CN109580575B - Antibiotic detection method based on molecular imprinting-Raman spectroscopy - Google Patents
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Abstract
The invention relates to an antibiotic detection method based on molecular imprinting-Raman spectroscopy, and belongs to the technical field of food detection. Antibiotic is taken as template molecules, a composite nano material (MIP-PNM-Au) consisting of a PNIPAM temperature-sensitive gel film imprinted by antibiotic molecules and nano gold is provided, and enrichment and ultra-sensitive Raman spectrum detection of the antibiotic are realized by utilizing the Raman enhancement effect of the composite material. The method combines the specific recognition function of molecular imprinting technology (MIP), the intelligent response characteristic of gel and the gold nanoparticle SERS property. The MIP-PNM-Au composite material improves the selective enrichment effect of the composite material through a molecular imprinting technology, and adjusts the parameters such as density, space and the like of nano particles by means of the temperature-sensitive property of gel, so that the surface plasma resonance and the electromagnetic field intensity are tuned, the dynamic generation of 'hot spots' is realized, and the Raman enhancement effect is optimized.
Description
Technical Field
The invention relates to an antibiotic detection method based on molecular imprinting-Raman spectroscopy, and belongs to the technical field of food detection.
Background
Antibiotics (Antibiotics) are a class of secondary metabolites produced by higher animals and plants or microorganisms during metabolism
It is a chemical substance capable of interfering the development of pathogenic bacteria, and has the property of resisting pathogen or other cell activity. Self-resistance
Since the discovery of biotin, biotin is widely used in human beings, aquatic products and the like due to its characteristics of high efficiency, low cost and easy mass culture
Controlling and treating bacterial diseases of livestock and poultry. However, over the twenty-first century, the phenomenon of antibiotics abuse worldwide
In China, particularly, according to relevant investigation, the usage amount of antibiotics in China in 2013 reaches 16.2 ten thousand tons, which accounts for about half of the world usage amount, wherein 48% of the antibiotics are used for human beings, 52% of the antibiotics are used for livestock, poultry and aquatic products, and more than 5 ten thousand tons of antibiotics are discharged into the environment. Although many countries in the world, including china, have already been provided with relevant documents to limit or prohibit the use of certain antibiotics, the abuse of these antibiotics is still often prohibited due to their high efficiency, low cost, and regulatory nature. Antibiotics are slowly decomposed and can remain in human bodies, and also can remain in the environment through excretion and other ways to pollute food, so that the drug resistance of bacteria in nature is enhanced. In addition, the excessive use of antibiotics also has toxic reaction to human bodies, and seriously threatens the life health of human beings. Therefore, the development of efficient, fast, pollution-free, and low-cost analytical techniques is the trend for future antibiotic detection.
At present, the detection methods of antibiotic residues at home and abroad mainly comprise biological assay methods (microbiological assay methods, radioreceptor assay methods and the like), physicochemical detection methods (wave spectrum methods, chromatography methods, combination technologies thereof and the like) and immunoassay methods (radioimmunoassay, enzyme-linked immunoassay methods, fluorescence immunoassay methods and the like). The methods are limited to different detection fields due to different advantages and disadvantages, such as simple operation and low price of the microbial detection method, but low detection sensitivity and long time consumption; the physicochemical detection method has high accuracy and sensitivity, but the operation procedure is complex, the detection cost is expensive, and rapid detection and analysis can not be carried out; the immunoassay method is an analysis method for detecting various substances (drugs, hormones, proteins, microorganisms and the like) by utilizing antigen-antibody specific binding reaction, has the advantages of high sensitivity, strong specificity, rapidness and low cost, and has the defect of high false positive rate. Therefore, the development of a simple, rapid and high-sensitivity antibiotic trace detection technology has great significance on food and environmental safety in China.
Surface-enhanced raman spectroscopy (SERS) has been widely used in molecular detection due to its advantages of being non-destructive, fast, convenient, and highly sensitiveAnd (4) the field of measurement. Studies have shown that the mechanism of SERS derives mainly from electromagnetic enhancement. The resonance local electromagnetic field generated by plasma excitation is greatly enhanced if a nanogap structure smaller than 10nm exists between two nanoparticles, and the region is generally and vividly called as a 'hot spot', and when the molecule is positioned at the special 'hot spot', the enhancement factor generated by the region can reach 108And the more hot spots that are formed, the greater the enhancement that will be exhibited.
