CN113970583B - Preparation and use methods of photoelectrochemical aptamer sensor for detecting kanamycin - Google Patents
Preparation and use methods of photoelectrochemical aptamer sensor for detecting kanamycin Download PDFInfo
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- 108091023037 Aptamer Proteins 0.000 title claims abstract description 90
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- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 description 1
- LSQZJLSUYDQPKJ-UHFFFAOYSA-N p-Hydroxyampicillin Natural products O=C1N2C(C(O)=O)C(C)(C)SC2C1NC(=O)C(N)C1=CC=C(O)C=C1 LSQZJLSUYDQPKJ-UHFFFAOYSA-N 0.000 description 1
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- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 description 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
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Abstract
A preparation and use method of a photoelectrochemical aptamer sensor for detecting kanamycin relates to a preparation and use method of a kanamycin photoelectrochemical aptamer sensor. The method aims to solve the technical problem that the existing photoelectrochemical aptamer sensor for detecting kanamycin is low in sensitivity. The preparation method comprises the following steps: 1. preparing TiO 2 NRA; 2. preparing Bi/BiOBr/TiO 2 NRA; 3. photoelectrochemical aptamer sensor BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO was prepared. Kanamycin was checked by standard curve method. The photoelectrochemical aptamer sensor has a linear detection range as wide as 1 pM-200 nM and a detection limit as low as 0.7pM, and can be used in the kanamycin detection field.
Description
Technical Field
The invention relates to a preparation and use method of a kanamycin photoelectrochemical aptamer sensor.
Background
Kanamycin (kanamycin, KAN) is an aminoglycoside antibiotic used to treat a variety of infections. It induces misinterpretation and blocks translocation by interacting with the 30S subunit of the prokaryotic ribosome. When excessive kanamycin is present in the human body through food intake or drug prescription, kanamycin causes serious side effects including hearing loss and toxicity to kidneys. Currently, countries such as European Union, china, japan, and the like clearly specify that the maximum residual amount (MRL) of kanamycin in milk is 200 μg/kg. Therefore, the amount of antibiotic used is critical and prior to sale and distribution, the antibiotic content of the food must be tested to ensure that residual antibiotic is present in excess of the MRL. The method for detecting antibiotics in food comprises high performance liquid chromatography, capillary electrophoresis, spectrophotometry, enzymology, etc. However, these detection methods are cumbersome to operate, have high cost, require specialized technician to operate, and are difficult to realize on-site rapid detection. Therefore, there is a need to develop a simple, rapid and highly sensitive analytical detection method to achieve rapid detection of KAN.
Photoelectrochemical (PEC) sensing uses a photoactive material at the electrode interface as a signal transducer and an electrical signal generated under light illumination as a readout signal. For PEC biosensors, a bio-element for specific recognition is also indispensable. The aptamer is a biological identification element and can be specifically combined with a target object. PEC biosensors based on aptamers have a prominent advantage in many applications. The high flexibility of the nucleic acid structure of the aptamer and the convenience of structural design make it possible to develop various novel aptamer sensors.
In the preparation method of the photoelectrochemical sensor for efficiently and sensitively detecting kanamycin, graphite-phase carbon nitride g-C 3N4 and MOFs (PCN-222) are firstly prepared, a compound of the g-C 3N4 and the MOFs is dripped on fluorine-doped SnO 2 transparent conductive glass (FTO electrode), the g-C 3N4 is of a lamellar structure with a band gap of 2.7eV, the MOFs are of needle-shaped structures with a band gap of about 1.65eV, the two structures are compounded, the g-C 3N4 provides a large specific surface area for the MOFs, and the MOFs@g3N4 electron recombination rate is low so that stronger photocurrent can be generated. The addition of kanamycin will combine with electrons on the guide band to produce a reduced cathode photocurrent. The sensor has the linear range of 1-1000nM for kanamycin, the detection limit of 0.127nM and lower sensitivity.
