CN115815588B - Method for detecting malachite green in aquatic product based on nano palladium/multilayer hollow sphere Pd/CuO@NiO - Google Patents
Method for detecting malachite green in aquatic product based on nano palladium/multilayer hollow sphere Pd/CuO@NiO Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 31
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 title abstract description 72
- 229940107698 malachite green Drugs 0.000 title abstract description 72
- 238000000034 method Methods 0.000 title abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 22
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- 238000006243 chemical reaction Methods 0.000 claims description 14
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- 238000001035 drying Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
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- 108091003079 Bovine Serum Albumin Proteins 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 229940098773 bovine serum albumin Drugs 0.000 description 11
- 230000012447 hatching Effects 0.000 description 11
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
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- WZKXBGJNNCGHIC-UHFFFAOYSA-N Leucomalachite green Chemical class C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)C)C1=CC=CC=C1 WZKXBGJNNCGHIC-UHFFFAOYSA-N 0.000 description 3
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- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for detecting malachite green in aquatic products based on nano palladium/multilayer hollow spherical Pd/CuO@NiO. Firstly, a Pd/CuO@NiO material is prepared, and the dual catalytic action of CuO@NiO and Pd is utilized to achieve the effect of signal amplification and is used for detecting malachite green. Firstly, preparing Pd/CuO@NiO-Ab2 solution; ab1 was then loaded onto gold nanoparticle electrodes. During detection, a sample containing malachite green is dripped on the electrode, ab1 on the electrode is combined with malachite green, and then Pd/CuO@NiO-Ab 2 solution is dripped, so that Ab2 is combined with malachite green to form a Pd/CuO@NiO-Ab 2 -malachite green-Ab 1 -gold-containing nanoparticle electrode. And (3) scanning and recording current change by using a time-current method, and realizing high-sensitivity detection of malachite green according to the linear relation between the obtained current difference and the concentration of malachite green solution.
Description
Technical Field
The invention relates to the technical field of aquatic product detection, in particular to a method for detecting malachite green in an aquatic product based on nano palladium/multilayer hollow sphere Pd/CuO@NiO.
Background
Malachite green is a toxic triphenylmethane chemical, both a dye and a bactericidal and parasiticidal chemical, and can be carcinogenic. Malachite green has been listed by the department of agriculture in 2002 as a contraband on aquatic products. However, malachite green has special effects on saprolegniasis of fish and saprolegniasis of fish eggs, no special drug for rapidly solving saprolegniasis of saprolegniasis exists on the market, and the product is forbidden for years in aquaculture, and is the root cause that aquaculture farmers are very stiff and make a reckless move continue to use malachite green illegally. Malachite green has strong toxicity to aquatic animal propagation and development and the like, and causes harm to human beings through a food chain. It is desirable to detect malachite green in an aquatic product. The existing detection means for detecting malachite green and the leucomalachite green metabolite mainly comprise spectrophotometry, raman spectroscopy, colloidal gold immunoassay, magnetic immunochromatography, high Performance Liquid Chromatography (HPLC), high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), enzyme-linked immunosorbent assay and the like, and the electrochemical immunosensor is a biosensor combining an immunological method with an electrochemical method, and utilizes the characteristic combination between antigen and antibody to ensure that the electrochemical immunosensor has the advantages of high sensitivity, high selectivity, rapid analysis, simple and convenient operation and the like.
Among noble metal nano-materials, pd noble metal nano-materials have very high catalytic performance, can promote the progress of a plurality of reactions, and can catalyze the decomposition of hydrogen peroxide. The hollow metal material has relatively high specific surface area and good electrocatalytic activity, and if the hollow spherical metal oxide with large specific surface area is used as a carrier of Pd nano particles, the double catalytic action of the hollow spherical metal oxide and the Pd nano particles is utilized to achieve the effect of signal amplification, and the hollow spherical metal oxide is combined with the detection of malachite green, so that the sensitivity of the detection of malachite green can be greatly improved. How to combine hollow spherical metal oxide and Pd nano particles and use the combined hollow spherical metal oxide and Pd nano particles for detecting malachite green is a problem to be solved.
Disclosure of Invention
Aiming at the prior art, the invention aims to provide a method for detecting malachite green in an aquatic product based on nano palladium/multi-layer hollow spherical Pd/CuO@NiO. The sensor based on nano palladium/multi-layer hollow sphere Pd/CuO@NiO for detecting Malachite Green (MG) in aquatic products is prepared, and the Malachite Green (MG) is detected.
