CN114858875A - Method for detecting kanamycin through self-enhanced photoelectrochemistry - Google Patents
Method for detecting kanamycin through self-enhanced photoelectrochemistry Download PDFInfo
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- SBUJHOSQTJFQJX-NOAMYHISSA-N kanamycin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O2)O)[C@H](N)C[C@@H]1N SBUJHOSQTJFQJX-NOAMYHISSA-N 0.000 title claims abstract description 64
- 229930027917 kanamycin Natural products 0.000 title claims abstract description 62
- 229960000318 kanamycin Drugs 0.000 title claims abstract description 62
- 229930182823 kanamycin A Natural products 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims description 12
- 108091023037 Aptamer Proteins 0.000 claims abstract description 31
- 238000001514 detection method Methods 0.000 claims abstract description 19
- 230000004044 response Effects 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 7
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 229960003405 ciprofloxacin Drugs 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 2
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
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- PGBHMTALBVVCIT-VCIWKGPPSA-N framycetin Chemical compound N[C@@H]1[C@@H](O)[C@H](O)[C@H](CN)O[C@@H]1O[C@H]1[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](N)C[C@@H](N)[C@@H]2O)O[C@@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CN)O2)N)O[C@@H]1CO PGBHMTALBVVCIT-VCIWKGPPSA-N 0.000 description 1
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- OOYGSFOGFJDDHP-KMCOLRRFSA-N kanamycin A sulfate Chemical compound OS(O)(=O)=O.O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O2)O)[C@H](N)C[C@@H]1N OOYGSFOGFJDDHP-KMCOLRRFSA-N 0.000 description 1
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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Abstract
Designs and synthesizes an amino-functionalized metal organic framework material (Cu-MOF-NH) 2 ) Modified copper sheet (Cu-MOF-NH) 2 /CuSs). Compared with before amino functionalization, Cu-MOF-NH 2 From 3.5eV to 2.6eV, the reduction in band gap being such that the Cu-MOF-NH 2 Has a wider light absorption range. Modifying kanamycin aptamer to Cu-MOF-NH through Schiff base 2 On the amino functional group in the/CuSs, a photoelectrochemical biosensor for detecting kanamycin is constructed. Present in Cu-MOF-NH 2 The cavity on the amino functional group can oxidize kanamycin, so that kanamycin itself becomes a signal enhancing substance to achieve the effect of self-enhancement. The detection range of the photoelectrochemistry biosensor is 0.5 nM-650 nM, and the detection limit is 0.1 nM. In addition, the biosensor has good stability, reproducibility and selectivity. The detection results of the actual samples are also fullIn particular, the recovery rate when detecting the kanamycin content in the fish is 95.7-105.0%, and the relative standard deviation is 3.5-4.9%.
Description
Technical Field
The invention belongs to the field of electrochemistry and analytical chemistry, and particularly relates to a method for detecting kanamycin by self-enhanced photoelectrochemistry.
Background
Kanamycin is an aminoglycoside antibiotic and has been widely used to treat serious infections caused by gram-positive and gram-negative bacteria. However, excessive intake of kanamycin can cause serious side effects such as hearing loss and antibiotic resistance. The existing methods for detecting kanamycin comprise spectrophotometry, fluorescence photometry, electrochemical methods and the like, and all the methods have certain defects.
Aiming at the defects of the prior art, the Cu-MOF-NH is synthesized by taking copper ions as metal ions and taking amino terephthalic acid as an organic ligand 2 Modified copper sheet (Cu-MOF-NH) 2 (ii)/CuSs); copper ions are used as metal ions, and terephthalic acid is used as an organic ligand to synthesize Cu-MOF modified copper sheets (Cu-MOF/CuSs).