In recent years, researchers at home and abroad use SERS for antibiotic detection, and obvious effect is achieved, L Liescu et al of Romani utilize silver sol as an enhanced substrate to carry out Raman spectrum detection on penicillin potassium [1]. Stiman et al detected chloramphenicol by using a silver sol solution prepared by a microwave heating method, and the measured characteristic peak position of chloramphenicol was substantially consistent with the result of simulation calculation using Gaussian98 [2 ]]The feasibility of using SERS for antibiotic detection is demonstrated. The Chenqianwang group takes hollow gold nano material as a substrate to carry out SERS spectrum detection on tetracycline solution, and the lowest detectable concentration is 0.1ppb [3 ]]. Likeqiang et al used a commercially available Klarite substrate to perform SERS detection on three sulfanilamide antibiotics (sulfadiazine, sulfadimidine and sulfamethoxazole) with a detectable minimum concentration of 10ppb [4,5 ppb ]]. The prepared gold sol is used by Xie et al in 2012 to detect nitrofurantoin and furaltadone solutions with different concentrations, and the lowest concentration of the nitrofurantoin and the furaltadone solutions which can be detected by the two solutions is 5ppm [6 ]]In 2013, Majun and the like prepare silver sol films by a self-assembly method, SERS (surface enhanced Raman scattering) spectrum detection is carried out on chloramphenicol, ciprofloxacin and enrofloxacin by using a micro-Raman system, and the lowest detection concentrations are respectively 120nmol L-1、15nmol·L-1And 120 nmol. L-1[7]. Whit et al of Maryland university in America designs a pumpless flowing SERS micro system for detecting three bactericides (methyl parathion, malachite green and thiram) in aquaculture water, can obviously distinguish the three bactericides, and the minimum detection concentrations of the three bactericides obtained through experiments are 5ppm, 0.1ppb and 1ppb [8 ppb ] respectively]。
There are also certain problems to be solved in applying SERS to the detection of antibiotics. Due to the fact that the nature and the source of the sample are different, the complexity of the matrix composition is different, and the antibiotics often exist in trace quantity and are difficult to directly detect through SERS, the key to the pretreatment of the sample is to be carried out simply, conveniently and efficiently. The solid phase extraction technology has been widely used in antibiotic detection as an effective method for improving the efficiency of sample pretreatment. The technology has the advantages of small solvent consumption, high treatment efficiency, simple operation, easy automation, capability of treating a large number of samples and the like, and is widely applied to the sample pretreatment process. However, the common solid phase extraction method lacks selectivity, so that other high-concentration pollutants can be extracted simultaneously while adsorbing the trace pollutants in the concentrated environment, the efficiency of sample pretreatment is influenced, and the application value of the method in the pretreatment of the trace pollutants in the environment is reduced.
[1]Lliescu T, Baia M, Pavel I. Raman and SERS investigations ofpotassium benzylpenicillin. J.Raman Spectroscopy, 2006, 37, 318-325.
[2]Si M Z, Kang Y P, Zhang Z G. Surface-enhanced Raman scattering(SERS) spectra ofchloramphenicol in Ag colloids prepared by microwave heatingmethod. J. Raman Spectroscopy, 2009, 40, 1319-1323.
[3]Li R, Zhang H, Chen Q W, et al. Improved surface-enhanced Ramanscattering onmicro-scale Au hollow spheres: Synthesis and application indetecting tetracycline. Analyst,2011, 136, 2527-2532.
[4]Lai K Q, Zhai F L, Zhang Y Y, et al. Application of surfaceenhanced Raman spectroscopy for analyses of restricted sulfa drugs. Sensingand Instrumentation for Food Quality and Safety, 2011, 5: 91-96.
[5]Zhang Y Y, Huang Y Q, Zhai F L, et al. Analyses of enrofloxacin,furazolidone and malachite green in fish products with surface-enhanced Ramanspectroscopy. Food Chemistry, 2012, 135:845-850.
