CN112461905A - 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 108091023037 Aptamer Proteins 0.000 claims abstract description 32
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 30
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 7
- 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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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
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- 238000001354 calcination Methods 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
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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
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- 238000002386 leaching Methods 0.000 claims 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims 1
- 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 abstract description 31
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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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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)2O/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 only by 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 after the reaction is finishedThe product is B-TiO2；
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 Cu2And (4) O powder. Finally, the obtained Cu2Mixing O with isopropanol and 3-aminopropyl trimethyl silane, stirring uniformly, and centrifugally washing to obtain the surface functionalized Cu with positive charges2O and then fully stirring with 3DNGH aqueous solution, thereby preparing a solid product Cu2O/3DNGH。
the B-TiO obtained in the step 1 and the step 22And Cu2Dispersing O/3DNGH in N, N-Dimethylformamide (DMF) to respectively obtain B-TiO2Dispersion liquid, Cu2O/3DNGH Dispersion of B-TiO2、Cu2Respectively dripping O/3DNGH dispersion liquid on ITO electrodes with fixed areas, placing the ITO electrodes under an infrared lamp for drying to obtain B-TiO2ITO electrode as photo-anode, Cu2The 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, at the photo-anode B-TiO2Dripping 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 solution at room temperature for reaction, and after the reaction is finished, rinsing the solution by 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)2ITO), and photocathode Cu2O/3DNGH/ITO constitutes light-assisted bipolar self-powered adapter couplingA 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: 0.05-0.15 mL;
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 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 50 mL: 2g, wherein the concentration of the graphene oxide dispersion liquid is 1 g/mL; the temperature of the solvothermal reaction is 150 ℃, and the reaction time is 10 h.
The dosage ratio of the copper nitrate, water and hydrazine hydrate solution is 0.25 g: 50mL of: 4 mL; wherein the concentration of the hydrazine hydrate solution is 0.5 mol/L.
Cu2The dosage proportion of O, isopropanol and 3-aminopropyltrimethylsilane is 0.1 g: 10mL of: 0.1mL, and the stirring time is 12-36 h.
Resulting positively charged surface functionalized Cu2The 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-TiO2Dispersion liquid, Cu2The concentration of the O/3DNGH dispersion liquid is 1-3 mg/mL; B-TiO2、Cu2The dropwise adding amount of the O/3DNGH dispersion liquid is 20-40 mu L, and the fixed area of the ITO is 0.09 pi cm2；
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 percent, and the dropping amount is 20 mu L; the reaction time of CHIT and GA is 1-2 h;
the SMZ aptamer sequence was:5′-NH2-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 adapter sensor prepared by the invention in detecting SMZ comprises the following specific steps:
(1) dropping SMZ solutions of different concentrations to aptamer/B-TiO2ITO 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 treated2Placing 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 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.
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 muL;
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-TiO2Nanoparticles as photoanode active material, Cu2O/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-TiO2Nanoparticles as photoanode active material, Cu2O/3DNGH is used as photocathode active material to construct a photo-assisted bipolar self-powered adapter sensor, the energy level matching between the two photocathodes is good, and the electric energy output performance is excellentAnd (3) distinguishing.
(2) Preparation of Cu by the invention2The 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/mLSMZ) 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 0.33 pg/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-TiO2And Cu2Transmission 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 photoanode and different photocathodes in step (3) of example 1, (B) a graph of the power density-current curve (P-I) relationship, (C) a digital photograph of the multimeter read voltage and (D) an open circuit potential value; wherein, Pt (a), 3DNGH/ITO (b), Cu2O/ITO(c)、Cu2O/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-TiO2preparation of
Measuring 1.7mL of tetrabutyl titanate, mixing with 2.5mL of ethanol, 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 autoclave, 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, transferring to a ceramic crucible, putting into a tube furnace, calcining for 1h at 350 ℃ in argon atmosphere at the heating rate of 10 ℃/min to obtain B-TiO2And (3) nanoparticles.