In order to achieve the above purpose, the invention adopts the following technical scheme:
In a first aspect of the invention, a nano palladium/multilayer hollow sphere Pd/CuO@NiO material is provided, and is prepared by the following method:
(1) Preparation of a metal organic framework material Cu-Ni-BTC: preparing Ni (NO 3)2·6H2 O into Ni (NO 3)2 solution, preparing trimethyl-1, 3, 5-benzene tricarboxylic acid into H 3 BTC solution by using DMF), adding Ni (NO 3)2 solution into H 3 BTC solution, stirring uniformly and vibrating to obtain mixed solution, taking the mixed solution to perform first microwave reaction to obtain metal organic frame material Ni-BTC, dispersing Ni-BTC into DMF, adding Cu (NO 3)2·3H2 O, performing second microwave reaction), washing, centrifuging and drying after the reaction is finished to obtain metal organic frame material Cu-Ni-BTC;
(2) Preparation of multilayer hollow sphere CuO@NiO: grinding Cu-Ni-BTC, calcining, and cooling to room temperature to obtain multi-layer hollow sphere CuO@NiO;
(3) Preparation of nano palladium/multilayer hollow sphere CuO@NiO: dispersing CuO@NiO in water, then adding sodium tetrachloropalladate and sodium citrate, adding NaBH 4 under stirring, continuously stirring, centrifuging, washing and drying the obtained mixture to obtain nano palladium/multi-layer hollow spherical Pd/CuO@NiO solid.
Preferably, in the step (1), the concentration of the Ni (NO 3)2·6H2 O solution is 20-30 g/L, the concentration of the H 3 BTC solution is 10-20 g/L, the volume ratio of the Ni (NO 3)2 solution to the H 3 BTC solution is 1:1, and the mass ratio of the Ni-BTC to Cu (NO 3)2·3H2 O is 1:1);
the temperature of the first microwave reaction and the second microwave reaction is 150 ℃, and the reaction time is 30min.
Preferably, in the step (2), the temperature rising rate of the calcination is 5 ℃/min; the calcination temperature is 500 ℃, and the calcination time is 2 hours.
Preferably, in the step (3), the concentration of CuO@NiO is 0.4-1.5 g/L; the addition amount ratio of the CuO@NiO, the sodium tetrachloropalladate, the sodium citrate and the NaBH 4 is (0.03-0.008) g: (0.20 to 0.30) mmol: (0.20 to 0.30) mmol: (0.004-0.008) mmol.
In a second aspect of the present invention, there is provided the use of nano palladium/multi-layer hollow sphere Pd/cuo@nio material as described in at least one of the following 1) to 3):
1) Amplifying the transmission signal;
2) Preparing an electrochemical sensor;
3) Decomposing hydrogen peroxide.
In a third aspect of the present invention, there is provided an electrochemical sensor comprising a first device and a second device;
The first device comprises an electrode, gold nanoparticles are loaded on the electrode, and the gold nanoparticles are connected with a first antibody;
The second device comprises nano palladium/multi-layer hollow sphere Pd/CuO@NiO, and the Pd/CuO@NiO is connected with a second antibody.
The first antibody and the second antibody may be the same or different, but both have specific selection for the antigen to be detected.
Preferably, the electrochemical sensor is prepared by the following method:
(1) Placing the pretreated electrode in potassium ferricyanide solution, and scanning at-0.2-0.6V potential to make the peak potential difference smaller than 110mV; scanning under the voltage of-0.2V by taking HAuCl 4 with the mass fraction of 1% as a base solution to obtain an electrode of electrodeposited gold nano particles; dropwise adding a second antibody solution onto the electrode, incubating for 1h, and then flushing with ultrapure water; then dripping bovine serum albumin solution, incubating for 1h, and flushing with ultrapure water to obtain a first device;
(2) Dispersing Pd/CuO@NiO as claimed in any one of claims 1 to 3 in ultrapure water, adding a second antibody solution, carrying out centrifugal separation after shaking incubation, dispersing a lower layer precipitate in a phosphate buffer solution to prepare a second device, and preserving at 4 ℃ for later use.
