CN113624740A - Establishment method of fruit and vegetable surface pesticide residue rapid detection model and fruit and vegetable surface pesticide residue rapid detection method - Google Patents
Establishment method of fruit and vegetable surface pesticide residue rapid detection model and fruit and vegetable surface pesticide residue rapid detection method Download PDFInfo
- Publication number
- CN113624740A CN113624740A CN202110922137.2A CN202110922137A CN113624740A CN 113624740 A CN113624740 A CN 113624740A CN 202110922137 A CN202110922137 A CN 202110922137A CN 113624740 A CN113624740 A CN 113624740A
- Authority
- CN
- China
- Prior art keywords
- pesticide
- fruit
- pesticide residue
- raman spectrum
- pesticide residues
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N2001/028—Sampling from a surface, swabbing, vaporising
Landscapes
- Health & Medical Sciences (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)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention belongs to the technical field of detection of pesticide residues on the surfaces of fruits and vegetables, and provides a method for establishing a rapid detection model of pesticide residues on the surfaces of fruits and vegetables and a rapid detection method of the pesticide residues on the surfaces of the fruits and vegetables. The establishing method of the invention is based on characteristic Raman spectrum information of pesticide residues of pesticide residue fruit and vegetable samples and the concentration of a series of pesticide residue standard solution with different concentrations to carry out fitting, so as to obtain a rapid detection model of pesticide residues on the surfaces of fruits and vegetables; the established model is used for detecting pesticide residues on the surfaces of the fruits and the vegetables, the fruits and the vegetables are not damaged, and the operation is simple; and the detection result has the same accuracy as that of the detection result of high performance liquid chromatography and mass spectrometry, and the result is accurate.
Description
Technical Field
The invention relates to the technical field of detection of pesticide residues on the surfaces of fruits and vegetables, and relates to a method for establishing a rapid detection model of pesticide residues on the surfaces of fruits and vegetables and a rapid detection method of the pesticide residues on the surfaces of the fruits and vegetables.
Background
In order to increase the yield of crops, a large amount of pesticides are often sprayed on the crops at different stages to kill pests. The main reason why the pesticide residues of fruits and vegetables exceed the standard is pesticide residues formed by gathering the pesticide sprayed on the surfaces of plant leaves, roots, stems or fruits. In order to prolong the storage time of fruits and vegetables, some merchants spray antibacterial agents and preservatives on the surfaces of the fruits and vegetables after the fruits and vegetables are picked so as to improve the appearance of the fruits and vegetables, and pesticide residues are in excess of standards. Researches show that the pesticide content on the surfaces of fruits and vegetables tends to be stable after decaying along with time, which indicates that the pesticide can be remained on the surfaces of the fruits and vegetables for a long time.
Eating fruits and vegetables with pesticide residues exceeding the standard brings different degrees of adverse effects on human health. Research results show that when the content of organic phosphorus in fruits and vegetables exceeds 1mg, the poisoning phenomenon of human bodies can be caused. The correct use of pesticides can bring great convenience to human production, but the abuse of pesticides can threaten the physical health and life safety of people. Therefore, the method has important significance for quickly and efficiently monitoring the pesticide residues on the surfaces of the fruits and the vegetables.
In addition, in the eating habits of most people, some fruits and vegetables with thick skins are removed, and most fruits and vegetables are eaten with skins. In the eating process, the pesticide remained on the surface of the fruits and vegetables enters the human body, and threatens the life health of people. The traditional fruit and vegetable pesticide residue detection method is mainly based on high performance liquid chromatography-mass spectrometry, and when the high performance liquid chromatography-mass spectrometry is carried out, the fruit and vegetable are required to be smashed, so that the method belongs to destructive detection, and the operation steps are complex, so that the requirement of large-batch field detection in practical application cannot be met.
Disclosure of Invention
In view of the above, the invention aims to provide a method for establishing a fruit and vegetable surface pesticide residue rapid detection model and a fruit and vegetable surface pesticide residue rapid detection method. The rapid detection method provided by the invention is simple to operate, does not damage fruits and vegetables, and has the same accuracy as a detection result combining a high performance liquid chromatography and a mass spectrum.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for establishing a rapid detection model for pesticide residues on surfaces of fruits and vegetables, which comprises the following steps:
loading a series of pesticide residue standard substance solutions with different concentrations on the surfaces of blank fruits and vegetables to obtain pesticide residue fruit and vegetable samples;
sticking pesticide residues on the surfaces of pesticide residue fruit and vegetable samples by using an adhesive tape to obtain the adhesive tape stuck with the pesticide residues;
adding colloidal gold and a coagulant into the side, to which the pesticide residues are adhered, of the adhesive tape to obtain a flexible surface enhanced Raman spectrum substrate;
carrying out Raman spectrum acquisition on the flexible surface-enhanced Raman spectrum substrate to obtain pesticide residue Raman spectrum information on the surface of the pesticide residue fruit and vegetable sample, and extracting characteristic Raman spectrum information of pesticide residue on the surface of the pesticide residue fruit and vegetable sample;
and fitting the characteristic Raman spectrum information of pesticide residues on the surfaces of the pesticide residue fruit and vegetable samples with the concentrations of the pesticide residue standard solutions with different concentrations to obtain a rapid detection model of the pesticide residues on the surfaces of the fruits and vegetables.
Preferably, the adhesive tape is a 3M9080 strong adhesive tape.
Preferably, the particle size of the colloidal gold is 30-50 nm.
