CN115070028A - Method for rapidly detecting pesticide and veterinary drug residues by gold-based nano material electrochemical sensor - Google Patents
Method for rapidly detecting pesticide and veterinary drug residues by gold-based nano material electrochemical sensor Download PDFInfo
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- CN115070028A CN115070028A CN202210519611.1A CN202210519611A CN115070028A CN 115070028 A CN115070028 A CN 115070028A CN 202210519611 A CN202210519611 A CN 202210519611A CN 115070028 A CN115070028 A CN 115070028A
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 83
- 239000010931 gold Substances 0.000 title claims abstract description 76
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- 238000000034 method Methods 0.000 title claims description 36
- 239000000273 veterinary drug Substances 0.000 title claims description 32
- 239000000575 pesticide Substances 0.000 title claims description 27
- HXHWSAZORRCQMX-UHFFFAOYSA-N albendazole Chemical compound CCCSC1=CC=C2NC(NC(=O)OC)=NC2=C1 HXHWSAZORRCQMX-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000956 alloy Substances 0.000 claims abstract description 35
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- 229960003439 mebendazole Drugs 0.000 claims abstract description 19
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- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 6
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- 238000006243 chemical reaction Methods 0.000 claims description 13
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
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- 238000001816 cooling Methods 0.000 claims description 6
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 3
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- 238000001514 detection method Methods 0.000 abstract description 16
- 239000000447 pesticide residue Substances 0.000 abstract description 6
- 125000002883 imidazolyl group Chemical group 0.000 description 7
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- 238000002965 ELISA Methods 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 2
- 238000000835 electrochemical detection Methods 0.000 description 2
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- 241001465754 Metazoa Species 0.000 description 1
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- 238000003917 TEM image Methods 0.000 description 1
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- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical group [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
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- CVXBEEMKQHEXEN-UHFFFAOYSA-N carbaryl Chemical compound C1=CC=C2C(OC(=O)NC)=CC=CC2=C1 CVXBEEMKQHEXEN-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
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- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 description 1
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- 230000002427 irreversible effect Effects 0.000 description 1
- QBSJMKIUCUGGNG-UHFFFAOYSA-N isoprocarb Chemical compound CNC(=O)OC1=CC=CC=C1C(C)C QBSJMKIUCUGGNG-UHFFFAOYSA-N 0.000 description 1
- 201000006370 kidney failure Diseases 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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Abstract
A gold-based nanomaterial, wherein the gold-based nanomaterial consists of two metal elements, namely Au and Cu, or Au and Ag; the gold-based nano material is spherical particles, has uniform particle size of 9-11nm, and is preferably 10 nm. The glassy carbon electrode modified by the gold-based alloy nano material is prepared by the gold-based nano material, pesticide residues such as mebendazole and albendazole in a sample to be detected can be rapidly and quantitatively detected by using the electrode to detect the pesticide residues on the premise of greatly reducing the cost of the electrode, and the detection limit is greatly lower than the national standard.
Description
Technical Field
The invention relates to an analytical detection method of trace agricultural chemicals, in particular to a method for detecting imidazole group-containing carbamate veterinary drug residues by using a gold-based nano material electrochemical sensor.
Background
In recent years, carbamate pesticides have been widely used because of their advantages such as broad spectrum and low toxicity. The carbamate pesticide mainly comprises carbofuran, butylbenzene carbofuran, isoprocarb, carbaryl, albendazole, mebendazole and the like. Among them, albendazole and mebendazole belong to highly effective broad-spectrum anthelmintics, have strong insecticidal action, and are generally used for expelling the insects of livestock. Pesticide and veterinary drug residues can cause pollution to agricultural products and the environment, and further affect human health. Because the carbamate veterinary drug can inhibit the enzymatic reaction of acetylcholinesterase, the carbamate veterinary drug mainly harms the reproductive system, the endocrine system, the nervous system and the immune system of a human body, can cause symptoms such as dizziness, hypodynamia, vomiting and the like, and can seriously cause immune diseases, renal failure, cancers and even death.