(2)Cu2Preparation of O/3DNGH
First, 50mL of a graphene oxide dispersion (1g/mL) and 2g of urea were stirred, transferred to an autoclave, and reacted at 180 ℃ for 12 hours to obtain 3 DNGH. Then, 0.25g of copper nitrate was dissolved in 50mL of water, 4mL of hydrazine hydrate solution (0.5mol/L) was added dropwise under magnetic stirring, after sufficient reaction, centrifugal washing and vacuum drying were carried out to obtain Cu2And (4) O powder. Next, 0.1g of Cu was weighed2Mixing 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 charges2And O. Finally, 50mg of positively charged surface functionalized Cu was weighed2O was thoroughly stirred with 10mL of 3DNGH aqueous solution (1g/mL) for 4h, thereby obtaining Cu2O/3DNGH。
FIG. 2 shows B-TiO obtained in example 12And Cu2Transmission electron micrograph of O/3DNGH shows that the prepared B-TiO2Uniformly distributed nanoparticles of 5-10 nm; for Cu2O/3DNGH composite material, the 3DNGH of the corrugated structure is coated with Cu with the diameter of about 500nm2And (4) an O ball.
(3) Manufacture of modified electrodes
ITO is pretreated before preparing the photo-anode and the photo-cathode. Placing the ITO electrode in 1M sodium hydroxide solution for boiling for 30 minutes, then ultrasonically cleaning the ITO electrode by using acetone, distilled water and ethanol in sequence, and drying the ITO electrode by using nitrogenAnd (5) standby. Packaging the cleaned ITO electrode with polyimide adhesive tape (gold finger), and exposing ITO to 0.09 π cm2. Weighing 2mg of B-TiO2And Cu2O/3DNGH was dispersed in 1mL of DMF to give B-TiO2、Cu2O/3DNGH Dispersion, 20. mu. L B-TiO2、Cu2The 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-TiO2ITO and photocathode Cu2O/3DNGH/ITO。
The photo-anode, different photo-cathodes Pt (a), 3DNGH/ITO (b), Cu2O/ITO(c)、Cu2O/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 anode and a photocathode, a multimeter is used for connecting the two electrodes, and a potential signal is directly collected. Wherein the concentration of PBS is 0.1mol/L, and the pH value is 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 shows the relationship diagram of (A) voltage-current curve (V-I), (B) power density-current curve (P-I), (C) digital photo of multimeter read-out voltage and (D) open circuit potential value of self-powered platform composed of 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, at the photo-anode B-TiO2Dripping 10 μ L of 0.1% CHIT solution on ITO, and drying under 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 completion of the reaction, the electrode surface was rinsed 2 times with PBS (pH 5.0, 0.1mol/L) to remove excess GA on the electrode surface. Tris-HCl (pH 7.4, 0.05mol/L) was used to make up the concentrateA SMZ aptamer solution at a degree of 3 μ M, the SMZ aptamer sequence being: 5' -NH2-TTA GCT TAT GCG TTG GCC GGG ATA AGG ATC CAG CCG TTG TAG ATT TGC GTT CTA ACT CTC-3'. Dripping 20 mu L of SMZ aptamer on an electrode, placing the electrode in a refrigerator at 4 ℃ for reaction for 12h, rinsing the electrode for 2 times by PBS (phosphate buffer solution) to remove excessive unadsorbed aptamer, dripping 20 mu L of 3% BSA (bovine serum albumin) solution to block nonspecific active sites, and finally obtaining the aptamer-modified photoanode (aptamer/B-TiO)2ITO), and photocathode Cu2O/3DNGH/ITO constitutes the photo-assisted bipolar self-powered 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 dropped onto the photoanode aptamer/B-TiO, respectively2On an ITO electrode and incubated at room temperature for a period of time. Finally, the photoanode aptamer/B-TiO is added2ITO, photocathode Cu2O/3DNGH/ITO was placed in a single-chamber cell containing 20mL of PBS (pH 5.0, 0.1mol/L) and subjected to electrochemical analysis by means of an electrochemical workstation two-electrode system under simultaneous vertical illumination of two photoelectrodes with a xenon lamp light source (intensity 25% to 100%).
The detection results are shown in FIG. 4:
FIGS. 4(A), (B) are digital photographs of multimeter read voltages and open circuit potential values for self-powered sensing platforms at different SMZ concentrations, from which it can be seen that the multimeter read output potential of the self-powered sensing platform gradually increases as the SMZ concentration increases; (C) the method is a relational graph (an embedded graph is a linear relational graph) of the SMZ concentration and the output potential of the self-powered sensing platform, a good linear relation is presented between the potential value and the SMZ concentration in a concentration range of 0.001-100 ng/mL, and the detection limit can reach 0.33 pg/mL;
example 2:
(1)B-TiO2preparation 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, and stirringAfter 0.5h, obtaining 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-TiO2And (3) nanoparticles.