Preferably, the colloidal gold is prepared by a method comprising the following steps:
mixing perchloric acid, sodium citrate and water, reacting, and concentrating the reaction liquid by 2.5 times to obtain the colloidal gold;
the dosage ratio of the perchlorauric acid to the sodium citrate to the water is 0.01 g: 0.005 g: 100 mL.
Preferably, the reaction temperature is 350-400 ℃, and the reaction time is 10-30 min.
Preferably, the coagulant comprises sodium chloride.
Preferably, the colloidal gold and the coagulant are used in the following amounts: every 1cm2The area with pesticide residues is coated with 80-120 mu L of colloidal gold and 0.05-0.075 mg of coagulant.
Preferably, the Raman spectrum acquisition instrument is a RamTracer-200-HS type portable Raman spectrometer combined with a diode frequency stabilization exciter with an excitation wavelength of 785 nm.
The invention also provides a rapid detection method of the fruit and vegetable surface pesticide residues, which comprises the following steps:
sticking pesticide residues on the surface of the fruit and vegetable sample to be detected by using an adhesive tape to obtain the adhesive tape stuck with the pesticide residues;
adding colloidal gold and a coagulant into the side, to which the pesticide residues are adhered, of the adhesive tape to obtain a flexible surface enhanced Raman spectrum substrate;
carrying out Raman spectrum collection on the flexible surface enhanced Raman spectrum substrate to obtain pesticide residue Raman spectrum information on the surface of the fruit and vegetable sample to be detected;
and substituting the Raman spectrum information of the pesticide residues on the surface of the fruit and vegetable sample to be detected into the fruit and vegetable surface pesticide residue rapid detection model obtained by the establishing method in the technical scheme to obtain the content of the pesticide residues on the surface of the fruit and vegetable sample to be detected.
The invention provides a method for establishing a rapid detection model for pesticide residues on surfaces of fruits and vegetables, which comprises the following steps: loading a series of pesticide residue standard substance solutions with different concentrations on the surfaces of blank fruits and vegetables to obtain pesticide residue fruit and vegetable samples; sticking pesticide residues on the surfaces of pesticide residue fruit and vegetable samples by using an adhesive tape to obtain the adhesive tape stuck with the pesticide residues; adding colloidal gold and a coagulant into the side, to which the pesticide residues are adhered, of the adhesive tape to obtain a flexible surface enhanced Raman spectrum substrate; carrying out Raman spectrum acquisition on the flexible surface-enhanced Raman spectrum substrate to obtain pesticide residue Raman spectrum information on the surface of the pesticide residue fruit and vegetable sample, and extracting characteristic Raman spectrum information of pesticide residue on the surface of the pesticide residue fruit and vegetable sample; and fitting the characteristic Raman spectrum information of pesticide residues on the surfaces of the pesticide residue fruit and vegetable samples with the concentrations of the pesticide residue standard solutions with different concentrations to obtain a rapid detection model of the pesticide residues on the surfaces of the fruits and vegetables.
The establishing method of the invention is based on characteristic Raman spectrum information of pesticide residues of pesticide residue fruit and vegetable samples and the concentration of a series of pesticide residue standard solution with different concentrations to carry out fitting, so as to obtain a rapid detection model of pesticide residues on the surfaces of fruits and vegetables; the established model is used for detecting pesticide residues on the surfaces of the fruits and the vegetables, the fruits and the vegetables are not damaged, and the operation is simple; and the detection result has the same accuracy as that of the detection result of high performance liquid chromatography and mass spectrometry, and the result is accurate.
Detailed Description
The invention provides a method for establishing a rapid detection model for pesticide residues on surfaces of fruits and vegetables, which comprises the following steps:
loading a series of pesticide residue standard substance solutions with different concentrations on the surfaces of blank fruits and vegetables to obtain pesticide residue fruit and vegetable samples;
sticking pesticide residues on the surfaces of pesticide residue fruit and vegetable samples by using an adhesive tape to obtain the adhesive tape stuck with the pesticide residues;
adding colloidal gold and a coagulant into the side, to which the pesticide residues are adhered, of the adhesive tape to obtain a flexible surface enhanced Raman spectrum substrate;
carrying out Raman spectrum acquisition on the flexible surface-enhanced Raman spectrum substrate to obtain pesticide residue Raman spectrum information on the surface of the pesticide residue fruit and vegetable sample, and extracting characteristic Raman spectrum information of pesticide residue on the surface of the pesticide residue fruit and vegetable sample;
and fitting the characteristic Raman spectrum information of pesticide residues on the surfaces of the pesticide residue fruit and vegetable samples with the concentrations of the pesticide residue standard solutions with different concentrations to obtain a rapid detection model of the pesticide residues on the surfaces of the fruits and vegetables.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
The method loads a series of pesticide residue standard substance solutions with different concentrations on the surfaces of the blank fruits and vegetables to obtain pesticide residue fruit and vegetable samples.
In a specific embodiment of the present invention, the fruits and vegetables preferably comprise tomatoes. In the invention, the blank fruits and vegetables refer to blank fruits and vegetables without any pesticide residues on the surfaces. In the present invention, the obtaining of the blank fruit and vegetable preferably comprises the following steps: and cleaning the commercially available fruits and vegetables to obtain blank fruits and vegetables. The cleaning parameters are not particularly limited, and the cleaning method can be used for removing pesticide residues on the surfaces of commercially available fruits and vegetables.