Cu-MOF-NH prepared by taking copper sheet as substrate 2 and/CuSs. Hydrothermal reaction of Cu-MOF-NH 2 Growing on a copper sheet, and then binding kanamycin aptamer to Cu-MOF-NH through Schiff base formed by carboxymethyl chitosan and glutaraldehyde 2 To obtain a photo-electrochemical (PEC) sensor. In the absence of kanamycin, a blank signal appeared. After addition of kanamycin, kanamycin was trapped by the aptamer and oxidized by light-generated holes. This causes the photocurrent signal to become large. In this self-enhanced PEC detection method, PEC signals are generated by kanamycin oxidation. Therefore, high sensitivity detection of kanamycin can be achieved.
Disclosure of Invention
The invention aims to invent a method for detecting kanamycin by self-enhanced photoelectrochemistry. The photoelectrochemical biosensor fully utilizes Cu-MOF-NH 2 The transfer of the middle excited state electron follows a mechanism of transferring from a ligand to a metal, and the electron hole recombination rate is remarkably reduced. At the same time, present in Cu-MOF-NH 2 The cavity on the amino functional group can oxidize kanamycin, so that kanamycin itself becomes a signal enhancing substance to achieve the effect of self-enhancement. Due to amino groupsIn comparison with Cu-MOF, Cu-MOF-NH 2 Has smaller band gap and larger light absorption range, on the basis, the kanamycin aptamer is combined to the Cu-MOF-NH through Schiff base formed by carboxymethyl chitosan and glutaraldehyde 2 On an amino functional group of CuSs, a self-enhanced photoelectrochemical biosensor for detecting kanamycin is prepared. And the flow of electrons inside the photoelectrochemical biosensor was studied. The prepared photoelectrochemical biosensor fully utilizes Cu-MOF-NH 2 Charge separation capability of (1). The photoelectrochemical biosensor successfully realizes the kanamycin detection based on the self-enhanced photocurrent, has the advantages of strong specificity and high sensitivity, and provides a new choice for the kanamycin detection.
The technical scheme for realizing the aim of the invention is as follows:
(1)Cu-MOF-NH 2 preparation of/CuSs and preparation of PEC biosensor
First, the copper sheet is processed. And ultrasonically cleaning the copper sheet for 5 minutes respectively by using dilute hydrochloric acid, absolute ethyl alcohol and deionized water, and removing an oxide layer and stains on the surface of the copper sheet to obtain the clean copper sheet. Then preparing Cu-MOF-NH 2 [ CuSs ]: dissolving 10-1358 mg of amino terephthalic acid in 2-100 mL of deionized water, adding 0.2-20 mL of 0.2M sodium hydroxide into the uniformly dissolved solution, stirring for 5 minutes, and then adding 1-100 mL of CuCl 2 ·2H 2 And stirring the O solution for 10 minutes to obtain a mixed solution. And then transferring the mixed solution and the clean copper sheet into a high-pressure reaction kettle with a polytetrafluoroethylene lining, wherein the volume of the high-pressure reaction kettle is 50-500 mL, and heating the high-pressure reaction kettle for 14 hours at the temperature of 50-200 ℃. Naturally cooling the reaction kettle to room temperature, and then carrying out reaction on the obtained Cu-MOF-NH 2 the/CuSs are washed with water and absolute ethanol and dried at 60 ℃. Then 1-100 mul of 1% CMS solution (CMS dissolved in 1% acetic acid solution) is dripped into Cu-MOF-NH 2 The surface of/CuSs. Drying at 50 deg.C, washing with 0.1M NaOH and deionized water for 3-5 times to obtain CMS modified Cu-MOF-NH 2 CuSs, i.e. CuSs/Cu-MOF-NH 2 a/CMC. Then dripping 1-5% GLD solution into the modified Cu-MOF-NH 2 CuSs surface, after 1 hour of reaction at 40 ℃, deionizedWashing with water, removing GLD molecules physically adsorbed on the surface of the electrode to obtain GLD modified CuSs/Cu-MOF-NH 2 CMC, i.e. CuSs/Cu-MOF-NH 2 (ii) CMC/GLD. Then, dripping 1-100 muL of 2 muM aptamer solution on the electrodes modified with CMS and GLD, and incubating for 12 hours at 4 ℃ to obtain aptamer modified CuSs/Cu-MOF-NH 2 /CMC/GLD, PEC biosensor for kanamycin detection (CuSs/Cu-MOF-NH) 2 /CMC/GLD/Ap). To detect kanamycin, different concentrations of kanamycin solution were first dropped on electrodes and then washed after 50min incubation at 40 ℃ to obtain CuSs/Cu-MOF-NH 2 Performing a photocurrent response test after performing/CMC/GLD/Ap/Kana; and carrying out quantitative analysis on the clarithromycin according to the photoelectric signal. Cu-MOF-NH 2 The principle of the/CuSs preparation and kanamycin detection is shown in FIG. 1.
