CN112461905B - Construction method of novel photo-assisted bipolar self-powered adapter sensor - Google Patents
Construction method of novel photo-assisted bipolar self-powered adapter sensor Download PDFInfo
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- 238000010276 construction Methods 0.000 title claims abstract description 10
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 claims abstract description 44
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 108091023037 Aptamer Proteins 0.000 claims abstract description 35
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
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- 239000000463 material Substances 0.000 claims abstract description 7
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000010405 anode material Substances 0.000 claims abstract description 3
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 3
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- 239000002077 nanosphere Substances 0.000 claims abstract description 3
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- 101100275473 Caenorhabditis elegans ctc-3 gene Proteins 0.000 claims description 3
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims 7
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- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims 1
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- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 10
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a construction method of a novel photo-assisted bipolar self-powered aptamer sensor, which simultaneously uses a universal meter as a direct reading strategy and comprises the following steps: step 1, preparing photo-anode material black titanium dioxide (B-TiO) 2 ) And photocathode material three-dimensional nitrogen-doped graphene hydrogel loaded cuprous oxide nanospheres (Cu) 2 O/3 DNGH); and 2, constructing a photo-assisted bipolar self-powered aptamer sensor for detecting the sulfamethazine. The novel photo-assisted bipolar self-powered adapter sensor constructed by the invention does not need an external power supply, the detection device supplies power for the detection process, and a simple multimeter is adopted as a direct reading strategy, so that the miniaturization and the portability are easy, and the field detection is realized. Meanwhile, the anode and the cathode of the sensor are both made of semiconductor materials, so that bioactive components and noble metal electrodes Pt are not used, the solar energy utilization efficiency is greatly improved, and the manufacturing cost is reduced.
Description
Technical Field
The invention belongs to the technical field of electrochemical biosensing, and relates to a construction method of a self-powered adapter sensor based on a photo-assisted bipolar fuel cell.
Background
The self-powered electrochemical sensor is a new electrochemical detection technology, is different from a traditional electrochemical sensing system, does not need an external power supply, can supply energy for the self-powered sensing process, and realizes the quantitative detection of a target by converting the concentration change of the target into the change of a power supply signal (such as open-circuit voltage, current density or power and the like). The self-powered electrochemical sensing technology has unique advantages in the aspects of promoting sensor miniaturization, convenience, low cost and the like, such as: an external power supply is not needed, electrochemical detection is realized by only two electrodes (an anode and a cathode), and miniaturization is facilitated; the simple voltmeter/ammeter can output the detection signal, so that the equipment cost is reduced, and the detection is easy and convenient; in addition, because no extra power supply is applied, the reaction of some electroactive substances on the surface of the electrode is avoided, and the specificity of the sensor is improved.
At present, the research of self-powered electrochemical sensors is mainly realized through a Biomass Fuel Cell (BFC) approach. However, the biomass fuel cell system has bioactive components, has the defects of complex operation, harsh and unstable reaction conditions and the like, and can only realize single energy conversion of biomass energy/electric energy. To overcome these problems, self-powered electrochemical sensors based on Photo Fuel Cells (PFCs) have attracted extensive attention by researchers. The PFC type self-powered electrochemical sensor adopts a photosensitive semiconductor material to replace a biocatalyst, converts solar energy and chemical energy into electric energy, is a two-dimensional energy conversion device, and has the advantages of fast electron transmission, simple operation, stable physicochemical properties, high output performance and the like. PFCs are classified into unipolar PFCs and bipolar PFCs according to the number of photo-electrodes in the battery. Currently, most of the research is mainly focused on unipolar PFC, i.e. only one electrode is made of photosensitive material and can respond to sunlight, and the other electrode is made of noble metal catalyst Pt, dye Prussian Blue (PB) or some electrocatalysts. In order to improve the solar energy utilization efficiency and reduce the use of noble metal catalysts, it is significant to design a bipolar PFC with both anode and cathode made of semiconductor photosensitive materials. The construction of a bipolar PFC is generally based on the fact that the n-type semiconductor photo-anode has a higher fermi level than the p-type semiconductor photo-cathode, ensuring that the drive electrons flow from the photo-anode to the photo-cathode. In addition, in the past reports, the self-powered electrochemical sensor still mainly relies on an electrochemical workstation to acquire and process signal data, so that the field detection is difficult to realize, and the practical application of the self-powered electrochemical sensor is hindered. Therefore, the invention adopts a simple multimeter as a direct reading strategy to replace a large-volume instrument such as an electrochemical workstation, and designs a portable self-powered electrochemical sensing device convenient for field detection.
