CN116026905A - Preparation method and application of electrochemical sensor based on synergistic effect of graphene nanoribbons and gold nanoparticles - Google Patents
Preparation method and application of electrochemical sensor based on synergistic effect of graphene nanoribbons and gold nanoparticles Download PDFInfo
- Publication number
- CN116026905A CN116026905A CN202310004469.1A CN202310004469A CN116026905A CN 116026905 A CN116026905 A CN 116026905A CN 202310004469 A CN202310004469 A CN 202310004469A CN 116026905 A CN116026905 A CN 116026905A
- Authority
- CN
- China
- Prior art keywords
- electrode
- graphene oxide
- modified
- glassy carbon
- gold nanoparticles
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 101
- 239000002074 nanoribbon Substances 0.000 title claims abstract description 91
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000010931 gold Substances 0.000 title claims abstract description 65
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 65
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 65
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- MBMQEIFVQACCCH-UHFFFAOYSA-N trans-Zearalenon Natural products O=C1OC(C)CCCC(=O)CCCC=CC2=CC(O)=CC(O)=C21 MBMQEIFVQACCCH-UHFFFAOYSA-N 0.000 claims abstract description 52
- MBMQEIFVQACCCH-QBODLPLBSA-N zearalenone Chemical compound O=C1O[C@@H](C)CCCC(=O)CCC\C=C\C2=CC(O)=CC(O)=C21 MBMQEIFVQACCCH-QBODLPLBSA-N 0.000 claims abstract description 52
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 46
- 239000012528 membrane Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001514 detection method Methods 0.000 claims abstract description 15
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000002484 cyclic voltammetry Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007853 buffer solution Substances 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 235000013305 food Nutrition 0.000 abstract description 13
- 230000035945 sensitivity Effects 0.000 abstract description 10
- 239000002127 nanobelt Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000004070 electrodeposition Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- -1 potassium ferricyanide Chemical compound 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000010828 elution Methods 0.000 description 7
- 230000004044 response Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 241001481789 Rupicapra Species 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001903 differential pulse voltammetry Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 241000209149 Zea Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 206010008531 Chills Diseases 0.000 description 1
- 208000020401 Depressive disease Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 208000007125 Neurotoxicity Syndromes Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 206010000210 abortion Diseases 0.000 description 1
- 231100000176 abortion Toxicity 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001318 differential pulse voltammogram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001076 estrogenic effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 201000003102 mental depression Diseases 0.000 description 1
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000003075 phytoestrogen Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 208000002254 stillbirth Diseases 0.000 description 1
- 231100000537 stillbirth Toxicity 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000004885 tandem mass spectrometry Methods 0.000 description 1
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method and application of an electrochemical sensor based on the synergistic effect of graphene nanoribbons and gold nanoparticles. According to the method, a molecularly imprinted membrane is polymerized on a graphene nanobelt and gold nanoparticle modified electrode in an electropolymerization mode to serve as a working electrode. The preparation steps of the working electrode are as follows: (1) Preparing graphene oxide nanoribbons by adopting an improved Hummers method; (2) Sequentially reducing and depositing graphene oxide nanoribbons and gold nanoparticles on a glassy carbon electrode by an electrodeposition method to prepare gold nanoparticles/reduced graphene oxide nanoribbon modified glassy carbon electrode; (3) The molecular imprinting film is prepared on the modified glassy carbon electrode by an electropolymerization method by taking zearalenone as a template molecule and o-phenylenediamine as a functional monomer, and the molecular imprinting film is a sensor for detecting zearalenone. The sensor has the advantages of high sensitivity and good selectivity, and has wide application prospect in the detection aspect of zearalenone in food.
Description
Technical Field
The invention relates to a preparation method of an electrochemical sensor based on the synergistic effect of graphene nanoribbons and gold nanoparticles and application of the electrochemical sensor in detection of zearalenone in foods, and belongs to the technical field of electrochemical analysis and detection.
