CN101988917A - Extraction method applied to liquid-phase chip and for detecting multiple harmful substances contained in foods - Google Patents
Extraction method applied to liquid-phase chip and for detecting multiple harmful substances contained in foods Download PDFInfo
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- CN101988917A CN101988917A CN201010187263XA CN201010187263A CN101988917A CN 101988917 A CN101988917 A CN 101988917A CN 201010187263X A CN201010187263X A CN 201010187263XA CN 201010187263 A CN201010187263 A CN 201010187263A CN 101988917 A CN101988917 A CN 101988917A
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Abstract
The invention relates to an extraction method applied to a liquid-phase chip technology and for detecting six harmful substances, i.e. SAL (Salbutamol), CLE (Clenbuterol), RAC (Ractopamine), SEM (Furacilin), SUDI (Sudan I) and DPA (Organophosphorus pesticide) which are contained in foods. The invention extracts a sample to be detected with the established extraction method by adding certain concentration of target residual standard substances to different samples without containing target residual substances and detects the target substances through an established liquid-phase chip system. Test results show that the extraction method has higher recovery rate, is freedom from interference on liquid-phase chip detection at the same time, can be applied to detecting the liquid-phase chip and has higher practicability.
Description
Technical field
The present invention relates to be applied to liquid-phase chip technology and detect salbutamol (Salbutamol in the food, SAL), Clenbuterol (Clenbuterol, CLE), Ractopamine (Ractopamine, RAC), nitrofurazone (Furacilin, SEM), Sudan red 1 (Sudan I, SUD1), organophosphorus pesticide (Organophosphorus pesticide, DPA) extracting method of six kinds of objectionable impuritiess.
Background technology
Nearly decades, along with the raising of people to food and environmental quality understanding and requirement, the food-safety problem that is caused by residues such as agricultural chemicals, veterinary drug, biotoxins more and more is subjected to people's attention.In order to guarantee food security, promote the development of international agricultural byproducts trade, FAO (Food and Agriculture Organization of the United Nation) (FA0), The World Health Organization (WHO) and countries in the world government pay much attention to residue problems such as agricultural chemicals, veterinary drug, food additives.Simultaneously, countries in the world with maximum residue limit(MRL) as the important technology barrier in the agricultural byproducts international trade.The limit standard that WHO/FAO formulates has 2510, the limit standard of varieties of food items has also been formulated in countries in the world such as European Union, the U.S. and Japan, simultaneously, the heavy losses that residual quantities such as agricultural chemicals in the food, veterinary drug, food additives exceed standard and bring are also had to painfully bear in countries in the world, and, also brought great harm for people ' s health, the exceed standard seriousness and the persistence of harm of residue become the focus that international community pays close attention to.
For residual detections such as agricultural chemicals, veterinary drug, food additives.Because many, chemical constitution of its kind and different, the to be measured component complexity of character, especially in recent years, efficiently, the continuing to bring out of low toxicity, low-residual farming, veterinary drug kind and new discovery biotoxin, the detection technique of many residues in the food is had higher requirement.The method that is used to detect the hazard residue material at present is many based on individual event purpose chemical detection, biochemistry detection and biological detecting method, and the extraction of objectionable impurities is also many based at a certain detection method with detect object and the extracting method set up in the related food.Urgent need provide a kind of fast, high flux, sensitive medicament residue parllel screening technology reliably, to tackle the test item that constantly increases variation.Therefore, take all factors into consideration from technology maturation degree and detection demand, are good general-purpose platforms of how residual high flux parallel detecting system in the developing food products based on the floated chip detection technology of the liquid phase of skeptophylaxis analysis, photoelectric technology because of characteristics such as it detects fast, sensitivity and high fluxs, are applicable to the effectively quick of this method and can extract simultaneously that the extracting method of multiple residuals is basis and the gordian technique that this technology can effectively be utilized in the food and set up.
Summary of the invention
The objective of the invention is to foundation and be applied to salbutamol (Salbutamol in the liquid-phase chip technology detection food, SAL), Clenbuterol (Clenbuterol, CLE), Ractopamine (Ractopamine, RAC), nitrofurazone (Furacilin, SEM), Sudan red 1 (Sudan I, SUD1), organophosphorus pesticide (Organophosphorus pesticide, DPA, AOVA) extracting method of six kinds of objectionable impuritiess.
Provided by the inventionly be applied to the extracting method that liquid-phase chip technology detects salbutamol, Clenbuterol, Ractopamine, nitrofurazone, Sudan red 1, six kinds of objectionable impuritiess of organophosphorus pesticide in the food and be: with in the testing sample in the ratio of 1ml acetonitrile/1g sample; add acetonitrile; obtain filtrate through centrifuging after homogenate and the ultrasonic Treatment; filtrate is concentrated near doing under blanket gas, nearly dry-eye disease is carried out liquid-phase chip after with dissolve with methanol and detected.