In the present invention, the kind of the pesticide residue standard is preferably selected according to the pesticide residue that the skilled person wants to detect, for example, when the skilled person wants to detect probenazole, carbendazim and chlorpyrifos on the surface of fruits and vegetables, the probenazole, the carbendazim and the chlorpyrifos are preferably selected as the pesticide residue standard.
In the present invention, the concentration of the series of pesticide residue standard solution with different concentrations is preferably 0.5mg/L, 1.0mg/L, 2.0mg/L, 3.0mg/L, 5.0mg/L, 6.0mg/L, 8.0mg/L and 10.0 mg/L.
In the present invention, the means of loading preferably comprises coating. After the coating, the invention preferably also comprises naturally drying the blank fruits and vegetables coated with the pesticide residue standard solution with a series of different concentrations.
In the invention, the operation of loading the pesticide residue standard solution with a series of different concentrations on the surface of the blank fruit and vegetable is preferably as follows: and (3) loading each pesticide residue standard solution on the surface of the blank fruit and vegetable, namely only one pesticide residue standard on the surface of the pesticide residue fruit and vegetable sample.
After the pesticide residue fruit and vegetable sample is obtained, the pesticide residue on the surface of the pesticide residue fruit and vegetable sample is stuck by using the adhesive tape, so that the adhesive tape with the pesticide residue is obtained.
In the invention, the number of the pesticide residue fruit and vegetable samples is 279 preferably; when a rapid detection model for pesticide residues on the surfaces of fruits and vegetables is established, 279 pesticide residue fruit and vegetable samples are preferably selected according to the ratio of 3: 1, dividing the model into a modeling set and a prediction set; i.e., 3/4 time of modeling for 279 samples and 1/4 time of prediction for 279 samples.
In the present invention, the tape is preferably a 3M9080 strong tape.
In the present invention, the sticking preferably comprises the steps of: and adhering the adhesive tape on the surface of the pesticide residue fruit and vegetable sample, and scraping back and forth for 10-20 s by using a scraper, and preferably scraping back and forth for 15 s.
After the adhesive tape with the pesticide residues is obtained, colloidal gold and a coagulant are added to the side, where the pesticide residues are adhered, of the adhesive tape, so that the flexible surface-enhanced Raman spectrum substrate is obtained.
In the present invention, the coagulant preferably includes sodium chloride, and more preferably sodium chloride. In the present invention, the coagulant is preferably used in the form of a coagulant solution, and the concentration of the coagulant solution is preferably 5.00 mg/mL. In a specific embodiment of the present invention, the coagulant is specifically preferably a sodium chloride solution having a concentration of 5.00 mg/mL.
In the invention, the particle size of the colloidal gold is preferably 30-50 nm.
In the present invention, the colloidal gold is preferably prepared by a method comprising the steps of:
and mixing the perchloric acid, the sodium citrate and water, reacting, and concentrating the reaction liquid by 2.5 times to obtain the colloidal gold.
In the present invention, the ratio of the amount of the perchlorauric acid to the amount of the sodium citrate to the amount of the water is preferably 0.01 g: 0.005 g: 100 mL. In the present invention, the perchloroauric acid is preferably used in the form of a perchloroauric acid solution, the concentration of which is preferably 0.01 wt%; the sodium citrate is preferably used in the form of a sodium citrate solution, preferably at a concentration of 1 wt%.
In the invention, the mixing sequence of the gold perchlorate, the sodium citrate and the water preferably comprises mixing the gold perchlorate and the water to obtain a gold perchlorate solution; mixing sodium citrate with water to obtain a sodium citrate solution; and heating the gold perchlorate solution to the reaction temperature, and adding a sodium citrate solution for reaction.
In the invention, the reaction temperature is preferably 350-400 ℃, and more preferably 360 ℃; the reaction time is preferably 10-30 min, and more preferably 25 min.
In a specific embodiment of the present invention, the method for preparing the colloidal gold preferably includes the following steps:
adding 100mL of 0.01 wt% high-chlorine auric acid into a 500mL three-neck round-bottom flask, setting the temperature of a constant-temperature magnetic stirrer to be 360 ℃, adding 0.5mL of 1 wt% trisodium citrate solution after boiling, heating for 25min, concentrating the reaction liquid by 2.5 times, cooling to obtain colloidal gold, and storing in a dark place.
In the invention, the dosage of the colloidal gold and the coagulant is as follows: every 1cm2The area with pesticide residues is coated with 80-120 mu L of colloidal gold and 0.05-0.075 mg of coagulant. In the invention, the dosage of the colloidal gold and the coagulant is as follows: when probenazole is detected, every 1cm280 mu L of colloidal gold and 0.05mg of coagulant are used in the area with the pesticide residues; when detecting carbendazim and Japanese premna herb, every 1cm2The area with pesticide residues was treated with 120. mu.L of colloidal gold and 0.075mg of coagulant.
After the flexible surface enhanced Raman spectrum substrate is obtained, the Raman spectrum acquisition is carried out on the flexible surface enhanced Raman spectrum substrate, the pesticide residue Raman spectrum information of the surface of the pesticide residue fruit and vegetable sample is obtained, and the characteristic Raman spectrum information of the pesticide residue on the surface of the pesticide residue fruit and vegetable sample is extracted.
In the invention, the Raman spectrum acquisition instrument is preferably a RamTracer-200-HS type portable Raman spectrometer combined with a diode frequency stabilization exciter with an excitation wavelength of 785 nm.