Preferably, in the step (1), the concentration of Pd/CuO@NiO is 1-3 mg/mL; the concentration of the malachite green antibody solution is 8-12 mug/mL; the concentration of the phosphate buffer is 1-15 mM, and the pH=7.4; the temperature of the vibration hatching is 4 ℃ and the time is 12 hours;
Preferably, in step (2), the concentration of the potassium ferricyanide solution is 5mM; the concentration of the malachite green antibody solution is 5-10 mug/mL; the concentration of the bovine serum albumin solution is 5-15 mg/mL.
In a fourth aspect of the invention there is provided the use of an electrochemical sensor for detecting an antigen, said antigen being malachite green.
In a fifth aspect of the present invention, there is provided a method of detecting malachite green in an aquatic product using an electrochemical sensor, comprising the steps of:
(1) Dripping malachite green solutions with different concentrations on the surface of the first device, incubating for 1h, and flushing with ultrapure water; then, the second device is continuously dripped for hatching, and the electrochemical sensor is obtained after the hatching is completed by cleaning and airing;
(2) Adopting a three-electrode system to perform measurement, taking the electrochemical sensor prepared in the step (1) as a working electrode, taking a saturated calomel electrode as a counter electrode and a platinum wire electrode as an auxiliary electrode, scanning in a phosphate buffer solution containing hydrogen peroxide by adopting a time-current method, recording current change, forming a linear relation between the obtained current difference and the concentration of malachite green solution, and drawing a working curve;
(3) Dripping a sample solution to be detected obtained by pretreatment of an aquatic product sample on the surface of a first device, incubating for 1h, and then flushing with ultrapure water; then, the second device is continuously dripped for hatching, and the electrochemical sensor is obtained after the hatching is completed by cleaning and airing; and (3) repeating the method in the step (2), and obtaining the concentration of malachite green in the sample solution to be detected according to the current change and the standard curve.
Preferably, in the step (1), the concentration of the malachite green solution is 0.0001-100 ng/mL; the incubation temperature is 4 ℃ and the incubation time is 1h.
Preferably, in the step (2), the concentration of the hydrogen peroxide is 5mM; pH of the phosphate buffer solution=7.4; the input voltage of the scan was-0.4V and the run time was 400s.
The invention has the beneficial effects that:
(1) According to the invention, the novel material multilayer hollow sphere Pd/CuO@NiO is utilized for the first time, and the double catalytic effects of the CuO@NiO and Pd nanoparticles are realized by combining the catalytic effects of the noble metal nanoparticles and the metal oxide, so that the signal amplification effect is realized, and the high-sensitivity detection of malachite green is realized by establishing a linear relationship between the current difference and the concentration of malachite green solution.
(2) The invention can be used for detecting various antigens by a sandwich electrochemical immunosensor method, for example, the detection of malachite green is realized, the detection limit is low 0.000042ng/mL, the linear range is wide by 0.0001-100 ng/mL, and the simple, quick, sensitive and specific detection can be realized.
Drawings
Fig. 1: the detection method of the invention is a schematic diagram;
fig. 2: a is a current change diagram, b is a standard curve;
fig. 3: alternating current impedance spectrum of electrochemical immunosensor.
Fig. 4: the specificity results of the electrochemical immunosensor are shown.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As described in the background section, malachite green has been listed as a contraband for aquatic products by the Ministry of agriculture in 2002. However, malachite green has special effects on saprolegniasis of fish and saprolegniasis of fish eggs, no special drug for rapidly solving saprolegniasis of saprolegniasis exists on the market, and the product is forbidden for years in aquaculture, and is the root cause that aquaculture farmers are very stiff and make a reckless move continue to use malachite green illegally. However, the content of malachite green in general aquatic products is low, and further improvement of the detection sensitivity of malachite green is required.