According to embodiments of the invention, sample is with after the acetonitrile dissolving, and the condition of homogenate is: under the 10000rpm behind the homogenate 10min; Ultrasonic treatment time is 2h, during every 20min-30min take out mixing once.
The optimum condition of above-mentioned centrifuging is: the centrifugal 5min of 2500rpm.
According to embodiments of the invention, the residue after the preferred above-mentioned centrifuging continues to extract one to twice with acetonitrile, merges filter liquor; With filter liquor centrifugal 5min under the 4000rpm condition, get supernatant solution and flow down in 45 ± 5 ℃ of nitrogen and be concentrated near doing, nearly dry-eye disease is carried out liquid-phase chip after with dissolve with methanol and is detected.
The present invention is by adding certain density object residue standard substance in the sample that variety classes is not contained the object residue material, the liquid-phase chip system that test sample is extracted and set up with the extracting method of setting up detects target substance, test findings shows that this extracting method recovery is higher, simultaneously liquid-phase chip is detected noiselessly, can be applicable to the detection of liquid-phase chip.Has stronger practicality.
Description of drawings
Fig. 1 tonyred liquid chromatographic detection is figure as a result;
Only add tonyred in Fig. 2 sample after the inventive method is extracted, carry out the liquid-phase chip testing result;
Fig. 3 adds behind salbutamol, Clenbuterol and the Ractopamine liquid chromatographic detection figure as a result in sample;
Fig. 4 adds behind the nitrofurazone liquid chromatographic detection figure as a result in sample;
Fig. 5 is added with behind the machine phosphorus insecticide gas chromatographic detection figure as a result in sample;
The liquid-phase chip that Fig. 6 detects six kinds of objectionable impuritiess in the sample simultaneously is figure as a result.
Embodiment
Following embodiment is used for further specifying of the present invention, but is not used for limiting the scope of the invention.
Be applied to the research that liquid-phase chip detects the extracting method of six kinds of objectionable impuritiess in the food.
Embodiment 1
One, the preparation of sample and extraction
Learn from else's experience respectively and detect each 3 parts of different food products (table 1) not containing object residue thing to be checked.
Table 1 simulation test sample residues contains scale (mg/kg)
The sample 10g that gets processing adds each object residue thing standard items according to measuring eventually in the table 1 respectively in the homogenate bottle, mixing is prepared into the testing sample that contains determinand.According to method of the present invention sample to be tested is extracted, and carry out purifying according to the requirement of existing disparity items detection method (explanation of face as follows), and carry out the mean value of high performance liquid chromatography (HPLC) and three parallel sample of gas chromatography detection computations and its recovery, testing result sees Table 2.
Said extracting method of the present invention is: add the 10mL acetonitrile in the 10g testing sample, ultrasonic 2h in the rearmounted ultrasonic cleaner of homogenate 10min under 10000rpm (during every 20min-30min take out mixing once) is cooled to room temperature after ultrasonic; The centrifugal 5min of 2500rpm, supernatant filters in the 50mL centrifuge tube with Buchner funnel, and residue merges filter liquor with 2 * 2.5mL acetonitrile extract mixing suction filtration twice; With the centrifugal 5min of filter liquor 4000rpm, get supernatant solution and flow down in (45 ± 5) ℃ nitrogen and be concentrated near doing.
Two, the purifying of tonyred composition and detection
After the sample 1 that will contain tonyred extracts by method of the present invention, carry out purifying in accordance with the following methods after, liquid phase chromatography detects its tonyred content, and calculates its recovery.
The tonyred purification process:
1) nitrogen is flowed down concentrating the nearly dry-eye disease obtain and add the 2mL n-hexane dissolution, slowly add in the alumina chromatographic column, is to guarantee the chromatography effect, when in post, keeping the normal hexane liquid level to be the 2mm left and right sides on sample, in the chromatography process of whole process, should not make post dry;
2) with normal hexane on a small quantity repeatedly drip washing concentrate bottle, inject chromatographic column in the lump, the pigment bandwidth of control aluminium oxide top layer absorption is less than 0.5cm, after treating that sample liquid flows out fully, look what that contain oils impurity in the sample and wash post with 10mL～30mL normal hexane, colourless until effluent, discard whole normal hexane leacheates;
3) with the normal hexane liquid 60mL wash-out that contains 5% acetone;
4) after collecting, concentrating, shift and be settled to 5mL, feed flow phase chromatographic determination behind the organic membrane filtration of 0.45 μ m with acetone.
