CN102628803B - Method for detecting pesticide and veterinary medicament residues in foods based on surface plasma resonance technology - Google Patents
Method for detecting pesticide and veterinary medicament residues in foods based on surface plasma resonance technology Download PDFInfo
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- CN102628803B CN102628803B CN201210110733.1A CN201210110733A CN102628803B CN 102628803 B CN102628803 B CN 102628803B CN 201210110733 A CN201210110733 A CN 201210110733A CN 102628803 B CN102628803 B CN 102628803B
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Abstract
The invention discloses a method for detecting pesticide and veterinary medicament residues in foods based on a surface plasma resonance technology, which belongs to the technical field of food safety hazard factor detection. The method comprises sensing surface aptamer fixing, sample marking, sample detecting and sensing element regenerating; the same sensing chip is used for detecting the contents of different pesticide and veterinary medicament residues by using the same sensing chip; and the method is characterized by comprising the following steps of: preparing lysozymes serving as marking molecular probes, and connecting lysozyme aptamers to the surface of the sensing chip; performing a series of treatment on a food sample, adding lysozyme markers for pesticide and veterinary medicament residual components, mixing, and competitively binding the aptamers which are modified by metal nanoparticles and correspond to the pesticide and veterinary medicament residual components; detecting the quantity of the lysozymes by using a surface plasma resonance detector to indirectly detect pesticide and veterinary medicament residues; and regenerating the sensing chip for detecting other pesticide and veterinary medicament residues. A general detection method with high stability, high repeatability and high sensitivity is provided for the detection of pesticide and veterinary medicament residues, and detection of various pesticide and veterinary medicament residues through plasma resonance sensing chips on the same surface is realized.
Description
Technical field
The present invention relates to a kind of food middle peasant detection of veterinary drugs in food technology.Particularly based on Applications of surface plasmon resonance, by aptamer and unmarked, mark sample, carry out specificity competition identification, adopt the method for the sensing element indirect detection food middle peasant residue of veterinary drug that lysozyme aptamers modifies.
Background technology
In recent years, food-safety problem becomes the focal issue of the people's livelihood that concerns, and agricultural and veterinary chemicals residual be restriction food security primary factor.The organophosphorus pesticide of one of tradition three major types agricultural chemicals, consumption is large, uses extensively, and residue problem receives much concern.Acetamiprid, because it is as a kind of spectrum pesticide, is inevitably present in fruits and vegetables.Chemical functional group's triphenylmethane in malachite green can be carcinogenic, and a lot of countries forbid, but still have fisherman to use when control infection of marine fishes fungi, also has forwarding agent to be used as sterilization.The Antibiotic Additive of using in animal fodder all over the world reaches more than 20 unexpectedly plants, as residues of veterinary drug such as kanamycins, Tetracyclines.Yet, use for a long time agricultural and veterinary chemicals can cause adjuvant accumulating in plant and animal body, people are edible to be had after the residual food of agricultural and veterinary chemicals, can cause very large harm to health.Therefore, setting up reliable, quick, sensitive detection method is one of residual important means of monitoring agricultural and veterinary chemicals.
Classical detection method generally relies on liquid chromatography, gas chromatography, gas Liquid Chromatography/Mass Spectrometry, but these detecting instruments are expensive, and testing cost is high, can not detect online.At present, immuno analytical method is the most general technology of application in the residual fast detecting of agricultural and veterinary chemicals.Yet existing immunoassay technology also cannot meet actual detection demand at aspects such as sensitivity, versatilities; The shortcomings such as that immune marker also exists is unstable, easy inactivation, have limited further developing of related immune analytical technology.
Applications of surface plasmon resonance has high sensitivity, response is fast, volume is little, need not mark, can keep the advantages such as biologically active of molecule, become one of detection technique of speed with fastest developing speed nearly ten years, be widely adopted.Enzyme linked immunosorbent assay, biology sensor detection method and fluorometry, still exist sensing chip to detect single-minded problem relatively, and testing cost is very high.For example, the instrument BIACore that adopts Surface Plasmon Resonance Technology to detect, its sensors chip CM5 cost is more than 2000 yuan of Renminbi.