Based on the above, the invention aims to provide a method for detecting malachite green in aquatic products based on nano palladium/multi-layer hollow sphere Pd/CuO@NiO. According to the invention, the nano palladium/multi-layer hollow spherical Pd/CuO@NiO material is prepared, nano palladium is loaded on the multi-layer hollow spherical CuO@NiO, and the nano Pd in the material has high catalytic performance, so that a plurality of reactions, such as catalytic hydrogen peroxide decomposition, can be promoted. The hollow metal material has relatively high specific surface area, the hollow spherical CuO@NiO metal oxide has good electrocatalytic activity, so that the hollow spherical CuO@NiO metal oxide with large specific surface area is used as a carrier of Pd nano particles, the double catalytic effects of the CuO@NiO and the Pd nano particles can be utilized to achieve the effect of signal amplification, and the Pd/CuO@NiO serving as a novel and special material has relatively high specific surface area so as to provide more active sites, and therefore has strong catalytic performance on H 2O2. Detecting malachite green by using nano palladium/multi-layer hollow spherical Pd/CuO@NiO materials, as shown in figure 1, firstly loading gold nanoparticles on an electrode, forming a gold-ammonia building by using amino groups on malachite green Ab 1 and the gold nanoparticles, and loading Ab 1 on the electrode; and combining the Pd/CuO@NiO with malachite green Ab 2 by combining the amino group on Ab 2 with palladium to obtain Pd/CuO@NiO-Ab 2 solution. during detection, sample liquid containing malachite green is dripped on the electrode, ab 1 on the electrode is combined with malachite green, redundant malachite green is washed off, pd/CuO@NiO-Ab 2 solution is dripped, so that Ab 2 loaded by the solution is combined with malachite green, The structure of Pd/CuO@NiO-Ab 2 -malachite green-Ab 1 -electrode containing gold nano particles is formed, namely the electrochemical sensor. The content of the malachite green can be determined, the working electrode in the three-electrode system of the electrochemical sensor crop is placed in PBS containing hydrogen peroxide, the concentration of the hydrogen peroxide is 5mM, and the double catalytic hydrogen peroxide of the CuO@NiO and Pd nano particles is decomposed into H 2 O and O 2. The more the malachite green content is, the more the Pd/CuO@NiO content is, the more hydrogen peroxide is catalytically decomposed, and the larger the current change is in the detection process, so that the effect of signal amplification is achieved. And by recording the current change, a standard curve of the concentration of the malachite green is established, so that the malachite green is detected. The electrochemical sensor of the present invention can also be used for highly sensitive detection of various groups of antigens.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present application, the technical scheme of the present application will be described in detail with reference to specific embodiments.
The test materials used in the examples of the present invention are all conventional in the art and are commercially available.
Description: in the invention, the preparation method of the malachite green antibody solution comprises the following steps: 1mg of malachite green antibody is weighed, added into 1mL of PBS buffer solution, 1mg/mL of malachite green antibody is prepared, and stored at-20 ℃. Before use, it was diluted to 7.5. Mu.g/mL and 10. Mu.g/mL with PBS buffer.
The preparation method of the bovine serum albumin solution comprises the following steps: 10mg of bovine serum albumin is weighed and added into 1mL of PBS buffer solution to prepare 10mg/mL of malachite green antibody, which is prepared on site.
Peacock Dan Kangti Ab 1 and peacock Dan Kangti Ab 2 were both: anti-malachite green monoclonal antibody, antibody type: murine IgG; purchased from Shenzhen Anti Biotechnology Co.
The concentration of the phosphate buffer solution was 10mM. The PBS buffer is prepared by the method: na 2HPO4 and NaH 2PO4(10mM),NaCl(140mM),KCl(1mM),MgCl2(1mM),CaCl2 (1 mM), the pH of the final solution was 7.4.
Example 1: preparation of nano palladium/multilayer hollow sphere Pd/CuO@NiO
(1) Preparation of metal organic framework material Cu-Ni-BTC
Adding 0.25g of Ni (NO 3)2·6H2 O) into 10mL of N, N-Dimethylformamide (DMF) solvent, stirring uniformly to prepare Ni (NO 3)2 solution, adding 0.15g of trimethyl-1, 3, 5-benzene tricarboxylic acid (H 3 BTC) into 10mL of N, N-Dimethylformamide (DMF) solvent, stirring uniformly to prepare H 3 BTC solution, adding Ni (NO 3)2 solution into H 3 BTC solution, stirring uniformly, vibrating for 30min, transferring the mixed solution into a reactor, carrying out microwave reaction for 30min at 150 ℃ to prepare a metal organic framework material Ni-BTC, dispersing Ni-BTC in the DMF solvent, adding 0.15g of Cu (NO 3)2·3H2 O) into the Ni-BTC solution, carrying out microwave reaction for 30min at 150 ℃, washing with absolute ethyl alcohol, centrifuging at 60 ℃, and drying at 60 ℃ to prepare the metal organic framework material Cu-Ni-BTC;
(2) Preparation of multilayer hollow sphere CuO@NiO
Grinding the prepared metal organic framework material Cu-Ni-BTC, putting the ground metal organic framework material Cu-Ni-BTC into an electric heating furnace, reacting for 2 hours at the heating rate of 5 ℃/min to 500 ℃, and cooling to room temperature to obtain multi-layer hollow sphere CuO@NiO;
(3) Preparation of detection antibody marker-nano palladium/multilayer hollow sphere CuO@NiO
Dispersing 0.02g of multi-layer hollow sphere CuO@NiO nano particles in 20mL of water, then adding 0.25mmol of sodium tetrachloropalladate and 0.25mmol of sodium citrate, adding 0.6mL of 0.01mol/L NaBH 4 under stirring, continuously stirring for 1h, centrifuging and washing the mixture, and vacuum-drying at 40 ℃ to obtain nano-palladium/multi-layer hollow sphere Pd/CuO@NiO solid.