Sulfadimidine (SMZ) is a broad-spectrum antibiotic, is used as a common feed additive in veterinary medicine and animal husbandry, and plays an important role in preventing and treating livestock and poultry diseases. However, the residual problem in animal-derived foods caused by excessive use of SMZ seriously threatens human health. At present, methods for detecting SMZ comprise enzyme-linked immunoassay, high performance liquid chromatography, fluorescence immunoassay and the like, and although the methods are accurate, most methods are time-consuming, labor-intensive, complex to operate and limited in practical application. Therefore, it is very necessary to develop a simple, fast, portable and low-cost analysis method.
Disclosure of Invention
The invention aims to provide a portable photo-assisted bipolar fuel cell self-powered adapter sensor which integrates the advantages of rapidness, simplicity, miniaturization, low cost and the like, is applied to detection of SMZ, and replaces an electrochemical workstation with a simple multimeter as a direct reading strategy.
The construction of the self-powered sensing device comprises the following steps:
Mixing tetrabutyl titanate with ethanol to obtain a solution A; mixing concentrated nitric acid, ethanol and water to obtain a solution B; dropwise adding the solution A into the solution B, uniformly stirring to obtain a mixed solution C, transferring the mixed solution C into a stainless steel high-pressure kettle to perform solvothermal reaction, and obtaining a solid product titanium dioxide after the reaction is finished; fully grinding the obtained titanium dioxide and sodium borohydride in a mortar, transferring the ground titanium dioxide and sodium borohydride to a ceramic crucible, calcining and reducing the ground titanium dioxide and the sodium borohydride in a tubular furnace under the argon atmosphere, and obtaining a solid product, namely B-TiO after the reaction is finished 2 ；
Firstly, stirring the graphene oxide dispersion liquid and urea, transferring the graphene oxide dispersion liquid and the urea into an autoclave for solvothermal reaction, and obtaining 3DNGH after the reaction is finished. Then dissolving copper nitrate in water, dripping hydrazine hydrate solution under magnetic stirring, fully reacting, centrifugally washing, and vacuum drying to obtain Cu 2 And (4) O powder. Finally, the obtained Cu 2 O, isopropanol and 3-aminopropyl trimethyl siliconMixing the alkyl, stirring uniformly, and centrifugally washing to obtain the surface functionalized Cu with positive charges 2 Then fully stirring the mixture with 3DNGH aqueous solution to prepare a solid product Cu 2 O/3DNGH。
the B-TiO obtained in the step 1 and the step 2 2 And Cu 2 Dispersing O/3DNGH in N, N-Dimethylformamide (DMF) to respectively obtain B-TiO 2 Dispersion liquid, cu 2 O/3DNGH Dispersion, B-TiO 2 、Cu 2 Respectively dripping O/3DNGH dispersion liquid on ITO electrodes with fixed areas, placing the ITO electrodes under an infrared lamp for drying to obtain B-TiO 2 ITO electrode as photo-anode, cu 2 The O/3DNGH/ITO electrode is used as a photocathode.
Step 4, constructing the photo-assisted bipolar self-powered adapter sensing device for detecting SMZ
Firstly, B-TiO is added to the photoanode 2 Dripping Chitosan (CHIT) solution on the ITO, and drying under an infrared lamp. And then, dripping a Glutaraldehyde (GA) solution on the surface of the electrode, placing the electrode at room temperature for reaction, and after the reaction is finished, rinsing the electrode by using PBS to remove the redundant GA on the surface of the electrode. Preparing an SMZ aptamer solution by using Tris-HCl as a solvent, dripping the SMZ aptamer on an electrode, after reacting for a period of time, rinsing by using PBS to remove excessive unadsorbed aptamer, then dripping Bovine Serum Albumin (BSA) solution to seal a non-specific active site, and finally obtaining an aptamer modified photoanode (aptamer/B-TiO) 2 ITO), and photocathode Cu 2 O/3DNGH/ITO constitutes the photo-assisted bipolar self-powered aptamer sensing device.
In the step 1, the method comprises the following steps of,
in the solution A, the dosage ratio of tetrabutyl titanate to ethanol is 1-3 mL: 0.05-5 mL;
in the solution B, the dosage ratio of concentrated nitric acid, ethanol and water is 0.05-0.15 mL: 0.05-5 mL: 0.1-1 mL;
when the solution A and the solution B are mixed, the ratio of tetrabutyl titanate to concentrated nitric acid is 1-3 mL:0.05 to 0.15mL;
the temperature of the solvothermal reaction is 160-200 ℃, and the reaction time is 10-14 h; the mass ratio of titanium dioxide to sodium borohydride is 3:1; the calcining temperature is 300-400 ℃, the time is 0.5-1.5 h, and the heating rate is 10 ℃/min.