Disclosure of Invention
The invention aims to solve the technical problem of low sensitivity of the existing photoelectrochemical aptamer sensor for detecting kanamycin, and provides a preparation and use method of the photoelectrochemical aptamer sensor for detecting kanamycin.
The preparation method of the photoelectrochemical aptamer sensor for detecting kanamycin comprises the following steps:
1. Preparation of TiO 2 NRA: evenly stirring deionized water and hydrochloric acid with the mass percentage concentration of 35-36% according to the volume ratio of 1 (1-1.2) to obtain a mixed solvent; then, butyl titanate is dropwise added into the mixed solvent, and the mixture is stirred uniformly to obtain a mixed solution; placing a cleaned FTO glass substrate into a reactor liner in an inclined manner, pouring the mixed solution, placing the reactor into a drying oven, keeping the temperature of 150-160 ℃ for 5-7 hours for reaction, placing the FTO glass substrate with a film into a muffle furnace for calcining for 1.5-2 hours at the temperature of 450-480 ℃ after the reaction is finished, and obtaining TiO 2 NRA on the FTO glass substrate, wherein the TiO 2 NRA/FTO is used for representing;
Further, the FTO glass substrate cleaned in the first step is obtained by sequentially placing the FTO glass substrate into acetone, ethanol and deionized water for ultrasonic cleaning for 5-10 min, and then drying.
Further, in the first step, the volume ratio of the butyl titanate to the mixed solvent is 1: (60-65);
2. preparation of Bi/BiOBr/TiO 2 NRA: adding 0.012-0.143 g KBr into 30mL glycol solution containing 0.079-0.632 gBi (NO 3)3·5H2 O and 0.36g glucose, stirring until the solution is completely dissolved and transparent to obtain precursor liquid, pouring the precursor liquid into an autoclave filled with TiO 2 NRA/FTO, placing the autoclave into a muffle furnace, reacting at 160-170 ℃ for 18-20 h, and washing the FTO glass substrate with the film with deionized water after the reaction is finished to obtain a Bi/BiOBr/TiO 2 NRA/FTO electrode;
3. preparation of photoelectrochemical aptamer sensor: dripping Chitosan (CS) solution with the mass percentage concentration of 0.1-0.15% onto a Bi/BiOBr/TiO 2 NRA/FTO electrode, drying, and then soaking the electrode in glutaraldehyde solution with the mass percentage concentration of 2.5-3.0% for 1-3 h; then dripping the kanamycin aptamer modified by the amino group on the surface of a Bi/BiOBr/TiO 2 NRA/FTO electrode for incubation for 3-6 h; then, the electrode is washed by PBS solution with pH of 7.4 to obtain an aptamer/Bi/BiOBr/TiO 2 NRA/FTO electrode; then the aptamer/Bi/BiOBr/TiO 2 NRA/FTO electrode is put into a Bovine Serum Albumin (BSA) solution with the mass percentage concentration of 1-3% to be incubated for 0.5-1 h, and then the solution is washed by PBS solution with the pH value of 7.4, so that the photoelectrochemical aptamer sensor for detecting kanamycin is obtained and is marked as BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO.
Further, the volume of the chitosan solution with the mass percentage concentration of 0.1-0.15% which is dripped on the Bi/BiOBr/TiO 2 NRA/FTO electrode is that 30-50 mu L of the chitosan solution with the mass percentage concentration of 0.1-0.15% is dripped on each square centimeter electrode.
Further, wherein the amino-modified kanamycin aptamer has a base sequence of 5'-NH 2-(CH2)6 -TGG-GGG-TTG-AGG-CTA-AGC-CGA-3'.