Summary of the invention
In order to solve existing surface plasma body technique, when detection agricultural and veterinary chemicals is residual, there is the problems such as chip selectivity, antibody poor stability, consumable quantity is large, fraud is expensive, greatly improve the residual detectability of agricultural and veterinary chemicals simultaneously, the invention provides a kind of surface plasma resonance sensor that adopts and detect the residual method of various agricultural and veterinary chemicals in food.That the method has is general, high stability, high sensitivity, simple operation and other advantages.
Technical scheme of the present invention is: a kind of food middle peasant detection of veterinary drugs in food method of application surface plasma resonance instrument, and utilize same sensing chip to detect the content of different agricultural and veterinary chemicals residual components; It is characterized in that comprising the following steps:
(1) sensing chip surface aptamers is fixed: the sensing chip of selecting Streptavidin SA to modify, by passing into 5-50 μ L concentration, be the 1-50 μ g/L lysozyme aptamers of mark biotin, on surface plasma sensing chip, fix lysozyme aptamers;
(2) agricultural and veterinary chemicals residual component to be measured is carried out to lysozyme mark, labeling method is different according to determinand group, and described labeling method comprises EDC/NHS method or glutaraldehyde method;
(3) the standard model storing solution of phosphate buffer configuration agricultural and veterinary chemicals residual component standard solution preparation: with 0.01-0.1mol/L(pH=7.4), storing solution concentration is 0.1ng/mL to 1mg/mL, with phosphate buffer, storing solution is mixed with to the standard solution of variable concentrations, after getting the standard solution of the unmarked residual component to be measured of variable concentrations and the residual component to be measured of lysozyme mark and fully mixing, competition is in conjunction with the aptamers of the corresponding aptamers of agricultural and veterinary chemicals residual component or Nanoparticle Modified, wherein the agricultural and veterinary chemicals residual component of lysozyme mark should be no less than the adaptive scale of construction adding,
(4) Criterion curve: adopt surface plasma resonance spectrometer to measure, the phosphate buffer of 0.02mol/L of take is measuring basis, by Micropump, pass into 5-100 μ L biased sample to be measured, record surface plasma body resonant vibration instrument spectrogram, by detecting the content of lysozyme, indirect detection agricultural and veterinary chemicals residual component; Get the surface plasma body resonant vibration spectrogram stationary value of variable concentrations testing sample, drawing curve, and carry out polynomial curve fitting, obtain and return typical curve;
(5) quantitatively detect: the agricultural and veterinary chemicals residual component sample for unknown content detects, and carries out equally according to step (three); Adopt surface plasma body resonant vibration detector to record the residual spectrogram of agricultural and veterinary chemicals; By the corresponding regression curve equation of stationary value substitution of residual component in spectrogram, calculate the concentration value of food middle peasant residue of veterinary drug component;
(6) passing into 0.01-0.05mol/L(pH is 2-3) glycocoll-hydrochloric acid buffer solution, rinse sensing chip surface, carry out sensing element regeneration, for other agricultural and veterinary chemicals residue detection.
Described labeling method comprises the crosslinked carboxyl of EDC/NHS method and amino or crosslinked two amino of glutaraldehyde method.
Can adopt aptamer is identification molecule, and aptamer sequence is directly related with determinand.
Described step (one) sensor surface aptamers is fixed, and comprises the steps:
(1) sensing chip of Streptavidin SA being modified inserts in surface plasma body resonant vibration detector, carries out online sensing surface modification in service aisle;
(2) pass into 0.02mol/L(pH=7.4) phosphate buffer;
(3) pass into the lysozyme aptamers solution that 5-50 μ L concentration is 1-50 μ g/L biotin modification, be coupled to online baseline stability;
(4) repeating step (2), to (3), obtains the sensing chip that lysozyme aptamers is modified.