(2) PEC measurement
To characterize the preparation of the PEC biosensor, the PEC biosensor was prepared at 5.0mM [ Fe (CN) containing 0.1M KCl 6 ] 3-/4- In solution, the Electrochemical Impedance Spectroscopy (EIS) response of the PEC biosensor was measured.
Measured Cu-MOF-NH 2 /CuSs 0.1M Na 2 SO 4 The scanning range of the model Schottky curve in the solution is-0.5-0.9V, and the scanning speed is 1000 Hz.
PEC signals were measured in 0.1M phosphate buffer at pH 7.4 at a potential of 0.4V using a white LED lamp as the illumination source.
Preferably, the aptamer sequence is 5' -NH 2 -(CH 2 ) 6 -TGG GGG TTG AGG CTA AGC CGA-3′。
Reagent
All reagents were analytical grade and were used directly without further purification. Cupric chloride dihydrate (CuCl) 2 ·2H 2 O) and 2-Aminoterephthalic acid (C) 8 H 7 NO 4 ,BDC-NH 2 ) Purchased from mclin biochemical technology limited (shanghai china). Kanamycin sulfate (purity is more than or equal to 94 percent, Kana), ofloxacin (purity is more than or equal to 98 percent), erythromycin (purity is more than or equal to 99 percent), ciprofloxacin (purity is more than or equal to 98 percent), chloramphenicol sulfate (purity is more than or equal to 99 percent) and neomycin (purity is more than or equal to 95 percent)) Streptomycin (purity > 90%), carboxymethyl Chitosan (CMS) and Glutaraldehyde (GLD) solutions (50 wt.%) were purchased from shanghai alatin biochemical technologies, inc. N, N-Dimethylformamide (DMF) and absolute ethanol were obtained from Bailingwei science and technology Co., Ltd (Shanghai, China). Copper sheets (CuSs, 99.9%) were provided by tianjinke mimiuiou chemical agents ltd. The 0.1M phosphate buffer for PEC measurements at pH 7.4 was composed of 0.1M sodium dihydrogen phosphate, 0.1M disodium hydrogen phosphate and 0.1mM potassium chloride. The sequence is 5' -NH 2 -(CH 2 ) 6 -TGG GGG TTG AGG CTA AGC CGA-3' amino-modified kanamycin aptamer, synthesized by Shanghai Biotechnology Ltd (Shanghai, China).
Instrument for measuring the position of a moving object
All PEC and electrochemical measurements were performed on a CHI660E electrochemical workstation (shanghai chen instruments ltd, china) containing a conventional three-electrode system. Cu-MOF-NH by scanning Electron microscopy (JEM-F200, Japan Electron optics laboratory) and Transmission Electron microscopy (JSM-6700F, Japan Electron optics laboratory) 2 The morphology of (a) is characterized. Ultraviolet absorption (UV-vis) and diffuse ultraviolet-visible reflectance (UV-vis DRS) were measured using a Cary5000 ultraviolet-visible near-infrared spectrophotometer, Agilent technologies, Inc. of America.
Advantages and effects of the invention
Under optimal experimental conditions, kanamycin was detected using a PEC biosensor. In the range of 0.5nM to 650nM, kanamycin concentration exhibits a good linear relationship with the photocurrent response of the PEC biosensor, with a detection limit of 0.1nM (S/N). The PEC biosensor has the characteristics of low detection limit and wider detection range.