The detection methods of the existing carbamate veterinary drugs mainly comprise a high performance liquid chromatography method, an enzyme inhibition method, a gas chromatography method, an immunoassay method, a sensor method and the like. The method for detecting the carbamate pesticide and veterinary drug by using the chromatography method and other methods needs a large-scale instrument, has high operation technology content and long detection period, and cannot carry out rapid pesticide residue detection analysis on a sample to be detected on site, so the method for constructing the carbamate pesticide and veterinary drug has good development prospect. At present, the most adopted methods in the aspect of rapid detection of carbamate veterinary drugs mainly comprise an enzyme-linked immunosorbent assay, an enzyme inhibition method, a fluorescence spectroscopy and a biosensor method. Although the method has the advantages of rapidness, sensitivity and the like, the bioactive substances in the enzyme-linked immunosorbent assay and biosensor method are difficult to store, easy to inactivate and high in cost, and false positive is easy to occur when an actual sample is detected, so that the result is deviated. Based on the method, the method for quickly detecting the carbamate pesticide and veterinary drug without participation of the bioactive substances has important research significance and application value. At present, a non-enzymatic substance is used as a sensitive material to modify an electrode, and an electrochemical sensor is constructed, so that the problem of insensitivity in detection caused by inactivation of a bioactive substance and the like can be effectively solved.
Electrochemical sensors have attracted much attention because of their advantages of being fast, low cost, high sensitivity, good selectivity, and capable of on-line detection. The performance of the electrochemical sensor can be changed by performing functional modification on the surface of the electrode. In addition, the variety of materials that can be used to modify the electrodes is abundant. Compared with an enzyme inhibition method, the electrochemical sensor has more stable performance and is less influenced by external factors, and the detection result can be mastered in real time through online detection. In addition, most of the carbamate veterinary drugs have-NO 2 and-N-or other unsaturated groups are easy to generate redox reaction on the electrode, so that the electrochemical sensor method for detecting the carbamate pesticide and animal medicine has good application prospect.
At present, few researches on detecting carbamate veterinary drugs by an electrochemical sensor method are carried out. In addition, metal electrochemical sensors generally use precious metals as sensitive elements, the precious metals are expensive, and the pure metals are soft, so that the problem of fusing can occur under an excessive voltage.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for rapidly detecting carbamate veterinary drug residues containing imidazolyl, and the method reduces the use amount of noble metal Au, reduces the cost and improves the stability by preparing a bimetallic alloy nano material electrode. The silver and copper in the alloy have excellent conductivity and good electrochemical performance.
The invention utilizes the principle that the carbamate veterinary drug containing imidazolyl is easy to generate irreversible electrochemical oxidation reaction on the surface of a gold-based nano material, prepares two gold-based nano materials of AuAg and AuCu as metal electrodes, and rapidly detects the carbamate veterinary drug containing imidazolyl by utilizing an electrochemical differential pulse voltammetry. In the electrochemical detection process, the gold-based alloy nano material presents a unique determined oxidation peak to the carbamate veterinary drug, so that qualitative detection is realized; the current density on the surface of the electrode and the pesticide concentration form a certain linear relation, so that quantitative detection is realized.
The technical scheme of the invention mainly comprises the steps of preparing a gold-based nano alloy material, detecting the performance of the gold-based nano alloy material, preparing a metal electrode, and quickly detecting the carbamate veterinary drug containing the imidazolyl by utilizing electrochemistry.
Preferably, the gold-based nano alloy is a nano composite material, and is further selected to be an AgCu nano material.
The embodiment of the invention provides a gold-based nano material, which consists of two metal elements of Au and Cu or Au and Ag; the gold-based nano material is spherical particles, has uniform particle size of 9-11nm, and is preferably 10 nm.
According to an embodiment of the present invention, for example, in the gold-based nanomaterial, the molar ratio of Au to Cu is 1:2 to 2:1, preferably 1: 1; and/or the molar ratio of Au to Ag is from 1:2 to 2:1, preferably 1: 1.
An embodiment of the present invention provides a method for preparing a gold-based nanomaterial comprising two metal elements, namely Au and Cu, the method comprising:
at normal temperature, putting chloroauric acid, copper acetylacetonate, oleylamine and oleic acid into a three-neck flask, and placing the three-neck flask in an oil bath pan for reaction at 180 ℃ for 2 hours; after the reaction is finished, cooling to room temperature, adding methanol with the same amount, shaking up, and performing centrifugal separation; centrifuging, removing supernatant, adding n-hexane and methanol, shaking, and centrifuging again; centrifuging, removing supernatant, adding n-hexane, transferring to a three-neck flask, adding activated carbon, and loading for 2h at normal temperature; after the load is finished, performing centrifugal separation; after centrifugal separation, adding acetic acid into the obtained material for treatment; after the treatment is finished, adding ethanol, shaking up, carrying out centrifugal separation for three times, and drying at room temperature to obtain the AuCu alloy nano material;
wherein, the molar ratio of the chloroauric acid to the copper acetylacetonate is 1:2-2:1, preferably 1: 1;
preferably, the volume ratio of oleylamine to oleic acid is 20:0.5-2, preferably 20: 1;
preferably, the molar ratio of oleylamine to chloroauric acid is from 0.1 to 0.5:1, preferably 0.3: 1;
preferably, the treatment by adding acetic acid is as follows: acetic acid is added for treatment for 1-2 hours, preferably 1.5 hours.
According to an embodiment of the present invention, for example, the gold-based nanomaterial is composed of two metal elements of Au and Ag, and the preparation method includes:
at normal temperature, chloroauric acid, silver nitrate, oleylamine and oleic acid are put into a three-neck flask and placed in an oil bath pan for reaction for 2 hours at 180 ℃; after the reaction is finished, cooling to room temperature, adding equivalent methanol, shaking uniformly, and then carrying out centrifugal separation; centrifuging, removing supernatant, sequentially adding n-hexane and methanol, shaking, and centrifuging again; centrifuging, removing supernatant, adding n-hexane, transferring into a three-neck flask, adding activated carbon, and loading at normal temperature for 2 h; after loading, carrying out centrifugal separation, and treating the obtained sample in aqua regia for 0.5h at room temperature; washing with deionized water after the treatment is finished, performing centrifugal separation, repeatedly washing until the pH of the supernatant is neutral, and drying at room temperature to obtain the gold and silver alloy nano material;
wherein the molar ratio of the chloroauric acid to the silver nitrate is 1:2-2:1, preferably 1: 1;
preferably, the volume ratio of oleylamine to oleic acid is 20:0.5 to 2, preferably 20: 1;
preferably, in the step of adding the activated carbon and loading for 2 hours at normal temperature, the metal accounts for 20 wt% of the activated carbon;
preferably, the molar ratio of oleylamine to chloroauric acid is from 0.1 to 0.5:1, preferably 0.3: 1.
According to an embodiment of the present invention, for example, the preparation method includes:
firstly, weighing 5mg of the gold-based alloy nano material prepared by the method by using an analytical balance, transferring 50 mu L of 5% perfluorosulfonic acid polymer solution and 950 mu L of ethanol into a glass bottle, ultrasonically mixing for 20min, and sealing for storage; and transferring 20 mu L of liquid containing the gold-based nano material to be dripped on the surface of the glassy carbon electrode, and airing for later use to obtain the glassy carbon electrode modified by the gold-based alloy nano material.
The embodiment of the invention provides a method for rapidly detecting pesticide and veterinary drug residues by a gold-based nanomaterial electrochemical sensor, which comprises the following steps:
adding 50mL of HAc-NaAc buffer solution into the electrolytic cell, and introducing nitrogen for 20 min; taking a calomel electrode as a reference electrode, a platinum electrode as a counter electrode, taking the glassy carbon electrode modified by the gold-based nano material prepared by the preparation method as a working electrode, and detecting the carbamate veterinary drugs with different concentrations at the same scanning speed by using a Differential Pulse Voltammetry (DPV).
According to one embodiment of the present invention, for example, the gold-based nanomaterial is an AuCu alloy nanomaterial, the veterinary drug residue is albendazole, and if an oxidation peak occurs at 0.948V, the presence of albendazole residue in the sample to be tested is indicated;
preferably, the albendazole concentration has a good linear relationship with the current density through the electrode surface, and the linear equation is 0.709x +799.22, which represents the relationship between the current density and the pesticide concentration, wherein x is the pesticide concentration in mg/L and y is the peak current density in μ a/cm 2 Therefore, the concentration of albendazole in the detected sample can be quantitatively calculated through the current density.
According to one embodiment of the present invention, for example, the gold-based nanomaterial is an AuCu alloy nanomaterial, and the veterinary drug residue is mebendazole, and if an oxidation peak occurs at 0.935V, the presence of mebendazole residue in the sample to be tested is indicated;
preferably, the concentration of mebendazole has a good linear relationship with the current density through the electrode surface, and the linear equation is y 16.468x +667.98, which represents the relationship between the current density and the concentration of pesticide, where x is the concentration of pesticide in mg/L and y is the peak current density in μ a/cm 2 And through calculation of the equation, the concentration of the mebendazole in the detected sample can be quantitatively calculated through current density.
According to one embodiment of the present invention, for example, the gold-based nanomaterial is AuAg alloy nanomaterial, the veterinary drug residue is albendazole, and if an oxidation peak occurs at 0.918V, the presence of albendazole residue in the sample to be tested is indicated;
preferably, the albendazole concentration has a good linear relationship with the peak current density, and the linear equation is that y is 53.228x +687.42, which represents the relationship between the current density and the pesticide concentration, wherein x is the pesticide concentration in mg/L, and y is the peak current density in μ A/cm 2 And the concentration of the albendazole in the detected sample can be quantitatively calculated through the calculation of the equation and the current density.
Drawings
Fig. 1 is a transmission electron micrograph of AuAg and AuCu nanomaterials.
Fig. 2 is the electrochemical activity of the AuCu nanomaterial treated with acetic acid for various times.
Fig. 3 is a DPV graph of albendazole at different concentrations measured with AuCu nanomaterials.
Fig. 4 is a linear plot of the current density of the AuCu nanomaterial as a function of albendazole concentration.
Fig. 5 is a DPV graph of different concentrations of mebendazole detected with AuCu nanomaterials.
Fig. 6 is a linear plot of current density of AuCu nanomaterials as a function of mebendazole concentration.
Fig. 7 is a DPV graph of albendazole at different concentrations measured using AuAg nanomaterials.
Fig. 8 is a linear plot of current density of AuAg nanomaterials as a function of albendazole concentration.
FIG. 9 is a DPV graph of albendazole at different concentrations measured using nanomaterials with an AuCu ratio of 1: 2.
Figure 10 is a DPV plot of various concentrations of albendazole measured with nanomaterials having an AuCu ratio of 2: 1.
Fig. 11 is a graph of DPV measured at different concentrations of mebendazole using nanomaterials with an AuCu ratio of 1: 2.
Fig. 12 is a graph of DPV measured at different concentrations of mebendazole using nanomaterials with an AuCu ratio of 2: 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments and the accompanying drawings. Those skilled in the art will appreciate that the present invention is not limited to the drawings and the following examples.
The embodiment of the invention provides a preparation method of an electrochemical sensor capable of detecting residue of carbamate veterinary drugs, which comprises the following steps:
1. preparation of gold and copper alloy nano material
At normal temperature, 0.1mmol of chloroauric acid, 0.1mmol of copper acetylacetonate, 10mL of oleylamine and 0.5mL of oleic acid are put into a three-neck flask and placed in an oil bath pan for reaction at 180 ℃ for 2 hours. After the reaction is finished, cooling to room temperature, adding methanol with the same amount, shaking up, and performing centrifugal separation. Centrifuging, removing supernatant, adding n-hexane and methanol, shaking, and centrifuging again. And after centrifugal separation, removing supernatant, adding n-hexane, transferring to a three-neck flask, adding activated carbon, and loading for 2 hours at normal temperature. And (4) centrifuging after loading is finished. After centrifugation, the resulting material was treated with acetic acid. After the treatment, adding ethanol, shaking up, centrifugally separating for three times, and drying at room temperature to obtain the gold and copper alloy nano material.
The preparation of the alloy nano material with gold and copper in different proportions only adjusts and controls the precursor proportion to be 1:2 and 2:1 respectively, and the other steps are the same.
2. Preparation of gold and silver alloy nano material
At normal temperature, 0.1mmol of chloroauric acid, 0.1mmol of silver nitrate, 10mL of oleylamine and 0.5mL of oleic acid are put into a three-neck flask and placed in an oil bath pan for reaction for 2 hours at 180 ℃. After the reaction is finished, cooling to room temperature, adding methanol with the same amount, shaking uniformly, and then carrying out centrifugal separation. Centrifuging, removing supernatant, sequentially adding n-hexane and methanol, shaking, and centrifuging again. After centrifugal separation, the supernatant was discarded, and n-hexane was added and transferred to a three-necked flask, and activated carbon (20% of the amount of metal loaded with activated carbon) was added and loaded for 2 hours at normal temperature. After loading, the sample was centrifuged and treated in aqua regia for 0.5h at room temperature. And washing with deionized water after the treatment is finished, performing centrifugal separation, repeatedly washing until the pH of the supernatant is neutral, and drying at room temperature to obtain the gold and silver alloy nano material.
3. Preparation of glassy carbon electrode modified by gold-based alloy nano material
Firstly, weighing 5mg of gold-based alloy nano material by using an analytical balance, transferring 50 mu L of 5% perfluorosulfonic acid polymer solution and 950 mu L of ethanol into a glass bottle, carrying out ultrasonic mixing for 20min, and carrying out sealed storage. And transferring 20 mu L of liquid containing the gold-based nano material to be dripped on the surface of the glassy carbon electrode, and airing for later use.
4. Electrochemical sensor for detecting carbamate veterinary drug
50mL HAc-NaAc buffer was added to the cell and nitrogen was passed through for 20 min. Taking a calomel electrode as a reference electrode, a platinum electrode as a counter electrode, a glassy carbon electrode modified by a gold-based nano material as a working electrode, and detecting carbamate veterinary drugs with different concentrations at the same sweep rate by using a Differential Pulse Voltammetry (DPV).
TABLE 1 electrochemical detection of pesticide standard sample by gold-based nanomaterial
As can be seen from the table 1, the albendazole and the mebendazole are detected by using two gold-based nano-material electrochemical sensors, and the results show that both the two materials can detect the carbamate veterinary drug containing the imidazole group, and the detection limit is lower than the national specified minimum residue limit; in particular for albendazole, the detection limit is significantly lower than the national standard.
The preparation of the alloy material can obviously reduce the material cost. The price of the precursor chloroauric acid (about 280 yuan/g) for preparing gold is far higher than that of the precursor copper acetylacetonate (about 0.75 yuan/g) for preparing copper. After the alloy is prepared, the material cost is reduced by more than 50%. The particle size of the material prepared by the embodiment of the invention is about 10nm, the material prepared into the nano alloy material has the advantages of increased hardness, increased specific surface area and improved electrochemical activity. By preparing the spherical alloy material with smaller particle size, the specific surface area of the material is increased due to the large surface area of the spherical material and the small volume of the spherical alloy material, and a part of silver or copper is further removed by a dealloying mode (part of copper is removed by acetic acid treatment and part of silver is removed by aqua regia treatment), so that the gold in the material is further exposed, the contact area of the material and pesticide is increased, and the sensitivity is improved.
The detection principle of the invention is that the nitrogen-hydrogen structure on the imidazole ring of the carbamate pesticide is oxidized on the surface of the gold-based nano material, and the nitrogen-hydrogen structure is oxidized into a nitrogen-oxygen structure.
As shown in fig. 1, the AuAg and AuCu nanomaterials prepared by the embodiment of the invention are spherical particles, have uniform particle sizes of about 10nm, and are uniformly dispersed on activated carbon. The alloy material has good structural stability, and does not have obvious shape change caused by loading activated carbon and processing by acetic acid or aqua regia.
As shown in fig. 2, AuCu treated with acetic acid for different lengths of time exhibited different electrochemical activities. The linear cyclic voltammetry spectrogram shows that the slope of a linear scanning curve of the gold-copper alloy nano material treated by acetic acid for 1.5h is smaller, the passing current is larger, and the electrochemical activity is better.
The albendazole and the mebendazole with different concentrations are detected by using a differential pulse voltammetry, as shown in fig. 3, at 0.948V, the AuCu alloy nano material presents a uniquely determined oxidation peak to the albendazole, and under the same sweep rate, the peak intensity is increased along with the increase of the concentration of the pesticide residue.
As shown in fig. 4, the albendazole concentration also has a good linear relationship with the current density passing through the electrode surface, and the linear equation is y ═ 0.709x +799.22, which represents the relationship between the current density and the pesticide concentration, where x is the pesticide concentration (in mg/L) and y is the peak current density (in μ a/cm) 2 ). Through the calculation of the equation, the current density calculation measured by the differential pulse voltammetry can be converted into the albendazole concentration.
As shown in fig. 5, at 0.935V, the AuCu alloy nanomaterial exhibits a uniquely defined oxidation peak to mebendazole, and at the same sweep rate, the peak intensity increases with the increase of the pesticide residue concentration.
As shown in fig. 6, the concentration of mebendazole also has a good linear relationship with the current density through the electrode surface, and the linear equation is y-16.468 x +667.98, which represents the relationship between the current density and the concentration of the pesticide, where x is the concentration of the pesticide (in mg/L) and y is the peak current density (in μ a/cm) 2 ). Through the calculation of the equation, the current density measured by the differential pulse voltammetry can be calculated and converted into the concentration of the mebendazole.
As shown in fig. 7, when the AuAg nanomaterial detects DPV curves of albendazole with different concentrations at the same sweep rate, a distinct peak is present at 0.918V, and the peak current density is increased with the increase of the concentration of pesticide residue.
As shown in fig. 8, the linear relationship between the albendazole concentration and the peak current density is good, and the linear equation is y 53.228x +687.42, which represents the relationship between the current density and the pesticide concentration, where x is the pesticide concentration (in mg/L) and y is the peak current density (in μ a/cm) 2 ). Through the calculation of the equation, the current density calculation measured by the differential pulse voltammetry can be converted into the albendazole concentration.
The electrochemical curves of the AuCu alloy in different concentrations of albendazole and mebendazole by differential pulse voltammetry are shown in FIGS. 9-12. The result shows that the AuCu ratio is 1:1, which is the optimal alloy ratio, and the electrochemical signal intensity is optimal. The detection stability of the AuCu alloy is superior to that of the AuAg alloy.
Claims (9)
1. The gold-based nanomaterial is characterized in that the gold-based nanomaterial consists of two metal elements, namely Au and Cu, or Au and Ag; the gold-based nano material is spherical particles, has uniform particle size of 9-11nm, and is preferably 10 nm.
2. The gold-based nanomaterial according to claim 1, characterized in that in the gold-based nanomaterial the molar ratio of Au and Cu is 1:2-2:1, preferably 1: 1; and/or the molar ratio of Au to Ag is from 1:2 to 2:1, preferably 1: 1.
3. The method for preparing gold-based nanomaterial according to claim 1 or 2, wherein the gold-based nanomaterial is composed of two metal elements of Au and Cu, the method comprising:
at normal temperature, putting chloroauric acid, copper acetylacetonate, oleylamine and oleic acid into a three-neck flask, and placing the three-neck flask in an oil bath pan for reaction at 180 ℃ for 2 hours; after the reaction is finished, cooling to room temperature, adding methanol with the same amount, shaking up, and performing centrifugal separation; centrifuging, removing supernatant, adding n-hexane and methanol, shaking, and centrifuging again; centrifuging, removing supernatant, adding n-hexane, transferring to a three-neck flask, adding activated carbon, and loading for 2h at normal temperature; after the load is finished, performing centrifugal separation; after centrifugal separation, adding acetic acid into the obtained material for treatment; after the treatment is finished, adding ethanol, shaking up, carrying out centrifugal separation for three times, and drying at room temperature to obtain the AuCu alloy nano material;
wherein, the molar ratio of the chloroauric acid to the copper acetylacetonate is 1:2-2:1, preferably 1: 1;
preferably, the volume ratio of oleylamine to oleic acid is 20:0.5 to 2, preferably 20: 1;
preferably, the molar ratio of oleylamine to chloroauric acid is from 0.1 to 0.5:1, preferably 0.3: 1;
preferably, the treatment by adding acetic acid is as follows: acetic acid is added for 1-2 hours, preferably 1.5 hours.
4. The method for preparing gold-based nanomaterial according to claim 1 or 2, wherein the gold-based nanomaterial is composed of two metal elements of Au and Ag, the method comprising:
at normal temperature, chloroauric acid, silver nitrate, oleylamine and oleic acid are put into a three-neck flask and placed in an oil bath pan for reaction for 2 hours at 180 ℃; after the reaction is finished, cooling to room temperature, adding equivalent methanol, shaking uniformly, and then carrying out centrifugal separation; centrifuging, removing supernatant, sequentially adding n-hexane and methanol, shaking, and centrifuging again; centrifuging, removing supernatant, adding n-hexane, transferring into a three-neck flask, adding activated carbon, and loading at normal temperature for 2 h; after loading, carrying out centrifugal separation, and treating the obtained sample in aqua regia for 0.5h at room temperature; washing with deionized water after the treatment is finished, performing centrifugal separation, repeatedly washing until the pH of the supernatant is neutral, and drying at room temperature to obtain the gold and silver alloy nano material;
wherein the molar ratio of the chloroauric acid to the silver nitrate is 1:2-2:1, preferably 1: 1;
preferably, the volume ratio of oleylamine to oleic acid is 20:0.5-2, preferably 20: 1;
preferably, in the step of adding the activated carbon and loading for 2 hours at normal temperature, the metal accounts for 20 wt% of the activated carbon;
preferably, the molar ratio of oleylamine to chloroauric acid is from 0.1 to 0.5:1, preferably 0.3: 1.
5. A preparation method of a glassy carbon electrode modified by gold-based alloy nano materials is characterized by comprising the following steps:
firstly weighing 5mg of the gold-based alloy nano material prepared according to the claim 3 or 4 by using an analytical balance, transferring 50 mu L of 5% perfluorosulfonic acid polymer solution and 950 mu L of ethanol into a glass bottle, ultrasonically mixing for 20min, and sealing for storage; and transferring 20 mu L of liquid containing the gold-based nano material to be dripped on the surface of the glassy carbon electrode, and airing for later use to obtain the glassy carbon electrode modified by the gold-based alloy nano material.
6. A method for rapidly detecting pesticide and veterinary drug residues by a gold-based nanomaterial electrochemical sensor is characterized by comprising the following steps:
adding 50mL of HAc-NaAc buffer solution into the electrolytic cell, and introducing nitrogen for 20 min; taking a calomel electrode as a reference electrode, a platinum electrode as a counter electrode, taking a glassy carbon electrode modified by gold-based nano materials prepared by the preparation method of claim 5 as a working electrode, and detecting carbamate veterinary drugs with different concentrations at the same sweep rate by using Differential Pulse Voltammetry (DPV).
7. The method as claimed in claim 6, wherein the gold-based nanomaterial is AuCu alloy nanomaterial, the veterinary drug residue is albendazole, and if an oxidation peak appears at 0.948V, the albendazole residue is present in the detected sample;
preferably, the albendazole concentration has a good linear relationship with the current density through the electrode surface, and the linear equation is 0.709x +799.22, which represents the relationship between the current density and the pesticide concentration, wherein x is the pesticide concentration in mg/L and y is the peak current density in μ a/cm 2 Therefore, the concentration of albendazole in the detected sample can be quantitatively calculated through the current density.
8. The method of claim 6, wherein the gold-based nanomaterial is AuCu alloy nanomaterial, the veterinary drug residue is mebendazole, and if an oxidation peak occurs at 0.935V, the mebendazole residue is present in the sample to be detected;
preferably, the concentration of mebendazole has a good linear relationship with the current density through the electrode surface, and the linear equation is y 16.468x +667.98, which represents the relationship between the current density and the concentration of pesticide, where x is the concentration of pesticide in mg/L and y is the peak current density in μ a/cm 2 And through calculation of the equation, the concentration of the mebendazole in the detected sample can be quantitatively calculated through current density.
9. The method according to claim 6, wherein the gold-based nanomaterial is AuAg alloy nanomaterial, the veterinary drug residue is albendazole, and if an oxidation peak appears at 0.918V, the albendazole residue is present in the detected sample;
preferably, the albendazole concentration has a good linear relationship with the peak current density, and the linear equation is that y is 53.228x +687.42, which represents the relationship between the current density and the pesticide concentration, wherein x is the pesticide concentration in mg/L, and y is the peak current density in μ A/cm 2 And the concentration of the albendazole in the detected sample can be quantitatively calculated through the calculation of the equation and the current density.
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