In the step 2, the step of the method is carried out,
the dosage ratio of the graphene oxide dispersion liquid to the urea is 50mL:2g, wherein the concentration of the graphene oxide dispersion liquid is 1g/mL; the temperature of the solvothermal reaction is 150 ℃, and the reaction time is 10h.
The dosage ratio of the copper nitrate, water and hydrazine hydrate solution is 0.25g:50mL of: 4mL; wherein the concentration of the hydrazine hydrate solution is 0.5mol/L.
Cu 2 The dosage proportion of O, isopropanol and 3-aminopropyltrimethylsilane is 0.1g:10mL of: 0.1mL, and the stirring time is 12-36 h.
Resulting positively charged surface functionalized Cu 2 The dosage ratio of the O to the 3DNGH aqueous solution is 25-75 mg: 5-15 mL, wherein the concentration of the 3DNGH aqueous solution is 1g/mL, and the stirring time is 2-6 h.
In step 3, B-TiO 2 Dispersion liquid, cu 2 The concentration of the O/3DNGH dispersion liquid is 1-3mg/mL; B-TiO 2 、Cu 2 The dripping amount of the O/3DNGH dispersion liquid is 20-40 mu L, and the fixed area of the ITO is 0.09 pi cm 2 ；
In the step 4, the process of the method,
the mass percentage concentration of the CHIT is 0.1 percent, and the dropping amount is 10 mu L;
the volume percentage concentration of the GA is 2.5%, and the dripping amount is 20 mu L; the reaction time of CHIT and GA is 1-2 h;
the SMZ aptamer sequence was: 5' -NH 2 -TTA GCT TAT GCG TTG GCC GGG ATA AGG ATC CAG CCG TTG TAG ATT TGC GTT CTA ACT CTC-3'; the concentration of the SMZ aptamer is 3 mu M, the dropping amount is 20-40 mu L, and the reaction time is 10-14 h; the mass percentage concentration of BSA is 3%.
The application of the photo-assisted bipolar self-powered aptamer sensor prepared by the invention to detection of SMZ comprises the following specific steps:
(1) Dropping SMZ solutions of different concentrations to aptamer/B-TiO 2 ITO photo anode, and incubating for a period of time at room temperature;
(2) The photoanode and the photocathode Cu treated in the step (1) are treated 2 Placing O/3DNGH/ITO into a single-chamber electrolytic cell containing PBS, vertically irradiating two photoelectrodes by a xenon lamp light source, connecting the two photoelectrodes by a universal meter, and directly collecting potential signals; making a standard curve of the logarithm value of the potential value and the SMZ concentration;
(3) And collecting potential signals of the SMZ solution with unknown concentration by adopting the method, and substituting the potential signals into the standard curve to obtain the concentration of the SMZ solution.
In order to verify the accuracy of the collected signals, electrochemical analysis was performed simultaneously through the two-electrode system of the electrochemical workstation.
In the step (1), the concentration of SMZ is 0.001-100100 ng/mL, specifically 0.001,0.005,0.01,0.05,0.1,0.5,1,5,10,50 and 100ng/mL, and the dropping amount is 10-30 mu L;
in the step (2), the amount of PBS is 20-30 mL; the intensity of the xenon lamp light source is 25-100%.
The invention has the beneficial effects that:
the invention prepares B-TiO 2 Nanoparticles as photoanode active material, cu 2 O/3DNGH is used as a photocathode active material, a photo-assisted bipolar self-powered aptamer sensor is successfully established, the SMZ is analyzed and detected, and the characteristics and advantages are expressed as follows:
(1) The invention prepares B-TiO 2 Nanoparticles as photoanode active material, cu 2 The O/3DNGH is used as a photocathode active material to construct a photo-assisted bipolar self-powered adapter sensor, the energy level matching between the two photo-electrodes is good, and the electric energy output performance is excellent.
(2) Preparation of Cu by the invention 2 The O/3DNGH is used as a photocathode active material, replaces an expensive platinum electrode, introduces a double-photosensitive electrode, reduces the cost and obviously improves the utilization rate of solar energy.
(3) The photo-assisted bipolar self-powered aptamer sensor provided by the invention realizes sensitive detection of SMZ, and the logarithmic value (lg C) of the concentration of the SMZ is within the concentration range of 0.001-100 ng/mL SMZ ) The sensor has a good linear relation with the potential Output (OCP) value of the self-powered sensing platform, and the detection limit can reach 0.33pg/mL.
(4) The novel photo-assisted bipolar self-powered adapter sensor constructed by the invention does not need an external power supply, and meanwhile, the universal meter is used as a direct reading strategy to replace an electrochemical workstation to collect data, so that the sensor is convenient to carry and can be operated outdoors, thereby achieving the effect of instant detection.
