CN112945931A - Raman rapid detection method of sulfamonomethoxine in dairy product - Google Patents
Raman rapid detection method of sulfamonomethoxine in dairy product Download PDFInfo
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- CN112945931A CN112945931A CN202110150340.2A CN202110150340A CN112945931A CN 112945931 A CN112945931 A CN 112945931A CN 202110150340 A CN202110150340 A CN 202110150340A CN 112945931 A CN112945931 A CN 112945931A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4055—Concentrating samples by solubility techniques
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4055—Concentrating samples by solubility techniques
- G01N2001/4061—Solvent extraction
Abstract
The invention discloses a Raman rapid detection method of sulfadimethoxine in dairy products, which comprises the following steps: s1) sample treatment: weighing a proper amount of dairy product sample, adding a protein precipitator and an organic extraction solvent, and centrifuging for 2-5min at 4000rpm/min by ultrasonic or vortex for 1-5 min; adding purified filler into the supernatant, performing ultrasonic treatment or vortex for 1-5min, and centrifuging at 4000rpm/min for 1-5 min; taking the upper layer liquid, drying with nitrogen, adding the complex solution after drying, and redissolving to form a liquid to be detected; s2) raman detection: and adding a proper amount of the solution to be detected, the metal sol and the auxiliary reinforcing reagent into the Raman detection pool, uniformly mixing and detecting. The detection method provided by the invention is simple and convenient to operate, the detection result meets the requirements of sulfamonomethoxine in national standards, the detection requirements of quick screening and rechecking of customs ports and time length supervision departments in various regions are met, the detection time is short, and the cost is low.
Description
Technical Field
The invention relates to a method for detecting dairy products, in particular to a Raman rapid detection method of sulfamonomethoxine in dairy products.
Background
Sulfonamides are a generic term for a class of drugs having a sulfanilamide structure, and are commonly used broad-spectrum antibacterial drugs. Sulfonamides are widely used in animal breeding for the prevention and treatment of bacterial infectious diseases due to their broad antimicrobial spectrum, high efficiency, low toxicity and low price. The sulfanilamide medicines often cause residue of the sulfanilamide medicines in edible tissues of animals due to long action and metabolism time of the sulfanilamide medicines in the animals, and if the food containing the sulfanilamide medicines residue is eaten for a long time, the sulfanilamide medicines are possibly accumulated in the bodies, so that the health of human bodies is seriously threatened. The harmfulness is mainly shown in that drug-resistant strains are generated in human bodies to cause anaphylactic reaction; damage to the immune system and blood system resulting in hematopoietic disorders; damage to the urinary system and teratogenicity, mutagenicity and carcinogenesis.
At present, the main detection methods of sulfanilamide comprise an enzyme-linked immunosorbent assay, solid phase extraction-high performance liquid chromatography, liquid chromatography-mass spectrometry and the like. The enzyme-linked immunosorbent assay is widely applied as a screening method, but false positive is easy to occur. Although the liquid chromatography and the liquid chromatography-mass spectrometry can obtain a relatively accurate result, the method often has a series of problems of expensive instruments and equipment, complex sample processing method, long detection time and the like, and cannot meet the real-time, on-site and effective requirements urgently needed by sample detection under the situation that the current food safety problem frequently occurs. Therefore, it is very important to develop a method with high speed, convenience and sensitivity. The Raman spectrum analysis method has the advantages of rich information, no need of sample treatment, quick and convenient detection, high specificity and the like, so that the method has unique advantages in food or drug inspection and can reflect the symmetric vibration of molecules without infrared activity and the vibration of nonpolar groups, and therefore, the Raman spectrum and the infrared spectrum are often combined together to carry out complete analysis on substance molecules together. However, in general, the raman signal of a sample is very weak, the Surface Enhanced Raman Spectroscopy (SERS) overcomes the defect of low sensitivity of the conventional raman spectroscopy, completely inherits the advantages of good raman spectroscopy specificity, no interference from water, capability of providing rich molecular structure information, support of simultaneous detection of multiple components and the like, and shows the superior capability of on-site rapid detection of food and drugs. With the marketization of portable raman spectrometers, SERS-based identification techniques have been rapidly developed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a Raman rapid detection method of sulfamonomethoxine in dairy products, which can meet the detection requirements of sulfamonomethoxine on food matrixes such as dairy products and the like on the aspects of simplicity, rapidness, low cost, high sensitivity and the like.