Example 2: establishment of malachite green standard curve
(1) Dispersing 2mg of nano palladium/multi-layer hollow spherical Pd/CuO@NiO in 1mL of ultrapure water, adding 1mL of detection antibody solution with the concentration of 10 mug/mL, oscillating and incubating for 12 hours at the temperature of 4 ℃, centrifugally separating, dispersing the lower-layer precipitate in 1mL of 10mM of phosphate buffer solution with the pH of 7.4, preparing a detection antibody incubator-nano palladium/multi-layer hollow spherical Pd/CuO@NiO-Ab 2 solution, and preserving at the temperature of 4 ℃ for standby to obtain a second device.
(2) Polishing the glassy carbon electrode by using aluminum oxide polishing powder of 1.0, 0.3 and 0.05 mu m in sequence, cleaning the glassy carbon electrode by using ultrapure water, and then placing the electrode in 5mM potassium ferricyanide solution for scanning at 0.1V potential to ensure that the peak potential difference is less than 110mV; 2mL of HAuCl 4 with mass fraction of 1% is taken as base solution, and the electrode of the electrodeposited gold nano particle is obtained by scanning for 30s under the voltage of-0.2V; dropping 6 mu L of 7.5 mu g/mL of peacock Dan Kangti Ab 1, incubating for 1h at 4 ℃, and flushing with ultrapure water; and 3 mu L of bovine serum albumin solution with the mass fraction of 10mg/mL is dripped on the surface of the electrode, incubated for 1h at 4 ℃ and flushed with ultrapure water, so as to obtain a first device.
(3) Respectively dripping 6 mu L of malachite green solution with the concentration of 0.0001, 0.001, 0.01, 0.1, 1, 5, 10, 50 and 100ng/mL to the surface of the first device, incubating for 1h at 4 ℃ and flushing with ultrapure water; and continuously dripping 5 mu L of detection antibody hatchery-nano palladium/multi-layer hollow spherical Pd/CuO@NiO-Ab 2 solution onto the surface of the first device, hatching for 1h in a refrigerator at 4 ℃, cleaning and airing to obtain the electrochemical sensor.
(4) The method comprises the steps of adopting a three-electrode system to carry out measurement, adopting an electrochemical sensor as a working electrode, adopting a saturated calomel electrode as a counter electrode and adopting a platinum wire electrode as an auxiliary electrode, adopting a time-current method to carry out scanning in a phosphate buffer solution containing hydrogen peroxide (5 mM) with pH of 7.4, and adopting an input voltage of-0.4V and running time of 400s; the current change was recorded, and the working curve was plotted as shown in fig. 2, based on the linear relationship between the current difference and the concentration of malachite green specific antigen. The equation for the operating curve is: current i=36.57×c malachite green +179.71,R2 =0.987. The detection range of the working curve is 0.0001-100 ng/mL, and the detection limit is 0.000042ng/mL.
