CN114646631A - Method for detecting bisphenol A residue based on Au @ ZIF-8 substrate - Google Patents

Method for detecting bisphenol A residue based on Au @ ZIF-8 substrate Download PDF

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CN114646631A
CN114646631A CN202210306297.9A CN202210306297A CN114646631A CN 114646631 A CN114646631 A CN 114646631A CN 202210306297 A CN202210306297 A CN 202210306297A CN 114646631 A CN114646631 A CN 114646631A
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bisphenol
solution
zif
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谢云飞
董祥辉
姚卫蓉
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Nanjing Fuzhe Future Food Research Institute Co ltd
Jiangnan University
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Nanjing Fuzhe Future Food Research Institute Co ltd
Jiangnan University
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Priority to PCT/CN2022/141671 priority patent/WO2023179134A1/en
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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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    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/80—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
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Abstract

The invention discloses a method for detecting bisphenol A residue based on an Au @ ZIF-8 substrate, and belongs to the field of food detection. The invention determines the Raman characteristic peak of bisphenol A; characteristic peak 1175cm with strong Raman characteristic peak signal and good peak shape‑1Establishing a quantitative analysis curve Y which is 6488.07X +9466.58 and a correlation coefficient R20.9660; then, pretreating the fish sample, and extracting by adopting an extraction solvent to obtain a solution to be detected; and then testing according to the Raman spectrogram and the standard curve of the solution to be tested to obtain the concentration of the bisphenol A in the sample to be tested. The method provided by the invention has the advantages that the minimum detection concentration of the bisphenol A in the fish meat is 0.1mg/kg, the qualitative and quantitative analysis can be carried out on the bisphenol A residue in the fish meat, and the detection time of a single sample is controlled within 3 min.

Description

Method for detecting bisphenol A residue based on Au @ ZIF-8 substrate
Technical Field
The invention relates to a method for detecting bisphenol A residue based on an Au @ ZIF-8 substrate, and belongs to the field of food detection.
Background
Bisphenol A is regarded as a toxic substance in a great number of countries at present, and a great number of laws and regulations are issued, so that the addition and use of bisphenol A in infant products are forbidden, and meanwhile, the migration amount of bisphenol A in the packaged products is regulated.
However, researches have shown that food is one of the main ways for human beings to contact bisphenol a, especially in recent years, water resource pollution is serious, a large amount of plastic waste enters lakes and rivers, bisphenol a in the plastic waste seeps into water and then flows into aquatic animals, so that aquatic products become serious disaster areas polluted by bisphenol a, and a great number of researchers report that the bisphenol a exists in the fish bodies. It has been reported that meat and fish products contain high levels of BPA and that long-term consumption of such foods is likely to cause significant damage to the human body. Therefore, a corresponding detection method is needed to be established for detecting the content of the bisphenol A in the fish meat, so that the food safety is guaranteed.
Surface Enhanced Raman Scattering (SERS) is a technology combining nanotechnology and common Raman spectroscopy, and uses a nanostructure to enhance Raman Scattering of an analyte and quench background fluorescence, so that the SERS has the advantages of high sensitivity, high screening speed and the like, and is widely applied to detection of pollutants in food in recent years, however, due to the influence of a complex food substrate and an Enhanced substrate, the SERS detection method is generally higher in detection limit, and further application of the SERS detection method in the field of food detection is limited. The traditional SERS substrate is mainly a noble metal sol, the substrate is expensive and poor in stability, and further application of the SERS technology is limited to a certain extent, so that the development of a novel substrate is urgently needed to expand the application range.
Au @ ZIF-8 is a metal-organic framework (MOFs) material, is a novel nano porous functional material, is commonly used in the field of catalysis, and has not been applied to the surface enhanced Raman technology.
Disclosure of Invention
[ problem ] to
At present, the detection method of bisphenol A mainly comprises liquid chromatography and high performance liquid chromatography tandem mass spectrometry, and the methods have the problems of expensive equipment, overlong detection time, operation of professional technicians and the like, so that the method for rapidly and massively screening the forbidden addition of bisphenol A while ensuring the accuracy and the precision has important significance. The SERS detection is rapid and convenient, the sensitivity is high, and the detection time is short, however, the traditional SERS method uses noble metal sol as a reinforced substrate, so the detection limit of the method is relatively higher than that of a high performance liquid chromatography tandem mass spectrometry, and how to develop a novel substrate and reduce the detection limit is a problem worth discussing.