In the invention, the method for extracting the characteristic Raman spectrum information of the pesticide residues on the surface of the pesticide residue fruit and vegetable sample preferably comprises the following steps:
performing density functional theory calculation on the Raman spectrum information of the pesticide residue standard product to obtain characteristic Raman spectrum information of the pesticide residue standard product;
and obtaining characteristic Raman spectrum information of pesticide residues on the surfaces of the pesticide residue fruit and vegetable samples based on the characteristic Raman spectrum information of the pesticide residue standard product.
In the invention, the density functional theory calculation is preferably calculated by using a Lee-Yang-Parr functional in a Becke type 3-parameter density functional model.
The method specifically comprises the following steps: calculating the Raman spectrum information of the pesticide residue standard product by using a density functional theory to obtain the characteristic Raman spectrum information of the pesticide residue standard product; and reading and obtaining the characteristic Raman spectrum information of pesticide residues on the surfaces of the pesticide residue fruit and vegetable samples based on the obtained characteristic Raman spectrum information of the pesticide residue standard product.
After the characteristic Raman spectrum information of pesticide residues on the surfaces of the pesticide residue fruit and vegetable samples is obtained, the characteristic Raman spectrum information of the pesticide residues on the surfaces of the pesticide residue fruit and vegetable samples is fitted with the concentrations of a series of pesticide residue standard solutions with different concentrations to obtain a rapid detection model of the pesticide residues on the surfaces of the fruit and vegetable samples.
The operation of the fitting is not particularly limited in the present invention, and may be performed by an operation known to those skilled in the art.
The invention also provides a rapid detection method of the fruit and vegetable surface pesticide residues, which comprises the following steps:
sticking pesticide residues on the surface of the fruit and vegetable sample to be detected by using an adhesive tape to obtain the adhesive tape stuck with the pesticide residues;
adding colloidal gold and a coagulant into the side, to which the pesticide residues are adhered, of the adhesive tape to obtain a flexible surface enhanced Raman spectrum substrate;
carrying out Raman spectrum collection on the flexible surface enhanced Raman spectrum substrate to obtain pesticide residue Raman spectrum information on the surface of the fruit and vegetable sample to be detected;
and substituting the Raman spectrum information of the pesticide residues on the surface of the fruit and vegetable sample to be tested into the fruit and vegetable surface pesticide residue rapid detection model obtained by the establishing method in the technical scheme to obtain the content of the pesticide residues on the surface of the fruit and vegetable sample to be tested.
The method utilizes the adhesive tape to pick the pesticide residues on the surface of the fruit and vegetable sample to be detected, so as to obtain the adhesive tape with the pesticide residues.
In the present invention, the step of sticking is preferably the same as the above technical solution, and is not described herein again.
After the adhesive tape with the pesticide residues is obtained, colloidal gold and a coagulant are added to the side, where the pesticide residues are adhered, of the adhesive tape, so that the flexible surface-enhanced Raman spectrum substrate is obtained.
In the invention, the preparation method and the addition amount of the colloidal gold, and the type and the addition amount of the coagulant are consistent with those of the technical scheme, and are not described again.
After the flexible surface enhanced Raman spectrum substrate is obtained, the Raman spectrum acquisition is carried out on the flexible surface enhanced Raman spectrum substrate, and the pesticide residue Raman spectrum information on the surface of the fruit and vegetable sample to be detected is obtained.
In the present invention, the parameters collected by the raman spectrum are preferably consistent with the above technical solution, and are not described herein again.
After the Raman spectrum information of the pesticide residues on the surface of the fruit and vegetable sample to be detected is obtained, the Raman spectrum information of the pesticide residues on the surface of the fruit and vegetable sample to be detected is substituted into the fruit and vegetable surface pesticide residue rapid detection model obtained by the establishing method in the technical scheme, and the content of the pesticide residues on the surface of the fruit and vegetable sample to be detected is obtained.
In the invention, in order to verify the accuracy of the detection method provided by the invention, the invention preferably further comprises the step of carrying out high performance liquid chromatography detection on the adhesive tape with the pesticide residues.
In the present invention, the high performance liquid chromatography detection comprises the following steps:
carrying out pesticide residue elution on the adhesive tape with the pesticide residue to obtain an upper machine sample of the pesticide residue;
and carrying out high performance liquid chromatography detection on the pesticide residue on the upper computer sample, and obtaining pesticide residue concentration information on the surface of the pesticide residue fruit and vegetable sample based on a pesticide residue concentration-chromatographic peak standard curve and a chromatography detection result of the upper computer sample.
The invention carries out pesticide residue elution on the adhesive tape with pesticide residue to obtain an upper machine sample of the pesticide residue.
In the present invention, the elution of the pesticide residue preferably comprises the steps of: and (4) placing the adhesive tape with the pesticide residues in an elution solvent for pesticide residue elution. In the present invention, the elution solvent preferably includes acetonitrile. In the present invention, the elution of the pesticide residue is preferably performed under ultrasonic conditions.
After the pesticide residue is eluted, the method preferably further comprises the step of concentrating the obtained pesticide residue eluent to obtain an upper computer sample of the pesticide residue. In the present invention, the concentration means preferably includes nitrogen blowing.
In the invention, the concentration of pesticide residues in the on-machine sample of the pesticide residues is preferably 0-20 mg/L.
After the on-machine sample of the pesticide residue is obtained, the invention carries out high performance liquid chromatography detection on the on-machine sample of the pesticide residue, and obtains the concentration information of the pesticide residue on the surface of the pesticide residue fruit and vegetable sample based on the concentration-chromatographic peak standard curve of the pesticide residue and the chromatographic detection result of the on-machine sample.