The method for quantitatively detecting kanamycin by using the photoelectrochemical aptamer sensor for detecting kanamycin is a standard curve method, and specifically comprises the following steps of:
1. respectively placing BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO sensors in 1 pM-200 nM kanamycin standard solution for 1h, and then flushing the electrodes with PBS solution with pH=7.4 to obtain KAN/BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO electrodes;
2. Providing a 500W xenon lamp light source and a 400nm cut-off filter on an electrochemical workstation, adopting a three-electrode system, taking KAN/BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO as a working electrode, taking a platinum sheet electrode as a counter electrode and a Saturated Calomel Electrode (SCE) as a reference electrode, carrying out ampere transient photocurrent-time test on electrolyte which is PBS buffer solution with pH value of 7.4 under the condition of 0.3V external bias to obtain photoelectric signals corresponding to different kanamycin concentrations, taking logarithm of the kanamycin concentration as an abscissa, and taking the corresponding photoelectric signals as longitudinal drawing to make a plotting standard curve;
3. Placing a BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO sensor in a kanamycin solution to be detected for 1h, and then flushing an electrode by using a PBS solution with pH=7.4 to obtain a test electrode; on an electrochemical workstation, a 500W xenon lamp light source and a 400nm cut-off filter are equipped, a three-electrode system is adopted, a test electrode is used as a working electrode, a platinum sheet electrode is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, an electrolyte is PBS buffer solution with pH=7.4, and an ampere transient photocurrent-time test is carried out under the external bias of 0.3V to obtain a photoelectric signal; and then the kanamycin concentration corresponding to the photoelectric signal is detected on a standard curve, so that the aim of detecting kanamycin is fulfilled.
The kanamycin photoelectrochemical aptamer sensor takes glucose as a green reducing agent, adopts a simple one-pot solvothermal method to prepare Bi/BiOBr and loads the Bi/BiOBr/TiO 2 NRA on TiO 2 NRA, and prepares the Bi/BiOBr/TiO 2 NRA ternary composite material. By means of three-phase combination of TiO 2 NRA, biOBr and Bi, the p-n heterojunction formed by TiO 2 NRA and BiOBr is combined with the Surface Plasmon Resonance (SPR) effect of Bi, the visible light utilization rate of the photoelectric material is improved, the photoelectric performance of the photoelectric material is improved, and therefore the sensitivity of the photoelectrochemical biosensor is improved. In addition, the p-n heterojunction constructed by BiOBr and TiO 2 NRA is beneficial to improving the transfer rate of electrons, and the SPR effect of the metal Bi is combined with the p-n heterojunction structure to greatly utilize a visible light source, so that the photoelectric performance of the photoelectrochemical aptamer sensor is improved.
The aptamer recognition element introduced by the invention improves the specific recognition capability of the photoelectrochemical sensor, reduces the interference of other antibiotics, and realizes the specific detection of kanamycin. When the photoelectrochemical kanamycin ligand sensor is used for detecting kanamycin, the sensor captures kanamycin based on the oxidation of semiconductor holes by an aptamer, and the generated photocurrent change is detected, so that the sensor has the advantages of low detection cost, high sensitivity, linear detection range of 1 pM-200 nM, wide linear detection range, detection limit of 0.7pM, simple equipment, easiness in operation and the like.
According to the invention, the amino-modified kanamycin aptamer is loaded on the surface of the Bi/BiOBr/TiO 2 NRA electrode, so that the specific recognition capability of the sensor is improved, and the constructed photoelectrochemical aptamer sensor has high sensitivity and good selectivity, is favorable for realizing accurate detection of kanamycin, and can be applied to the field of food quality safety detection.
Drawings
FIG. 1 is an SEM photograph of the NRA of TiO 2 prepared in step one of example 1;
FIG. 2 is a SEM photograph of BiOBr/TiO 2 NRA prepared in the comparative operation of step two of example 1;
FIG. 3 is an SEM photograph of Bi/BiOBr/TiO 2 NRA prepared in step two of example 1.