[ solution ]
In order to solve at least one problem, the invention provides a method for rapidly detecting bisphenol A residues by using a surface enhanced Raman method, which is simple to operate and short in detection time, and can effectively improve the detection efficiency under the condition of ensuring the accuracy.
The first object of the present invention is to provide a method for quantitatively detecting bisphenol A, comprising the steps of:
(1) preparation of the surface-enhanced Raman substrate: au @ ZIF-8 is used as a novel surface enhanced Raman core-shell substrate;
(2) determination of the characteristic Peak 1175cm of bisphenol A-1；
(3) Adding bisphenol A into a blank sample solution to be tested to prepare a plurality of groups of bisphenol A sample solutions to be tested with gradient concentrations as standard curve simulation solutions; carrying out surface enhanced Raman detection on the standard curve simulation solution to obtain a Raman spectrum of the standard curve simulation solution; by calculating the characteristic peak 1175cm of the simulated liquid-1Making a standard curve according to the linear relation between the integral peak intensity and the concentration of bisphenol A in the simulated liquid; wherein, the concentration of bisphenol A in the simulation liquid is the ratio of the mass of bisphenol A to the volume of the sample liquid to be detected; neglecting the quality of bisphenol A in the blank sample liquid to be detected, wherein the blank sample liquid to be detected is only used as a solvent;
(4) and (4) carrying out Raman detection on the sample liquid to be detected, and then obtaining the content of the bisphenol A in the sample liquid to be detected according to the standard curve in the step (3).
In one embodiment of the invention, the preparation method of the novel core-shell substrate in the step (1) comprises the steps of wrapping the surface of the gold nanoparticles with polyvinylpyrrolidone as a bridging agent, and sequentially adding a precursor solution (zinc nitrate solution and 2-methylimidazole solution) of ZIF-8 into the gold nanoparticles modified by the bridging agent to finally obtain the novel core-shell substrate Au @ ZIF-8.
In one embodiment of the present invention, the preparation method of the novel core-shell substrate in step (1) specifically comprises:
preparing gold sol: mixing the potassium chloroaurate solution with ultrapure water, heating, stirring and heating to boil, adding the trisodium citrate solution, and continuously stirring to obtain a dark red gold sol solution;
modifying the gold sol: mixing the prepared gold sol solution with 2.5% of polyvinylpyrrolidone aqueous solution, and stirring to obtain polyvinylpyrrolidone modified gold sol;
preparing a novel core-shell substrate: taking the modified gold sol, centrifuging, removing supernatant after centrifuging, adding methanol, and uniformly mixing to obtain a modified gold sol solution; and adding the modified gold sol solution into a zinc nitrate solution, stirring, continuously adding a 2-methylimidazole solution, stirring, standing, centrifuging after the reaction is finished, washing a product with methanol, and drying the product to obtain the novel core-shell substrate Au @ ZIF-8.
In one embodiment of the present invention, the novel core-shell substrate Au @ ZIF-8 is used when Au @ ZIF-8 is dispersed in methanol.
In one embodiment of the invention, in the step (1) of preparing the Au @ ZIF-8, the volume ratio of the gold sol to the 2.5% polyvinylpyrrolidone aqueous solution is 1: 4.
In one embodiment of the present invention, in the step (1) of preparing Au @ ZIF-8, the concentrations of the zinc nitrate solution and the 2-methylimidazole solution are 20 to 30mmol/L, and the preferred concentrations of the zinc nitrate solution and the 2-methylimidazole solution are 25 mmol/L.
In one embodiment of the present invention, in the step (1) of preparing Au @ ZIF-8, the zinc nitrate solution and the 2-methylimidazole solution are used in a volume ratio of 1: 3.
In one embodiment of the invention, in the step (1) of preparing the Au @ ZIF-8, the amount of the zinc nitrate solution is 0.1mL, and the amount of the 2-methylimidazole solution is 0.3 mL.
In one embodiment of the invention, in the step (1) of preparing the Au @ ZIF-8, the amount of the zinc nitrate solution is 0.8mL, and the amount of the 2-methylimidazole solution is 2.4 mL.