In the invention, the parameters detected by the high performance liquid chromatography are preferably different according to different detected substances.
In a specific embodiment of the present invention, when probenazole and carbendazim are detected, the parameters of the high performance liquid chromatography detection preferably include: the chromatographic column is Zorbax Eclipse XDB C18250X 4.6mm, 5 μm, using methanol and water as mobile phase, and performing gradient elution according to the gradient elution procedure of Table 1; the detection wavelength is 276 nm; the flow rate is 1 mL/min; the sample injection amount is 20 mu L; the column temperature was 30 ℃.
When chlorpyrifos is detected, the parameters of the high performance liquid chromatography detection preferably comprise: the chromatographic column is Zorbax Eclipse XDB C18150X 2.1mm, 3.5 μm, using methanol and water as mobile phase, and performing gradient elution according to the gradient elution procedure of Table 1; the detection wavelength is 300 nm; the flow rate is 0.3 mL/min; the sample injection amount is 10 mu L; the column temperature was 30 ℃.
TABLE 1 gradient elution procedure
In the invention, the types of the pesticide residues in the concentration-chromatographic peak standard curve of the pesticide residues are preferably selected according to the types of the pesticide residues to be actually measured, and in a specific embodiment of the invention, the pesticide residues preferably comprise thiabendazole, carbendazim and chlorpyrifos; the concentration-chromatographic peak standard curve of pesticide residues comprises a concentration-chromatographic peak standard curve of thiabendazole, a concentration-chromatographic peak standard curve of carbendazim and a concentration-chromatographic peak standard curve of chlorpyrifos.
The method for acquiring the concentration-chromatographic peak standard curve of the pesticide residues is not limited, and the standard curve acquisition method known by the technical personnel in the field can be adopted. In a specific embodiment of the present invention, the concentration-chromatographic peak standard curves of thiabendazole, carbendazim and chlorpyrifos are shown in table 2.
TABLE 2 concentration-chromatographic peak standard curve of pesticides
The following describes in detail the method for establishing a fruit and vegetable surface pesticide residue rapid detection model and the method for rapidly detecting fruit and vegetable surface pesticide residues provided by the present invention with reference to the following embodiments, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparing colloidal gold:
adding 100mL of 0.01 wt% high-chlorine auric acid into a 500mL three-neck round-bottom flask, setting the temperature of a constant-temperature magnetic stirrer to be 360 ℃, quickly adding 0.5mL of 1 wt% trisodium citrate solution after boiling (350 ℃), heating for 25min, cooling, concentrating the reaction liquid by 2.5 times to obtain colloidal gold, and storing in a dark place; the particle size of the colloidal gold is 50 nm.
Respectively weighing 10mg of pesticide standard products of thiabendazole, carbendazim and chlorpyrifos by an electronic balance, placing the pesticide standard products into a 100mL volumetric flask, using acetonitrile as a solvent to prepare 100mg/L standard solution, then respectively diluting the three standard solutions to the concentrations of 0.5mg/L, 1.0mg/L, 2.0mg/L, 3.0mg/L, 5.0mg/L, 6.0mg/L, 8.0mg/L and 10.0mg/L, and storing in a dark place.
297 commercial tomato samples were taken and washed clean with water until no pesticide residue was on the surface, and blank tomato samples were obtained.
Taking 93 blank tomato samples, smearing thiabendazole standard solutions with different concentrations, and naturally drying to obtain thiabendazole tomato samples; smearing 93 blank tomato samples with carbendazim standard solution, and naturally drying to obtain carbendazim tomato samples; and (3) smearing chlorpyrifos standard solutions with different concentrations on 93 blank tomato samples, and naturally drying to obtain chlorpyrifos tomato samples. The tomato samples containing pesticide residues are collectively referred to as pesticide residue tomato samples hereinafter.
The 297 tomato pesticide residues were sampled according to the ratio of 3: 1 into a modeling set and a prediction set.
Establishing a rapid pesticide residue detection model for the pesticide residue tomato samples in the modeling set according to the following steps of S1-S4, and specifically comprising the following steps of:
s1, adhering the 3M9080 adhesive tape to the surface of the sample of the pesticide residue tomato, and scraping the sample back and forth for 15 seconds by using a scraper to obtain the adhesive tape adhered with the pesticide residue.
S2, fixing the adhesive tape (with the size of 1.2cm multiplied by 2.0cm) with the pesticide residue on the glass slide with the adhesive side facing upwards, and when detecting thiabendazole, every 1cm280 mu L of colloidal gold and 10 mu L of sodium chloride solution with the concentration of 5.00mg/L are used in the area with the pesticide residues; when detecting carbendazim and Japanese premna herbEvery 1cm2And obtaining the flexible surface enhanced Raman spectrum substrate by using 120 mu L of colloidal gold and 15 mu L of sodium chloride solution with the concentration of 5.00mg/L in the area with the pesticide residues.
