and 20mL water form In liquid, 30 min of ultrasonic extraction takes extracting solution, and 5000 r/min centrifuge 5 min, obtain supernatant；（2）Sample purification：Take step（1）10 mL of supernatant of acquisition crosses Multifunctional cleanup column MycoSep226 AflaZon+ It is purified；After purification, 5.0 mL of scavenging solution is taken, uses N2Drying, then with 1.0 mL pure water constant volumes, machine is obtained after the dissolving that is vortexed Liquid；（3）Chromatographiccondition：By step（2）The upper machine liquid obtained is passed through equipped with the quarternary low pressure of DAD detectors or binary high pressure Liquid chromatographic system carries out chromatography, chromatographic column：ODS reverse-phase chromatographic columns, 250*4.6 mm, 5 μm；Mobile phase is：Methanol With water gradient elution, 0 ~ 10 min, methanol is 7 with water volume ratio：93；10 ~ 20 min, methanol are 98 with water volume ratio：2；20 ~ 27 min, methanol are 7 with water volume ratio:93;Sample size：20 µL；Flow velocity：1.0 mL/min；Column temperature：30℃；Detect wave It is long：258 nm；（4）Qualitative analysis of samples：According to step（3）The retention time and characteristic light spectrogram that chromatography obtains, the guarantor with standard specimen Time and characteristic light spectrogram is stayed to be compared, if the two is coincide, is shown containing toxoflavin；（5）Sample amounts are analyzed：Standard specimen is prepared：Toxoflavin is dissolved in water, it is respectively 0.05,0.1,0.2 to be configured to concentration, 0.4,1.0,2.0,5.0,10.0 μ g/mL series standards use liquid；Peak area is responded as ordinate, standard specimen concentration using standard specimen For abscissa, unit is μ g/mL, draws calibration curve；According to step（3）The response peak area that chromatography obtains, using outer Mark method carries out quantitative analysis to toxoflavin content in sample.
- 2. according to the method described in claim 1, it is characterized in that, the concentration is respectively 0.05,0.1,0.2,0.4, 1.0,2.0,5.0,10.0 μ g/mL series standards are as follows using the preparation method of liquid：Weigh 0.0100 g toxoflavin standard items In 10 ml volumetric flasks, after methanol dissolving, scale is settled to, is configured to 1.0 mg/mL standard mother liquors；It is positioned over -18 DEG C of refrigerators In, it can preserve 3 months；Before use, after taking out placement room temperature, 200 μ L standards mother liquors are taken in 10 mL volumetric flasks, water constant volume It to scale, shakes up, the centre for being configured to 20.0 μ g/mL uses liquid；25 μ L, 50 μ L, 100 μ L, 200 μ L, 500 μ are taken respectively Using liquid and 50 μ L among L, 1.0 mL, for 100 μ L standards mother liquors in 10 mL volumetric flasks, water is settled to scale.
- 3. according to the method described in claim 1, it is characterized in that, it is described detection food for cereal fermented product, white fungus and its Product, potato product.
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| CN106872619A (en) * | 2017-04-24 | 2017-06-20 | 南通博泰美术图案设计有限公司 | The assay method of aflatoxin |
| CN110305139B (en) * | 2019-06-14 | 2021-01-19 | 深圳市疾病预防控制中心（深圳市卫生检验中心、深圳市预防医学研究所） | Toxoflavin hapten for indirectly detecting zymotic acid and synthetic method thereof |
| CN110294762B (en) * | 2019-06-14 | 2020-12-15 | 深圳市疾病预防控制中心（深圳市卫生检验中心、深圳市预防医学研究所） | Artificial antigen for detecting acidosis of rice fermentum and application thereof |
| CN110672769A (en) * | 2019-10-27 | 2020-01-10 | 贵州省兽药饲料监察所(贵州省兽药残留监测中心) | Method for measuring residual quantity of cantharidin yellow pigment in poultry eggs |
| CN110749689A (en) * | 2019-11-07 | 2020-02-04 | 贵州省兽药饲料监察所(贵州省兽药残留监测中心) | Method for measuring content of cantharis yellow colorant in feed |
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