Example 3: representation of malachite green electrode layer-by-layer modification
(1) Polishing the glassy carbon electrode by using aluminum oxide polishing powder of 1.0, 0.3 and 0.05 mu m in sequence, cleaning the glassy carbon electrode by using ultrapure water, and then placing the electrode in a 5mM potassium ferricyanide solution to measure the impedance condition of the electrode as a;
(2) Taking 2mL of HAuCl 4 with mass fraction of 1% as a base solution, scanning for 30s at voltage of-0.2V to obtain an electrode of electrodeposited gold nano particles, placing the electrode in 5mM potassium ferricyanide solution, and measuring the impedance condition of the electrode as b;
(3) Dropping 6 mu L of 7.5 mu g/mL of peacock Dan Kangti Ab 1, incubating for 1h at 4 ℃, flushing with ultrapure water, placing the electrode in 5mM potassium ferricyanide solution, and measuring the impedance condition of the electrode as c;
(4) Dripping 3 mu L of bovine serum albumin solution with the mass fraction of 10mg/mL to the surface of an electrode, incubating for 1h at 4 ℃, flushing with ultrapure water, placing the electrode in 5mM potassium ferricyanide solution, and measuring the impedance condition of the electrode as d;
(5) Continuously dripping 6 mu L of malachite green solution with the concentration of 10ng/mL to the surface of the electrode, incubating for 1h at 4 ℃ and flushing with ultrapure water; placing the electrode in 5mM potassium ferricyanide solution, and measuring the impedance condition of the electrode as e;
(6) Continuously dripping 5 mu L of detection antibody hatchery-nano palladium/multi-layer hollow sphere Pd/CuO@NiO-Ab 2 solution to the surface of an electrode, hatching for 1h in a refrigerator at 4 ℃, cleaning, placing the electrode in 5mM potassium ferricyanide solution, and measuring the impedance condition of the electrode as f;
(4) The change in resistance of the recording electrode layer by layer is shown in fig. 3, and it can be seen that when the bare electrode is covered with a gold coating, the resistance becomes smaller, indicating that gold promotes the electrode electron transfer process. With the modification of the malachite Dan Kangti Ab 1, bovine serum albumin, malachite green, pd/CuO@NiO-Ab 2, the electrode impedance tended to increase. This is due to the barrier of macromolecular proteins to electron transfer and also indicates the success of layer-by-layer modification.
Example 4: detection of malachite green in grass carp
(1) Polishing the glassy carbon electrode by using aluminum oxide polishing powder of 1.0, 0.3 and 0.05 mu m in sequence, cleaning the glassy carbon electrode by using ultrapure water, and then placing the electrode in 5mM potassium ferricyanide solution for scanning at 0.1V potential to ensure that the peak potential difference is less than 110mV; 2mL of HAuCl 4 with mass fraction of 1% is taken as base solution, and the electrode of the electrodeposited gold nano particle is obtained by scanning for 30s under the voltage of-0.2V; dropping 6 mu L of 7.5 mu g/mL of peacock Dan Kangti Ab 1, incubating for 1h at 4 ℃, and flushing with ultrapure water; and 3 mu L of bovine serum albumin solution with the mass fraction of 10mg/mL is dripped on the surface of the electrode, incubated for 1h at 4 ℃ and flushed with ultrapure water, so as to obtain a first device.
(2) Taking a grass carp, crushing and fully and uniformly mixing the grass carp with a crusher, adding 10mL of acetonitrile into 5.0g of a fish sample for extraction, concentrating the extract to be nearly dry, re-dissolving the extract by 6mL of acetonitrile, purifying the extract by a DCS-MCAX column (purchased from sigma aldrich trade Co., ltd.), concentrating the obtained purified solution, adding 2mL of distilled water to obtain a sample solution to be tested, dropwise adding the obtained sample solution to the surface of a first device, incubating for 1h at 4 ℃, and flushing with ultrapure water; and continuously dripping 5 mu L of detection antibody hatchery-nano palladium/multi-layer hollow spherical Pd/CuO@NiO-Ab 2 solution onto the surface of the first device, hatching for 1h in a refrigerator at 4 ℃, cleaning and airing to obtain the electrochemical sensor.
(3) The method comprises the steps of adopting a three-electrode system to carry out measurement, adopting an electrochemical sensor as a working electrode, adopting a saturated calomel electrode as a counter electrode and adopting a platinum wire electrode as an auxiliary electrode, adopting a time-current method to carry out scanning in a phosphate buffer solution containing hydrogen peroxide (5 mM) with pH of 7.4, and adopting an input voltage of-0.4V and running time of 400s; the current was recorded and the measured results were taken into a standard curve to calculate the concentration of malachite green.
(4) The pretreated grass carp sample was assayed using an enzyme-linked immunosorbent assay (ELISA) method (ELISA was purchased from Biotechnology (Shanghai) Co., ltd.). The results show that the detection results of the method are basically consistent with those of ELISA (enzyme-Linked immuno sorbent assay) methods, and the difference of the detection results of the two methods is less than 9.7%, which indicates the application potential of the method in complex samples.