Drawings
FIG. 1 is a schematic diagram of a constructed photo-assisted bipolar self-powered aptamer sensor;
FIG. 2 shows the preparation of B-TiO 2 And Cu 2 Transmission electron micrographs of O/3 DNGH;
FIG. 3 (A) is a graph of the voltage-current curve (V-I) of a self-powered platform consisting of a B-TiO2/ITO photo-anode and different photo-cathodes in step (3) of example 1, (B) a graph of the power density-current curve (P-I), (C) a digital photograph of the multimeter read voltage and (D) an open circuit potential value; wherein, pt (a), 3DNGH/ITO (b) and Cu 2 O/ITO(c)、Cu 2 O/3DNGH/ITO(d)；。
FIGS. 4 (A), (B) are digital photographs of multimeter readout voltages from a self-powered sensing platform at different SMZ concentrations and open circuit potential values; (C) The SMZ concentration is a relational graph (an embedded graph is a linear relational graph) of the output potential of the self-powered sensing platform; (D) And (E) is a selectivity and stability test chart of the sensor.
Detailed Description
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
Fig. 1 is a mechanism diagram of a constructed photo-assisted bipolar self-powered aptamer sensor.
Example 1:
(1)B-TiO 2 preparation of
Measuring 1.7mL of tetrabutyl titanate and 2.5mL of ethanol, mixing, and uniformly stirring to obtain a solution A; weighing 0.1mL of concentrated nitric acid, 2.5mL of ethanol and 0.5mL of water, mixing, and uniformly stirring to obtain a solution B; dropwise adding the solution A into the solution B, stirring for 0.5h to obtain a mixed solution C, transferring the mixed solution C into a stainless steel high-pressure kettle, and reacting for 12h at 180 ℃ to obtain a solid product titanium dioxide; weighing 200mg of titanium dioxide and 66.66mg of sodium borohydride, mixing, fully grinding in a mortar, and transferringPutting the mixture into a ceramic crucible, putting the ceramic crucible into a tube furnace, calcining the ceramic crucible for 1h at 350 ℃ in an argon atmosphere at the heating rate of 10 ℃/min to obtain B-TiO 2 And (3) nanoparticles.
(2)Cu 2 Preparation of O/3DNGH
First, 50mL of graphene oxide dispersion (1 g/mL) and 2g of urea were stirred, transferred to an autoclave, and reacted at 180 ℃ for 12 hours to obtain 3DNGH. Then, 0.25g of copper nitrate was dissolved in 50mL of water, 4mL of hydrazine hydrate solution (0.5 mol/L) was added dropwise under magnetic stirring, after sufficient reaction, centrifugal washing and vacuum drying were carried out to obtain Cu 2 And (4) O powder. Next, 0.1g of Cu was weighed 2 Mixing O with 10mL of isopropanol and 0.1mL of 3-aminopropyltrimethylsilane, fully stirring for 24h, and centrifugally washing to obtain the surface functionalized Cu with positive charges 2 And (O). Finally, 50mg of positively charged surface functionalized Cu was weighed 2 O was sufficiently stirred with 10mL of a 3DNGH aqueous solution (1 g/mL) for 4 hours, thereby obtaining Cu 2 O/3DNGH。
FIG. 2 shows B-TiO obtained in example 1 2 And Cu 2 Transmission electron micrograph of O/3DNGH shows that the prepared B-TiO 2 Uniformly distributed nanoparticles of 5-10 nm; for Cu 2 The O/3DNGH composite material has a corrugated structure, and the 3DNGH is coated with Cu with the diameter of about 500nm 2 And (4) O balls.
(3) Manufacture of modified electrodes
Before preparing the photo anode and the photo cathode, ITO is pretreated. And (3) placing the ITO electrode in a 1M sodium hydroxide solution, boiling for 30 minutes, then sequentially carrying out ultrasonic cleaning by using acetone, distilled water and ethanol, and drying by using nitrogen for later use. Packaging the cleaned ITO electrode with polyimide adhesive tape (gold finger), and exposing ITO to 0.09 π cm 2 . Weighing 2mg of B-TiO 2 And Cu 2 O/3DNGH is respectively dispersed in 1mL DMF to obtain B-TiO 2 、Cu 2 O/3DNGH Dispersion, 20. Mu.L of B-TiO was transferred 2 、Cu 2 The O/3DNGH dispersion liquid is respectively and uniformly dripped on an ITO electrode, and is dried under an infrared lamp to obtain a photoanode B-TiO 2 ITO and photocathode Cu 2 O/3DNGH/ITO。
Photo-anode, different photo-cathodes Pt (a), 3DNGH/ITO (b) and Cu 2 O/ITO(c)、Cu 2 O/3DNGH/ITO (d) is put into a single-chamber electrolytic cell containing Phosphate Buffered Saline (PBS), a xenon lamp perpendicular to two photoelectrodes simultaneously irradiates an optical anode and an optical cathode, a universal meter is used for connecting the two electrodes, and potential signals are directly collected. Wherein the PBS concentration is 0.1mol/L and the pH =5.