(2)Cu2Preparation of O/3DNGH
First, 50mL of a graphene oxide dispersion (1g/mL) and 2g of urea were stirred, transferred to an autoclave, and reacted at 180 ℃ for 12 hours to obtain 3 DNGH. Then, 0.25g of copper nitrate was dissolved in 50mL of water, 4mL of hydrazine hydrate solution (0.5mol/L) was added dropwise under magnetic stirring, after sufficient reaction, centrifugal washing and vacuum drying were carried out to obtain Cu2And (4) O powder. Next, 0.1g of Cu was weighed2Mixing 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 charges2And O. Finally, 25mg of positively charged surface functionalized Cu was weighed2O was sufficiently stirred with 5mL of 3DNGH aqueous solution (1g/mL) for 2 hours to obtain Cu2O/3DNGH。
Steps (3) and (4) were the same as Steps (3) and (4) of example 1.
Example 3:
(1)B-TiO2preparation 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-TiO2And (3) nanoparticles.
(2)Cu2Preparation of O/3DNGH
First, 50mL of a graphene oxide dispersion (1g/mL) and 2g of urea were stirred, and transferred to an autoclaveAnd reacting at 180 ℃ for 12h to obtain 3 DNGH. Then, 0.25g of copper nitrate was dissolved in 50mL of water, 4mL of hydrazine hydrate solution (0.5mol/L) was added dropwise under magnetic stirring, after sufficient reaction, centrifugal washing and vacuum drying were carried out to obtain Cu2And (4) O powder. Next, 0.1g of Cu was weighed2Mixing 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 charges2And O. Finally, 75mg of positively charged surface functionalized Cu was weighed2O was thoroughly stirred with 15mL of 3DNGH aqueous solution (1g/mL) for 6h, thereby obtaining Cu2O/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-TiO2：
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 finished2；
Step 2, preparing a photocathode material three-dimensional nitrogen-doped graphene hydrogel loaded cuprous oxide nanosphere Cu2O/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 Cu2O powder;
finally, the obtained Cu2Mixing O with isopropanol and 3-aminopropyl trimethyl silane, stirring uniformly, and centrifugally washing to obtain the surface functionalized Cu with positive charges2O and then fully stirring with 3DNGH aqueous solution, thereby preparing a solid product Cu2O/3DNGH；
Step 3, manufacturing of the modified electrode:
the B-TiO obtained in the step 1 and the step 22And Cu2O/3DNGH is dispersed in N, N-dimethylformamide DMF to respectively obtain B-TiO2Dispersion liquid, Cu2O/3DNGH Dispersion of B-TiO2、Cu2Respectively dripping O/3DNGH dispersion liquid on ITO electrodes with fixed areas, placing the ITO electrodes under an infrared lamp for drying to obtain B-TiO2ITO electrode as photo-anode, Cu2An O/3DNGH/ITO electrode is used as a photocathode;
and 4, constructing a light-assisted bipolar self-powered adapter sensing device for detecting SMZ:
firstly, at the photo-anode B-TiO2Dripping 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 aptamer2ITO, and photocathode Cu2O/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: 0.05-5 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: 0.05-0.15 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 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 ratio of the graphene oxide dispersion liquid to the urea is 50 mL: 2g, wherein the concentration of the graphene oxide dispersion liquid is 1 g/mL; the temperature of the solvothermal reaction is 150 ℃, and the reaction time is 10 h;
the dosage ratio of the copper nitrate, water and hydrazine hydrate solution is 0.25 g: 50mL of: 4 mL; wherein the concentration of the hydrazine hydrate solution is 0.5 mol/L;
Cu2the dosage proportion of O, isopropanol and 3-aminopropyltrimethylsilane is 0.1 g: 10mL of: 0.1mL, and the stirring time is 12-36 h;
resulting positively charged surface functionalized Cu2The 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.
5. The method of claim 1, wherein in step 3, B-TiO2Dispersion liquid, Cu2The concentration of the O/3DNGH dispersion liquid is 1-3 mg/mL; B-TiO2、Cu2The dropwise adding amount of the O/3DNGH dispersion liquid is 20-40 mu L, and the fixed area of the ITO is 0.09 pi cm2。
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' -NH2-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 sensing device constructed by the construction method according to any one of claims 1 to 7 for detecting SMZ.
9. The use according to claim 8, characterized by the specific steps of:
(1) dropping SMZ solutions of different concentrations to aptamer/B-TiO2ITO 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 treated2Placing 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 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 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%.
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