Liquid chromatographic detection is Fig. 1 as a result: testing result shows under the situation that only contains tonyred, carry out carrying out the detection of liquid-phase chip method after the sample extraction according to the inventive method, have only the tonyred testing result positive, illustrate that this extracting method effectively and to the detection of other project does not produce interference.Reference liquid chromatography testing result illustrates this extracting method recovery height, is suitable for the extraction of tonyred in the food.
Simultaneously sample 2 is directly extracted unpurified extract and carry out the liquid-phase chip detection.Adopt tonyred positive criteria product (2mg/kg) as positive control; The PBS that adopts 0.1mol/L pH=7.2 is as negative control; Adopt the known sample that does not contain six kinds of objectionable impuritiess to extract simultaneously, directly carry out liquid-phase chip after extracting simultaneously and detect as the negative control sample.Testing result as shown in Figure 2, the positive contrast in A1 hole, the B1 hole is a sample detection, the negative contrast in C1 hole, the negative control sample in D1 hole.
Three, the purifying of salbutamol, Clenbuterol and Ractopamine and detection.
After sample 2 extracted, carry out purifying in accordance with the following methods after liquid phase chromatography detect its salbutamol, Clenbuterol and Ractopamine content, and calculate its recovery.
Salbutamol, Clenbuterol and Ractopamine purification process:
1) nitrogen is flowed down the concentrated nearly dry-eye disease that obtains with behind hydrochloric acid-dissolve with methanol solution, add 5mL normal hexane mixing 1min on vortex mixer at every turn, behind the centrifugal 5min of 1500r/min, organic phase is removed the coprocessing secondary with sharp mouth suction pipe;
2) water that keeps is regulated pH to 12 with 2.0mol/L NaOH solution, and with 3 * 5mL ethyl acetate-butanol solution extracting water, each mixing 2min behind the centrifugal 5min of 2500r/min, gets upper organic phase in another centrifuge tube with sharp mouth suction pipe;
3) ethyl acetate-normal butyl alcohol extracted solution that merges is flowed down in (70 ± 5) ℃ nitrogen be concentrated near doing, with 1mL hydrochloric acid-dissolve with methanol solution residue.
4) series connection of two SCX pillars is connected be installed on the vacuum filtration device, maintenances elution flow rate is 1mL/min, activates pillar with 5mL methyl alcohol, 5mL water and 5mL 0.030mol/L hydrochloric acid solution successively; The 1mL sample extracting solution is added on the pillar; Again with 1mL hydrochloric acid-methanol solution washing test tube also is transferred in the pillar together; Use 5mL water, 5mL methyl alcohol drip washing pillar successively.After solvent streams is crossed solid-phase extraction column, keep the vacuum suction state to keep 5min at least.
5) under vacuum plant, put the scale collection tube well,, and collect eluent with 5mL 4% methanolic ammonia solution wash-out.Eluent flowed down in (70 ± 5) ℃ nitrogen be concentrated near doing, with the dissolve with methanol residue and be settled to 2.0mL, behind the mistake 0.45 μ m filter membrane, feed flow phase chromatographic determination.Liquid chromatographic detection is Fig. 3 as a result.
After the sample 2 that is added with salbutamol, Clenbuterol and Ractopamine that final concentration is 10mg/kg being extracted back and purifying, adopt HPLC to detect, three kinds of residue of veterinary drug materials all are detected, and the testing result and the recovery see Table 2.
Four, the purifying of nitrofurazone and detection
After sample 2 extracted, carry out purifying in accordance with the following methods after liquid phase chromatography detect its nitrofurazone content, and calculate its recovery.
The nitrofurazone purification process:
1) with the nearly dry-eye disease of 1.0mL acetic acid ethyl dissolution, adds the distilled water of pH value simultaneously, mix and shake 1min, the centrifugal 3min of 2500r/min to 7-7.5;
2) after the centrifugal layering, organic phase moves in another centrifuge tube, and water extracts once with 8mL ethyl acetate again, and aqueous phase discarded merges organic phase;
3) organic phase dries up under 50 ℃ of airflows.Be settled to 1.0mL with constant volume liquid, by the 0.45um membrane filtration to sample bottle, feed flow phase chromatographic determination.
4) with the nearly dry-eye disease of 1.0mL acetic acid ethyl dissolution, add the distilled water of pH value simultaneously, mix and shake 1min, the centrifugal 3min of 2500r/min to 7-7.5;
5) after the centrifugal layering, organic phase moves in another centrifuge tube, and water extracts once with 8mL ethyl acetate again, and aqueous phase discarded merges organic phase;
6) organic phase dries up under 50 ℃ of airflows.Be settled to 1.0mL with constant volume liquid, by the 0.45um membrane filtration to sample bottle, feed flow phase chromatographic determination.
Nitrofurazone liquid phase chromatogram testing result Fig. 4.