The technical scheme adopted by the invention for solving the technical problems is to provide a Raman rapid detection method of sulfamonomethoxine in dairy products, which comprises the following steps: s1) sample treatment: weighing a proper amount of dairy product sample, adding a protein precipitator and an organic extraction solvent, and centrifuging for 2-5min at 4000rpm/min by ultrasonic or vortex for 1-5 min; adding purified filler into the supernatant, performing ultrasonic treatment or vortex for 1-5min, and centrifuging at 4000rpm/min for 1-5 min; taking the upper layer liquid, drying with nitrogen, adding the complex solution after drying, and redissolving to form a liquid to be detected; s2) raman detection: and adding a proper amount of the solution to be detected, the metal sol and the auxiliary reinforcing reagent into the Raman detection pool, uniformly mixing and detecting.
Further, the dairy product sample in the step S1 is a fresh milk sample or a milk product.
Further, the protein precipitant in step S1 is a mixed solution of zinc acetate and saturated potassium ferrocyanide with a mass concentration of 20% -40%, or the protein precipitant in step S1 is an aqueous solution of trichloroacetic acid with a mass concentration of 8% -15%.
Further, the organic extraction solvent in step S1 includes one of petroleum ether, ethyl acetate, and n-hexane.
Further, the sample is processed by vortexing and centrifuging in step S1 until a significant precipitation phenomenon occurs.
Further, the purification filler in the step S1 includes one of C18, neutral alumina and florisil.
Further, the re-solution in the step S1 is one of an ethanol aqueous solution with a volume concentration of 10% to 20% and a methanol aqueous solution with a volume concentration of 10% to 20%, and 500 μ L of the re-solution is added.
Further, the metal sol in the step S2 is a nano metal sol including gold nanoparticles or silver nanoparticles.
Further, the auxiliary enhancing reagent in step S2 is a sodium chloride solution with a molar concentration of 0.01-1M.
Further, the detection process in step S2 is as follows: detecting the concentration of the sample in the bottle according to a volume ratio of 1: 0.5-2: and 0.1-1, adding the solution to be detected, the nano metal sol and the sodium chloride solution, uniformly mixing, and detecting in a Raman sample detection pool by using a portable Raman spectrometer.
Compared with the prior art, the invention has the following beneficial effects: the Raman rapid detection method of the sulfamonomethoxine in the dairy product, provided by the invention, has the advantages that a dairy product sample is collected on site, the surface enhanced Raman scattering effect of the metal nanoparticles is combined through simple pretreatment, the operation is simple and convenient, and the detection requirements of the sulfamonomethoxine in food matrixes such as dairy products and the like on the aspects of simplicity, rapidness, low cost, high sensitivity and the like are met. The detection result meets the requirements of sulfadimethoxine in national standard GB31650-2019 food safety national standard and maximum veterinary drug residue in food, meets the detection requirements of quick screening and rechecking of customs ports and time length supervision departments in various regions, and has short detection time and low cost.
Drawings
FIG. 1 is a graph of the signals of the labeled detection of sulfadimethoxine in pasteurized whole milk in accordance with an embodiment of the present invention;
FIG. 2 is a graph of the signals of the sulfamonomethoxine labeled detection in pasteurized skim milk in the example;
FIG. 3 is a graph of the signal of sulfamonomethoxine in fresh cow milk.
Detailed Description
The invention is further described below with reference to the figures and examples.
The invention provides a Raman rapid detection method of sulfamonomethoxine in dairy products, which comprises the following steps:
s1) sample treatment: weighing a proper amount of dairy product sample, adding a protein precipitator and an organic extraction solvent, performing ultrasonic treatment or vortex for 1-5min, centrifuging at 4000rpm/min for 2-5min until obvious precipitation occurs, and removing protein which is subjected to coagulation after the protein precipitator is added; adding the supernatant into the purification filler, performing ultrasonic treatment or vortex for 1-5min, and centrifuging at 4000rpm/min for 1-5min until obvious precipitation occurs to remove the purification filler; taking the upper layer liquid, drying with nitrogen, adding the complex solution after drying, and redissolving to form the liquid to be detected.