In order to verify the accuracy of the collected signals, electrochemical analysis was performed simultaneously through the two-electrode system of the electrochemical workstation.
FIG. 3 is a graph showing the relationship between (A) voltage-current curve (V-I), (B) power density-current curve (P-I), (C) digital photograph of multimeter read-out voltage and (D) open circuit potential value of a self-powered platform composed of a B-TiO2/ITO photo-anode and different photo-cathodes (Pt (a), 3DNGH/ITO (B), cu2O/ITO (C), cu2O/3DNGH/ITO (D)). As can be seen from FIG. 3, the self-powered platform composed of the photo-anode B-TiO2/ITO and the photo-cathode Cu2O/3DNGH/ITO has the best electrical output performance; meanwhile, the output potential value of the self-powered platform directly read by the multimeter is consistent with the potential value measured by the electrochemical workstation, and the accuracy of reading data by the multimeter is proved.
(4) Construction of light-assisted bipolar self-powered adapter sensing device
Firstly, B-TiO is added to the photoanode 2 Dripping 10 mu L of 0.1% CHIT solution on the ITO, and drying under an infrared lamp. Subsequently, 20. Mu.L of 2.5% GA solution was dropped on the electrode surface and allowed to react at room temperature for 1 hour, and after the reaction was completed, the surface was rinsed 2 times with PBS (pH =5.0,0.1 mol/L) to remove excess GA on the electrode surface. SMZ aptamer solution was formulated with Tris-HCl (pH =7.4, 0.05mol/L) at a concentration of 3 μ M, with the SMZ aptamer sequence: 5' -NH 2 -TTA GCT TAT GCG TTG GCC GGG ATA AGG ATC CAG CCG TTG TAG ATT TGC GTT CTA ACT CTC-3'. Dripping 20 uL of SMZ aptamer on an electrode, placing the electrode in a refrigerator at 4 ℃ for reaction for 12h, rinsing the electrode with PBS for 2 times to remove excessive unadsorbed aptamer, dripping 20 uL of 3% BSA solution to block non-specific active sites, and finally obtaining the aptamer-modified photoanode (aptamer/B-TiO) 2 ITO), and photocathode Cu 2 O/3DNGH/ITO constitutes a photo-assisted bipolar self-energized aptamer sensing device.
Detection of SMZ by light-assisted bipolar self-powered adapter sensing device
Thereafter, 20. Mu.L of SMZ at concentrations of 0.001,0.005,0.01,0.05,0.1,0.5,1,5,10,50 and 100ng/mL were respectively dropped onto the photo-anode aptamer/B-TiO 2 On an ITO electrode and incubated at room temperature for a period of time. Finally, the photoanode aptamer/B-TiO is added 2 ITO, photocathode Cu 2 O/3DNGH/ITO was placed in a single-chamber cell containing 20mL of PBS (pH =5.0,0.1 mol/L) and subjected to electrochemical analysis via an electrochemical workstation two-electrode system under simultaneous vertical illumination of two photoelectrodes by a xenon lamp source (intensity 25% to 100%).
The detection results are shown in fig. 4:
FIGS. 4 (A) and (B) are digital photographs of multimeter readout voltages and open circuit potential values of self-powered sensing platforms at different SMZ concentrations, from which it can be seen that the multimeter readout output potentials of the self-powered sensing platforms gradually increase as the SMZ concentration increases; (C) The sensor is a relational graph (an inset graph is a linear relational graph) of SMZ concentration and output potential of a self-powered sensing platform, a good linear relation is presented between a potential value and the SMZ concentration in a concentration range of 0.001-100 ng/mL, and the detection limit can reach 0.33pg/mL;
example 2:
(1)B-TiO 2 preparation of nanoparticles
Measuring 1mL of tetrabutyl titanate and 1.5mL of ethanol, and mixing and stirring uniformly to obtain a solution A; weighing 0.05mL of concentrated nitric acid, 1.25mL of ethanol and 0.25mL of water, mixing, and uniformly stirring to obtain a solution B; dropwise adding the solution A into the solution B, stirring for 0.5h to obtain a mixed solution C, transferring the mixed solution C into a stainless steel high-pressure kettle, and reacting for 10h at 180 ℃ to obtain a solid product titanium dioxide; weighing 100mg of titanium dioxide and 33.33mg of sodium borohydride, mixing, fully grinding in a mortar, transferring to a ceramic crucible, putting into a tube furnace, calcining for 1h at 300 ℃ in argon atmosphere at the heating rate of 10 ℃/min to obtain B-TiO 2 And (3) nanoparticles.