Example 5: specificity study of the sensor
(1) Polishing the glassy carbon electrode by using aluminum oxide polishing powder of 1.0, 0.3 and 0.05 mu m in sequence, cleaning the glassy carbon electrode by using ultrapure water, and then placing the electrode in a 5mM potassium ferricyanide solution for scanning at 0.1V potential to ensure that the peak potential difference is less than 110mV; 2mL of HAuCl 4 with mass fraction of 1% is taken as base solution, and the electrode of the electrodeposited gold nano particle is obtained by scanning for 30s under the voltage of-0.2V; dropping 6 mu L of 7.5 mu g/mL of peacock Dan Kangti Ab 1, incubating for 1h at 4 ℃, and flushing with ultrapure water; and 3 mu L of bovine serum albumin solution with the mass fraction of 10mg/mL is dripped on the surface of the electrode, incubated for 1h at 4 ℃ and flushed with ultrapure water, so as to obtain a first device.
(2) Respectively dripping 6 mu L of malachite green, chloramphenicol and leucomalachite green solution with the concentration of 10ng/mL to the surface of the first device, incubating for 1h at 4 ℃, and flushing with ultrapure water; and continuously dripping 5 mu L of detection antibody hatchery-nano palladium/multi-layer hollow spherical Pd/CuO@NiO-Ab 2 solution onto the surface of the first device, hatching for 1h in a refrigerator at 4 ℃, cleaning and airing to obtain the electrochemical sensor.
(3) The method comprises the steps of adopting a three-electrode system to carry out measurement, adopting an electrochemical sensor as a working electrode, adopting a saturated calomel electrode as a counter electrode and adopting a platinum wire electrode as an auxiliary electrode, adopting a time-current method to carry out scanning in a phosphate buffer solution containing hydrogen peroxide (5 mM) with pH of 7.4, and adopting an input voltage of-0.4V and running time of 400s;
as a result, as shown in FIG. 4, the sensor has a good signal response to malachite green and substantially no response to malachite green analogues such as chloramphenicol and leucomalachite green, indicating a good specificity of the method.
Example 6: reproducibility study of sensor
(1) Polishing the glassy carbon electrode by using aluminum oxide polishing powder of 1.0, 0.3 and 0.05 mu m sequentially for five electrodes, cleaning the glassy carbon electrode by using ultrapure water, and then placing the electrodes in a 5mM potassium ferricyanide solution for scanning at 0.1V potential to ensure that the peak potential difference is less than 110mV; 2mL of HAuCl 4 with mass fraction of 1% is taken as base solution, and the electrode of the electrodeposited gold nano particle is obtained by scanning for 30s under the voltage of-0.2V; dropping 6 mu L of 7.5 mu g/mL of peacock Dan Kangti Ab 1, incubating for 1h at 4 ℃, and flushing with ultrapure water; and 3 mu L of bovine serum albumin solution with the mass fraction of 10mg/mL is dripped on the surface of the electrode, incubated for 1h at 4 ℃ and flushed with ultrapure water, so as to obtain a first device.
(2) Dropping 6 mu L of malachite green solution with the concentration of 10ng/mL to the surface of the first device, incubating for 1h at 4 ℃, and flushing with ultrapure water; and continuously dripping 5 mu L of detection antibody hatchery-nano palladium/multi-layer hollow spherical Pd/CuO@NiO-Ab 2 solution onto the surface of the first device, hatching for 1h in a refrigerator at 4 ℃, cleaning and airing to obtain the electrochemical sensor.
(3) The method comprises the steps of adopting a three-electrode system to carry out measurement, adopting an electrochemical sensor as a working electrode, adopting a saturated calomel electrode as a counter electrode and adopting a platinum wire electrode as an auxiliary electrode, adopting a time-current method to carry out scanning in a phosphate buffer solution containing hydrogen peroxide (5 mM) with pH of 7.4, and adopting an input voltage of-0.4V and running time of 400s; the currents were recorded and the currents measured for the five electrodes were 175.2, 172.8, 180.5, 169.8, 178.5. Mu.A, respectively.
The results show that the relative standard deviation of signals of the five electrodes is less than 4.29%, which shows that the method has good repeatability.