In one embodiment of the invention, in the step (1) of preparing the Au @ ZIF-8, the amount of the zinc nitrate solution is 4mL, and the amount of the 2-methylimidazole solution is 12 mL.
In one embodiment of the invention, in the preparation process of the Au @ ZIF-8 in the step (1), the volume ratio of the zinc nitrate solution to the modified gold sol is 0.1-4: 20, and the preferable volume ratio is 0.1: 20.
In one embodiment of the invention, the preparation method of Au @ ZIF-8 in the step (1) comprises the following steps: 10mL of prepared gold sol is mixed with 40 mL2.5% polyvinylpyrrolidone aqueous solution, and the mixture is stirred for 24 hours to obtain the polyvinylpyrrolidone modified gold sol. Taking 15mL of modified gold sol, centrifuging (10000r, 10min), centrifuging, removing supernatant, adding 5mL of methanol, and mixing uniformly to obtain the modified gold sol solution. And (2) taking the modified gold sol solution, respectively adding 0.1mL of 25mmol/L zinc nitrate solution, stirring for 5min, continuously adding 0.3mL of 25 mmol/L2-methylimidazole solution, stirring for 5min, standing for 15min, centrifuging (10000r, 10min) after the reaction is finished, washing for 3 times by using methanol, and putting the product into a 60 ℃ oven for drying overnight to obtain the Au @ ZIF-8 material.
In one embodiment of the present invention, the preparation method of the gold sol in step (1) specifically comprises: mixing 3mL of potassium chloroaurate solution with the concentration of 10mg/mL with 47mL of ultrapure water, heating while stirring until boiling, adding 2mL of trisodium citrate solution with the mass fraction of 1%, and continuously stirring for 20min to obtain a deep red gold sol solution.
In one embodiment of the present invention, the solvent used for dissolving the standard bisphenol a in step (2) is one of methanol, ethyl acetate or acetone.
In one embodiment of the present invention, the concentration of the bisphenol A solution in the step (2) is a gradient concentration of 0.05 to 100 mg/L.
In one embodiment of the present invention, the concentration of the bisphenol A solution in step (2) is a gradient concentration, and is 100, 50, 25, 10, 5, 1, 0.1, and 0.05mg/L in this order.
In one embodiment of the present invention, the volume ratio of bisphenol a solution to the novel core-shell substrate in step (2) is 1:1-4, further optimized to 1: 3.
in one embodiment of the present invention, the raman test conditions of the qualitative spectrum peak of the standard bisphenol a in step (2) are as follows: scanning with a laser Raman spectrometer with 785nm excitation light source for 3s for 2 times.
In one embodiment of the invention, in the step (2), the bisphenol A solution and the Au @ ZIF-8 are uniformly mixed and then are dripped onto a glass sheet wrapped by tinfoil for detection, and the detection is further optimized to be 3 min.
In an embodiment of the present invention, the method for extracting the sample solution to be tested comprises: sample to be tested and Na2CO3Mixing the solution and the extraction solvent uniformly, centrifuging and taking supernatant; and (4) repeatedly extracting the residues once, combining the supernatants obtained by the two extractions, blowing nitrogen to dry, and redissolving to obtain a sample solution to be detected.
In one embodiment of the present invention, the sample to be tested of the sample solution to be tested is fish meat or livestock and poultry meat.
In an embodiment of the present invention, the sample to be tested of the sample solution to be tested is pretreated fish, specifically, fish is minced to obtain minced fish.
In one embodiment of the present invention, the extraction solvent in step (3) is acetonitrile.
In one embodiment of the present invention, the ratio of the extraction solvent to the fish meat in step (3) is 10: 5.
In one embodiment of the present invention, Na is used in step (3)2CO3The mass fraction of the solution is 10 percent and Na2CO3The volume mass ratio of the solution to the fish meat is 2 mL: 5g of the total weight.
In one embodiment of the invention, the centrifugation in step (3) is performed at 10000r/min at 4 ℃ for 10 min.
In one embodiment of the present invention, the mixing in step (3) is vortex mixing.
In one embodiment of the present invention, the reconstitution in step (3) is performed by adding methanol.
In one embodiment of the present invention, the gradient concentrations of the multiple groups of sample solutions to be tested of bisphenol A in step (3) are 0.05-100 mg/L.