[6]Xie Y F, Zhu X Y, Sun Y Y, et al. Rapid detection method fornitrofuran antibiotics residues by surface-enhanced Raman spectroscopy. EurFood Res Technol, 2012, 235: 555-561.
[7] Majun, Koddy, Korea Red, et al, surface enhanced Raman spectroscopy studies using silver sol membranes to probe antibiotics in water spectroscopic, spectroscopic and spectroscopic analyses, 2013, 33 (10): 2688-2693.
[8]Yazdi S H, White l M. Mutiplexed detection of aquaculturefungicides using a pump-free optofluidic SERS microsystem. Analyst, 2013,138: 100-103.
Disclosure of Invention
The patent uses tetracycline antibiotics as template molecules, provides a composite nanomaterial (MIP-PNM-Au) consisting of a PNIPAM temperature-sensitive gel film imprinted by the antibiotics and nanogold, and realizes enrichment and ultra-sensitive Raman spectrum detection of the antibiotics by utilizing the Raman enhancement effect of the composite nanomaterial. The method combines the specific recognition function of molecular imprinting technology (MIP), the intelligent response characteristic of gel and the gold nanoparticle SERS property. The MIP-PNM-Au composite material improves the selective enrichment effect of the composite material through a molecular imprinting technology, and adjusts the parameters such as density, space and the like of nano particles by means of the temperature-sensitive property of gel, so that the surface plasma resonance and the electromagnetic field intensity are tuned, the dynamic generation of 'hot spots' is realized, and the Raman enhancement effect is optimized. In addition, the interference of macromolecular substances in the object to be detected can be eliminated through the three-dimensional network structure of the gel and the expansion-contraction property of the gel to the temperature, so that the antibiotics can be rapidly and selectively captured and enriched, and the method can be applied to the ultra-sensitive SERS detection of the antibiotics in complex samples.
An antibiotic detection method based on molecular imprinting-Raman spectroscopy comprises the following steps:
adding a solution consisting of 1-3 g of N-isopropylacrylamide, 0.2-0.4 g of tetracycline, 15-25 mg of sodium hexadecylsulfonate, 15-25 mg of a crosslinking agent N, N-methylene bisacrylamide, 120-160 m of L deionized water and 20-30 m of L nano gold sol solution into a flask with a condensation reflux and magnetic stirring device, uniformly dispersing under an ultrasonic field, heating to 65-75 ℃ under the protection of nitrogen flow, rapidly adding the prepared 8-12 m of L ammonium persulfate solution, pouring the solution into a mold for reaction to generate a film-shaped gel, and after the reaction is finished, carrying out electric field dialysis purification to remove substances such as a surfactant, unreacted monomers and the like to obtain the PNM-Au composite hydrogel;
and 4, drawing a standard curve: preparing tetracycline aqueous solutions with different concentrations, respectively dispersing the Raman spectrum substrate in a tetracycline standard solution for adsorption, filtering, spreading on a glass slide, detecting by using a solid laser head of a surface enhanced Raman spectrum, and drawing a curve relation between a response value and the concentration to obtain a standard curve;
In one embodiment, in the step 1, the temperature of the deionized water is 0-4 ℃; k2CO3The solution concentration was 0.2 mol. L-1；NaBH4The concentration of the solution was 0.5 mg. m L-1。
In one embodiment, in the step 2, the reaction process is carried out for 4 hours at 65-75 ℃, and the concentration of the ammonium persulfate solution is 0.0184 mol. L-1(ii) a 0.2-0.4 g of methoxy polyethylene glycol methacrylate monomer is also added in the reaction process.
In one embodiment, in the step 3, the elution condition is that the elution is carried out for 0.5-1 h under the action of ultrasonic waves.
In one embodiment, in the step 4, the concentration range of the tetracycline aqueous solution is 0.5ng/m L-10000 ng/m L, and the adsorption temperature is 32-35 ℃.
In one embodiment, the sample to be tested is milk, wastewater, surface water or food extract.
Advantageous effects
1. The invention provides an antibiotic detection method based on molecular imprinting-Raman spectroscopy, which adopts a composite nano material (MIP-PNM-Au) consisting of a PNIPAM temperature-sensitive gel film and nano gold, and realizes enrichment of antibiotics and ultra-sensitive Raman spectroscopy detection by utilizing the Raman enhancement effect of the composite material. The method has the advantages of good sensitivity, high accuracy and short detection time. 2. The hydrogel adopts a film shape, so that the temperature sensitivity of the hydrogel can be observed in the sample treatment process; 3. the temperature-sensitive gel can adsorb a sample under the gel expansion condition, so that the effects of quick adsorption and detection are realized.