FIG. 4 is an AC impedance plot of the TiO 2NRA/FTO、BiOBr/TiO2 NRA/FTO binary composite, bi/BiOBr/TiO 2 NRA/FTO electrode material, aptamer/Bi/BiOBr/TiO 2 NRA/FTO and BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO electrodes prepared in example 1.
FIG. 5 is a graph of time-current testing of the TiO 2NRA/FTO、BiOBr/TiO2 NRA/FTO binary composite, bi/BiOBr/TiO 2 NRA/FTO electrode material, aptamer/Bi/BiOBr/TiO 2 NRA/FTO and BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO electrodes prepared in example 1.
FIG. 6 is a graph showing the current response of a photoelectrochemical aptamer sensor for detecting kanamycin prepared in example 1 to detect kanamycin at different concentrations.
FIG. 7 is a linear graph of the detection of kanamycin at various concentrations using the photoelectrochemical aptamer sensor for detecting kanamycin prepared in example 1.
FIG. 8 is a graph of anti-interference assays of photoelectrochemical aptamer sensors for detection of kanamycin prepared in example 2 against different interferents.
Detailed Description
Example 1: the preparation method of the photoelectrochemical aptamer sensor for detecting kanamycin in the embodiment comprises the following steps:
1. Preparation of TiO 2 NRA: firstly, placing an FTO glass substrate with length multiplied by width multiplied by 2cm multiplied by 1cm into acetone, ethanol and deionized water in sequence, respectively carrying out ultrasonic treatment for 5min for cleaning, and drying for later use; evenly stirring deionized water and hydrochloric acid with the mass percentage concentration of 36% according to the volume ratio of 1:1 to obtain a mixed solvent; then 2mL of butyl titanate is dripped into 60mL of mixed solvent, and the mixed solvent is obtained after uniform stirring; placing a cleaned FTO glass substrate into a reaction kettle liner in an inclined manner, pouring the mixed solution, placing the reaction kettle into a drying oven, keeping the reaction kettle at 150 ℃ for 6 hours for reaction, placing the FTO glass substrate with a film into a muffle furnace again after the reaction is finished, calcining the FTO glass substrate for 1.5 hours at 450 ℃ to obtain TiO 2 NRA, which is expressed as TiO 2 NRA/FTO, on the FTO glass substrate;
2. Preparation of Bi/BiOBr/TiO 2 NRA: adding 0.0714g KBr into 30mL glycol solution containing 0.316g Bi (NO 3)3·5H2 O and 0.36g glucose), stirring until the solution is completely dissolved and transparent to obtain precursor liquid, pouring the precursor liquid into an autoclave filled with TiO 2 NRA/FTO, placing the autoclave into a muffle furnace, reacting for 18h at 160 ℃, and washing the FTO glass substrate sample with the film with deionized water after the reaction is finished to obtain a Bi/BiOBr/TiO 2 NRA/FTO electrode;
Simultaneously removing glucose in the precursor liquid in the second step, and preparing a BiOBr/TiO 2 NRA/FTO electrode as a comparison electrode in the second step;
3. Preparation of photoelectrochemical aptamer sensor: dropping 50 mu L of Chitosan (CS) solution with the mass percentage concentration of 0.1% on the Bi/BiOBr/TiO 2 NRA/FTO electrode, drying, and then placing the electrode in 5mL of glutaraldehyde solution with the mass percentage concentration of 2.5% for soaking for 1h; then, 50 mu L of amino-modified kanamycin aptamer is dripped on the surface of the Bi/BiOBr/TiO 2 NRA/FTO electrode for 3 hours of incubation; then, the electrode is washed by PBS solution with pH of 7.4 to obtain an aptamer/Bi/BiOBr/TiO 2 NRA/FTO electrode; then, the aptamer/Bi/BiOBr/TiO 2 NRA/FTO electrode is put into 5mL of Bovine Serum Albumin (BSA) solution with the mass percentage concentration of 3% for incubation for 1h, and then the solution is washed with PBS solution with the pH value of 7.4, so that the photoelectrochemical aptamer sensor for detecting kanamycin is obtained and is marked as BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO. Wherein the amino-modified kanamycin-adapted base sequence is 5'-NH 2-(CH2)6 -TGG-GGG-TTG-AGG-CTA-AGC-CGA-3'.