In one embodiment of the present invention, the gradient concentrations in step (3) are 100mg/L, 50mg/L, 25mg/L, 10mg/L, 5mg/L, 1mg/L, 0.1mg/L, 0.05 mg/L.
In one embodiment of the present invention, the volume ratio of the standard curve simulation solution to the gold sol in step (3) is 1:1-4, further optimized to 1: 3.
in one embodiment of the present invention, the raman spectrum detection conditions in step (3) are: scanning with a laser Raman spectrometer with 785nm excitation light source for 3s for 2 times.
In one embodiment of the invention, the extraction method of the sample solution to be detected is that 5g of minced fish is weighed by an analytical balance and put into a 50mL centrifuge tube, and 2mL of Na with the mass fraction of 10% is added2CO3Mixing the solution and 10mL acetonitrile by vortex; centrifuging at 4 deg.C at 10000r/min for 10min, collecting organic layer, extracting the residue in centrifuge tube again according to the above steps, and mixing the supernatants obtained by two extractions; and (3) taking all the supernatant, blowing the supernatant to be dry at 45 ℃ by nitrogen, and adding 2mL of methanol for redissolving to obtain a fish sample solution to be detected.
In one embodiment of the invention, the volume ratio of the sample solution to be measured to Au @ ZIF-8 in the step (4) is 1:1-4, further optimized to 1: 3.
in one embodiment of the present invention, the conditions for raman spectrum detection in step (4) are: scanning with 785nm laser Raman spectrometer for 3s for 2 times.
In one embodiment of the invention, the raman detection is performed within 3min after the sample solution to be detected and the gold sol are uniformly mixed in step (4).
It is a second object of the present invention to provide a method for detecting surface enhanced raman spectroscopy of bisphenol a in fish comprising the steps of:
(1) preparation of the surface-enhanced Raman substrate: au @ ZIF-8 is used as a novel surface enhanced Raman core-shell substrate;
(2) qualitative spectrum peak of bisphenol A as standard: dissolving a standard bisphenol A to obtain a multi-gradient-concentration bisphenol A solution; mixing the multi-gradient-concentration bisphenol A solution and Au @ ZIF-8, and detecting the surface enhanced Raman spectrum to obtain the Raman spectrum of the multi-gradient-concentration bisphenol A standard solution; comparing bisphenol A solid, bisphenol A standard solution with multiple gradient concentrations and Raman spectrum of substrate to confirm that the quantitative characteristic peak of bisphenol A is 1175cm-1；
(3) Mixing minced fish meat with Na2CO3Mixing the solution and the extraction solvent uniformly, centrifuging and taking supernatant; repeatedly extracting the residue once, mixing the supernatants obtained by the two extractions, blowing nitrogen to dry, and redissolving to obtain fish meat blank extract;
adding bisphenol A into a blank sample solution to be tested to prepare a plurality of groups of bisphenol A sample solutions to be tested with gradient concentrations as standard curve simulation solutions; carrying out surface enhanced Raman detection on the standard curve simulation liquid to obtain a Raman spectrum of the standard curve simulation liquid; by calculating the characteristic peak 1175cm of the simulated liquid-1Making a standard curve according to the linear relation between the integral peak intensity and the concentration of bisphenol A in the simulated liquid; wherein, the concentration of bisphenol A in the simulation liquid is the ratio of the mass of bisphenol A to the volume of the sample liquid to be detected; neglecting the mass of bisphenol A in the blank sample liquid to be tested, wherein the blank sample liquid to be tested is only used as a solvent;
(4) obtaining a sample liquid to be detected from the sample to be detected according to the extraction method of the hollow sample liquid to be detected in the step (3); and (4) carrying out Raman detection on the obtained sample liquid to be detected to obtain a Raman spectrum of the sample liquid to be detected, and then obtaining the content of the bisphenol A in the sample liquid to be detected according to the standard curve in the step (3).
The third purpose of the invention is to provide the application of the method in the food detection field.
The fourth purpose of the invention is to provide the application of the method of the invention in detecting bisphenol A in fish meat or livestock and poultry meat.
[ advantageous effects ]
(1) The invention develops a novel Raman enhanced substrate Au @ ZIF-8 material.