The protein precipitant can select trichloroacetic acid with mass concentration of 8-15%, or select mixed solution of zinc acetate and saturated potassium ferrocyanide with mass concentration of 20-40%, and zinc ferricyanide generated by chemical reaction of zinc acetate and potassium ferrocyanide is complexed with protein in the sample to form precipitate, so as to remove protein in the sample. The two reagents act synergistically, and the addition of the reagents can better remove proteins from the sample.
The organic extraction solvent comprises one of petroleum ether, ethyl acetate and n-hexane; the purifying filler comprises one of C18, neutral alumina and Florisil; the complex solution is one of water solution, ethanol water solution with volume concentration of 10-20% and methanol water solution with volume concentration of 10-20%, and 500 mu L of the complex solution is added.
S2) raman detection: and adding a proper amount of the solution to be detected, the metal sol and the auxiliary reinforcing reagent into the Raman detection pool, uniformly mixing and detecting. In order to avoid affecting the sensitivity and causing the final test signal value of the instrument to be lower, the specific detection process is as follows: detecting the concentration of the sample in the bottle according to a volume ratio of 1: 0.5-2: and 0.1-1, adding the solution to be detected, the nano metal sol and the sodium chloride solution, uniformly mixing, and detecting in a Raman sample detection pool by using a portable Raman spectrometer. The metal sol is a nano metal sol containing gold nanoparticles or silver nanoparticles, and the auxiliary reinforcing agent is a sodium chloride solution with the molar concentration of 0.01-1M.
Example one
The method for detecting different concentrations of pasteurized skim milk samples comprises the following steps:
preparing a standard substance: prepare standard sulfadimethoxine solution with concentration of 0.1 mg/kg.
Adding a standard to a sample and pretreating: and (3) adding the standard of the samples according to the middle limit value point of GB31650 plus 2019 food safety national standard and the maximum veterinary drug residue in food to ensure that the added standard concentration meets the requirement of the national standard limit value.
Taking 1mL milk, adding 50 μ L30% zinc sulfate, 50 μ L saturated potassium ferrocyanide, adding 2mL ethyl acetate, vortex and shake for 2min, and centrifuging at 4000rpm/min for 2 min. Taking all supernatant, adding 0.3g neutral alumina, vortex oscillating for 2min, and centrifuging at 4000rpm/min for 1 min. Taking all the upper layer liquid, drying with nitrogen, adding 200 mu L of water for redissolving after drying.
During the determination, 50 μ L of the solution to be determined is taken, 20 μ L of 1M NaCl is added, 100 μ L of gold nanoparticles are added, the mixture is rapidly and uniformly mixed, the detection is carried out on a machine, the detection result is shown in figure 1, the characteristic peaks are 664 and 822cm-1。
Example two
Adopting standard substances with a series of concentrations in the example I and adopting the same labeling method to perform labeling, pretreatment and detection on the pasteurized whole milk sample, wherein the detection result is shown in figure 2, and the characteristic peaks are 664 and 822cm-1。
EXAMPLE III
Adopting a series of standard substances with concentration in the first embodiment and adopting the same labeling method to perform labeling, pretreatment and detection on a fresh milk sample, wherein the detection result is shown in figure 3, and the characteristic peaks are 664 and 822cm-1。
In the detection process of the embodiment, the detection time of the sample is not more than 20min, the cost of single experimental material detection is within 5-10 yuan, compared with the traditional detection methods such as liquid chromatography, gas chromatography, mass spectrometry and the like, the method is not only quick and cheap, but also meets the detection requirements of quick screening and rechecking of customs ports and market supervision departments in various regions.