The SEM photograph of the TiO 2 NRA/FTO obtained in the step one of example 1 is shown in fig. 1, in which fig. 1A is an SEM image of the top of the TiO 2 NRA, fig. 1B is a cross-sectional SEM image of the TiO 2 NRA, respectively, and it can be seen from fig. 1 that the TiO 2 NRA is tightly combined with the FTO and the rod-shaped TiO 2 NRA is aligned in order to uniformly cover the surface of the FTO. This provides support for subsequent material loads and provides sufficient load space.
The SEM image of the comparative BiOBr/TiO 2 NRA prepared in step two of example 1 is shown in fig. 2, and it can be seen from fig. 2 that the biobrs of the lamellar structure are stacked on top of TiO 2 NRA to form a chrysanthemum-like biobrs.
As shown in FIG. 3, the SEM image of Bi/BiOBr/TiO 2 NRA obtained in the second step in example 1 shows that as glucose is added, part of the metal Bi is gradually generated on the surface of BiOBr and takes on a smooth spherical shape.
Alternating current impedance testing and time-current testing were performed on the TiO 2NRA/FTO、BiOBr/TiO2 NRA/FTO binary composite, bi/BiOBr/TiO 2 NRA/FTO electrode material, aptamer/Bi/BiOBr/TiO 2 NRA/FTO and BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO electrodes prepared in this example 1. As shown in fig. 4 and 5. In fig. 4, the semicircular diameter of the curve reflects the magnitude of the resistance to the electrons, and the smaller the diameter, the smaller the resistance to the electrons in the process of transferring, the greater the electron transfer rate. The a-e curves in the figure represent TiO2NRA/FTO、BiOBr/TiO2NRA/FTO、Bi/BiOBr/TiO2NRA/FTO、aptamer/Bi/BiOBr/TiO2NRA/FTO and BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO curves in sequence. The minimum semicircle diameter of curve c corresponds to a larger current, indicating that the photoelectric properties of Bi/BiOBr/TiO 2 NRA are stronger than those of TiO 2 NRA (curve a) and BiOBr/TiO 2 NRA (curve b). However, with the addition of kanamycin aptamer and BSA, the semi-circle diameters of curve d and curve e gradually increased, and the corresponding currents further decreased. This is because the aptamer and BSA belong to an insulating biological macromolecule, and prevent movement of electrons. This series of curve changes illustrates the successful preparation of photoelectrochemical aptamer sensors for detection of kanamycin.
For quantitative detection of kanamycin content, kanamycin was detected using the photoelectrochemical aptamer sensor prepared in example 1, using a standard curve method, and the specific procedure was as follows:
1. Preparing kanamycin standard solutions with the concentration of 200nM, 100nM, 50nM, 10nM, 1nM, 500pM, 100pM, 50pM, 10pM, 5pM and 1pM respectively; photoelectrochemical aptamer sensors for detecting kanamycin were respectively immersed in kanamycin standard solutions of different concentrations for incubation for 1h. After the reaction, the mixture was washed with PBS buffer solution having a pH of 7.4 and dried. The electrode obtained was designated KAN/BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO.