Can adopt lysozyme mark determinand, identify with the competition of aptamer generation specificity together with unmarked sample.
In described step (three), nano particle can be metal nanoparticle or magnetic nano-particle or macromolecular compound.
In described step (four) and (five) by detecting the content of lysozyme, the concentration value of indirect detection agricultural and veterinary chemicals residual component, that improves surface plasma sensing chip can reusing, is applicable to the detection of various agricultural and veterinary chemicals residual components.
Beneficial effect of the present invention:
(1) the present invention solves the poor problem of selectivity of food middle peasant detection of veterinary drugs in food chip, introduce the lysozyme molecular probe that serves as a mark, adopt biotin labeled aptamers effects on surface plasma resonance sensing chip to modify, the residual measurement of agricultural and veterinary chemicals is converted to the measurement to lysozyme, realize the versatility of sensing chip, to different agricultural and veterinary chemicals are residual, detect.The concrete principle that detects is shown in accompanying drawing 1;
(2) the present invention solves chip poor stability problem, adopts aptamers as the general part of chip surface, and regeneration easily.Phase antagonist reusability is strong, has greatly extended the serviceable life of chip, reduces testing cost;
(3) the present invention solves the large problem of reagent consumption, after adopting that the agricultural and veterinary chemicals of testing sample middle peasant residue of veterinary drug and lysozyme mark is residual and fully mixing, adds the residual aptamers of appropriate agricultural and veterinary chemicals, and combination can be at war with.With respect to competition in the past, suppress in conjunction with thought, need not add excessive aptamers, both realized response signal amplification, also saved reagent consumption;
(3) the present invention has improved detection sensitivity, can select the residual aptamers of agricultural and veterinary chemicals of Nanoparticle Modified in operation, and while detecting based on surface plasma body resonant vibration, signal significantly increases.
Accompanying drawing explanation
Fig. 1 is that biotoxin of the present invention detects schematic diagram; Wherein
for agricultural and veterinary chemicals residue,
for the agricultural and veterinary chemicals residue of lysozyme mark,
for the aptamers of agricultural and veterinary chemicals residue,
for the aptamers of lysozyme,
for nano particle.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment: select two kinds of typical residue of veterinary drug kanamycins and residues of pesticides organophosphorus analog PAPMP detected object, concrete operation step is as follows:
(1) sensor surface aptamers is fixed: the sensing chip of selecting Streptavidin SA to modify is the 30 μ g/L lysozyme aptamers of mark biotin by passing into 20 μ L concentration, fixes lysozyme aptamers on surface plasma sensing chip;
(2) molecular probe label coupling: determinand is carried out to coupling mark by glutaraldehyde method and lysozyme, labeling method, according to determinand group different choice, comprises EDC/NHS method, glutaraldehyde method etc., as kanamycins, can adopt glutaraldehyde method to be connected with lysozyme, stand-by; Or it is stand-by directly to buy kanamycins-lysozyme conjugate;
(3) standard solution preparation: take kanamycins standard items 10 mg, be dissolved in 0.02mol/L(pH=7.4) phosphate buffer is settled to 10 mL, is the standard stock solution of 1 mg/mL; With phosphate buffer, storing solution is mixed with to the standard solution of variable concentrations, concentration, in pg/mL ~ ng/mL level, is followed successively by 0 ng/mL, 50 ng/mL, 100 ng/mL, 200 ng/mL, 400 ng/mL, 600ng/mL;
(4) Specification Curve of Increasing: be that the unlabelled standard solution of 0 ng/mL fully mixes with appropriate lysozyme mark kanamycins solution by above-mentioned concentration; The aptamers that adds again the corresponding aptamers of agricultural and veterinary chemicals residual component or Nanoparticle Modified, wherein the agricultural and veterinary chemicals residual component of lysozyme mark should be no less than the adaptive scale of construction adding; Adopting surface plasma resonance spectrometer to measure, pass into 0.02mol/L(pH=7.4) phosphate buffer is as measuring basis, then pumps into biased sample to be measured, after surface plasma resonance response value stabilization, recording surface plasma resonance optical spectrum figure;