Drawings
Fig. 1 shows the ultraviolet absorption spectrum of the composite nanomaterial (MIP-PNM-Au) prepared in example 1 and AuNPs in a room temperature free state, and it can be seen from the graph that the wavelength of L SPR of AuNPs is about 509nm, and the wavelength of L SPR of AuNPs on MIP-PNM-Au is about 529 nm, and a significant red shift occurs.
FIG. 2 is a graph showing the linearity of the detection of a tetracycline standard solution by the method of example 1 of the present invention, and it can be seen that the linearity of the detection method of the present invention is good.
Detailed Description
Example 1
adding a solution consisting of 1g of N-isopropyl acrylamide, 0.2g of tetracycline, 15mg of sodium hexadecylsulfonate, 15mg of a cross-linking agent N, N-methylene bisacrylamide, 120m L deionized water and 20m L nano gold sol solution into a flask with a condensation reflux and magnetic stirring device, uniformly dispersing under an ultrasonic field, heating to 65 ℃ under the protection of nitrogen flow, rapidly adding the prepared 8m L ammonium persulfate solution, pouring the solution into a mold for reaction, generating film-shaped gel after the reaction is finished, and after the gel is cut, purifying by electric field dialysis to remove substances such as a surfactant, unreacted monomers and the like to obtain the PNM-Au composite hydrogel;
and 4, drawing a standard curve, namely preparing tetracycline aqueous solutions with different concentrations, wherein the concentrations of the tetracycline aqueous solutions are 0.5ng/m L, 1ng/m L, 5ng/m L, 10ng/m L, 100ng/m L, 200ng/m L, 5000ng/m L and 10000ng/m L, respectively dispersing the Raman spectrum substrate in the tetracycline standard solution for adsorption, wherein the adsorption temperature is 32 ℃, filtering, spreading on a glass slide, detecting by using a solid laser head for surface enhanced Raman spectrum, and drawing a response value (1315 cm is adopted)-1Absorbance value) and concentration to obtain a standard curve;
Example 2
adding a solution consisting of 3g of N-isopropyl acrylamide, 0.4g of tetracycline, 25mg of sodium hexadecylsulfonate, 25mg of a crosslinking agent N, N-methylene bisacrylamide, 160m of L deionized water and 30m of L nano gold sol solution into a flask with a condensation reflux and magnetic stirring device, uniformly dispersing under an ultrasonic field, heating to 75 ℃ under the protection of nitrogen flow, rapidly adding a prepared 12m of L ammonium persulfate solution, pouring the solution into a mold for reaction, generating film-shaped gel after the reaction is finished, and after the gel is cut, purifying by electric field dialysis to remove substances such as a surfactant, unreacted monomers and the like to obtain the PNM-Au composite hydrogel;
and 4, drawing a standard curve, namely preparing tetracycline aqueous solutions with different concentrations, wherein the concentrations of the tetracycline aqueous solutions are 0.5ng/m L, 1ng/m L, 5ng/m L, 10ng/m L, 100ng/m L, 200ng/m L, 5000ng/m L and 10000ng/m L, respectively dispersing the Raman spectrum substrate in the tetracycline standard solution for adsorption, wherein the adsorption temperature is 35 ℃, filtering, spreading on a glass slide, detecting by using a solid laser head for surface enhanced Raman spectrum, and drawing a response value (1315 cm is adopted)-1Absorbance value) and concentration to obtain a standard curve;
Example 3
adding a solution consisting of 2g of N-isopropylacrylamide, 0.3g of tetracycline, 20mg of sodium hexadecylsulfonate, 20mg of a crosslinking agent N, N-methylene bisacrylamide, 140m of L deionized water and 25m of L nano gold sol solution into a flask with a condensation reflux and magnetic stirring device, uniformly dispersing under an ultrasonic field, heating to 70 ℃ under the protection of nitrogen flow, rapidly adding the prepared 10m of L ammonium persulfate solution, pouring the solution into a mold for reaction, generating film-shaped gel after the reaction is finished, and after the gel is cut, purifying by electric field dialysis to remove substances such as a surfactant and unreacted monomers to obtain the PNM-Au composite hydrogel;
and 4, drawing a standard curve, namely preparing tetracycline aqueous solutions with different concentrations, wherein the concentrations of the tetracycline aqueous solutions are 0.5ng/m L, 1ng/m L, 5ng/m L, 10ng/m L, 100ng/m L, 200ng/m L, 5000ng/m L and 10000ng/m L, respectively dispersing the Raman spectrum substrate in the tetracycline standard solution for adsorption, wherein the adsorption temperature is 33 ℃, filtering, spreading on a glass slide, detecting by using a solid laser head for surface enhanced Raman spectrum, and drawing a response value (1315 cm is adopted)-1Absorbance value) and concentration to obtain a standard curve;
Example 4
adding a solution consisting of 2g of N-isopropylacrylamide, 0.3g of tetracycline, 20mg of sodium hexadecylsulfonate, 20mg of a crosslinking agent N, N-methylene bisacrylamide, 0.3g of methoxy polyethylene glycol methacrylate monomer, 140m of L deionized water and 25m of L nano gold sol solution into a flask with a condensation reflux and magnetic stirring device, uniformly dispersing under an ultrasonic field, heating to 70 ℃ under the protection of nitrogen flow, quickly adding the prepared 10m of L ammonium persulfate solution, pouring the solution into a mold for reaction, generating film-shaped gel after the reaction is finished, cutting the gel, purifying by electric field dialysis, removing substances such as a surfactant, unreacted monomers and the like, and obtaining the PNM-Au composite hydrogel;
and 4, drawing a standard curve, namely preparing tetracycline aqueous solutions with different concentrations, wherein the concentrations of the tetracycline aqueous solutions are 0.5ng/m L, 1ng/m L, 5ng/m L, 10ng/m L, 100ng/m L, 200ng/m L, 5000ng/m L and 10000ng/m L, respectively dispersing the Raman spectrum substrate in the tetracycline standard solution for adsorption, wherein the adsorption temperature is 33 ℃, filtering, spreading on a glass slide, detecting by using a solid laser head for surface enhanced Raman spectrum, and drawing a response value (1315 cm is adopted)-1Absorbance value) and concentration to obtain a standard curve;
Comparative example 1
The differences from example 1 are: the adsorption temperature in the standard curve plotting step was 25 ℃.
Comparative example 2
The differences from example 1 are: the adsorption temperature in the standard curve plotting step was 40 ℃.
Comparative example 3
The differences from example 1 are: the absorption temperature of the Raman spectrum substrate dispersed in the sample to be detected adopts 33 ℃.
Investigation of linear relationships
The relationship between the logarithm of the response value and the concentration of the detection method in the above examples and comparative examples was plotted as a curve, regression calculation was performed by a linear method to obtain a regression equation, and a correlation coefficient R was calculated2As shown below, where I is absorbance and C is the tetracycline concentration ng/m L.
The linear relationship in example 1 is shown in fig. 2, and it can be seen that the antibiotic concentration and the logarithm of the absorbance value in the invention are in a linear relationship, and the detection method of the invention can effectively detect the tetracycline concentration in the sample, and has good linearity, which indicates that the detection accuracy is high.
Repeatability survey
Standard solutions containing 200ng/m L of tetracycline were prepared, each experiment was repeated 6 times using each example and control, and the antibiotic concentration of the standard solutions was calculated by linear relationship, and the relative standard deviation RSD was calculated as follows:
as can be seen from the table, the method has the advantage of good repeatability of the detection method.
Investigation of sample recovery
Cleaning wastewater of a breeding factory is adopted, and is filtered by a quartz sand filter and an ultrafiltration membrane with the molecular weight cutoff of 20 ten thousand in sequence, the COD of the wastewater is about 110 mg/L, 200ng/m L tetracycline is added into filtrate, and the sample adding recovery rate is calculated by the method, and the result is as follows:
as can be seen from the table, the detection method provided by the invention has a good detection recovery rate within the range of 95-105%; meanwhile, it can be seen that the hydrophilic monomer is adopted to modify the gel material in the embodiment 4, so that the hydrophilicity of the surface of the gel material is improved, the influence of organic matters in the wastewater on the surface is reduced, and the detection accuracy is improved, in addition, the adsorption process in the comparison example 1 and the comparison example 2 is not in the range of the contraction temperature interval of the temperature-sensitive gel, so that other components in the wastewater have influence on the detection process, and the detection recovery rate is poor; it can be seen from example 3 and comparative example 1 that, since adsorption can be performed at low temperature during the adsorption process of the sample, the temperature-sensitive gel can rapidly adsorb the target substance in the sample when being in the expanded state, while the hydrogel is in the contracted state when being treated at higher temperature in comparative example 3, which is not favorable for rapid adsorption of tetracycline in the sample, resulting in a high recovery rate.
Claims (6)
1. An antibiotic detection method based on molecular imprinting-Raman spectroscopy is characterized by comprising the following steps:
step 1, preparing nano gold sol, namely adding 4-6 m L1% HAuCl into 120-180 m L deionized water4Stirring, and adding 1-3 m L K2CO3Finally, quickly adding 5-10 m L NaBH into the solution4Stirring the solution for 3-6 min to obtain an alcoholic red nanogold sol (AuNPs) solution;
adding a solution consisting of 1-3 g of N-isopropylacrylamide, 0.2-0.4 g of tetracycline, 15-25 mg of sodium hexadecylsulfonate, 15-25 mg of a crosslinking agent N, N-methylene bisacrylamide, 120-160 m of L deionized water and 20-30 m of L nano gold sol solution into a flask with a condensation reflux and magnetic stirring device, uniformly dispersing under an ultrasonic field, heating to 65-75 ℃ under the protection of nitrogen flow, rapidly adding the prepared 8-12 m of L ammonium persulfate solution, pouring the solution into a mold for reaction to generate a film-shaped gel, and after the reaction is finished, carrying out electric field dialysis purification to remove a surfactant and unreacted monomers to obtain the PNM-Au composite hydrogel;
step 3, preparing a Raman spectrum substrate: taking PNM-Au composite hydrogel, then eluting with dilute HCl solution with the pH value of 6.0-6.5 and deionized water in sequence, and drying to obtain a Raman spectrum substrate;
and 4, drawing a standard curve: preparing tetracycline aqueous solutions with different concentrations, respectively dispersing the Raman spectrum substrate in a tetracycline standard solution for adsorption, filtering, spreading on a glass slide, detecting by using a solid laser head of a surface enhanced Raman spectrum, and drawing a curve relation between a response value and the concentration to obtain a standard curve;
step 5, sample detection: and dispersing the Raman spectrum substrate in a sample to be detected for adsorption, detecting by adopting a solid laser head of the surface enhanced Raman spectrum, and calculating the tetracycline content in the sample to be detected according to a standard curve.
2. The method for detecting antibiotics based on molecular imprinting-Raman spectroscopy according to claim 1, wherein in the step 1, the temperature of deionized water is 0-4 ℃; k2CO3The solution concentration was 0.2 mol. L-1；NaBH4The concentration of the solution was 0.5 mg. m L-1。
3. The method for detecting antibiotics based on molecular imprinting-Raman spectroscopy according to claim 1, wherein in the step 2, the reaction process is carried out for 4 hours at 65-75 ℃, and the concentration of the ammonium persulfate solution is 0.0184 mol-L-1(ii) a 0.2-0.4 g of methoxy polyethylene glycol methacrylate monomer is also added in the reaction process.
4. The method for detecting the antibiotic based on the molecular imprinting-Raman spectroscopy according to claim 1, wherein in the step 3, the elution condition is that the elution is carried out for 0.5-1 h under the action of ultrasonic waves.
5. The method for detecting antibiotics based on molecular imprinting-Raman spectroscopy of claim 1, wherein in the step 4, the concentration range of the tetracycline aqueous solution is 0.5ng/m L-10000 ng/m L, and the adsorption temperature is 32-35 ℃.
6. The method for detecting antibiotics based on molecular imprinting-Raman spectroscopy of claim 1, wherein the sample to be detected is milk, wastewater, surface water or food extract.
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