S3, carrying out Raman spectrum collection on the flexible surface enhanced Raman spectrum substrate by adopting a RamTracer-200-HS type portable Raman spectrometer in combination with a 785nm diode frequency stabilization exciter to obtain the pesticide residue Raman spectrum information on the surface of the pesticide residue fruit and vegetable sample, and extracting to obtain the characteristic Raman spectrum information of the pesticide residue on the surface of the pesticide residue fruit and vegetable sample based on the characteristic Raman spectrum information of the pesticide residue standard sample;
the method for acquiring the characteristic Raman spectrum information of the pesticide residue standard sample comprises the following steps: performing density functional theoretical calculation on the Raman spectrum information of the probenazole, the carbendazim and the chlorpyrifos standard substance in a B3LYP/6-31G group in Gaussian View 6.0 software based on the Raman spectrum information of the probenazole, the carbendazim and the chlorpyrifos standard substance to obtain the characteristic Raman spectrum information of the probenazole, the carbendazim and the chlorpyrifos standard substance;
the results were: the main characteristic peak of thiabendazole is 630cm-1、785cm-1、903cm-1、1009cm-1、1272cm-1And 1327cm-1(ii) a The main characteristic peak of carbendazim is 634cm-1、730cm-1、765cm-1、1004cm-1、1029cm-1、1106cm-1、1224cm-1、1260cm-1And 1312cm-1(ii) a The main characteristic peak of chlorpyrifos is 528cm-1、610cm-1、675cm-1、750cm-1、1095cm-1、1237cm-1And 1266cm-1。
S4, fitting the characteristic Raman spectrum information of the pesticide residue on the surface of the pesticide residue tomato sample with the concentrations of a series of pesticide residue standard solution with different concentrations to obtain a rapid pesticide residue detection model of the pesticide residue tomato sample.
The accuracy of the obtained pesticide residue rapid detection model is verified by using the pesticide residue tomato sample with concentrated prediction, and the method comprises the following steps:
and adhering a 3M9080 adhesive tape to the surface of the predicted concentrated pesticide residue fruit and vegetable sample, and scraping the sample back and forth for 15 seconds by using a scraper to obtain the adhesive tape adhered with pesticide residues.
Fixing adhesive tape (size of 1.2cm × 2.0cm) with pesticide residue on the glass slide with adhesive side facing upward, and detecting thiabendazole every 1cm280 mu L of colloidal gold and 10 mu L of sodium chloride solution with the concentration of 5.00mg/L are used in the area with the pesticide residues; when detecting carbendazim and Japanese premna herb, every 1cm2And obtaining the flexible surface enhanced Raman spectrum substrate by using 120 mu L of colloidal gold and 15 mu L of sodium chloride solution with the concentration of 5.00mg/L in the area with the pesticide residues.
And carrying out Raman spectrum acquisition on the flexible surface enhanced Raman spectrum substrate by adopting a RamTracer-200-HS type portable Raman spectrometer in combination with a 785nm diode frequency stabilization exciter to obtain the pesticide residue Raman spectrum information on the surface of the pesticide residue fruit and vegetable sample.
And substituting the raman spectrum information of the pesticide residues on the surfaces of the pesticide residue fruit and vegetable samples into the pesticide residue rapid detection model obtained in the step S4, wherein the result is shown in table 3.
And (3) determining the true value of the pesticide residues in the concentrated pesticide residue tomato sample by prediction:
dipping the adhesive tape with the pesticide residues obtained in the step S1 in acetonitrile for ultrasonic elution, then placing the adhesive tape in a water bath nitrogen blowing instrument, and concentrating the adhesive tape to 1mL under nitrogen flow to obtain an upper machine sample of the pesticide residues;
and carrying out high performance liquid chromatography detection on the pesticide residue on the upper computer sample, and obtaining pesticide residue concentration information on the surface of the pesticide residue fruit and vegetable sample based on a pesticide residue concentration-chromatographic peak standard curve and a chromatography detection result of the upper computer sample.
The parameters of the high performance liquid chromatography detection comprise: when probenazole and carbendazim are detected, the parameters of the high performance liquid chromatography detection preferably comprise: the chromatographic column is Zorbax Eclipse XDB C18250X 4.6mm, 5 μm, using methanol and water as mobile phase, and performing gradient elution according to the gradient elution procedure of Table 1; the detection wavelength is 276 nm; the flow rate is 1 mL/min; the sample injection amount is 20 mu L; the column temperature was 30 ℃.
When chlorpyrifos is detected, the parameters of the high performance liquid chromatography detection preferably comprise: the chromatographic column is Zorbax Eclipse XDB C18，150×2.1mm3.5 μm, using methanol and water as mobile phase, and performing gradient elution according to the gradient elution procedure in table 1; the detection wavelength is 300 nm; the flow rate is 0.3 mL/min; the sample injection amount is 10 mu L; the column temperature was 30 ℃.
The concentration-chromatographic peak standard curves of thiabendazole, carbendazim and chlorpyrifos standard products are shown in table 2.
The actual values of the resulting predicted concentrated tomato samples with pesticide residues are shown in table 3.
Table 3 prediction of measured values and model predicted values of concentrated pesticide residue fruit and vegetable samples
As can be seen from table 3: the calculated value of the model is basically consistent with the true value, and the application requirement of pesticide residue detection can be met.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A method for establishing a rapid detection model for pesticide residues on surfaces of fruits and vegetables comprises the following steps:
loading a series of pesticide residue standard substance solutions with different concentrations on the surfaces of blank fruits and vegetables to obtain pesticide residue fruit and vegetable samples;
sticking pesticide residues on the surfaces of pesticide residue fruit and vegetable samples by using an adhesive tape to obtain the adhesive tape stuck with the pesticide residues;
adding colloidal gold and a coagulant into the side, to which the pesticide residues are adhered, of the adhesive tape to obtain a flexible surface enhanced Raman spectrum substrate;
carrying out Raman spectrum acquisition on the flexible surface-enhanced Raman spectrum substrate to obtain pesticide residue Raman spectrum information on the surface of the pesticide residue fruit and vegetable sample, and extracting characteristic Raman spectrum information of pesticide residue on the surface of the pesticide residue fruit and vegetable sample;
and fitting the characteristic Raman spectrum information of pesticide residues on the surfaces of the pesticide residue fruit and vegetable samples with the concentrations of the pesticide residue standard solutions with different concentrations to obtain a rapid detection model of the pesticide residues on the surfaces of the fruits and vegetables.