(5) pass into 0.02mol/L(pH=2.4) glycocoll-hydrochloric acid solution, rinse sensing chip surface, destroy the combination of lysozyme and aptamers, complete sensing element regeneration;
(6) concentration, passes into the standard model measuring method to be measured of other concentration (50-600ng/mL) successively with (4) from low to high, obtains respective surfaces plasma resonance optical spectrum figure; Get the surface plasma spectrogram stationary value of yapamicin relict, drawing standard curve, and carry out polynomial curve fitting, obtain concentration-stationary value and be related to regression curve equation;
(7), after sensing chip regeneration, actual unknown concentration testing sample is fully mixed with appropriate lysozyme mark kanamycins solution by step (4); In the surface plasma body resonant vibration spectrometer pumping into, record the spectrogram of kanamycins residual component simultaneously, determine corresponding stationary value, substitution is typical curve separately, determine each component concentration, detectability can reach pg/mL ~ ng/mL level, lower than the highest permission content of national regulation;
(8) again pass into 0.02mol/L(pH=2.4) glycocoll-hydrochloric acid solution, rinse surface plasmon resonance sensing chip, carry out chip regeneration, for PAPMP residual component, measure; Aptamers is transformed to PAPMP aptamers, and kanamycins-lysozyme conjugate becomes PAPMP-lysozyme conjugate; During PAPMP detects, in step (3), the solution concentration of preparation changes 0pg/mL into, 200ng/mL, 500ng/mL, 1 μ g/mL, 2 μ g/mL, 4 μ g/mL.Detectability can reach ng/mL ~ μ g/mL level, lower than the highest permission content of national regulation.
The present invention is accurate and convenient for what narrate, take in an embodiment kanamycins and PAPMP is described in detail as example, but the present invention is equally applicable to the residual mensuration of other agricultural and veterinary chemicals in food, as accurate detection and the qualitative analysis of estradiol, TCs etc.Regenerate solution used of sensor surface is selected 0.02mol/L(pH=2.4) glycocoll-hydrochloric acid solution, but can also select salt solusion or weak acid and weak base solution or high ionic strength electrolyte solution, as 0.5mol/L sodium hydroxide solution or 10mmol/L glycocoll/hydrochloric acid buffer solution, destroy the combination of lysozyme and aptamers.Therefore foregoing is all within protection domain of the present invention.In addition, according to the method for embodiment, detect sample, compare with existing surface plasma detection technique, accuracy improves 2 ~ 10 times, probe life is more than 10 times, the little molecular weight (< 1000Da) materials such as estradiol that existing surface plasma detection technique can not accurately detect, can adopt method of the present invention to obtain testing result accurately.
Claims (7)
1. a food middle peasant detection of veterinary drugs in food method for application surface plasma resonance instrument, utilizes same sensing chip to detect the content of different agricultural and veterinary chemicals residual components; It is characterized in that comprising the following steps:
(1) sensing chip surface aptamers is fixed: the sensing chip of selecting Streptavidin SA to modify, by passing into 5-50 μ L concentration, be the 1-50 μ g/L lysozyme aptamers of mark biotin, on surface plasma sensing chip, fix lysozyme aptamers;
(2) agricultural and veterinary chemicals residual component to be measured is carried out to lysozyme mark, labeling method is different according to determinand group, and described labeling method comprises EDC/NHS method or glutaraldehyde method;
(3) standard solution preparation: the standard model storing solution of the phosphate buffer configuration agricultural and veterinary chemicals residual component of the pH=7.4 of use 0.01-0.1mol/L, storing solution concentration is 0.1ng/mL to 1mg/mL, with phosphate buffer, storing solution is mixed with to the standard solution of variable concentrations, after getting the standard solution of the unmarked residual component to be measured of variable concentrations and the residual component to be measured of lysozyme mark and fully mixing, competition is in conjunction with the aptamers of the corresponding aptamers of agricultural and veterinary chemicals residual component or Nanoparticle Modified, wherein the agricultural and veterinary chemicals residual component of lysozyme mark should be no less than the adaptive scale of construction adding,