2. A500W xenon lamp light source and a 400nm cut-off filter are arranged on an electrochemical workstation, a three-electrode system is adopted, KAN/BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO is used as a working electrode, a platinum sheet electrode is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, an electrolyte is 0.1M PBS (pH, 7.4) buffer solution, and an ampere transient photocurrent-time (i-t) test is carried out under the additional bias of 0.3V. The photocurrents corresponding to kanamycin solutions of different concentrations are shown in fig. 6, wherein the concentration of KAN is, in order from a to k: the greater the concentration of KAN, the greater the current value I, 1pM, 5pM, 10pM, 50pM, 100pM, 500pM, 1nM, 10nM, 50nM, 100nM and 200 nM. As the concentration of KAN increases. Standard curves were plotted on the ordinate with Δi (Δi=i 0 -I, where I 0 and I represent the photo current values of the aptamer sensor before and after incubation of KAN, respectively) and the logarithm of KAN concentration on the abscissa, and the resulting standard curves are shown in fig. 7. As can be seen from FIG. 7, the ΔI shows a linear relationship with the logarithm of KAN concentration in the linear range of 1pM to 200 nM. The resulting linear equation was Δi (μa) = 8.08916lg (C/nM) +36.76843, and the correlation coefficient was 0.998. At a signal-to-noise ratio of 3 (S/n=3), the detection limit (S/n=3) was 0.7pM. The sensor is illustrated to have a wide detection range and a low detection limit for detecting kanamycin.
3. And (3) placing the prepared BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO in a target solution to be detected of an actual sample, and obtaining a delta I value by adopting a calculation method in the second step according to the detected photoelectric response signal. The concentration of KAN in the target was determined based on a standard curve to complete kanamycin detection.
Example 2: to examine the stability, reproducibility and selectivity of the photoelectrochemical aptamer sensor for detecting kanamycin, 5 independent working electrodes were prepared, respectively, and kanamycin at the same concentration was detected under the same experimental conditions. The specific operation process is as follows:
1. Preparation of TiO 2 NRA: 1. preparation of TiO 2 NRA: firstly, placing 5 FTO glass substrates with length multiplied by width=2cm multiplied by 1cm into acetone, ethanol and deionized water in sequence, respectively carrying out ultrasonic treatment for 5min for cleaning, and drying for later use; evenly stirring deionized water and hydrochloric acid with the mass percentage concentration of 36% according to the volume ratio of 1:1 to obtain a mixed solvent; then 1mL of butyl titanate is dripped into 60mL of mixed solvent, and the mixed solvent is obtained after uniform stirring; placing a cleaned FTO glass substrate into a reaction kettle liner in an inclined manner, pouring the mixed solution, placing the reaction kettle into a drying oven, keeping the reaction kettle at 150 ℃ for 6 hours for reaction, placing the FTO glass substrate with a film into a muffle furnace again after the reaction is finished, calcining the FTO glass substrate for 1.5 hours at 450 ℃ to obtain TiO 2 NRA, which is expressed as TiO 2 NRA/FTO, on the FTO glass substrate;
2. Preparation of Bi/BiOBr/TiO 2 NRA: adding 0.0714g KBr into 30mL glycol solution containing 0.316g Bi (NO 3)3·5H2 O and 0.36g glucose), stirring until the solution is completely dissolved and transparent to obtain precursor liquid, pouring the precursor liquid into an autoclave filled with TiO 2 NRA/FTO, placing the autoclave into a muffle furnace, reacting at 160 ℃ for 18h, and washing the FTO glass substrate sample with the film with deionized water after the reaction is finished to obtain a Bi/BiOBr/TiO 2 NRA/FTO electrode;
3. Preparation of a photoelectrochemical kanamycin aptamer sensor:
mu.L of a 0.1% Chitosan (CS) solution was applied dropwise to 5 Bi/BiOBr/TiO 2 NRA/FTO electrodes, which were dried and then placed in 5mL of a 2.5% glutaraldehyde solution for 1h. Then, the amino-modified kanamycin aptamer is dripped on the surface of the Bi/BiOBr/TiO 2 NRA/FTO electrode for 3 hours. The electrode was then rinsed with PBS at pH 7.4 to give aptamer/Bi/BiOBr/TiO 2 NRA/FTO. The aptamer/Bi/BiOBr/TiO 2 NRA/FTO electrode was placed in 5mL of 3% Bovine Serum Albumin (BSA) solution for 1h incubation, then washed with PBS solution at pH 7.4, and the resulting 5 photoelectrochemical aptamer sensors for detecting kanamycin, designated BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO. Wherein the amino-modified kanamycin-adapted base sequence is 5'-NH 2-(CH2)6 -TGG-GGG-TTG-AGG-CTA-AGC-CGA-3'.