(2) The recovery rate of the detection method by adding the standard reaches 99.68-102.35%, which shows that the method has better precision and accuracy.
(3) The lowest detection concentration of bisphenol A in the fish meat detected by the method is 0.1 mg/kg.
(4) The method can be used for qualitatively and quantitatively analyzing the bisphenol A residue in the fish, the detection time of a single sample is controlled within 3min, and a rapid and convenient detection method is provided for rapid qualitative screening and preliminary quantitative detection of the bisphenol A residue in the fish.
Drawings
FIG. 1 shows a comparison of enhanced Raman spectra for bisphenol A; wherein a is the bisphenol A solid Raman spectrum and b enhances the Raman spectrum.
FIG. 2 is a Raman spectrum of solutions of bisphenol A at different concentrations; wherein a to j are respectively solid, substrate, 0.05mg/L, 0.1mg/L, 1mg/L, 5mg/L, 10mg/L, 25mg/L, 50mg/L, 100mg/L solution).
FIG. 3 shows a cross-sectional view of bisphenol A1172 cm-1Is a quantitative analysis curve of the characteristic peak.
FIG. 4 is a comparison graph of Raman spectra of fish labeled extract solutions of different concentrations; wherein a is a blank fish flesh extracting solution, b is 0.1mg/kg, c is 0.2mg/kg, and d is 1 mg/kg.
FIG. 5 shows 1175cm-1And (3) a Raman intensity contrast diagram of the mixture of the liquid to be detected and Au @ ZIF-8 in different proportions, wherein a is 1:1, b is 1:2, c is 1:3, and d is 1: 4.
FIG. 6 is a comparison of Raman intensity at 1175cm-1 for different mixing times, a for 30s, b for 60s, c for 120s, d for 180s, e for 240s, and f for 300 s.
FIG. 7 is a comparison of the enhancement effect of the gold sol substrate and the Au @ ZIF-8 substrate.
FIG. 8 is a transmission electron microscope image of Au @ ZIF-8 substrates with different shell thicknesses, (a) is a shell thickness of 3nm, (b) is a shell thickness of 20nm, and (c) is a shell thickness of 50 nm.
FIG. 9 is a comparison of the enhancement effect of Au @ ZIF-8 substrates of different sizes, wherein a is bisphenol A solid, b is the shell thickness of 3nm, c is the shell thickness of 20nm, and d is the shell thickness of 50 nm.
FIG. 10 is a comparison of the detection limits of actual samples for gold sol substrate and Au @ ZIF-8 substrate detection, wherein a is a gold sol test blank sample, b is a gold sol test 10mg/kg spiked, c is a gold sol test 20mg/kg spiked, d is a 50mg/kg spiked, e is a Au @ ZIF-8 test blank sample, f is a Au @ ZIF-8 test 0.1mg/kg spiked, g is a Au @ ZIF-8 test 0.2mg/kg spiked, and h is a Au @ ZIF-8 test 1mg/kg spiked.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
Example 1
A method for quantitatively detecting bisphenol A in fish meat comprises the following steps:
(1) preparation of the raman-enhanced substrate:
soaking the used glassware (round-bottom flask) and rotor in aqua regia for 12h, taking out, washing with ultrapure water for three times, and oven-drying at 60 deg.C; preparing trisodium citrate aqueous solution with the mass fraction of 1% and potassium chloroaurate solution with the mass fraction of 10mg/mL for later use; heating the oil bath pan to 120 ℃ and keeping the temperature constant; setting parameters of a magnetic stirrer: 565 r/min;
adding 47mL of ultrapure water and 3mL of potassium chloroaurate into a round-bottom flask, and fully mixing; putting the round-bottom flask into a 120 ℃ oil bath pot, stirring by using a magnetic stirrer and keeping the temperature constant until the solution is boiled; adding 2mL of 1% trisodium citrate aqueous solution, and continuously stirring at constant temperature of 120 ℃ for 20 min; cooling to normal temperature to obtain gold sol for later use;
and secondly, mixing 10mL of prepared gold sol with 40 mL2.5% of polyvinylpyrrolidone aqueous solution, and stirring for 24h to obtain the polyvinylpyrrolidone modified gold sol.