(2)Cu 2 Preparation of O/3DNGH
First, 50mL of graphene oxide dispersion (1 g/mL) and 2g of urea were stirred, transferred to an autoclave, and reacted at 180 ℃ for 12 hours to obtain 3DNGH. Then, will0.25g of copper nitrate is dissolved in 50mL of water, 4mL of hydrazine hydrate solution (0.5 mol/L) is dripped in under magnetic stirring, centrifugal washing and vacuum drying are carried out after full reaction, and Cu is obtained 2 And (4) O powder. Next, 0.1g of Cu was weighed 2 Mixing O with 10mL of isopropanol and 0.1mL of 3-aminopropyltrimethylsilane, fully stirring for 12h, and centrifugally washing to obtain the surface functionalized Cu with positive charges 2 And O. Finally, 25mg of positively charged surface functionalized Cu was weighed 2 O was sufficiently stirred with 5mL of a 3DNGH aqueous solution (1 g/mL) for 2 hours to obtain Cu 2 O/3DNGH。
Steps (3) and (4) were the same as Steps (3) and (4) of example 1.
Example 3:
(1)B-TiO 2 preparation of nanoparticles
Weighing 3mL of tetrabutyl titanate and 4mL of ethanol, mixing, and uniformly stirring to obtain a solution A; weighing 0.15mL of concentrated nitric acid, 3.75mL of ethanol and 0.75mL of water, mixing, and uniformly stirring to obtain a solution B; dropwise adding the solution A into the solution B, stirring for 0.5h to obtain a mixed solution C, transferring the mixed solution C into a stainless steel autoclave, and reacting for 14h at 180 ℃ to obtain a solid product titanium dioxide; weighing 300mg of titanium dioxide and 100mg of sodium borohydride, mixing, fully grinding in a mortar, transferring to a ceramic crucible, putting into a tube furnace, calcining for 1h at 400 ℃ in argon atmosphere at the heating rate of 10 ℃/min to obtain B-TiO 2 And (3) nanoparticles.
(2)Cu 2 Preparation of O/3DNGH
First, 50mL of a graphene oxide dispersion (1 g/mL) and 2g of urea were stirred, transferred to an autoclave, and reacted at 180 ℃ for 12 hours to obtain 3DNGH. Then, 0.25g of copper nitrate was dissolved in 50mL of water, 4mL of hydrazine hydrate solution (0.5 mol/L) was added dropwise under magnetic stirring, after sufficient reaction, centrifugal washing and vacuum drying were carried out to obtain Cu 2 And (4) O powder. Next, 0.1g of Cu was weighed 2 Mixing O with 10mL of isopropanol and 0.1mL of 3-aminopropyltrimethylsilane, fully stirring for 36h, and centrifugally washing to obtain the surface functionalized Cu with positive charges 2 And O. Finally, 75mg of positively charged surface functionalized Cu was weighed 2 O was sufficiently stirred with 15mL of a 3DNGH aqueous solution (1 g/mL) for 6 hours to obtain Cu 2 O/3DNGH。
Steps (3) and (4) were the same as Steps (3) and (4) of example 1.
Claims (10)
1. A construction method of a novel photo-assisted bipolar self-powered aptamer sensing device is characterized by comprising the following steps:
step 1, preparing photo-anode material black titanium dioxide B-TiO 2 ：
Mixing tetrabutyl titanate with ethanol to obtain a solution A;
mixing concentrated nitric acid, ethanol and water to obtain a solution B;
dropwise adding the solution A into the solution B, uniformly stirring to obtain a mixed solution C, transferring the mixed solution C into a stainless steel high-pressure kettle to perform solvothermal reaction, and obtaining a solid product titanium dioxide after the reaction is finished; fully grinding the obtained titanium dioxide and sodium borohydride in a mortar, transferring the ground titanium dioxide and sodium borohydride to a ceramic crucible, calcining and reducing the ground titanium dioxide and the sodium borohydride in a tubular furnace under the argon atmosphere, and obtaining a solid product, namely B-TiO after the reaction is finished 2 ；
Step 2, preparing a photocathode material three-dimensional nitrogen-doped graphene hydrogel loaded cuprous oxide nanosphere Cu 2 O/3DNGH：
Firstly, stirring graphene oxide dispersion liquid and urea, transferring the graphene oxide dispersion liquid and the urea into an autoclave for solvothermal reaction, and obtaining 3DNGH after the reaction is finished;
then dissolving copper nitrate in water, dripping hydrazine hydrate solution under magnetic stirring, fully reacting, centrifugally washing, and vacuum drying to obtain Cu 2 O powder;
finally, the obtained Cu 2 Mixing O with isopropanol and 3-aminopropyl trimethyl silane, stirring uniformly, and centrifugally washing to obtain the surface functionalized Cu with positive charges 2 O and then fully stirring with 3DNGH aqueous solution, thereby preparing a solid product Cu 2 O/3DNGH；
Step 3, manufacturing of the modified electrode:
the B-TiO obtained in the step 1 and the step 2 2 And Cu 2 O/3DNGH is dispersed in N, N-dimethylformamide DMF to respectively obtain B-TiO 2 Dispersion liquid, cu 2 O/3DNGH Dispersion of B-TiO 2 、Cu 2 Respectively dripping O/3DNGH dispersion liquid on ITO electrodes with fixed areas, placing the ITO electrodes under an infrared lamp for drying to obtain B-TiO 2 ITO electrode as photo-anode, cu 2 An O/3DNGH/ITO electrode is used as a photocathode;
step 4, constructing a light-assisted bipolar self-powered adapter sensing device for detecting SMZ:
firstly, at the photo-anode B-TiO 2 Dripping chitosan CHIT solution on the ITO, and drying under an infrared lamp;
dripping a glutaraldehyde GA solution on the surface of the electrode, placing the electrode at room temperature for reaction, leaching the electrode with PBS after the reaction is finished, and removing redundant GA on the surface of the electrode;
preparing an SMZ aptamer solution by using Tris-HCl as a solvent, dropwise adding the SMZ aptamer on an electrode, after reacting for a period of time, leaching by using PBS to remove excessive unadsorbed aptamer, then dropwise adding bovine serum albumin BSA solution to seal nonspecific active sites, and finally obtaining the photoanode aptamer/B-TiO modified by the aptamer 2 ITO, and photocathode Cu 2 O/3DNGH/ITO constitutes the photo-assisted bipolar self-powered aptamer sensing device.
2. The method of claim 1, wherein, in step 1,
in the solution A, the dosage ratio of tetrabutyl titanate to ethanol is 1-3 mL:0.05 to 5mL;
in the solution B, the dosage ratio of concentrated nitric acid, ethanol and water is 0.05-0.15 mL: 0.05-5 mL: 0.1-1 mL;
when the solution A and the solution B are mixed, the ratio of tetrabutyl titanate to concentrated nitric acid is 1-3 mL: 0.05-0.15 mL.
3. The construction method according to claim 1, wherein in the step 1, the temperature of the solvothermal reaction is 160-200 ℃, and the reaction time is 10-14 h; the mass ratio of titanium dioxide to sodium borohydride is 3:1; the calcination temperature is 300-400 ℃, the calcination time is 0.5-1.5 h, and the heating rate is 10 ℃/min.
4. The method of claim 1, wherein in step 2,
the dosage proportion of the graphene oxide dispersion liquid to the urea is 50mL:2g, wherein the concentration of the graphene oxide dispersion liquid is 1g/mL; the temperature of the solvothermal reaction is 150 ℃, and the reaction time is 10h;
the dosage ratio of the copper nitrate, water and hydrazine hydrate solution is 0.25g:50mL of: 4mL; wherein the concentration of the hydrazine hydrate solution is 0.5mol/L;
Cu 2 the dosage proportion of O, isopropanol and 3-aminopropyltrimethylsilane is 0.1g:10mL of: 0.1mL, and the stirring time is 12-36 h;
resulting positively charged surface functionalized Cu 2 The dosage ratio of the O to the 3DNGH aqueous solution is 25-75 mg:5 to 15mL, wherein the concentration of the 3DNGH aqueous solution is 1g/mL, and the stirring time is 2 to 6 hours.
5. The method of claim 1, wherein in step 3, B-TiO 2 Dispersion liquid, cu 2 The concentration of the O/3DNGH dispersion liquid is 1-3mg/mL; B-TiO2 2 、Cu 2 The dripping amount of the O/3DNGH dispersion liquid is 20-40 mu L, and the fixed area of the ITO is 0.09 pi cm 2 。
6. The method of claim 1, wherein, in step 4,
the mass percentage concentration of the CHIT is 0.1 percent, and the dropping amount is 10 mu L;
the volume percentage concentration of the GA is 2.5 percent, and the dropping amount is 20 mu L; the reaction time of CHIT and GA is 1-2 h.
7. The method of claim 1, wherein, in step 4,
the SMZ aptamer sequence was: 5' -NH 2 -TTA GCT TAT GCG TTG GCC GGG ATA AGG ATC CAG CCG TTG TAG ATT TGC GTT CTA ACT CTC-3'; the concentration of the SMZ aptamer is 3 mu M, the dropping amount is 20-40 mu L, and the reaction time is 10-14 h; the mass percentage concentration of BSA is 3%.