Example 7: stability study of sensor
(1) Polishing the glassy carbon electrode by using 1.0, 0.3 and 0.05 mu m aluminum oxide polishing powder sequentially for 3 electrode electrodes, cleaning the glassy carbon electrode by using ultrapure water, and then placing the electrode in 5mM potassium ferricyanide solution, and scanning the electrode under the potential of 0.1V to ensure that the peak potential difference is less than 110mV; 2mL of HAuCl 4 with mass fraction of 1% is taken as base solution, and the electrode of the electrodeposited gold nano particle is obtained by scanning for 30s under the voltage of-0.2V; dropping 6 mu L of 7.5 mu g/mL of peacock Dan Kangti Ab 1, incubating for 1h at 4 ℃, and flushing with ultrapure water; and 3 mu L of bovine serum albumin solution with the mass fraction of 10mg/mL is dripped on the surface of the electrode, incubated for 1h at 4 ℃ and flushed with ultrapure water, so as to obtain a first device.
(2) Respectively using a first device which is just prepared, storing for one week at 4 ℃ and storing for two weeks at 4 ℃, dripping 6 mu L of malachite green solution with the concentration of 10ng/mL to the surface of the first device, incubating for 1h at 4 ℃, and flushing with ultrapure water; and continuously dripping 5 mu L of detection antibody hatchery-nano palladium/multi-layer hollow spherical Pd/CuO@NiO-Ab 2 solution to the surface of the electrode, hatching for 1h in a refrigerator at 4 ℃, cleaning and airing to obtain the electrochemical sensor.
(3) The method comprises the steps of adopting a three-electrode system to carry out measurement, adopting an electrochemical sensor as a working electrode, adopting a saturated calomel electrode as a counter electrode and adopting a platinum wire electrode as an auxiliary electrode, adopting a time-current method to carry out scanning in a phosphate buffer solution containing hydrogen peroxide (5 mM) with pH of 7.4, and adopting an input voltage of-0.4V and running time of 400s; the current of three electrodes was recorded, and the three measured currents were 173.8, 165.5, 153.8 μA, respectively.
The results show that the response of the sensor to malachite green is maintained at 95.2% for one week and at about 91.9% for two weeks, indicating that the sensor has good stability.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (2)
1. The nano palladium/multilayer hollow sphere Pd/CuO@NiO material is characterized by being prepared by the following steps:
(1) Preparation of a metal organic framework material Cu-Ni-BTC: preparing Ni (NO 3)2•6H2 O into Ni (NO 3)2 solution, preparing trimethyl-1, 3, 5-benzene tricarboxylic acid into H 3 BTC solution by using DMF, adding Ni (NO 3)2 solution into H 3 BTC solution, stirring uniformly and vibrating to obtain mixed solution, taking the mixed solution to perform a first microwave reaction to obtain a metal organic frame material Ni-BTC, dispersing Ni-BTC into DMF, adding Cu (NO 3)2•3H2 O, performing a second microwave reaction, washing, centrifuging and drying after the reaction is finished to obtain a metal organic frame material Cu-Ni-BTC, wherein the concentration of the Ni (NO 3)2•6H2 O solution is 20-30 g/L, the concentration of the H 3 BTC solution is 10-20 g/L, the volume ratio of the Ni (NO 3)2 solution to the H 3 BTC solution is 1:1, the mass ratio of the Ni-BTC to the Cu (NO 3)2•3H2 O) is 1:1, and the microwave reaction time is 150 min for both the first microwave reaction and the second microwave reaction;
(2) Preparation of multilayer hollow sphere CuO@NiO: grinding Cu-Ni-BTC, calcining, and cooling to room temperature to obtain multi-layer hollow sphere CuO@NiO; the temperature rising rate of the calcination is 5 ℃/min; the calcination temperature is 500 ℃, and the calcination time is 2 h;
(3) Preparation of nano palladium/multilayer hollow sphere CuO@NiO: dispersing CuO@NiO in water, then adding sodium tetrachloropalladate and sodium citrate, adding NaBH4 under stirring, continuously stirring, centrifuging, washing and drying the obtained mixture to obtain nano palladium/multilayer hollow spherical Pd/CuO@NiO solid; the concentration of the CuO@NiO is 0.4-1.5 g/L; the addition amount ratio of CuO@NiO, sodium tetrachloropalladate, sodium citrate and NaBH4 is (0.03-0.008 g): (0.20-0.30) mmol: (0.20-0.30) mmol: (0.004-0.008) mmol.
2. The use of the nano-palladium/multi-layer hollow sphere Pd/cuo@nio material of claim 1 for preparing an electrochemical sensor.
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