5 Independent photoelectrochemical aptamer sensors for detecting kanamycin were incubated with 100nM standard kanamycin standard solution for 1h, then washed with PBS solution at pH7.4, and dried to obtain electrodes designated as KAN/BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO electrodes. A500W xenon lamp light source and a 400nm cut-off filter are arranged on an electrochemical workstation, a three-electrode system is adopted, KAN/BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO is used as a working electrode, a platinum sheet electrode is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, an electrolyte is 0.1M PBS buffer solution with pH of 7.4, and an ampere transient photocurrent-time (i-t) test is carried out under the external bias of 0.3V. Reproducibility of the sensor was evaluated by calculating the Relative Standard Deviation (RSD) of 5 individual electrodes from the response signal of the photocurrent, with the calculation result of RSD being 4.73%. The photoelectrochemical aptamer sensor prepared in example 2 was demonstrated to have good reproducibility. The switching was recorded for 10 consecutive times at 600s, and the photocurrent response signal was hardly changed significantly, which indicates that the inventive sensor for detecting kanamycin has good stability.
To verify the selectivity of the photoelectrochemical kanamycin aptamer sensor prepared in example 2, oxytetracycline, chloramphenicol, aureomycin, ofloxacin, amoxicillin, and kanamycin "mixed samples" containing these 5 antibiotics were selected as interferents. Wherein, the concentration of kanamycin and the concentration of the interfering substance are 100nM. An ampere transient photocurrent-time (i-t) test was performed on an electrochemical workstation using a 500W xenon lamp light source equipped with a 400nm cutoff filter at an applied bias of 0.3V. As shown in FIG. 8, it can be seen from FIG. 8 that the photoelectrochemical kanamycin sensor prepared in example 2 has a significant photocurrent response only to a sample containing kanamycin, while the response signal to other interferents is relatively weak. These results confirm that the photoelectrochemical kanamycin aptamer sensor of the invention has higher selectivity for chloramphenicol.
Claims (5)
1. A method for preparing a photoelectrochemical aptamer sensor for detecting kanamycin, characterized in that the method comprises the following steps:
1. preparation of TiO 2 NRA: evenly stirring deionized water and hydrochloric acid with the mass percentage concentration of 35-36% according to the volume ratio of 1 (1-1.2) to obtain a mixed solvent; then, butyl titanate is dropwise added into the mixed solvent, and the mixture is stirred uniformly to obtain a mixed solution; placing a cleaned FTO glass substrate into a reactor liner in an inclined manner, pouring the mixed solution, placing the reactor into a drying oven, keeping the temperature of 150-160 ℃ for 5-7 hours for reaction, placing the FTO glass substrate with a film into a muffle furnace for calcining for 1.5-2 hours at the temperature of 450-480 ℃ after the reaction is finished, and obtaining TiO 2 NRA on the FTO glass substrate, wherein the TiO 2 NRA/FTO is used for representing;
2. preparation of Bi/BiOBr/TiO 2 NRA: adding 0.012-0.143 g KBr into 30mL glycol solution containing 0.079-0.632 gBi (NO 3)3·5H2 O and 0.36g glucose, stirring until the solution is completely dissolved and transparent to obtain precursor liquid, pouring the precursor liquid into an autoclave filled with TiO 2 NRA/FTO, placing the autoclave into a muffle furnace, reacting at 160-170 ℃ for 18-20 h, and washing the FTO glass substrate with the film with deionized water after the reaction is finished to obtain a Bi/BiOBr/TiO 2 NRA/FTO electrode;