(4) Criterion curve: adopt surface plasma resonance spectrometer to measure, the phosphate buffer of 0.02mol/L of take is measuring basis, by Micropump, pass into 5-100 μ L biased sample to be measured, record surface plasma body resonant vibration instrument spectrogram, by detecting the content of lysozyme, indirect detection agricultural and veterinary chemicals residual component; Get the surface plasma body resonant vibration spectrogram stationary value of variable concentrations testing sample, drawing curve, and carry out polynomial curve fitting, obtain and return typical curve;
(5) quantitatively detect: the agricultural and veterinary chemicals residual component sample for unknown content detects, and carries out equally according to step (three); Adopt surface plasma body resonant vibration detector to record the residual spectrogram of agricultural and veterinary chemicals; By the regression curve equation of the recurrence typical curve of stationary value substitution step (four) acquisition of residual component in spectrogram, calculate the concentration value of food middle peasant residue of veterinary drug component;
(6) pass into glycocoll-hydrochloric acid buffer solution that the pH of 0.01-0.05mol/L is 2-3, rinse sensing chip surface, carry out sensing element regeneration, for other agricultural and veterinary chemicals residue detection.
2. method according to claim 1, is characterized in that described labeling method comprises that selecting EDC/NHS method to be cross-linked carboxyl and amino or glutaraldehyde method is cross-linked two amino.
3. method according to claim 1, it is characterized in that adopting aptamer is identification molecule, aptamer sequence is directly related with determinand.
4. method according to claim 1, is characterized in that described step () sensing chip surface aptamers fixes, and specifically comprises the steps:
(1) sensing chip of Streptavidin SA being modified inserts in surface plasma body resonant vibration detector, carries out online sensing surface modification in service aisle;
(2) pass into the phosphate buffer of the pH=7.4 of 0.02mol/L;
(3) pass into the lysozyme aptamers solution that 5-50 μ L concentration is 1-50 μ g/L biotin modification, be coupled to online baseline stability;
(4) repeating step (2), to (3), obtains the sensing chip that lysozyme aptamers is modified.
5. method according to claim 1, is characterized in that adopting lysozyme mark determinand, identifies together with unmarked sample with the competition of aptamer generation specificity.
6. method according to claim 1, is characterized in that in described step (three), nano particle is metal nanoparticle or magnetic nano-particle or macromolecular compound.
7. method according to claim 1, it is characterized in that in described step (four) and (five) by detecting the content of lysozyme, the concentration value of indirect detection agricultural and veterinary chemicals residual component, that improves surface plasma sensing chip can reusing, is applicable to the detection of various agricultural and veterinary chemicals residual components.
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| CN103454253B (en) * | 2013-06-25 | 2016-04-06 | 复旦大学 | Based on the organic phosphorus detection method of surface plasma body resonant vibration |
| CN103335972B (en) * | 2013-07-16 | 2015-01-07 | 江南大学 | Detection method of kanamycin residue based on nucleic acid aptamer |
| CN103472219B (en) * | 2013-09-30 | 2014-06-11 | 湖南农业大学 | Method combining immune magnetic nanoparticles and SPR technique to detect deltamethrin |
| CN103884682B (en) * | 2014-03-20 | 2016-09-07 | 暨南大学 | Surface plasma body resonant vibration biochip and preparation method and application |
| CN106996923A (en) * | 2017-02-17 | 2017-08-01 | 丁利 | The method that a variety of environmental hormones are detected based on the surface plasma resonance technology that regenerated liquid optimizes simultaneously |
| CN106970048A (en) * | 2017-02-17 | 2017-07-21 | 丁利 | The method for detecting a variety of agricultural and veterinary chemicals residuals in food simultaneously based on the surface plasma resonance technology that regenerated liquid optimizes |
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