According to the method, based on the SERS technology, the metal nanoparticles are used as an SERS substrate, the residual sulfadimethoxine in the dairy product is enriched and separated through pretreatment, and a portable Raman spectrum device is applied to obtain an SERS spectrogram of the sulfadimethoxine. The invention has the advantages that: 1. the invention combines a simple, high-efficiency and cheap pretreatment scheme to finish the quick detection of pasteurized whole milk, pasteurized skim milk and fresh milk; the detection time of the method is within 20min, the single detection cost is controlled within 5-10 yuan, and compared with methods such as liquid chromatography, gas chromatography, mass spectrometry and the like, the cost is only 10-20%. 2. The method has the advantages of good impurity removal effect, good detection accuracy, no false positive and false negative errors, and capability of meeting the detection requirements of rapid screening and rechecking of customs ports and market supervision departments in various regions. 3. The sensitivity is high, the detection can be carried out to 0.1mg/kg, and the requirements of national standard limit GB31650-2019 national standard for food safety and maximum veterinary drug residue in food are met.
Although the present invention has been described with respect to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A Raman rapid detection method of sulfamonomethoxine in dairy products is characterized by comprising the following steps:
s1) sample treatment: weighing a proper amount of dairy product sample, adding a protein precipitator and an organic extraction solvent, and centrifuging for 2-5min at 4000rpm/min by ultrasonic or vortex for 1-5 min; adding purified filler into the supernatant, performing ultrasonic treatment or vortex for 1-5min, and centrifuging at 4000rpm/min for 1-5 min; taking the upper layer liquid, drying with nitrogen, adding the complex solution after drying, and redissolving to form a liquid to be detected;
s2) raman detection: and adding a proper amount of the solution to be detected, the metal sol and the auxiliary reinforcing reagent into the Raman detection pool, uniformly mixing and detecting.
2. The method for Raman-rapid detection of sulfadimethoxine in dairy products according to claim 1, wherein the dairy product sample in step S1 is fresh milk or milk product.
3. The method for Raman rapid detection of sulfadimethoxine in dairy products according to claim 1, wherein the protein precipitant in step S1 is a mixed solution of zinc acetate and saturated potassium ferrocyanide with a mass concentration of 20% -40%, or the protein precipitant in step S1 is an aqueous solution of trichloroacetic acid with a mass concentration of 8% -15%.
4. The method for Raman rapid detection of sulfadimethoxine in dairy products according to claim 1, wherein the organic extraction solvent in step S1 comprises one of petroleum ether, ethyl acetate and n-hexane.
5. The method for Raman rapid detection of sulfadimethoxine in dairy products according to claim 1, wherein the sample is subjected to vortex and centrifugation in step S1 until significant precipitation occurs.
6. The method for Raman rapid detection of sulfadimethoxine in dairy products according to claim 1, wherein the purification filler in step S1 comprises one of C18, neutral alumina and Florisil silica.
7. The Raman rapid detection method of sulfadimethoxine in dairy products of claim 1, wherein the reconstituted solution in step S1 is one of an aqueous solution of ethanol with a volume concentration of 10% -20% and an aqueous solution of methanol with a volume concentration of 10% -20%, and the volume of the reconstituted solution is 200-500 μ L.
8. The method for Raman rapid detection of sulfadimethoxine in dairy products according to claim 1, wherein the metal sol in step S2 is a nano metal sol containing gold nanoparticles or silver nanoparticles.
9. The method for Raman scattering detection of sulfadimethoxine in dairy products of claim 8, wherein the auxiliary enhancing reagent in step S2 is sodium chloride solution with molar concentration of 0.01-1M.
10. The method for Raman rapid detection of sulfadimethoxine in dairy products according to claim 9, wherein the detection process in step S2 is as follows: detecting the concentration of the sample in the bottle according to a volume ratio of 1: 0.5-2: and 0.1-1, adding the solution to be detected, the nano metal sol and the sodium chloride solution, uniformly mixing, and detecting in a Raman sample detection pool by using a portable Raman spectrometer.
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Cited By (1)
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| CN110672580A (en) * | 2019-09-28 | 2020-01-10 | 上海如海光电科技有限公司 | Raman rapid detection method for tetrahydrocannabinol in food beverage and vegetable oil |
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