3. Preparation of photoelectrochemical aptamer sensor: dripping chitosan solution with the mass percentage concentration of 0.1-0.15% onto the Bi/BiOBr/TiO 2 NRA/FTO electrode, drying, and then soaking the electrode in glutaraldehyde solution with the mass percentage concentration of 2.5-3.0% for 1-3 h; then dripping the kanamycin aptamer modified by the amino group on the surface of a Bi/BiOBr/TiO 2 NRA/FTO electrode for incubation for 3-6 h; wherein the amino modified kanamycin aptamer has a base sequence of 5'-NH 2-(CH2)6 -TGG-GGG-TTG-AGG-CTA-AGC-CGA-3'; then, the electrode is washed by PBS solution with pH of 7.4 to obtain an aptamer/Bi/BiOBr/TiO 2 NRA/FTO electrode; then the aptamer/Bi/BiOBr/TiO 2 NRA/FTO electrode is put into bovine serum albumin solution with the mass percentage concentration of 1-3% to be incubated for 0.5-1 h, and then the solution is washed by PBS solution with the pH value of 7.4, so that the photoelectrochemical aptamer sensor for detecting kanamycin is obtained and is marked as BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO.
2. The method for preparing a photoelectrochemical aptamer sensor for detecting kanamycin according to claim 1, wherein the FTO glass substrate washed in the first step is obtained by sequentially placing the FTO glass substrate in acetone, ethanol and deionized water, ultrasonically washing for 5-10 min, and drying.
3. The method for preparing a photoelectrochemical aptamer sensor for detecting kanamycin according to claim 1 or 2, wherein the volume ratio of butyl titanate to the mixed solvent in the first step is 1: (60-65).
4. The method for preparing a photoelectrochemical aptamer sensor for detecting kanamycin according to claim 1 or 2, wherein the volume of the chitosan solution with the mass percentage concentration of 0.1% -0.15% dropwise added to the Bi/BiOBr/TiO 2 NRA/FTO electrode in the third step is 30-50 μl of the chitosan solution with the mass percentage concentration of 0.1% -0.15% dropwise added to each square centimeter electrode.
5. A method of using a photoelectrochemical aptamer sensor for detecting kanamycin prepared according to claim 1, wherein the method is performed as follows:
1. Respectively placing BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO sensors in 1 pM-200 nM kanamycin standard solution for 1h, and then flushing the electrodes with PBS solution with pH=7.4 to obtain KAN/BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO electrodes;
2. Providing a 500W xenon lamp light source and a 400nm cut-off filter on an electrochemical workstation, adopting a three-electrode system, taking KAN/BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO as a working electrode, taking a platinum sheet electrode as a counter electrode and a Saturated Calomel Electrode (SCE) as a reference electrode, carrying out ampere transient photocurrent-time test on electrolyte which is PBS buffer solution with pH value of 7.4 under the condition of 0.3V external bias to obtain photoelectric signals corresponding to different kanamycin concentrations, taking logarithm of the kanamycin concentration as an abscissa, and taking the corresponding photoelectric signals as longitudinal drawing to make a plotting standard curve;
3. Placing a BSA/aptamer/Bi/BiOBr/TiO 2 NRA/FTO sensor in a kanamycin solution to be detected for 1h, and then flushing an electrode by using a PBS solution with pH=7.4 to obtain a test electrode; on an electrochemical workstation, a 500W xenon lamp light source and a 400nm cut-off filter are equipped, a three-electrode system is adopted, a test electrode is used as a working electrode, a platinum sheet electrode is used as a counter electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, an electrolyte is PBS buffer solution with pH=7.4, and an ampere transient photocurrent-time test is carried out under the external bias of 0.3V to obtain a photoelectric signal; and then the kanamycin concentration corresponding to the photoelectric signal is detected on a standard curve.
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