③ taking 15mL of the modified gold sol, centrifuging (10000r, 10min), discarding the supernatant after centrifuging, adding 5mL of methanol, and uniformly mixing to obtain the polyvinylpyrrolidone modified gold sol. Taking polyvinylpyrrolidone modified gold sol, adding 0.1mL of 25mmol/L zinc nitrate solution, stirring for 5min, continuously adding 0.3mL of 25 mmol/L2-methylimidazole solution, stirring for 5min, standing for 15min, centrifuging (10000r, 10min) after the reaction is finished, washing for 3 times by using methanol, and putting the product into a 60 ℃ oven for drying overnight to obtain Au @ ZIF-8 materials with different thicknesses. When used, Au @ ZIF-8 was dispersed in 5mL of methanol.
(2) Qualitative spectrum peak of bisphenol A as standard:
weighing 5mg of bisphenol A standard substance, dissolving the bisphenol A standard substance with ultrapure water, transferring the solution to a 5mL brown volumetric flask to obtain a 1mg/mL standard solution, gradually diluting the solution with ultrapure water to obtain 100, 50, 25, 10, 5, 1, 0.1 and 0.05mg/L bisphenol A standard solution, and storing the solution at 4 ℃ for later use;
mixing 10 mu L of bisphenol A standard solution with 30 mu L of Au @ ZIF-8, dripping the mixture onto a glass sheet wrapped by tinfoil, and scanning by a laser Raman spectrometer with an excitation light source of 785nm for 3s and 2 times to obtain a Raman spectrum of the bisphenol A standard solution (figure 1);
as can be seen from fig. 1: the characteristic peak of bisphenol A is 636cm-1，821cm-1，1172cm-1，1602cm-1。
In the range of 400-1800 cm-1In the range of 636cm-1Vibration of 6b skeleton of p-substituted benzene at position 821cm-1Position 10a vibration of p-substituted benzene, 1172cm-1The vibration was 9a for p-substituted benzene at position 1602cm-1 and 9b for p-substituted benzene at position 1602 cm-1.
(3) Standard curve
Mixing 10 mu L of bisphenol A standard solution with 30 mu L of Au @ ZIF-8, dripping the mixture onto a glass sheet wrapped by tinfoil, scanning by a laser Raman spectrometer with an excitation light source of 785nm for 3s and 2 times to obtain Raman spectra of standard solutions with different concentrations of bisphenol A, wherein the Raman spectra are 1172cm higher than other Raman peaks-1The Raman signal intensity of the peak is higher and the stability is good, so 1172cm is selected-1The Raman signal intensity of the peak is plotted with the concentration of bisphenol ATo the standard curve, as shown in fig. 3, the linear equation of the standard curve is Y-6488.07X +9466.58, and the correlation coefficient R is20.9660, indicating 1172cm-1The Raman intensity of the peak has a good linear relation with the concentration of bisphenol A.
(4) Spiked sample detection (test for recovery):
weighing 5g of minced fish meat by using an analytical balance, putting the fish meat into a 50mL centrifuge tube, adding bisphenol A standard solutions with the concentrations of 0.25mg/L, 0.5 mg/L and 2.5mg/L respectively, uniformly mixing by vortex, adding 2mL of Na with the mass fraction of 10%2CO3Mixing the solution and 10mL of acetonitrile by vortex; centrifuging at 4 deg.C at 10000r/min for 10min, collecting organic layer, extracting the residue in centrifuge tube again according to the above steps, and mixing the supernatants obtained by two extractions; taking all the supernatant, blowing the supernatant to be dry at 45 ℃ by nitrogen, and adding 2mL of methanol for redissolving to obtain a fish labeled extracting solution;
mixing 10 mu L of bisphenol A fish meat labeling extract with 30 mu L of Au @ ZIF-8, dripping the mixture onto a glass sheet wrapped by tinfoil, scanning by a laser Raman spectrometer with an excitation light source of 785nm for 3s, wherein the scanning frequency is 2 times to obtain a Raman spectrogram, and as shown in figure 4, under the labeling concentration of 0.1mg/kg, the characteristic peak of bisphenol A can be observed, so the detection limit is 0.1 mg/kg. And (4) substituting the Raman peak signal intensity corresponding to the selected peak into the standard curve obtained in the step (3), so that the standard adding recovery rate is 99.68-102.35%, and the standard adding recovery rate can be used for measuring the content of bisphenol A in the fish.
