CN110672581A - Detection method of enrofloxacin and application thereof - Google Patents
Detection method of enrofloxacin and application thereof Download PDFInfo
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- CN110672581A CN110672581A CN201910929508.2A CN201910929508A CN110672581A CN 110672581 A CN110672581 A CN 110672581A CN 201910929508 A CN201910929508 A CN 201910929508A CN 110672581 A CN110672581 A CN 110672581A
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Abstract
The invention provides a method for detecting enrofloxacin, which comprises the specific operation that a sample containing enrofloxacin is dripped on a nano-gold particle modified Raman substrate with surface activity, and a Raman spectrometer is used for collecting enrofloxacin surface enhanced Raman spectrum after a solvent is evaporated to dryness. The invention also provides application of the detection method in detecting the residual amount of enrofloxacin in water or aquatic products. The method can detect 100 mu g/kg of enrofloxacin residue in the aquatic product and 0.1 mu g/mL of enrofloxacin residue in the water body at the lowest energy. The new method has proper detection sensitivity, greatly shortens the detection time and saves the detection cost.
Description
Technical Field
The invention relates to the technical field of enrofloxacin detection, in particular to a method for detecting enrofloxacin and application thereof, which utilize a surface enhanced Raman spectroscopy technology.
Background
China is the first large aquatic product producing country and export country in the world, but in recent years, frequent outbreak of aquatic product safety incidents endanger the benefits of consumers and become a bottleneck restricting normal export of aquatic products in China. In a plurality of aquatic product safety events, the phenomenon of overproof fishing medicine residue caused by improper use, excessive use and even illegal use of the fishing medicine is the most serious. Enrofloxacin is a third-generation fluoroquinolone antibiotic, and is added to feed and drinking water as a prophylactic agent for diseases. However, enrofloxacin also has certain toxic and side effects on human bodies, and the adverse reactions determined by the existing medicine comprise toxic effects on a digestive system, a nervous system and skin. In animal experiments, enrofloxacin shows embryotoxicity and mutagenic effect on experimental animals. Therefore, the problem of residue of enrofloxacin has attracted a great deal of attention.
At present, the standard methods for detecting enrofloxacin in aquatic products mainly comprise liquid chromatography and liquid chromatography-mass spectrometry. The current national standard methods are as follows: the Ministry of agriculture 1025, bulletin-14-2008 (liquid chromatography), GB 21312-. Although these methods have high sensitivity, these detection methods are not suitable for rapid screening due to their time and labor consuming and expensive cost. The agricultural department 1025 bulletin-8-2008 uses an enzyme linked immunosorbent assay, and the agricultural department 1077 bulletin-7-2008 uses a colloidal gold immunopermeation assay, but both of the two methods have high cross reaction rate and poor specific selectivity for enrofloxacin determination. The novel method for detecting enrofloxacin, which is simple, convenient, rapid and accurate in research and development, has very important significance for enhancing the monitoring of the quality safety of aquatic products and promoting the development of aquatic product trade.
Disclosure of Invention
Aiming at the defects of the existing standard method for detecting enrofloxacin, the invention provides a method for detecting enrofloxacin and application thereof in detecting residual amount of enrofloxacin in water bodies and aquatic products.
In order to achieve the above object, the technical solution provided by the present invention comprises:
the first aspect of the invention provides a method for detecting enrofloxacin, which comprises the steps of dripping a sample containing enrofloxacin on a nano gold particle modified Raman substrate with surface activity, and collecting the surface enhanced Raman spectrum of enrofloxacin by using a Raman spectrometer after a solvent is evaporated to dryness.
Further, the enrofloxacin surface enhanced Raman spectrum has 1625, 1480, 1450, 1395, 1340 and 640cm-1Processing the characteristic peak.
Further, the gold nanoparticles adopt gold sol.
Further, the preparation method of the colloidal gold comprises the following steps:
accurately weighing chloroauric acid to prepare aqueous solution of chloroauric acid with a preset concentration, putting the prepared aqueous solution of chloroauric acid into a container, heating to boil, rapidly adding a proper amount of trisodium citrate aqueous solution while stirring, continuously heating for a preset time, stopping heating, cooling the obtained gold sol to room temperature, and storing at low temperature in a dark place.
Further, the preparation method of the colloidal gold comprises the following specific steps: accurately weigh 0.0787g of chloroauric acid in a 1L volumetric flask to make 2X 10-450mL of 2X 10 aqueous solution of chloroauric acid-4Putting a mol/L chloroauric acid aqueous solution into a three-neck flask, heating the three-neck flask in an oil bath pan until the chloroauric acid aqueous solution is boiled, quickly adding 0.74mL trisodium citrate aqueous solution with the mass concentration of 1% under magnetic stirring, continuing heating for 5min, stopping heating, then putting the gold sol into water, cooling to room temperature, and placing the gold sol into a refrigerator for dark storage at 4 ℃.
In order to verify the feasibility of the detection method, an enrofloxacin standard solution is also used, and the preparation method of the enrofloxacin standard solution is as follows:
standard stock solution (100. mu.g/mL): accurately weighing about 10mg of enrofloxacin reference substance, placing the enrofloxacin reference substance into a 100mL measuring flask, adding acetonitrile to dissolve and dilute the enrofloxacin reference substance to a scale, and preparing a standard stock solution of 100 mu g/mL. Storing at-18 ℃ in the dark.
Standard working solution (10. mu.g/mL): precisely measuring 1.0mL of the standard stock solution, placing the standard stock solution into a 10mL measuring flask, adding water to dilute the standard stock solution to a scale, and preparing a standard working solution containing about 10 mu g of enrofloxacin per milliliter. Storing at-18 ℃ in the absence of light
The second aspect of the invention provides an application of any one of the detection methods in detecting the residual amount of enrofloxacin in a water body or an aquatic product.
Further, the step of detecting the residual amount of enrofloxacin in the water body comprises the following steps: taking a proper amount of culture water sample, centrifuging, taking a sample solution, adding a proper amount of KI solution into a Raman sample pool, and adding HNO3Adding a proper amount of concentrated gold sol into the solution, uniformly mixing, standing and then measuring by a Raman spectrometer.
Further, the step of detecting the residual amount of enrofloxacin in the water body specifically comprises the following steps: taking a proper amount of culture water sample, centrifuging at 4600rpm/min, putting 200 mu L of sample solution into a Raman sample pool, adding 20 mu L of 0.1mol/L KI solution, adding 10 mu L of 0.01% HNO3Adding 10 μ L of concentrated gold sol into the solution, mixing, standing for about 30s, and measuring with Raman spectrometer.
Further, the application can detect 0.1 mu g/mL enrofloxacin residue in the water body at the lowest. Further, the step of detecting the residual amount of enrofloxacin in the aquatic product comprises the following steps: weighing a sample, adding acetonitrile formate, performing oscillation extraction, adding anhydrous sodium sulfate, uniformly mixing, dewatering and centrifuging; adding acetonitrile formate into the supernatant, repeatedly extracting for one time, combining the supernatant extract obtained in the two times, and drying by using nitrogen; adding formic acid solution to dissolve residue, vortex oscillating, adding n-hexane, shaking, centrifuging, discarding supernatant, taking lower layer liquid in Raman sample pool, adding KI solution and HNO3Adding a proper amount of concentrated gold sol into the solution, uniformly mixing, and standing for measurement by a Raman spectrometer.
Furthermore, the step of detecting the residual amount of enrofloxacin in the aquatic product specifically comprises the following steps: weighing 5.0g of sample, placing in a 50mL centrifuge tube, adding 5mL of 1% acetonitrile formate, shaking for 10min, adding 2g of anhydrous sodium sulfate, mixing, dewatering, and centrifuging with 4600Centrifuging at r/min for 5min, transferring the supernatant into another 15mL centrifuge tube, adding 5mL 1% acetonitrile formate, extracting once again, combining the two supernatant extractive solutions, and blowing with nitrogen. Adding 1.0mL of 0.2% formic acid solution to dissolve the residue, performing vortex oscillation for 1min, adding 2mL of n-hexane, shaking for 1min, centrifuging for 5min at 4600r/min in a centrifuge, discarding the supernatant, placing 200 μ L of the lower layer liquid in a Raman sample cell, adding 20 μ L of 0.1mol/L KI solution, adding 10 μ L of 0.01% HNO3Adding 10 mu L of concentrated gold sol into the solution, uniformly mixing, standing for about 30s, and then determining by a Raman spectrometer.
Furthermore, the application can detect the residue of the enrofloxacin with the concentration of 100 mu g/kg in the aquatic products at the lowest, and meets the limit requirement of the No. 235 bulletin of Ministry of agriculture on the maximum residue of the enrofloxacin in the aquatic products.
Raman spectroscopy is the scattering spectrum of a substance. The raman spectroscopy is a method for analyzing molecular structures by analyzing a scattering spectrum with a frequency different from that of incident light based on a raman scattering effect to obtain information on molecular vibration and rotation. However, the raman scattering effect is very weak, and the surface enhanced raman technique (SERS) uses a specially treated metal (usually gold or silver) with rough surface to increase the raman signal to 10 by effectively adsorbing the substance to be measured on the metal surface3-106And (4) doubling. As the application of the novel nano particle system pushes the SERS technology to a new step, even the Raman signal can be amplified to 1014-1015And (4) doubling to reach the single molecule detection level.
By adopting the technical scheme, compared with the prior art, the invention has the beneficial effects that:
the method combines the SERS active substrate modified by the nano-gold particles and the surface enhanced Raman spectroscopy technology, and is applied to detecting enrofloxacin residue in fishery medicine of water and aquatic products. The new method has proper detection sensitivity, greatly shortens the detection time and saves the detection cost.
Drawings
FIG. 1 is a surface enhanced Raman spectrum of an enrofloxacin extract from aquaculture water in an embodiment of the present invention;
FIG. 2 is a surface enhanced Raman spectrum of the enrofloxacin extract from the fish meat according to an embodiment of the present invention;
FIG. 3 is a surface enhanced Raman spectrum of the enrofloxacin extract in the abalone-positive sample in accordance with one embodiment of the present invention;
FIG. 4 is a surface enhanced Raman spectrum of the enrofloxacin extract in the aquaculture water negative sample in accordance with one embodiment of the present invention.
Detailed Description
The present invention will be described in detail and specifically with reference to the following examples and drawings so as to provide a better understanding of the invention, but the following examples do not limit the scope of the invention.
Example one
The embodiment is a method for detecting enrofloxacin residual quantity in aquaculture water by adopting a SERS active substrate modified by combining gold nanoparticles and a surface enhanced Raman spectroscopy technology.
Adding a plurality of volumes of enrofloxacin standard working solution into the aquaculture water to prepare aquaculture water samples with the concentrations of 0 mug/mL, 0.05 mug/mL and 0.1 mug/mL. The extraction method comprises the following steps: taking a proper amount of culture water sample, centrifuging at 4600r/min, putting 200 mu L of sample solution into a Raman sample pool, adding 20 mu L of 0.1mol/L KI solution, adding 10 mu L of 0.01% HNO3And adding 10 mu L of concentrated gold sol into the solution, mixing uniformly, standing for about 30s, and then testing.
As can be seen from FIG. 1, 1625, 1480, 1395, 1340, 640cm are represented by-1The characteristic peak is still visible, and the method can detect the residual enrofloxacin amount of 0.1 mu g/mL at the lowest energy.
Example two
The embodiment is a method for detecting enrofloxacin residual quantity in aquatic products by adopting a SERS active substrate modified by combining gold nanoparticles and a surface enhanced Raman spectroscopy technology.
Adding a plurality of volumes of enrofloxacin standard working solution into the homogenized blank fish sample to prepare fish samples with the concentration of 0 mug/kg, 50 mug/kg and 100 mug/kg. Extraction methodThe method comprises the following steps: weighing 5.0g of sample, placing the sample in a 50mL centrifuge tube, adding 5mL of 1% acetonitrile formate, carrying out oscillation extraction for 10min, adding 2g of anhydrous sodium sulfate, carrying out uniform mixing and dewatering, centrifuging the mixture for 5min at 4600r/min on a centrifuge, transferring the supernatant into another 15mL centrifuge tube, adding 5mL of 1% acetonitrile formate, repeatedly extracting once, combining the two supernatant extracting solutions, and drying the mixture by using nitrogen. Adding 1.0mL of 0.2% formic acid solution to dissolve the residue, performing vortex oscillation for 1min, adding 2mL of n-hexane, shaking for 1min, centrifuging for 5min at 4600r/min in a centrifuge, discarding the supernatant, placing 200 μ L of the lower layer liquid in a Raman sample cell, adding 20 μ L of 0.1mol/L KI solution, adding 10 μ L of 0.01% HNO3Adding 10 mu L of concentrated gold sol into the solution, uniformly mixing, standing for about 30s, and then determining by a Raman spectrometer.
As can be seen from FIG. 2, the distances of 1625, 1450, 1395, 1340 and 640cm are the same as those of the reference-1The characteristic peak is still visible, the method can detect 100 mu g/kg enrofloxacin residue at the lowest energy, and the limit requirement of the 235 th bulletin of the Ministry of agriculture on the maximum residual amount of enrofloxacin in aquatic products is met.
EXAMPLE III
The embodiment is that the enrofloxacin residual quantity in the abalone positive sample is detected by adopting a detection method of enrofloxacin by combining a gold nanoparticle modified SERS active substrate and a surface enhanced Raman spectroscopy technology. The specific implementation steps are as follows:
weighing 5.0g of sample and a blank labeled sample, respectively placing the sample and the blank labeled sample in 50mL centrifuge tubes, adding 5mL of 1% formic acid acetonitrile, oscillating and extracting for 10min, adding 2g of anhydrous sodium sulfate, uniformly mixing and dewatering, centrifuging for 5min at 4600r/min on a centrifuge, transferring a supernatant into another 15mL centrifuge tube, adding 5mL of 1% formic acid acetonitrile, repeatedly extracting once, combining supernatant extracting solutions of two times, and drying by using nitrogen. Adding 1.0mL of 0.2% formic acid solution to dissolve the residue, performing vortex oscillation for 1min, adding 2mL of n-hexane, shaking for 1min, centrifuging for 5min at 4600r/min in a centrifuge, discarding the supernatant, placing 200 μ L of the lower layer liquid in a Raman sample cell, adding 20 μ L of 0.1mol/L KI solution, adding 10 μ L of 0.01% HNO3Adding 10 μ L of concentrated gold sol, mixing, standing for about 30s, and measuring with Raman spectrometerAnd (4) measuring by a spectrometer. The results are shown in FIG. 3.
Example four
The embodiment is a method for detecting enrofloxacin residual quantity in a culture water negative sample by adopting a SERS active substrate modified by combining gold nanoparticles and a surface enhanced Raman spectroscopy technology. The specific implementation steps are as follows:
taking a proper amount of culture water sample and a blank labeled sample, centrifuging at 4600r/min, taking 200 mu L of sample solution to a Raman sample pool, adding 20 mu L of 0.1mol/L KI solution, adding 10 mu L of 0.01% HNO3And adding 10 mu L of concentrated gold sol into the solution, mixing uniformly, standing for about 30s, and then testing. The results are shown in FIG. 4.
According to the embodiments, the invention creatively discovers a detection method of enrofloxacin in water and aquatic products and an application thereof. The method overcomes the defects of the existing standard method for detecting enrofloxacin, has proper detection sensitivity, greatly shortens the detection time and saves the detection cost.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (9)
1. The method for detecting the enrofloxacin is characterized by comprising the steps of dropwise adding a sample containing the enrofloxacin on a nano gold particle modified Raman substrate with surface activity, and collecting an enrofloxacin surface enhanced Raman spectrum by using a Raman spectrometer after a solvent is evaporated to dryness.
2. The method for detecting enrofloxacin according to claim 1, wherein the surface enhanced Raman spectrum of enrofloxacin has 1625, 1480, 1450, 1395, 1340, 640cm-1Processing the characteristic peak.
3. The method for detecting enrofloxacin as claimed in claim 1, wherein the gold nanoparticles are gold sol.
4. The method for detecting enrofloxacin according to claim 3, wherein the colloidal gold is prepared by the following method:
accurately weighing chloroauric acid to prepare aqueous solution of chloroauric acid with a preset concentration, putting the prepared aqueous solution of chloroauric acid into a container, heating to boil, rapidly adding a proper amount of trisodium citrate aqueous solution while stirring, continuously heating for a preset time, stopping heating, cooling the obtained gold sol to room temperature, and storing at low temperature in a dark place.
5. The application of the detection method of any one of claims 1 to 4 in detecting the residual amount of enrofloxacin in a water body or an aquatic product.
6. The use of claim 5, wherein the step of detecting the residual amount of enrofloxacin in the body of water comprises: taking a proper amount of culture water sample, centrifuging, taking a sample solution, adding a proper amount of KI solution into a Raman sample pool, and adding HNO3Adding a proper amount of concentrated gold sol into the solution, uniformly mixing, standing and then measuring by a Raman spectrometer.
7. The use of claim 6, wherein the use detects a minimum of 0.1 μ g/mL enrofloxacin residue in the body of water.
8. The use of claim 5, wherein the step of detecting residual amount of enrofloxacin in the aquatic product comprises: weighing a sample, adding acetonitrile formate, performing oscillation extraction, adding anhydrous sodium sulfate, uniformly mixing, dewatering and centrifuging; adding acetonitrile formate into the supernatant, repeatedly extracting for one time, combining the supernatant extract obtained in the two times, and drying by using nitrogen; adding formic acid solution to dissolve residue, vortex oscillating, adding n-hexane, shaking, centrifuging, discarding supernatant, and collecting lower layer liquidAdding KI solution and HNO into the Manan sample cell3Adding a proper amount of concentrated gold sol into the solution, uniformly mixing, and standing for measurement by a Raman spectrometer.
9. The use of claim 8, wherein the use detects a minimum of 100 μ g/kg enrofloxacin residual in the aquatic product.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106645084A (en) * | 2016-11-21 | 2017-05-10 | 佳木斯大学 | Active substrate for detecting enrofloxacin by utilizing surface-enhanced Raman spectroscopy as well as preparation method and application thereof |
| CN107290470A (en) * | 2017-06-22 | 2017-10-24 | 中山市农产品质量监督检验所 | A kind of method of sulfamido and quinolones medicament relict in quick measure egg |
| CN109731559A (en) * | 2019-03-21 | 2019-05-10 | 吉林师范大学 | Enrofloxacin HCL in trace film preparation and selective enumeration method water based on Surface enhanced Raman scattering |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106645084A (en) * | 2016-11-21 | 2017-05-10 | 佳木斯大学 | Active substrate for detecting enrofloxacin by utilizing surface-enhanced Raman spectroscopy as well as preparation method and application thereof |
| CN107290470A (en) * | 2017-06-22 | 2017-10-24 | 中山市农产品质量监督检验所 | A kind of method of sulfamido and quinolones medicament relict in quick measure egg |
| CN109731559A (en) * | 2019-03-21 | 2019-05-10 | 吉林师范大学 | Enrofloxacin HCL in trace film preparation and selective enumeration method water based on Surface enhanced Raman scattering |
Non-Patent Citations (2)
| Title |
|---|
| YUANYUAN ZHANG等: "Analyses of enrofloxacin, furazolidone and malachite green in fish products with surface-enhanced Raman spectroscopy", 《FOOD CHEMISTRY》 * |
| 李耀: "基于表面增强拉曼光谱技术对鸭肉中喹诺酮类抗生素残留检测研究", 《中国优秀硕士学位论文全文数据库农业科技辑》 * |
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