2. The method of building of claim 1, wherein the tape is 3M9080 power tape.
3. The method according to claim 1, wherein the colloidal gold has a particle size of 30 to 50 nm.
4. The method for establishing, according to claim 1, characterized in that the colloidal gold is prepared by a method comprising the following steps:
mixing perchloric acid, sodium citrate and water, reacting, and concentrating the reaction liquid by 2.5 times to obtain the colloidal gold;
the dosage ratio of the perchlorauric acid to the sodium citrate to the water is 0.01 g: 0.005 g: 100 mL.
5. The method according to claim 4, wherein the reaction temperature is 350-400 ℃ and the reaction time is 10-30 min.
6. The method of establishing as claimed in claim 1, wherein said coagulant comprises sodium chloride.
7. The method of establishing according to claim 4, 5 or 6, wherein the colloidal gold and the coagulant are used in amounts of: every 1cm2The area with pesticide residues is coated with 80-120 mu L of colloidal gold and 0.05-0.075 mg of coagulant.
8. The method of construction of claim 1, wherein the raman spectroscopy collection instrument is a portable raman spectrometer model ramtarget-200-HS in combination with a 785nm excitation wavelength diode frequency stabilized exciter.
9. A quick detection method for pesticide residues on the surfaces of fruits and vegetables comprises the following steps:
sticking pesticide residues on the surface of the fruit and vegetable sample to be detected by using an adhesive tape to obtain the adhesive tape stuck with the pesticide residues;
adding colloidal gold and a coagulant into the side, to which the pesticide residues are adhered, of the adhesive tape to obtain a flexible surface enhanced Raman spectrum substrate;
carrying out Raman spectrum collection on the flexible surface enhanced Raman spectrum substrate to obtain pesticide residue Raman spectrum information on the surface of the fruit and vegetable sample to be detected;
substituting the Raman spectrum information of the pesticide residues on the surface of the fruit and vegetable sample to be detected into the fruit and vegetable surface pesticide residue rapid detection model obtained by the establishing method of any one of claims 1 to 8 to obtain the content of the pesticide residues on the surface of the fruit and vegetable sample to be detected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110922137.2A CN113624740A (en) | 2021-08-12 | 2021-08-12 | Establishment method of fruit and vegetable surface pesticide residue rapid detection model and fruit and vegetable surface pesticide residue rapid detection method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110922137.2A CN113624740A (en) | 2021-08-12 | 2021-08-12 | Establishment method of fruit and vegetable surface pesticide residue rapid detection model and fruit and vegetable surface pesticide residue rapid detection method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113624740A true CN113624740A (en) | 2021-11-09 |
Family
ID=78384716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110922137.2A Pending CN113624740A (en) | 2021-08-12 | 2021-08-12 | Establishment method of fruit and vegetable surface pesticide residue rapid detection model and fruit and vegetable surface pesticide residue rapid detection method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113624740A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103472051A (en) * | 2013-09-20 | 2013-12-25 | 华东交通大学 | SERS (Surface Enhanced Raman Spectroscopy) detection method for pesticide residues in fruits |
| CN104142321A (en) * | 2014-07-24 | 2014-11-12 | 江西农业大学 | Method for fast detecting surface enhancing Raman spectrums of pesticide residues in tea leaves |
| CN104931483A (en) * | 2015-06-30 | 2015-09-23 | 北京工商大学 | Raman spectrum detection method for pesticide residues in fruits and vegetables |
| CN106153594A (en) * | 2015-03-23 | 2016-11-23 | 中国科学院宁波材料技术与工程研究所 | Surface enhanced raman spectroscopy detection adhesive tape, its preparation method and application |
| CN106841167A (en) * | 2017-03-27 | 2017-06-13 | 北京工商大学 | The lossless detection method of garden stuff pesticide residue |
| CN107044974A (en) * | 2017-03-28 | 2017-08-15 | 北京工业大学 | 2,4 dichlorphenoxyacetic acid method for detecting residue in a kind of fruits and vegetables |
| CN108267438A (en) * | 2018-04-27 | 2018-07-10 | 中国农业大学 | A kind of raman spectral signal analysis method for remaining blended |
| CN109900674A (en) * | 2019-03-15 | 2019-06-18 | 深圳华中科技大学研究院 | A kind of nanogold array surface enhancing Raman chip and the preparation method and application thereof |
| CN111855638A (en) * | 2020-07-21 | 2020-10-30 | 华南理工大学 | Device and method for nondestructive detection of pollutants on surfaces of fruits and vegetables based on adhesive tape sticking |
| CN113125409A (en) * | 2021-03-25 | 2021-07-16 | 云南省烟草质量监督检测站 | Method for rapidly detecting butralin in tobacco by surface enhanced Raman scattering |
-
2021
- 2021-08-12 CN CN202110922137.2A patent/CN113624740A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103472051A (en) * | 2013-09-20 | 2013-12-25 | 华东交通大学 | SERS (Surface Enhanced Raman Spectroscopy) detection method for pesticide residues in fruits |