Example 2
The extraction solvent in the fish meat extract of example 1 was adjusted to ethyl acetate, acetonitrile or n-hexane, and the other solvents were determined in accordance with example 1.
The detection result is as follows: when the extraction solvent is ethyl acetate or n-hexane, the characteristic peak of bisphenol A is not appeared, and the extraction effect of acetonitrile is better.
Example 3
The volume ratio of the standard curve simulation solution and Au @ ZIF-8 in example 1, and the volume ratio of the bisphenol A fish meat standard-added extract to the gold sol were adjusted to 1:1, 1:2, 1:3, and 1:4, and the others were kept the same as those in example 1, and the detection was performed.
The detection result is as follows: selected 1175cm-1The raman peak is taken as a reference, and the gold sol and the solution to be detected are mixed according to different proportions, and the result is shown in fig. 5, wherein the volume of the gold sol and the volume of the solution to be detected are 1: and 3, the signal intensity is highest.
Example 4
The mixing time of the standard curve simulation solution and Au @ ZIF-8 in example 1 was adjusted to 30s, 60s, 120s, 180s, 240s, and 300s, and the others were kept the same as those in example 1, and detection was performed.
The detection result is as follows: selecting a Raman peak at 1175cm-1 as a reference, and mixing Au @ ZIF-8 with the liquid to be detected according to different time, wherein the result is shown in figure 6, the mixing time is 180s, and the signal intensity is highest.
Comparative example 1
Referring to example 1, omitting the second and third steps of step (1), i.e., using the conventional gold sol, and comparing the remaining conditions with the Au @ ZIF-8 enhancing effect.
The detection result is as follows: the bisphenol A is observed to be in 636cm by taking gold sol as a substrate or Au @ ZIF-8 as a substrate-1，821cm-1，1172cm-1And the peak is shown, the Au @ ZIF-8 substrate has an enhancement effect, and the characteristic peak strength of the Au @ ZIF-8 substrate after enhancement is higher than that of the gold sol by comparing the characteristic peak strengths of the two substrates.
When the traditional gold sol is used for detection, the detection limit is 10mg/kg, the Au @ ZIF-8 material is used as the detection limit to be 0.1mg/kg, and the detection limit is reduced by two orders of magnitude.
Comparative example 2
Referring to example 1, the amount of the precursor solution used was changed during the synthesis, and the remaining conditions were unchanged. The proportion of the zinc nitrate solution and the 2-methylimidazole solution is respectively 0.1mL of 25mmol/L zinc nitrate solution and 0.3mL of 25 mmol/L2-methylimidazole solution; 0.8mL of 25mmol/L zinc nitrate solution and 2.4mL of 25 mmol/L2-methylimidazole solution; 4mL of a 25mmol/L zinc nitrate solution and 12mL of a 25 mmol/L2-methylimidazole solution.
The detection result is as follows: the thickness of the obtained Au @ ZIF-8 substrate shell is different by changing the use amount of the synthetic precursor solution, and the effect of the thickness of the 3nm shell is the best by comparison.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

1. A method for quantitatively detecting bisphenol A is characterized by comprising the following steps:
(1) preparation of the surface-enhanced Raman substrate: au @ ZIF-8 is used as a novel surface enhanced Raman core-shell substrate;
(2) qualitative spectrum peak of standard bisphenol a: dissolving a standard bisphenol A to obtain a bisphenol A solution; mixing the bisphenol A solution and Au @ ZIF-8, and detecting the surface enhanced Raman spectrum to obtain a bisphenol A characteristic peak 1175cm-1；
(3) Adding bisphenol A into a blank sample solution to be tested to prepare a plurality of groups of bisphenol A sample solutions to be tested with gradient concentrations as standard curve simulation solutions; carrying out surface enhanced Raman detection on the standard curve simulation liquid to obtain a Raman spectrum of the standard curve simulation liquid; by calculating the characteristic peak 1175cm of the simulated liquid-1Making a standard curve according to the linear relation between the integral peak intensity and the concentration of bisphenol A in the simulated liquid; wherein, the concentration of bisphenol A in the simulation liquid is the ratio of the mass of bisphenol A to the volume of the sample liquid to be detected; neglecting the quality of bisphenol A in the blank sample liquid to be detected, wherein the blank sample liquid to be detected is only used as a solvent;
(4) obtaining a sample liquid to be detected from the sample to be detected according to the extraction method of the hollow sample liquid to be detected in the step (3); and (3) carrying out Raman detection on the obtained sample liquid to be detected to obtain a Raman spectrum of the sample liquid to be detected, and then obtaining the content of the bisphenol A in the sample liquid to be detected according to the standard curve in the step (2).
2. The method according to claim 1, wherein the preparation method of the novel core-shell substrate in the step (1) is specifically as follows:
preparing gold sol: mixing the potassium chloroaurate solution with ultrapure water, heating, stirring and heating to boil, adding the trisodium citrate solution, and continuously stirring to obtain a dark red gold sol solution;
secondly, gold sol modification: mixing the prepared gold sol solution with 2.5% of polyvinylpyrrolidone aqueous solution, and stirring to obtain polyvinylpyrrolidone modified gold sol;
preparing a novel core-shell substrate: taking the modified gold sol, centrifuging, removing supernatant after centrifuging, adding methanol, and uniformly mixing to obtain a modified gold sol solution; and adding the modified gold sol solution into a zinc nitrate solution, stirring, continuously adding a 2-methylimidazole solution, stirring, standing, centrifuging after the reaction is finished, washing a product with methanol, and drying the product to obtain the novel core-shell substrate Au @ ZIF-8.
3. The method as set forth in any one of claims 1 to 2, wherein the ratio of the zinc nitrate solution to the 2-methylimidazole solution is 1:3 by volume in the preparation of Au @ ZIF-8 in step (1).
4. The method as claimed in any one of claims 1 to 3, wherein in the step (1) of preparing the Au @ ZIF-8, the volume ratio of the zinc nitrate solution to the modified gold sol is 0.1-4: 20.
5. The method according to any one of claims 1 to 4, wherein the concentration of the bisphenol A solution in the step (2) is a gradient concentration of 0.05 to 100 mg/L.
6. The method of any of claims 1-5, wherein the bisphenol A solution and the novel core shell substrate in step (2) are present in a volume ratio of from 1:1 to 4.
7. The method according to any one of claims 1 to 6, wherein the volume ratio of the standard curve simulating solution to the gold sol in the step (3) is 1:1 to 4.
8. The method as claimed in any one of claims 1 to 7, wherein the Raman detection is performed within 120s to 240s after the sample solution to be detected and Au @ ZIF-8 are mixed uniformly.
9. The method according to any one of claims 1 to 8, wherein the sample to be measured of the sample solution is fish meat or livestock and poultry meat.
10. Use of the method of any one of claims 1 to 9 for detecting bisphenol a in fish or livestock meat.
CN202210306297.9A 2022-03-25 2022-03-25 Method for detecting bisphenol A residue based on Au @ ZIF-8 substrate Pending CN114646631A (en)

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CN101995400B (en) * 2010-09-29 2012-01-11 江南大学 Surface enhanced Raman spectroscopy detection method of bisphenol A
CN104749159A (en) * 2013-12-30 2015-07-01 同方威视技术股份有限公司 Pesticide residue detection method
CN107436300B (en) * 2016-05-26 2019-08-16 中国科学院化学研究所 Surface enhanced Raman scattering substrate material and preparation method thereof
CN107101990B (en) * 2017-04-06 2019-09-06 佳木斯大学 The surface enhanced Raman detection method of bisphenol A residues in a kind of milk
CN110286116A (en) * 2019-08-05 2019-09-27 河南理工大学 A kind of preparation method of high-performance SERS active-substrate ZIF-8/Ag-Au/Si-NPA
CN111337473B (en) * 2020-03-10 2021-06-08 中国科学院城市环境研究所 Detection method of free chlorine in water based on Raman spectrum
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CN112630207B (en) * 2020-12-24 2021-12-28 江南大学 Method for rapidly detecting zilpaterol residue in pork
CN113857486A (en) * 2021-08-17 2021-12-31 中国科学院化学研究所 Surface-enhanced Raman scattering substrate material and preparation method and application thereof
CN114646631A (en) * 2022-03-25 2022-06-21 江南大学 Method for detecting bisphenol A residue based on Au @ ZIF-8 substrate

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