8. Use of a photo-assisted bipolar self-energized aptamer sensor device constructed according to the construction method of any one of claims 1 to 7 for detecting sulfadimidine SMZ.
9. The use according to claim 8, characterized by the specific steps of:
(1) Dropping SMZ solutions of different concentrations to aptamer/B-TiO 2 ITO photo anode and incubating for a period of time at room temperature;
(2) Photo-anode and photo-cathode Cu treated in the step (1) 2 Placing O/3DNGH/ITO into a single-chamber electrolytic cell containing PBS, vertically irradiating two photoelectrodes by a xenon lamp light source simultaneously, connecting the two photoelectrodes by using a universal meter, and directly collecting a potential signal; making a standard curve of the logarithm value of the potential value and the concentration of SMZ;
(3) And collecting potential signals of the SMZ solution with unknown concentration by adopting the method, and substituting the potential signals into the standard curve to obtain the concentration of the SMZ solution.
10. The use according to claim 9,
in the step (1), the concentration of SMZ is 0.001-100100 ng/mL, and the dripping amount is 10-30 mu L;
in the step (2), the amount of PBS is 20-30 mL; the intensity of the xenon lamp light source is 25-100%.
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| CN113281388B (en) * | 2021-04-30 | 2023-12-08 | 深圳万知达科技有限公司 | Preparation method of cathode self-powered aptamer sensor based on light combustion-supporting material battery and application of cathode self-powered aptamer sensor in detection of MC-LR |
| CN113340954B (en) * | 2021-05-14 | 2023-04-11 | 江苏大学 | Construction method of photo-assisted bipolar self-powered aptamer sensor for detecting lincomycin |
| CN113588735B (en) * | 2021-07-21 | 2023-12-22 | 深圳万知达科技有限公司 | Construction method of photoelectric/visual dual-mode sensor and application of photoelectric/visual dual-mode sensor in vomitoxin detection |
| CN114199967B (en) * | 2021-11-11 | 2023-08-22 | 江苏大学 | Construction method and application of ratio type self-energy-supply aptamer sensor based on light combustion-supporting material battery |
| CN114577883B (en) * | 2022-01-11 | 2023-10-20 | 湖南圣测生物科技有限公司 | Construction method of multichannel-chip type self-powered sensor for high-throughput detection of porcine diarrhea coronaviruses |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108896631A (en) * | 2018-03-29 | 2018-11-27 | 河南大学 | It is a kind of using the titanium dioxide heterogeneous junction structure of copper sulfide-as the construction method of the optical electro-chemistry aptamer sensor of bracket |
| CN109100407A (en) * | 2018-08-24 | 2018-12-28 | 江苏大学 | A kind of preparation of sketch-based user interface principle sunlight driving portable light electrochemical sensor |
| CN109283233A (en) * | 2018-11-20 | 2019-01-29 | 常州工学院 | It is a kind of for detecting the self energizing sensor of Microcystin |
| CN110988064A (en) * | 2019-12-02 | 2020-04-10 | 江苏新时代农业科技有限责任公司 | BiPO4Preparation method of/3 DNGH three-dimensional photoelectric functional nano material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5164089B2 (en) * | 2004-07-14 | 2013-03-13 | 独立行政法人物質・材料研究機構 | Pt / CeO2 / conductive carbon nanoheteroanode material and method for producing the same |
-
2020
- 2020-10-19 CN CN202011118553.9A patent/CN112461905B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108896631A (en) * | 2018-03-29 | 2018-11-27 | 河南大学 | It is a kind of using the titanium dioxide heterogeneous junction structure of copper sulfide-as the construction method of the optical electro-chemistry aptamer sensor of bracket |
| CN109100407A (en) * | 2018-08-24 | 2018-12-28 | 江苏大学 | A kind of preparation of sketch-based user interface principle sunlight driving portable light electrochemical sensor |
| CN109283233A (en) * | 2018-11-20 | 2019-01-29 | 常州工学院 | It is a kind of for detecting the self energizing sensor of Microcystin |
| CN110988064A (en) * | 2019-12-02 | 2020-04-10 | 江苏新时代农业科技有限责任公司 | BiPO4Preparation method of/3 DNGH three-dimensional photoelectric functional nano material |
Non-Patent Citations (2)
| Title |
|---|
| A novel self-powered aptasensor for digoxin monitoring based on the dual-photoelectrode membrane/mediator-free photofuel cell;Meng Zhang et al;《Biosensors and Bioelectronics》;20200306;第156卷;112135 * |
| Novel synthesis of nano needle-like Cu2O-GO-TiO2 and CuO-GO-TiO2 for the high photocatalytic performance of anionic and cationic pollutants;Jingjing Zhao et al;《Solid State Sciences》;20190325;第91卷;77-88 * |
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