Being after the sample of 300mg/kg nitrofurazone extracts to being added with final concentration, adopt HPLC to detect, the nitrofurazone in the sample is detected, and the testing result and the recovery see Table 2.
Five, the purifying of organophosphorus pesticide and detection.
After the sample that will contain organophosphorus pesticide extracts by the inventive method, carry out purifying in accordance with the following methods after, detect its organophosphorus pesticide content with vapor-phase chromatography, and calculate its recovery.
The organophosphorus pesticide purification process:
1) adds the nearly dry-eye disease of 2.0ml acetic acid ethyl dissolution, abundant mixing 2min on vortex mixer, whole acticarbon pillars of crossing;
2) use the 4.0ml eluent ethyl acetate;
3) with 2.0ml ethyl acetate+normal hexane (1+1) wash-out;
4) merge eluent, 40 ℃ of nitrogen flow down and are concentrated into 0.5ml, and the air feed analysis of hplc is with the external standard method peak area quantification.
The organophosphorus pesticide gas chromatographic detection is Fig. 5 as a result.
Being after the sample of 10mg/kg organophosphorus pesticide extracts to being added with final concentration, adopt gas chromatography to detect, organophosphorus pesticide is detected in the sample, and the testing result and the recovery see Table 2.
Table 2 adds standard substance sample detection result
Annotate: "+" expression testing result is positive, and "-" expression testing result is negative.
Six, six kinds of residuals detect simultaneously
After adopting method of the present invention that the sample that contains six kinds of residuals is simultaneously extracted, adopt six kinds of positive criteria product (10mg/kg) as positive control, the PBS that adopts 0.1mmol/L pH=7.2 is as negative control, adopt the known sample that does not contain six kinds of objectionable impuritiess to extract simultaneously as the sample negative control, use to have wrapped to be detected by the liquid-phase chip of six kinds of good residuals antigens and with microballoon the extract that obtains is carried out testing result and show: this extracting method directly extracts six kinds of residuals and is applicable to six kinds of objectionable impuritiess of liquid-phase chip fast detecting (Fig. 6).The A1 hole is a detection background among the figure, positive control test hole, B1 hole, and the C1 hole is the pattern detection hole, the negative contrast in D1 hole.
By the compare recovery height of this extracting method of explanation of six kinds of residuals that adopt liquid chromatography and vapor-phase chromatography that extraction is obtained, the testing result of liquid-phase chip proves that this extracting method is applicable to that the liquid-phase chip method detects salbutamol (Salbutamol in the food simultaneously, SAL), Clenbuterol (Clenbuterol, CLE), Ractopamine (Ractopamine, RAC), nitrofurazone (Furacilin, SEM), Sudan red 1 (Sudan I, SUD1), organophosphorus pesticide (Organophosphorus pesticide, DPA, AOVA) six kinds of objectionable impuritiess.
Claims (4)
1. be applied to the extracting method that liquid-phase chip technology detects salbutamol, Clenbuterol, Ractopamine, nitrofurazone, Sudan red 1, six kinds of objectionable impuritiess of organophosphorus pesticide in the food; comprise the steps: with in the testing sample in the ratio of 1ml acetonitrile/1g sample; add acetonitrile; obtain filtrate through centrifuging after homogenate and the ultrasonic Treatment; filtrate is concentrated near doing under blanket gas, nearly dry-eye disease is carried out liquid-phase chip after with dissolve with methanol and detected.
2. the extracting method of salbutamol according to claim 1, Clenbuterol, Ractopamine, nitrofurazone, Sudan red 1, six kinds of objectionable impuritiess of organophosphorus pesticide, it is characterized in that sample with after the acetonitrile dissolving, the condition of homogenate is: under the 10000rpm behind the homogenate 10min; Ultrasonic treatment time is 2h, during every 20min-30min take out mixing once.
3. the extracting method of salbutamol according to claim 1, Clenbuterol, Ractopamine, nitrofurazone, Sudan red 1, six kinds of objectionable impuritiess of organophosphorus pesticide is characterized in that the condition of above-mentioned centrifuging is: the centrifugal 5min of 2500rpm.
4. the extracting method of salbutamol according to claim 1, Clenbuterol, Ractopamine, nitrofurazone, Sudan red 1, six kinds of objectionable impuritiess of organophosphorus pesticide, it is characterized in that the residue after the above-mentioned centrifuging continues to extract one to twice with acetonitrile, merges filter liquor; With filter liquor centrifugal 5min under the 4000rpm condition, get supernatant solution and flow down in 45 ± 5 ℃ of nitrogen and be concentrated near doing, nearly dry-eye disease adds dissolve with methanol and carries out liquid-phase chip and detect.
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| CN112034068A (en) * | 2020-09-08 | 2020-12-04 | 河南诺玛科技有限公司 | Systemic pesticide detection method applied to fruits and vegetables |
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