| CN104142321A (en) * | 2014-07-24 | 2014-11-12 | 江西农业大学 | Method for fast detecting surface enhancing Raman spectrums of pesticide residues in tea leaves |
| CN106153594A (en) * | 2015-03-23 | 2016-11-23 | 中国科学院宁波材料技术与工程研究所 | Surface enhanced raman spectroscopy detection adhesive tape, its preparation method and application |
| CN104931483A (en) * | 2015-06-30 | 2015-09-23 | 北京工商大学 | Raman spectrum detection method for pesticide residues in fruits and vegetables |
| CN106841167A (en) * | 2017-03-27 | 2017-06-13 | 北京工商大学 | The lossless detection method of garden stuff pesticide residue |
| CN107044974A (en) * | 2017-03-28 | 2017-08-15 | 北京工业大学 | 2,4 dichlorphenoxyacetic acid method for detecting residue in a kind of fruits and vegetables |
| CN108267438A (en) * | 2018-04-27 | 2018-07-10 | 中国农业大学 | A kind of raman spectral signal analysis method for remaining blended |
| CN109900674A (en) * | 2019-03-15 | 2019-06-18 | 深圳华中科技大学研究院 | A kind of nanogold array surface enhancing Raman chip and the preparation method and application thereof |
| CN111855638A (en) * | 2020-07-21 | 2020-10-30 | 华南理工大学 | Device and method for nondestructive detection of pollutants on surfaces of fruits and vegetables based on adhesive tape sticking |
| CN113125409A (en) * | 2021-03-25 | 2021-07-16 | 云南省烟草质量监督检测站 | Method for rapidly detecting butralin in tobacco by surface enhanced Raman scattering |
Non-Patent Citations (3)
| Title |
|---|
| XINYING GONG 等: "Screening pesticide residues on fruit peels using portable Raman spectrometer combined with adhesive tape sampling", 《FOOD CHEMISTRY》, pages 255 * |
| 宁翠芳: "双金属表面增强拉曼散射纳米探针的制备及其分析检测应用", 《中国优秀硕士学位论文全文数据库基础科学辑》, pages 7 * |
| 陈玉锋 等: "《几种苯并咪唑类分子拉曼光谱的理论研究》", 30 June 2017, pages: 92 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | Determination of carbendazim in tea using surface enhanced Raman spectroscopy | |
| KR0167122B1 (en) | Process or preparation of poor pesticide active principles concentrates from plants | |
| Ugare et al. | Dissipation kinetics of forchlorfenuron, 6-benzyl aminopurine, gibberellic acid and ethephon residues in table grapes (Vitis vinifera) | |
| Xu et al. | Indirect glyphosate detection based on ninhydrin reaction and surface-enhanced Raman scattering spectroscopy | |
| CN107044974A (en) | 2,4 dichlorphenoxyacetic acid method for detecting residue in a kind of fruits and vegetables | |
| CN108037110A (en) | The method that surface Raman enhancement technology based on silver nanoparticle colloidal sol substrate quickly detects probenazole pesticide in rape | |
| Mottese et al. | Traceability of Opuntia ficus‐indica L. Miller by ICP‐MS multi‐element profile and chemometric approach | |
| CN106770175A (en) | A kind of method that utilization SERS detects paraquat | |
| Kamel et al. | Degradation of the acaricides abamectin, flufenoxuron and amitraz on Saudi Arabian dates | |
| Aharonson et al. | Determination of residues of benomyl, its hydrolysis product, and thiabendazole in various crops | |
| Putzbach et al. | Determination of Bitter Orange alkaloids in dietary supplements standard reference materials by liquid chromatography with ultraviolet absorbance and fluorescence detection | |
| CN113624740A (en) | Establishment method of fruit and vegetable surface pesticide residue rapid detection model and fruit and vegetable surface pesticide residue rapid detection method | |
| CN104316638B (en) | Detect the LC-MS/MS assay method of 7 kinds of invertebrate poisons in vegetables and fruit simultaneously | |
| CN108905992A (en) | A kind of solid phase microextraction adsorbent for anabasine pesticide detection | |
| Singh et al. | Development and validation of an HPLC method for determination of spirotetramat and spirotetramat cis enol in various vegetables and soil | |
| CN106770789B (en) | Ultra-high performance liquid chromatography method for simultaneously detecting contents of aflatoxin B1 and M1 in liver, kidney and chicken of broiler chicken | |
| CN109187773A (en) | The measuring method of diquat dibromide or paraquat residual quantity in a kind of food | |
| CN106770780A (en) | The detection method of active material in precious Rogor raw material or the product containing precious Rogor | |
| US20200325435A1 (en) | Apparatus and methods for measuring, monitoring, and controlling chemical concentrations of active ingredients in plant and plant crop treatment solutions | |
| CN104458968A (en) | GC-EI-MS (gas chromatography-electron impact ionization-mass spectrometry) measuring method of residual quantity of spirotetramat in fruit and vegetable | |
| CN205374395U (en) | Solid phase extraction column | |
| CN109470683B (en) | Method for carrying out 2,4-D rapid detection by combining SERS substrate with multivariate linear regression model | |
| CN113607861A (en) | Analysis method for detecting 48 pesticide residues in vegetables through liquid chromatography tandem mass spectrometry by combining magnetic stirring with sol-gel | |
| Gupta et al. | Biosensors involved in fruit and vegetable processing industries | |
| Francoeur et al. | Simultaneous determination of captan and captafol in apples and potatoes by thin layer chromatography and in situ fluorometry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |