CN111579546A - Rapid detection method of sulfathiazole - Google Patents
Rapid detection method of sulfathiazole Download PDFInfo
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- CN111579546A CN111579546A CN202010479203.9A CN202010479203A CN111579546A CN 111579546 A CN111579546 A CN 111579546A CN 202010479203 A CN202010479203 A CN 202010479203A CN 111579546 A CN111579546 A CN 111579546A
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- JNMRHUJNCSQMMB-UHFFFAOYSA-N sulfathiazole Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CS1 JNMRHUJNCSQMMB-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229960001544 sulfathiazole Drugs 0.000 title claims abstract description 54
- 238000001514 detection method Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 35
- 241001465754 Metazoa Species 0.000 claims abstract description 21
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 210000002700 urine Anatomy 0.000 claims description 20
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052737 gold Inorganic materials 0.000 claims description 13
- 239000010931 gold Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 238000001228 spectrum Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 8
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 8
- 229940038773 trisodium citrate Drugs 0.000 claims description 8
- 239000012224 working solution Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001237 Raman spectrum Methods 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- 238000004364 calculation method Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 229910001112 rose gold Inorganic materials 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000000703 high-speed centrifugation Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000004088 simulation Methods 0.000 claims description 2
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 claims description 2
- 229960004306 sulfadiazine Drugs 0.000 claims description 2
- 238000003775 Density Functional Theory Methods 0.000 abstract description 6
- 229940123317 Sulfonamide antibiotic Drugs 0.000 abstract description 6
- 238000004445 quantitative analysis Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000012216 screening Methods 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 abstract description 3
- 229940124530 sulfonamide Drugs 0.000 abstract 1
- 235000013305 food Nutrition 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 241000282898 Sus scrofa Species 0.000 description 4
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- 229940088710 antibiotic agent Drugs 0.000 description 4
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- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003640 drug residue Substances 0.000 description 4
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- 238000004057 DFT-B3LYP calculation Methods 0.000 description 2
- QIAFMBKCNZACKA-UHFFFAOYSA-N N-benzoylglycine Chemical compound OC(=O)CNC(=O)C1=CC=CC=C1 QIAFMBKCNZACKA-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
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- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000000507 anthelmentic effect Effects 0.000 description 1
- 229940124339 anthelmintic agent Drugs 0.000 description 1
- 239000000921 anthelmintic agent Substances 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229960002135 sulfadimidine Drugs 0.000 description 1
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- 229940116269 uric acid Drugs 0.000 description 1
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Classifications
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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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- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The application provides a method for rapidly detecting sulfathiazole in an animal body, and a Raman characteristic peak of the sulfathiazole is determined by using a density functional theory. And establishing a quantitative analysis curve by using the characteristic peak intensity with high Raman peak intensity and good peak shape. The standard recovery rate experiment shows that the method has better accuracy and precision. The lowest detection concentration of the sulfathiazole in the animal body detected by the method is 1 mg/L. The method qualitatively and quantitatively analyzes sulfonamide antibiotic residues in the animal body, the detection of a single sample is completed within 3min, and a rapid and convenient detection method is provided for rapid qualitative screening and preliminary quantitative detection of the sulfonamide thiazole residues in the animal body.
Description
Technical Field
The invention relates to the field of biological rapid detection, in particular to a method for rapidly detecting sulfathiazole in an animal body.
Background
Veterinary residue refers to the parent compound of the veterinary drug and/or metabolites thereof, as well as veterinary-related impurities, contained in any edible part of the animal product. Including antibiotics, anthelmintics, antiprotozoals, trypanosomimetics, and the like.
Veterinary drugs and feed additives remaining in animal-derived foods pose a potential threat to human health as the food chain enters the human body, and the threat has attracted more and more attention of people. With the change of the demand of people on animal-derived food, the international requirement on the drug residue of the animal-derived food is higher and higher, the drug residue in the animal-derived food gradually becomes a focus of worldwide attention, and the antibiotic residue is greatly concerned. A large amount of antibiotics are frequently used, so that drug-resistant pathogenic bacteria in animal bodies can easily infect humans; and antibiotic drug residues can cause bacteria in the human body to generate drug resistance, disturb the micro-ecology of the human body and generate various toxic and side effects. Veterinary drugs and additives remaining in animal food pose a potential threat to human health as the food chain enters the human body, and the threat has attracted more and more attention of people. Therefore, the antibiotic is simply, quickly and conveniently detected on site in trace amount, and the method can play a key role in effectively supervising the medicine, ensuring the public life health and protecting the environment.
The detection method of sulfonamide antibiotics in animal tissues and urine mainly comprises a high performance liquid chromatography, a liquid chromatography-mass spectrometry, an enzyme linked immunosorbent assay and the like. The defects of long pretreatment process time, complex operation, strong operation technology, expensive instrument and equipment and the like of the chromatography and mass spectrometry generally exist, and the requirement of rapidly screening a large number of samples on site is difficult to meet. The ELISA method has the advantages of large sample amount, low cost, simple and portable instrument, but the ELISA method has more influencing factors and needs to improve the sensitivity and the stability. The working efficiency of detection personnel is improved while the detection precision is ensured, and the research of a rapid, simple, real-time and accurate detection method has very important significance.
Disclosure of Invention
Aiming at the defects in the technology, the invention provides a method for rapidly analyzing sulfathiazole in an animal body by adopting a surface-enhanced Raman spectroscopy technology, and provides a qualitative and quantitative analysis method for the surface-enhanced Raman spectroscopy by adopting gold gel as an enhanced substrate.
In order to achieve the purpose, the method for rapidly detecting sulfathiazole provided by the invention adopts surface-enhanced Raman spectroscopy to rapidly analyze and detect a sample, and comprises the following steps:
s1: preparing a Raman enhancement base solution;
s2, preparing a standard sample;
s3: rapidly detecting a sample;
s4: and (6) analyzing data results.
In step S1, a gold nanoparticle strengthening base solution is prepared, trisodium citrate is added to a boiling chloroauric acid solution, and a gold sol is obtained after stirring.
Wherein, 100mL of chloroauric acid solution with the concentration of 1mmol/L is heated, stirred and heated to boiling, 1.85mL of trisodium citrate solution is quickly added into a beaker, heated and continuously stirred for 10min, and then the deep red gold sol solution is obtained.
In step S2, the method includes the following sub-steps:
s21: dissolving a sulfathiazole standard substance, and then gradually diluting the sulfathiazole standard substance into a solution with a certain gradient concentration;
s22, processing the negative sample of the animal urine, and then adding the sulfathiazole solution obtained in S21 to obtain a positive sample;
and S23, adding an extracting agent into the positive sample for extraction, and detecting by using a Raman spectrometer.
In step S21, weighing a sulfathiazole standard substance, dissolving the sulfathiazole standard substance by using an organic solvent, putting the sulfathiazole standard substance into a brown volumetric flask, gradually diluting the sulfathiazole standard substance into a standard working solution by using the same organic solvent, and storing the standard working solution at 4 ℃ for later use; the organic solvent is one of methanol, ethanol or ethylene glycol.
In step S22, the animal urine negative sample is placed in a centrifuge tube, and subjected to high-speed centrifugation to remove the precipitate, and the supernatant is taken and added to the standard working solution to prepare the positive sample.
In step S23, ethyl acetate or acetonitrile is added to the positive sample as an extractant, the positive sample is vortexed and set, nitrogen blowing is performed, and then a corresponding extractant is added to a constant volume for detection.
Before step S1, data simulation calculation needs to be performed on sulfathiazole, and a theoretical raman spectrum peak is calculated, so as to determine a qualitative spectrum peak of the standard.
In step S3, when the surface raman spectroscopy is used for detection, the parameters are: wave number range 400 to 2000cm-1765nm laser wavelength, 400mW power, 2cm resolution-1Integration time 10 s.
When the Raman signal is detected on the machine, 200 mu L of gold gel, 20 mu L of liquid to be detected and 300 mu L of sodium chloride solution are sequentially added into a sample feeding bottle, and the Raman signal is collected on an instrument within 5s after shaking up.
The invention has the beneficial effects that: the method for rapidly detecting the surface enhanced Raman spectroscopy of the sulfonamide antibiotics in the animal excrement is preliminarily explored. And determining the Raman characteristic peak of the sulfathiazole by using a density functional theory. And establishing a quantitative analysis curve by using the characteristic peak intensity with high Raman peak intensity and good peak shape. The standard recovery rate experiment shows that the method has better accuracy and precision. The lowest concentration detected by the method is 1mg/L of the lowest detection concentration of the sulfathiazole. The method qualitatively and quantitatively analyzes the sulfathiazole residues in the animal body, the detection of a single sample is completed within 3min, and a rapid and convenient detection method is provided for rapid qualitative screening and preliminary quantitative detection of the sulfathiazole residues.
Drawings
FIG. 1 is a spectrum diagram of the experimental sulfathiazole in the invention;
FIG. 2 is the surface enhanced Raman spectrum of sulfathiazole of the present invention;
FIG. 3 is a spectrum of concentration of sulfathiazole standard solution;
FIG. 4 is a quantitative analysis curve of sulfathiazole.
Detailed Description
In order to more clearly describe the present invention, the present invention will be further described with reference to the accompanying drawings.
The surface enhanced Raman spectroscopy technology is characterized in that gold and silver nanoparticles are used as carriers, when molecules to be detected are adsorbed to rough gold and silver surfaces, the action surface area of light and the molecules can be greatly increased, the electromagnetic field of the metal surface can be greatly enhanced, and the intensity of the obtained Raman signal is 10 common6More than twice. The surface enhanced Raman spectroscopy technology has the advantages of simple pretreatment of experimental samples, high detection speed of single sample, high detection sensitivity and the like, so that the surface enhanced Raman spectroscopy technology is widely applied to rapid monitoring of quality safety problems such as trace pesticide residues, antibiotic drug residues and the like in food and agricultural products, and is compared with the prior art.
Firstly, preparing gold sol: 1.000g of chloroauric acid solid is accurately weighed, dissolved in a beaker by deionized water and transferred to a 100mL volumetric flask, and the volume is determined to the scale mark. Taking 2.06mL of prepared chloroauric acid solution, transferring the chloroauric acid solution into a 50mL volumetric flask, and fixing the volume to a scale mark by using deionized water to obtain the chloroauric acid solution with the concentration of 1 mmol/L; accurately weighing 0.100g of trisodium citrate solid, dissolving the trisodium citrate solid in a beaker by using deionized water, transferring the beaker to a 10mL volumetric flask, and fixing the volume to a scale mark to obtain a trisodium citrate solution with the concentration of 0.01 g/mL; placing a beaker filled with 100mL of chloroauric acid solution on an electric heating furnace, stirring and heating to boil, quickly adding 1.85mL of trisodium citrate solution into the beaker, heating and continuously stirring for 10min to obtain a dark red gold sol solution;
accurately weighing 0.5g of sodium chloride solid, dissolving the sodium chloride solid in a beaker by using deionized water, transferring the beaker to a 50mL volumetric flask, and fixing the volume to a scale mark to obtain a 1% sodium chloride solution; during detection, 200 mu L of gold colloid, 20 mu L of liquid to be detected and 100 mu L of sodium chloride solution are sequentially added into a sample feeding bottle in sequence, and the sample feeding bottle is shaken up for 5s and then is used for detecting and collecting Raman signals. Collecting parameters: wave number range 400 to 2000cm-1Laser wavelength of 785nm, power of 400mW, resolution of 2cm-1Integration time 10 s. The acquired data were processed for planning with MATLAB R2012 b.
Weighing 0.0100g of standard sulfamethazine, sulfadiazine and sulfathiazole, dissolving in methanol in a beaker, transferring to a 100ml brown volumetric flask to obtain a 100mg/L standard solution, gradually diluting with methanol to obtain standard working solution with the concentration of 20, 18, 16, 14, 12, 10, 8, 6, 4, 2 and 1mg/L, and storing at 4 ℃ for later use; taking 100mL of the cow urine negative sample, centrifuging for 5min at 4500r/min, removing the precipitate, taking 5mL of supernatant, preparing the cow urine sample containing 20, 18, 16, 14, 12, 10, 8, 6, 4, 2 and 1mg/L of sulfathiazole, and storing at 4 ℃ for later use.
Because the sulfonamide antibiotics are almost insoluble in water and can be dissolved in an organic solvent, most of water in pig urine or cow urine is removed, and the main components of the water comprise urea, uric acid, hippuric acid and electrolyte, and the water is mostly water-soluble substances, the organic solvent is adopted for extraction, and ethyl acetate is adopted as an extractant for extraction and extraction in the application; more specifically, 1mL of a cow urine sample is taken, 3mL of ethyl acetate is added, vortex extraction is carried out for 2min, standing and layering are carried out, an upper ethyl acetate layer is taken and is blown to be dry at 40 ℃ by nitrogen, ethyl acetate is used for dissolving and fixing the volume to 1mL, and a machine is used for detection; in the application, ethyl acetate is adopted to effectively carry out solution on the sulfonamide antibiotics, and ethyl acetate is used as the peculiar smell of esters to effectively cover the bad smell in animal urine, so that in the detection process, detection personnel obtain more comfortable sensory experience.
Before carrying out related detection, theoretical spectrum calculation needs to be carried out on corresponding sulfonamide antibiotics, a sulfathiazole molecular model is constructed by adopting related software, a B3LYP method is used according to a density functional theory, structure optimization is carried out by using the related software, and a theoretical Raman spectrum peak is calculated.
Constructing a sulfathiazole molecular model by using GaussView 5.0 software, performing structure optimization by using a B3LYP method and Guassian09w software according to a Density Functional Theory (DFT) and calculating a theoretical Raman spectrum peak. FIG. 1 shows the experimental spectrum of sulfathiazole (a) and the theoretical calculated spectrum of sulfathiazole (b). In the range of 400-1800 cm-1In the range of 1585, 1518, 862, 823, 707 and 672cm-1The experimental spectrum is slightly deviated from the theoretical spectrum but basically coincided with the theoretical spectrum, and the Raman spectrum peaks 1634 and 1102cm calculated by theory-1No peaks were observed in the experimental spectra, 1072, 1015 and 641cm-1And so on, are not present in the theoretical calculations. The spectral peak attribution of the main characteristic peaks is 1585cm respectively through comparison-1(1576cm-1) The point of the vibration is 1118cm-1(1126cm-1) The point represents the in-plane C-H deformation vibration, 823cm-1(832cm-1) The point represents the in-plane C-S, C-N bending vibration, 707cm-1(701cm-1) The point represents in-plane C-S stretching vibration and the like.
The following table shows the assignment of the main peaks to sulphathiazole:
FIG. 2(a) is the surface enhanced Raman spectrum of 20mg/L standard Sulfathiazole solution, and (b) is the table of ethyl acetateSurface enhanced Raman spectroscopy, (c) surface enhanced Raman spectroscopy of a negative cow urine sample subjected to pretreatment, and (d) surface enhanced Raman spectroscopy of a gold nano enhanced substrate. As can be seen from fig. 2(d), the gold nano-enhanced substrate has no raman peak, which indicates that the gold sol used does not affect the solution raman signal of the target; as can be seen by comparing FIGS. 2(a), (b) and (c), 1100cm-1～1600cm-1The spectral peaks of the sulfathiazole in the range partially overlap with the spectral peaks of the ethyl acetate and the negative cow urine samples, so that 641, 672, 924 and 1072cm in the surface enhanced Raman spectrum of the sulfathiazole standard solution are used-1The peak at (A) is taken as the peak of the qualitative spectrum of sulfathiazole.
Diluting the prepared standard sulfathiazole solution into standard working solution with gradient concentrations of 10, 5, 2, 1, 0.8 and 0.5mg/L, detecting on a computer, and collecting surface enhanced Raman spectra, wherein the concentrations a to f are respectively 10, 5, 2, 1, 0.8 and 0.5mg/L as shown in FIG. 3. As seen from FIG. 2, the concentrations of 640, 671, 924 and 1071cm at 0.8mg/L were found to be-1The peak can be resolved, and the peak can not be resolved when the concentration is 0.5mg/L, so the lowest detection concentration of the standard solution of the sulfathiazole is 0.8 mg/L.
The prepared swine urine sample containing 20, 18, 16, 14, 12, 10, 8, 6, 4, 2 and 1mg/L gradient concentration of sulfathiazole antibiotics is pretreated, computer detection is carried out, and surface enhanced Raman spectrum is collected. 1072cm which can be distinguished when taking the concentration of the sulfathiazole standard solution as the lowest detection concentration and has better peak pattern-1Establishing a quantitative analysis curve of peak intensity and concentration, wherein a linear equation is that y is 0.0082x +0.7744 and a correlation coefficient R is in a range of 1-20 mg/L as shown in figure 42The lowest concentration detected was 1 mg/L0.9936. Adding a standard solution of sulfathiazole into the pig urine to prepare pig urine samples with the concentrations of 5, 11 and 17mg/L, and configuring 3 parallel samples for each concentration so as to detect the accuracy and precision of the method. The average recovery rate of the sample is 92.68-107.28%, and the relative standard deviation is 2.90-5.52%.
The Raman characteristic peak of the sulfathiazole is determined by using a density functional theory. And establishing quantitative analysis curves of the three antibiotics in the cow urine by using the characteristic peak intensity with high Raman peak intensity and good peak pattern. The standard recovery rate experiment shows that the method has better accuracy and precision. The lowest detection concentration of the sulfathiazole in the cow urine detected by the method is 1 mg/L. The method qualitatively and quantitatively analyzes the sulfathiazole residues in the cow urine, the detection of a single sample is completed within 3min, and a rapid and convenient detection method is provided for rapid qualitative screening and preliminary quantitative detection of the sulfathiazole residues in the cow urine.
Claims (10)
1. A rapid detection method of sulfathiazole is characterized in that a sample is rapidly analyzed and detected by adopting surface enhanced Raman spectroscopy, and the method comprises the following steps:
s1: preparing a Raman enhancement base solution;
s2, preparing a standard sample;
s3: rapidly detecting a sample;
s4: and (6) analyzing data results.
2. The method for rapidly detecting sulfathiazole according to claim 1, wherein in step S1, a gold nano-enhancing base solution is prepared, trisodium citrate is added into a boiling chloroauric acid solution, and gold sol is obtained after stirring.
3. The method for rapidly detecting sulfathiazole according to claim 2, characterized in that 100mL of chloroauric acid solution with concentration of 1mmol/L is heated, stirred and heated to boiling, 1.85mL of trisodium citrate solution is rapidly added into a beaker, heated and continuously stirred for 10min, and then a dark red gold sol solution is obtained.
4. The method for rapidly detecting sulfathiazole according to claim 1, wherein in step S2, the method comprises the following sub-steps:
s21: dissolving a sulfathiazole standard substance, and then gradually diluting the sulfathiazole standard substance into a solution with a certain gradient concentration;
s22, processing the negative sample of the animal urine, and then adding the sulfathiazole solution obtained in S21 to obtain a positive sample;
and S23, adding an extracting agent into the positive sample for extraction, and detecting by using a Raman spectrometer.
5. The method for rapidly detecting sulfathiazole according to claim 4, characterized in that in step S21, the sulfathiazole standard substance is weighed, dissolved by organic solvent and put into a brown volumetric flask, and then gradually diluted by the same organic solvent into standard working solution, and stored at 4 ℃ for later use; the organic solvent is one of methanol, ethanol or ethylene glycol.
6. The method for rapidly detecting sulfathiazole according to claim 4, wherein in step S22, the negative sample of animal urine is put into a centrifuge tube, high speed centrifugation is performed to remove the precipitate, and the supernatant is taken and added with standard working solution to prepare a positive sample.
7. The method for rapidly detecting sulfathiazole according to claim 4, characterized in that in step S23, ethyl acetate or acetonitrile is added to a positive sample as an extractant, nitrogen blowing is performed after vortex standing, and then a corresponding extractant is added for constant volume for detection.
8. The method for rapidly detecting sulfadiazine according to claim 1, wherein before step S1, the sulfathiazole is subjected to data simulation calculation to calculate its theoretical raman spectrum peak, so as to determine the qualitative spectrum peak of the standard.
9. The method for rapidly detecting sulfathiazole according to claim 1, wherein in step S3, when the surface raman spectroscopy is used for detection, the parameters are as follows: wave number range 400 to 2000cm-1765nm laser wavelength, 400mW power, 2cm resolution-1Integration time 10 s.
10. The method for rapidly detecting sulfathiazole according to claim 1, characterized in that 200 μ L of gold gel, 20 μ L of solution to be detected and 300 μ L of sodium chloride solution are sequentially added into a sample feeding bottle during on-machine detection, and Raman signals are collected by an instrument within 5s after shaking up.
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