Background
Zearalenone, an estrogenic fumarotoxin, is classified as either phytoestrogen or mycoestrogen. The zearalenone has high heat resistance and is completely destroyed after being treated for 1h at 110 ℃. Whereas eating food containing zearalenone in gestational animals (including humans) can cause abortion, stillbirth and teratogenesis. Eating various foods containing zearalenone can also cause central nervous system poisoning symptoms such as nausea, chill, headache, mental depression, etc. Therefore, limit standards for zearalenone in foods have been established in many countries. The content of zearalenone in various foods is required to be less than or equal to 60 mug/kg as in national standards for Chinese food safety (GB 2761-2017). The existing detection methods of zearalenone mainly comprise gas chromatography, liquid chromatography, gas chromatography-tandem mass spectrometry, liquid chromatography-tandem mass spectrometry and the like. Although these detection methods have good repeatability and accuracy, they all have the disadvantages of complex operation, high cost, environmental pollution, and generally require complex pretreatment processes. In recent years, electrochemical sensors have received attention because of their low cost, simple operation, high sensitivity, rapid response, and easy miniaturization of the devices. However, the electrochemical method is easily affected by the matrix effect, and it is difficult to specifically detect a target analyte in the face of a complex sample, and therefore, when detecting a harmful substance in a complex sample using an electrochemical sensor, it is necessary to introduce a material having excellent specific properties to improve the selectivity of the sensor. The molecularly imprinted electrochemical sensor can well solve the problems because of combining the molecularly imprinted polymer with high selectivity and high chemical stability.
In addition, zearalenone is usually present in food products at lower concentrations, and therefore the detection method requires more sensitivity. The preparation of the molecular imprinting material directly on the surface of the glassy carbon electrode often has the defects of limited imprinting sites, insensitive electric signal response and the like, and the high sensitivity advantage of the electrochemical sensor is difficult to embody. Therefore, the surface of the electrode can be modified by utilizing various conductive materials so as to improve the specific surface area and the conductivity of the electrode, thereby realizing high-sensitivity detection of the target.
Carbon nanotubes have excellent electron conductivity and can be used for electrode modification, but their high hydrophobicity makes them easy to aggregate, limiting their application as modified materials for increasing peak current. The graphene nanoribbon obtained by longitudinally cutting the carbon nano tube through chemical oxidation has larger surface area, and a large amount of oxygen-containing functional groups (such as hydroxyl and carboxyl) are brought to the surface of the graphene nanoribbon in the longitudinal shearing process, so that the hydrophilicity can be obviously improved, and the agglomeration performance can be effectively reduced. However, a large number of oxygen-containing functional groups on the surface of the graphene nanoribbon can reduce the electron transfer efficiency and affect the conductivity. Fortunately, the graphene nanoribbon is electrodeposited on the surface of the electrode by an electrodeposition method, so that the graphene nanoribbon can be modified on the electrode, a large number of oxygen-containing functional groups can be removed, and the good conductivity of the graphene nanoribbon is recovered.
In addition, gold nanoparticles are another commonly used material for improving stability and sensitivity of electrochemical sensors due to their high conductivity and high specific surface area. Especially when the gold nano particles and the carbon material are used for modifying the electrode, a synergistic effect can be generated, the electrochemical signal is obviously improved, and the sensitivity of the sensor is further improved. Therefore, the graphene nanoribbon and the gold nanoparticle electrode are selected for modification, the sensitivity of the sensor is greatly improved by utilizing the synergistic effect of the graphene nanoribbon and the gold nanoparticle electrode, and the electrochemical sensor for detecting zearalenone in food is constructed by combining the high selectivity of a molecularly imprinted material.
Disclosure of Invention
The invention aims to solve the problems of the existing analysis method in the process of detecting zearalenone, combines the synergistic amplification effect of graphene nanoribbons and gold nanoparticles on electrochemical signals after modifying electrodes with high selectivity of a molecularly imprinted material, provides a preparation method of an electrochemical sensor based on the synergistic effect of graphene nanoribbons and gold nanoparticles, and is applied to the detection of zearalenone in foods.
Compared with the existing detection method, the electrochemical analysis method has the advantages of good selectivity, high sensitivity, less time consumption, simple operation, rapid response and the like.
The technical scheme of the invention is as follows: according to the invention, the reduced graphene oxide nanobelt and the gold nanoparticles are introduced as the sensitization materials of the electrodes, the modification of the electrodes can increase the specific surface area of the electrodes to increase the number of recognition sites, and the synergistic effect of the reduced graphene oxide nanobelt and the gold nanoparticles can effectively promote the transfer of electrons, so that the sensitivity of the sensor is further improved. And then placing the modified electrode in a polymerization solution containing zearalenone and a functional monomer, preparing a molecular imprinting film on the surface of the modified electrode by an electropolymerization method, and removing zearalenone molecules on the imprinting film by chemical elution to prepare the sensor. The sensor is placed in a solution containing zearalenone for adsorption, and the high-sensitivity and high-selectivity detection of the zearalenone is realized through the change of electrochemical signals after the zearalenone with different concentrations is adsorbed.
The preparation method of the electrochemical sensor based on the synergistic effect of the graphene nanoribbons and the gold nanoparticles comprises the following specific steps:
(1) Pretreatment of a glassy carbon electrode: polishing the glassy carbon electrode on the chamois leather to a mirror surface by using alumina powder of 0.50 and 0.05 mu m, sequentially ultrasonically cleaning the glassy carbon electrode for 1min by using deionized water and ethanol respectively, and washing the glassy carbon electrode cleanly by using deionized water after each ultrasonic treatment to obtain a pretreated glassy carbon electrode;
(2) Dispersing 0.1-1 g sodium nitrate in 5-100 mL concentrated sulfuric acid, adding 0.2-2 g carbon nano tube into the solution, and stirring for 15min. The mixture is ice-bathed, 1-10 g potassium permanganate is added under vigorous stirring, the ice-bath is taken out, and the reaction is stirred for 2.5h at 35 ℃. Under vigorous stirring, 50-200 mL of water is added, the reaction is continued for 45min, hydrogen peroxide and the rest potassium permanganate are added for reaction, 1mol/L hydrochloric acid and deionized water are used for washing, and the graphene oxide nanoribbon is obtained after drying at 60 ℃ for 24 h.
(3) Ultrasonically dispersing 0.1-1 g of graphene oxide nanoribbons in 25mL of PBS buffer solution with pH=8 to obtain suspension of the graphene oxide nanoribbons; placing a glassy carbon electrode in the suspension of the graphene oxide nanoribbon, using a platinum sheet electrode as an auxiliary electrode and an Ag/AgCl electrode as a reference electrode, and scanning for 8-15 circles by using a cyclic voltammetry at a scanning speed of 50mV/s and a voltage range of-1.4V-0V to obtain a glassy carbon electrode modified by the reduced graphene oxide nanoribbon;
(4) Placing a glassy carbon electrode modified by reduced graphene oxide nanoribbons in 1.0mmol/L HAuCl 4 Depositing 300-700 s at-0.2 mV by using a constant current method in the solution to obtain gold nano particles/reduced graphene oxide nanoribbon modified glassy carbon electrodes;
(5) Taking acetic acid buffer solution as a solvent, taking zearalenone as a target molecule and o-phenylenediamine as a functional monomer, and obtaining a polymerization solution; and (3) placing the glassy carbon electrode modified by the gold nanoparticle/reduced graphene oxide nanoribbon in the polymerization solution, electropolymerizing the molecularly imprinted membrane on the electrode by using a cyclic voltammetry, and then taking out and washing cleanly for later use.
(6) Eluting the modified electrode obtained in the step (5) in the prepared mixed solution of methanol, acetic acid and water for 30-45 min to obtain the molecular imprinting membrane/gold nano particle/reduced graphene oxide nano band modified glassy carbon electrode, namely the sensor for detecting zearalenone.
Further, the molar ratio of zearalenone to o-phenylenediamine in the step (5) is as follows: 1:10; the cyclic voltammetry parameters in the step (5) are as follows: the scan voltage range is: -0.2V Σ -1.3V, scan rate 100mV/s, number of scan turns 30 turns; the elution conditions in the step (6) are as follows: v (V) Methanol :V Acetic acid :V Water and its preparation method ＝7:3:5。
The detection method of the zearalenone in food based on the synergistic effect of graphene nanoribbons and gold nanoparticles comprises the following steps:
a. preparing zearalenone solutions with different concentrations by adopting deionized water and ethanol (3:1) solutions;
b. placing the molecularly imprinted membrane/gold nanoparticle/reduced graphene oxide nanoribbon modified glassy carbon electrode in a zearalenone solution for adsorption for 15min;
c. the absorbed electrode is used as a working electrode, a platinum sheet electrode is used as an auxiliary electrode, an Ag/AgCl electrode is used as a reference electrode to form a three-electrode system, and the system is placed in a potassium ferricyanide solution with the concentration of 2.5 mmol/L;
d. by [ Fe (CN) 6 ] 3-/4- As an oxidation-reduction probe, using a differential pulse voltammetry to obtain corresponding current values after absorbing zearalenone with different concentrations, and taking a peak current difference value as an ordinate and the concentration as an abscissa to make a standard curve;
e. and (3) placing the molecularly imprinted membrane/gold nanoparticle/reduced graphene oxide nanoribbon modified glassy carbon electrode in a zearalenone solution with unknown concentration for adsorption, then placing a three-electrode system in a potassium ferricyanide solution for detection to obtain a corresponding current value, and calculating the concentration of the zearalenone according to a standard curve.
Further, the electrochemical parameters of the differential pulse voltammetry are as follows: the scanning potential range is: -0.2V-0.6V, scan rate 100mV/s.
Compared with the prior art, the invention has the beneficial effects that: the invention combines the synergistic amplification effect of the reduced graphene oxide nanobelt and gold nanoparticles on electrochemical signals after modifying electrodes with high selectivity of a molecularly imprinted material, provides a preparation method of a molecularly imprinted electrochemical sensor based on the synergistic effect of the graphene nanobelt and the gold nanoparticles, and is applied to detection of zearalenone in foods. The sensor prepared by the invention is used for detecting the zearalenone in food, and has the advantages of simple equipment, convenient operation, good selectivity, high sensitivity and obvious popularization and application potential compared with other methods for detecting the zearalenone.
Drawings
Fig. 1 is a flow chart of preparation of a molecularly imprinted membrane/gold nanoparticle/reduced graphene oxide nanoribbon modified electrode.
Fig. 2 is a cyclic voltammogram of different modified electrodes, (a) bare glassy carbon electrode, (b) reduced graphene oxide nanoribbon modified electrode, (c) gold nanoparticle/reduced graphene oxide nanoribbon modified electrode, (d) molecularly imprinted membrane/gold nanoparticle/reduced graphene oxide nanoribbon modified electrode (before elution), (e) molecularly imprinted membrane/gold nanoparticle/reduced graphene oxide nanoribbon modified electrode (after elution), (f) molecularly imprinted membrane/gold nanoparticle/reduced graphene oxide nanoribbon modified electrode (after adsorption of 150ng/mL corn graphene ketone).
Fig. 3 is a differential pulse voltammogram of different modified electrodes, (a) bare glassy carbon electrode, (b) reduced graphene oxide nanoribbon modified electrode, (c) gold nanoparticle/reduced graphene oxide nanoribbon modified electrode, (d) molecularly imprinted membrane/gold nanoparticle/reduced graphene oxide nanoribbon modified electrode (before elution), (e) molecularly imprinted membrane/gold nanoparticle/reduced graphene oxide nanoribbon modified electrode (after elution), (f) molecularly imprinted membrane/gold nanoparticle/reduced graphene oxide nanoribbon modified electrode (after adsorption of 150ng/mL corn graphene ketone).
FIG. 4 is a graph of current signal of the sensor as a function of zearalenone concentration.
FIG. 5 is a standard curve of response signal of the sensor versus zearalenone concentration.
Detailed Description
The present invention is further illustrated by the following examples which will assist those skilled in the art in understanding the invention in detail and are not intended to limit the scope of the invention.
Example 1
The preparation of the electrochemical sensor based on the synergistic effect of graphene nanoribbons and gold nanoparticles is shown in figure 1.
(1) Pretreatment of a glassy carbon electrode: polishing the glassy carbon electrode to a mirror surface on the chamois leather by using alumina powder of 0.50 and 0.05 mu m, sequentially ultrasonically cleaning the glassy carbon electrode by using deionized water and ethanol for 1min respectively, and washing the glassy carbon electrode by using deionized water after each ultrasonic treatment to obtain the pretreated glassy carbon electrode.
(2) 0.1g of sodium nitrate was dispersed in 5mL of concentrated sulfuric acid, and 0.2g of carbon nanotubes was added to the above solution and stirred for 15min. The mixture was ice-bathed, 1g of potassium permanganate was added with vigorous stirring, the ice-bath was removed, and the reaction was stirred at 35℃for 2.5h. Under vigorous stirring, 50mL of water is added, the reaction is continued for 45min, hydrogen peroxide and the rest potassium permanganate are added for reaction, 1mol/L hydrochloric acid and deionized water are used for washing, and the graphene oxide nanoribbon is obtained after drying at 60 ℃ for 24 h.
(3) Ultrasonically dispersing 0.1g of graphene oxide nanoribbons in 25mL of PBS buffer solution with pH=8 to obtain suspension of the graphene oxide nanoribbons; placing the pretreated glassy carbon electrode in the step (1) into the dispersion liquid of the graphene oxide nanoribbon, taking a platinum sheet electrode as an auxiliary electrode and an Ag/AgCl electrode as a reference electrode, and scanning for 15 circles by using a cyclic voltammetry at a scanning speed of 50mV/s and a voltage range of-1.4V-0V to obtain a reduced graphene oxide nanoribbon modified electrode;
(4) Placing a reduced graphene oxide nanoribbon modified electrode at 1mmol/L HAuCl 4 Depositing gold nanoparticles on an electrode by a constant current method at-0.2 mV for 600s in the solution to obtain gold nanoparticles/reduced graphene oxide nanoribbon modified electrode;
(5) Taking acetic acid buffer solution as a solvent, taking zearalenone as a target molecule and o-phenylenediamine as a functional monomer, and obtaining a polymerization solution; and (3) placing the gold nanoparticle/reduced graphene oxide nanoribbon modified electrode in the polymerization solution, electropolymerizing the molecularly imprinted membrane on the electrode by using a cyclic voltammetry, and then taking out and washing cleanly for later use.
(6) Eluting the modified electrode obtained in the step (5) in the prepared mixed solution of methanol, acetic acid and water for 30min to obtain the molecular imprinting membrane/gold nano particles/reduced graphene modified glassy carbon electrode, namely the sensor for detecting zearalenone.
Example 2
Preparation of an electrochemical sensor based on the synergistic effect of graphene nanoribbons and gold nanoparticles.
(1) Pretreatment of a glassy carbon electrode: polishing the glassy carbon electrode to a mirror surface on the chamois leather by using alumina powder of 0.50 and 0.05 mu m, sequentially ultrasonically cleaning the glassy carbon electrode by using deionized water and ethanol for 1min respectively, and washing the glassy carbon electrode by using deionized water after each ultrasonic treatment to obtain the pretreated glassy carbon electrode.
(2) 0.5g of sodium nitrate was dispersed in 50mL of concentrated sulfuric acid, and 1g of carbon nanotube was added to the above solution and stirred for 15min. The mixture was ice-bathed, 5g of potassium permanganate was added with vigorous stirring, the ice-bath was taken out, and the reaction was stirred at 35℃for 2.5h. Under vigorous stirring, 100mL of water is added, the reaction is continued for 45min, hydrogen peroxide and the rest potassium permanganate are added for reaction, 1mol/L hydrochloric acid and deionized water are used for washing, and the graphene oxide nanoribbon is obtained after drying at 60 ℃ for 24 h.
(3) Ultrasonically dispersing 0.5g of graphene oxide nanoribbons in 25mL of PBS buffer solution with pH=8 to obtain suspension of the graphene oxide nanoribbons; placing the pretreated glassy carbon electrode in the step (1) into the dispersion liquid of the graphene oxide nanoribbon, taking a platinum sheet electrode as an auxiliary electrode and an Ag/AgCl electrode as a reference electrode, and scanning for 12 circles by using a cyclic voltammetry at a scanning speed of 50mV/s and a voltage range of-1.4V-0V to obtain a reduced graphene oxide nanoribbon modified electrode;
(4) Placing a reduced graphene oxide nanoribbon modified electrode at 1mmol/L HAuCl 4 Depositing gold nanoparticles on an electrode by a constant current method at-0.2 mV for 400s in the solution to obtain gold nanoparticles/reduced graphene oxide nanoribbon modified electrode;
(5) Taking acetic acid buffer solution as a solvent, taking zearalenone as a target molecule and o-phenylenediamine as a functional monomer, and obtaining a polymerization solution; and (3) placing the gold nanoparticle/reduced graphene oxide nanoribbon modified electrode in the polymerization solution, electropolymerizing the molecularly imprinted membrane on the electrode by using a cyclic voltammetry, and then taking out and washing cleanly for later use.
(6) Eluting the modified electrode obtained in the step (5) in the prepared mixed solution of methanol, acetic acid and water for 40min to obtain the molecular imprinting membrane/gold nano particles/reduced graphene oxide nanoribbon modified electrode, namely the sensor for detecting zearalenone.
Example 3
Preparation of an electrochemical sensor based on the synergistic effect of graphene nanoribbons and gold nanoparticles.
(1) Pretreatment of a glassy carbon electrode: polishing the glassy carbon electrode to a mirror surface on the chamois leather by using alumina powder of 0.50 and 0.05 mu m, sequentially ultrasonically cleaning the glassy carbon electrode by using deionized water and ethanol for 1min respectively, and washing the glassy carbon electrode by using deionized water after each ultrasonic treatment to obtain the pretreated glassy carbon electrode.
(2) 1g of sodium nitrate was dispersed in 100mL of concentrated sulfuric acid, and 2g of carbon nanotubes was added to the above solution and stirred for 15min. The mixture was ice-bathed, 10g of potassium permanganate was added with vigorous stirring, the ice-bath was taken out, and the reaction was stirred at 35℃for 2.5h. Under vigorous stirring, 200mL of water is added, the reaction is continued for 45min, hydrogen peroxide and the rest potassium permanganate are added for reaction, 1mol/L hydrochloric acid and deionized water are used for washing, and the graphene oxide nanoribbon is obtained after drying at 60 ℃ for 24 h.
(3) 1g of graphene oxide nanoribbons are dispersed in 25mL of PBS buffer solution with pH=8 by ultrasonic, so as to obtain suspension of the graphene oxide nanoribbons; placing the pretreated glassy carbon electrode in the step (1) into the dispersion liquid of the graphene oxide nanoribbon, taking a platinum sheet electrode as an auxiliary electrode and an Ag/AgCl electrode as a reference electrode, and scanning for 8 circles by using a cyclic voltammetry at a scanning speed of 50mV/s and a voltage range of-1.4V-0V to obtain a reduced graphene oxide nanoribbon modified electrode;
(4) Placing a reduced graphene oxide nanoribbon modified electrode at 1mmol/L HAuCl 4 Depositing gold nanoparticles on an electrode by a constant current method for 300s under-0.2 mV to obtain gold nanoparticles/reduced graphene oxide nanoribbon modified electrode;
(5) Taking acetic acid buffer solution as a solvent, taking zearalenone as a target molecule and o-phenylenediamine as a functional monomer, and obtaining a polymerization solution; and (3) placing the gold nanoparticle/reduced graphene oxide nanoribbon modified electrode in the polymerization solution, electropolymerizing the molecularly imprinted membrane on the electrode by using a cyclic voltammetry, and then taking out and washing cleanly for later use.
(6) Eluting the modified electrode obtained in the step (5) in the prepared mixed solution of methanol, acetic acid and water for 45min to obtain the molecular imprinting membrane/gold nano particles/reduced graphene oxide nanoribbon modified electrode, namely the sensor for detecting zearalenone.
Example 4
The sensor obtained in example 3 was used for the determination of zearalenone:
(1) Cyclic voltammetry of the sensor.
The molecularly imprinted membrane/gold nanoparticle/reduced graphene oxide nanoribbon modified electrode is used as a working electrode, a platinum sheet electrode is used as an auxiliary electrode, an Ag/AgCl electrode is used as a reference electrode to form a three-electrode system, and the system is placed in a 2.5mmol/L potassium ferricyanide solution for cyclic voltammetry scanning (the scanning parameters are that the voltage range is-0.1V-0.6V and the scanning speed is 50 mV/s). The cyclic voltammetry characterization result is shown in fig. 2, and as shown in the figure, the molecularly imprinted membrane/gold nanoparticle/reduced graphene oxide nanoribbon modified electrode before elution has a surface covered with the molecularly imprinted membrane with insulativity, so that electron transfer between potassium ferricyanide and the electrode is blocked, and a current signal is very low. The peak current signal of potassium ferricyanide is obviously increased by the eluted molecularly imprinted membrane/gold nanoparticle/reduced graphene oxide nanoribbon modified electrode, because zearalenone in the imprinted membrane is eluted, specific recognition holes are left, and the holes become channels for electron transfer. After the eluted molecularly imprinted membrane/gold nanoparticle/reduced graphene oxide nanoribbon modified electrode is immersed in a solution containing zearalenone, partial specific recognition holes are occupied by the zearalenone molecules, electron transfer is blocked again, and at the moment, the peak current value is reduced.
(2) Differential pulse voltammetry of the sensor.
The molecular imprinting film/gold nanoparticle/reduced graphene oxide nanoribbon modified electrode is used as a working electrode, a platinum sheet electrode is used as an auxiliary electrode, an Ag/AgCl electrode is used as a reference electrode to form a three-electrode system, and the system is placed in 2.5mmol/L potassium ferricyanide solution to perform differential pulse voltammetric scanning (the scanning parameters are that scanning electricity isThe bit range is-0.2V-0.6V, the scanning rate is 100 mV/s). Placing the eluted molecularly imprinted membrane/gold nanoparticle/reduced graphene oxide nanoribbon modified electrode in potassium ferricyanide solution, and scanning to obtain blank current I 0 The method comprises the steps of carrying out a first treatment on the surface of the Then the electrode is placed in a zearalenone solution with a certain concentration to complete adsorption, and then scanned to obtain a current I, and the response current of the sensor is delta I=I-I 0 The measurement results are shown in FIG. 3 and FIG. 4. The measured Δi values were plotted against zearalenone concentration to obtain a standard curve for the determination of zearalenone (see fig. 5). The linear range of the zearalenone is measured to be 1-500ng/mL, and the detection limit is 0.34ng/mL. In addition, the sensor is placed in an environment of 4 ℃ for 10 days, the response current value is still 96.79% of the original signal, and the sensor has high stability.
Claims (4)
1. The preparation method and application of the electrochemical sensor based on the synergistic effect of the graphene nanoribbon and the gold nanoparticles are characterized in that the graphene nanoribbon and the gold nanoparticles are sequentially modified on a glassy carbon electrode in an electro-reduction deposition mode, and then a molecularly imprinted membrane is polymerized on the surface of the modified electrode in an electro-polymerization mode to prepare the electrochemical sensor.
2. The method for preparing the electrochemical sensor based on the synergistic effect of graphene nanoribbons and gold nanoparticles according to claim 1, which is characterized in that the construction method of the sensor is specifically as follows:
(1) Dispersing 0.1-1 g sodium nitrate in 5-100 mL concentrated sulfuric acid, adding 0.2-2 g carbon nano tube into the solution, and stirring for 15min. The mixture is ice-bathed, 1-10 g potassium permanganate is added under vigorous stirring, the ice-bath is taken out, and the reaction is stirred for 2.5h at 35 ℃. Under vigorous stirring, 50-200 mL of water is added, the reaction is continued for 45min, hydrogen peroxide and the rest potassium permanganate are added for reaction, 1mol/L hydrochloric acid and deionized water are used for washing, and the graphene oxide nanoribbon is obtained after drying at 60 ℃ for 24 h.
(2) Ultrasonically dispersing 0.1-1 g of graphene oxide nanoribbons in 25mL of PBS buffer solution with pH=8 to obtain suspension of the graphene oxide nanoribbons; placing a glassy carbon electrode in the suspension of the graphene oxide nanoribbon, using a platinum sheet electrode as an auxiliary electrode and an Ag/AgCl electrode as a reference electrode, and scanning for 8-15 circles by using a cyclic voltammetry at a scanning speed of 50mV/s and a voltage range of-1.4V-0V to obtain a glassy carbon electrode modified by the reduced graphene oxide nanoribbon;
(3) Placing a glassy carbon electrode modified by reduced graphene oxide nanoribbons in 1.0mmol/L HAuCl 4 Depositing 300-700 s at-0.2 mV by using a constant current method in the solution to obtain gold nano particles/reduced graphene oxide nanoribbon modified glassy carbon electrodes;
(4) Taking acetic acid buffer solution as a solvent, taking zearalenone as a target molecule and o-phenylenediamine as a functional monomer, and obtaining a polymerization solution; and (3) placing the glassy carbon electrode modified by the gold nanoparticle/reduced graphene oxide nanoribbon in the polymerization solution, electropolymerizing the molecularly imprinted membrane on the electrode by using a cyclic voltammetry, and then taking out and washing cleanly for later use.
(5) Eluting the modified electrode obtained in the step (4) in the prepared mixed solution of methanol, acetic acid and water for 30-45 min to obtain the molecular imprinting membrane/gold nano particle/reduced graphene oxide nano band modified glassy carbon electrode, namely the sensor for detecting zearalenone.
3. The preparation method and the application of the electrochemical sensor based on the synergistic effect of graphene nanoribbons and gold nanoparticles are characterized in that the method is characterized in that a three-electrode system is formed by using a glassy carbon electrode modified by a molecularly imprinted membrane/gold nanoparticles/reduced graphene nanoribbons as a working electrode, a platinum sheet electrode as an auxiliary electrode and an Ag/AgCl electrode as a reference electrode under the synergistic effect of reduced graphene oxide nanoribbons and gold nanoparticles, and the method realizes high-sensitivity and high-selectivity detection of zearalenone.
4. The application of the electrochemical sensor based on the synergistic effect of graphene nanoribbons and gold nanoparticles according to claim 3, wherein the linear range of the molecular imprinting electrochemical sensor based on the synergistic effect of graphene nanoribbons and gold nanoparticles for detecting zearalenone is 1-500ng/mL, and the detection limit is 0.34ng/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310004469.1A CN116026905A (en) | 2023-01-03 | 2023-01-03 | Preparation method and application of electrochemical sensor based on synergistic effect of graphene nanoribbons and gold nanoparticles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310004469.1A CN116026905A (en) | 2023-01-03 | 2023-01-03 | Preparation method and application of electrochemical sensor based on synergistic effect of graphene nanoribbons and gold nanoparticles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116026905A true CN116026905A (en) | 2023-04-28 |
Family
ID=86071906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310004469.1A Pending CN116026905A (en) | 2023-01-03 | 2023-01-03 | Preparation method and application of electrochemical sensor based on synergistic effect of graphene nanoribbons and gold nanoparticles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116026905A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106018530A (en) * | 2016-03-31 | 2016-10-12 | 广东工业大学 | Bisphenol A molecularly imprinted electrochemical sensor and preparation method and application thereof |
| CN106226370A (en) * | 2016-08-08 | 2016-12-14 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of preparation method of glyphosate molecular imprinting electrochemical sensor |
| CN107085022A (en) * | 2017-05-02 | 2017-08-22 | 广东药科大学 | The preparation and application of the molecular imprinting electrochemical sensor of 3 nitrotyrosines |
-
2023
- 2023-01-03 CN CN202310004469.1A patent/CN116026905A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106018530A (en) * | 2016-03-31 | 2016-10-12 | 广东工业大学 | Bisphenol A molecularly imprinted electrochemical sensor and preparation method and application thereof |
| CN106226370A (en) * | 2016-08-08 | 2016-12-14 | 中国农业科学院农业质量标准与检测技术研究所 | A kind of preparation method of glyphosate molecular imprinting electrochemical sensor |
| CN107085022A (en) * | 2017-05-02 | 2017-08-22 | 广东药科大学 | The preparation and application of the molecular imprinting electrochemical sensor of 3 nitrotyrosines |
Non-Patent Citations (1)
| Title |
|---|
| BINBIN ZHOU 等: "Construction of AuNPs/reduced graphene nanoribbons co-modified molecularly imprinted electrochemical sensor for the detection of zearalenone", 《FOOD CHEMISTRY》, 2 May 2023 (2023-05-02), pages 1 - 8 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shahrokhian et al. | Application of thionine-nafion supported on multi-walled carbon nanotube for preparation of a modified electrode in simultaneous voltammetric detection of dopamine and ascorbic acid | |
| Guan et al. | Hybrid carbon nanotubes modified glassy carbon electrode for selective, sensitive and simultaneous detection of dopamine and uric acid | |
| CN102850795B (en) | Preparation method of ferrocene-grafted polyethyleneimine-graphene composite material | |
| CN110794015B (en) | Preparation method and application of graphene/polypyrrole nanocomposite modified molecularly imprinted sensor for detecting nonyl phenol | |
| CN109916973B (en) | Ball-milled graphene-MOFs composite material, and preparation and application thereof | |
| CN109916979A (en) | A kind of tetrabromobisphenol A molecular imprinting electrochemical sensor, preparation method and applications | |
| Shahrokhian et al. | Simultaneous Voltammetric Determination of Uric Acid and Ascorbic Acid Using a Carbon‐Paste Electrode Modified with Multi‐Walled Carbon Nanotubes/Nafion and Cobalt (II) nitrosalophen | |
| CN115112744A (en) | Electrochemical sensor and preparation method and application thereof | |
| Wang et al. | An ultrasensitive molecularly imprinted electrochemical sensor based on graphene oxide/carboxylated multiwalled carbon nanotube/ionic liquid/gold nanoparticle composites for vanillin analysis | |
| Huang et al. | Ultrasensitive determination of metronidazole using flower-like cobalt anchored on reduced graphene oxide nanocomposite electrochemical sensor | |
| CN107132259B (en) | Doped graphene-based cholesterol sensor and preparation and application thereof | |
| CN105954334B (en) | A kind of molecular imprinting electrochemical sensor and its application for detecting diphenylamines | |
| Jin et al. | PdPt bimetallic alloy nanowires-based electrochemical sensor for sensitive detection of ascorbic acid | |
| Lv et al. | Cu2+ modified Zr-based metal organic framework-CTAB-graphene for sensitive electrochemical detection of sunset yellow | |
| Tao et al. | Tris (2, 2′-bipyridyl) ruthenium (II) electrochemiluminescence sensor based on carbon nanotube/organically modified silicate films | |
| CN116026905A (en) | Preparation method and application of electrochemical sensor based on synergistic effect of graphene nanoribbons and gold nanoparticles | |
| CN116124848A (en) | Preparation method and application of molecularly imprinted electrochemical sensor | |
| CN111099651B (en) | Nano spherical silver sulfide high-dispersion loaded nitrogen-doped graphene composite material, modified electrode and application of nano spherical silver sulfide high-dispersion loaded nitrogen-doped graphene composite material | |
| CN115616055A (en) | Furacilin detection method based on molecular imprinting sensor | |
| CN112326753B (en) | Preparation method and application of triclosan molecular imprinting membrane electrochemical sensor | |
| Chen et al. | Glassy Carbon Electrode Modified with Gold nanoparticles/thiol-β-cyclodextrin—graphene for the Determination of Nonylphenol | |
| Zarrin et al. | A Sensitive Electrochemical Sensor Due to Novel Bionanocomposite to Determine Tartrazine | |
| CN111257382A (en) | Daidzein molecular imprinting electrochemical sensor and preparation method thereof | |
| CN108872336B (en) | Method for detecting content of pentachlorophenol in paper packaging material | |
| Dewi et al. | Electrochemical performance of gold nanoparticles decorated on Multi-walled Carbon Nanotube (MWCNT) Screen-printed Electrode (SPE) |
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 |