Drawings
FIG. 1 schematic of the preparation of self-enhanced PEC biosensors and kanamycin determination principle. CMC: carboxymethyl chitosan, GLD: glutaraldehyde, Ap: aptamer, Kana: kanamycin.
FIG. 2Cu-MOF-NH 2 Scanning electron microscopy (A), transmission electron microscopy (B), and high-resolution transmission electron microscopy (C, D).
FIG. 3 photocurrent (A) and electrochemical impedance spectroscopy (B) responses during stepwise modification of the electrode.
FIG. 4Cu-MOF-NH 2 Model Schottky curve (A), Tauc plot (ahv) 2 Hv (B), Cu-MOF and Cu-MOF-NH 2 Energy level structure arrangement diagram (C) and ultraviolet visible absorption spectrum (D).
Figure 5 optimization of experimental conditions: bias potential (a), aptamer concentration (B), incubation time (C) and incubation temperature (D).
Fig. 6 PEC responses of the biosensor to different concentrations of kanamycin. From a to q: 650nM, 600nM, 550nM, 500nM, 450nM, 400nM, 350nM, 300nM, 250nM, 200nM, 150nM, 100nM, 50nM, 25nM, 5nM, 0.5nM and 0nM (A), inset is an enlarged view of the dotted line; linear relationship between PEC response of biosensor and kanamycin concentration (B).
Fig. 7 selectivity of PEC biosensor (a), stability of PEC biosensor after 20 days storage (B), reproducibility of 5 PEC biosensors (n-5) (C). The concentration of kanamycin used to determine selectivity, stability and reproducibility of the PEC biosensor was 200 nM.
Detailed Description
The following examples further illustrate the method of operation of the present invention, but are not to be construed as further limiting the invention.
Example 1: Cu-MOF-NH 2 Analytical characterization of morphology and composition of/CuSs
To study Cu-MOF-NH 2 The morphology of the/CuSs is measured by scanning electron microscope images and transmission electron microscope images. Cu-MOF-NH as shown in FIG. 2A, B 2 Has the shape of an approximate cuboid with the side length of about 400 nm. The 0.21 and 0.26nm lattice fringes in FIGS. 2C and 2D, respectively, can be attributed to Cu-MOF-NH 2 Crystal planes of (200) and (201). The scanning electron microscope image and the transmission electron microscope image show that the Cu-MOF-NH 2 the/CuSs have been synthesized successfully.
Example 2: Cu-MOF-NH 2 PEC performance of/CuSs
Cu-MOF-NH in contrast to copper sheets 2 /CuSs(CuSs/Cu-MOF-NH 2 ) The photocurrent response of (a) was significantly increased (fig. 3A). This is because of the Cu-MOF-NH 2 /CuSs has a large specific surface area. After aptamer modification (CuSs/Cu-MOF-NH) 2 /CMC/GLD/Ap), the photoelectric response of the electrode is slightly reduced due to the relatively weak conductivity of CMC, GLD and DNA strands. After addition of kanamycin (CuSs/Cu-MOF-NH) 2 /CMC/GLD/Ap/Kana), the photocurrent response is obviously enhanced. This is because kanamycin is oxidized and acts as an electron donor, supplying electrons to the electrodes and enhancing the PEC signal.
In the presence of 5mM [ Fe (CN) ] containing 0.1M KCl 6 ] 3-/4- In solution, the Electrochemical Impedance Spectroscopy (EIS) response of the PEC biosensor was measured. Cu-MOF-NH 2 The Ret value of the/CuSs electrode is smaller than that of the copper sheet (FIG. 3B). This is due to the Cu-MOF-NH 2 the/CuSs have larger specific surface area and stronger conductivity. Sequentially modifying CMC, GLD and aptamer to Cu-MOF-NH 2 after/CuSs, Ret values gradually increase because of steric effects and the relatively poor conductivity of CMC, GLD and DNA strands. Photocurrent response and EIS indicated that the biosensor was successfully prepared.
MOFs are generally considered as insulating materials having high band gaps, and thus various methods have been attempted to reduce the band gap of the MOFs. By NH 2 、OH、CH 3 And Cl and other different functional groups are a feasible and effective method for modifying the organic ligand. For example, when an amino group is modified onto an organic ligand, the lone pair of electrons on the N atom in the amino group interacts with the pi-orbitals of the benzene ring, providing electron density for the opposite bond orbitals, resulting in band transitions that result in higher HOMO energies, thereby reducing the band gap.
Synthesis of Cu-MOF-NH using aminoterephthalic acid 2 . As can be seen from FIG. 4C, due to the presence of amino groups, Cu-MOF-NH 2 The band gap of (a) is reduced from 3.5eV to 2.6eV of Cu-MOF, and the electronic transition is favored by the reduction of the band gap. Meanwhile, as can be seen from FIG. 4D, due to the presence of amino groups, Cu-MOF-NH 2 The light absorption intensity of the compound is obviously stronger than that of Cu-MOF, which indicates that Cu-MOF-NH 2 More photoelectric charges can be generated. Furthermore, Cu-MOF-NH 2 There was also an absorption peak at 330nm, indicating Cu-MOF-NH 2 Has wider light utilization range.
Example 3: preparation of self-enhanced PEC biosensors and PEC response mechanism
Firstly, Cu-MOF-NH is prepared by taking a copper sheet as a substrate 2 and/CuSs. Hydrothermal reaction of Cu-MOF-NH 2 Growing on a copper sheet, and then binding kanamycin aptamer to Cu-MOF-NH through Schiff base formed by carboxymethyl chitosan and glutaraldehyde 2 On the amino function of (a). In the absence of kanamycin, a blank signal appeared. After addition of kanamycin, kanamycin was trapped by the aptamer and oxidized by light-generated holes. This causes the photocurrent signal to become large. In this self-enhanced PEC detection method, PEC signals are generated by kanamycin oxidation. Therefore, high sensitivity detection of kanamycin can be achieved.
For Cu-MOF-NH 2 In other words, the charge transfer in the excited state by illumination follows the LMCT mechanism, i.e. the transfer of electrons from the organic ligand to the central metal. This results in a hole being left on the N atom of the organic ligand, while the electron resides on the central metal, and thus the central copper ion exhibits two valencies, which is consistent with the results of HRTEM analysis. The electron transfer mechanism of LMCT is Cu-MOF-NH 2 Has superior charge separation capability to conventional semiconductors. Kanamycin is an antibiotic and is easily oxidized. After being captured by the aptamer, the kanamycin is oxidized by a hole on an N atom, and the Cu-MOF-NH is fully utilized 2 Excellent charge separation ability. Meanwhile, kanamycin plays a role of an electron donor, and the photocurrent response of the biosensor is remarkably improved.
Example 4: optimization of the Experimental conditions
Aptamers play an important role in the detection of kanamycin by PEC biosensors. Thus, the concentration of the aptamer was optimized. As shown in FIG. 5B, in the range of 0.5. mu.M to 2. mu.M, the photocurrent signal gradually increased as the aptamer concentration increased. This is because kanamycin capture increases gradually with increasing aptamer concentration, which can enhance the photocurrent response of the PEC biosensor. When the aptamer concentration is too high, steric hindrance effect of the aptamer during electron transfer occurs, thereby decreasing the photocurrent signal, as shown in fig. 5B, when the aptamer concentration exceeds 2 μ M, the photocurrent signal decreases as the aptamer concentration increases. Thus, 2 μ M aptamer was selected to prepare PEC biosensors.
The photocurrent response of the PEC biosensor prepared with the optimal concentration of the aptamer was tested in the range of-0.2V to 0.6V. As shown in fig. 5A, the photocurrent signal increased with an increase in applied voltage, reaching a maximum value at 0.4V. When the applied voltage exceeds 0.4V, the photocurrent signal gradually decreases. Therefore 0.4V was chosen as the test potential in subsequent experiments.
In addition, the effect of incubation time and incubation temperature on kanamycin capture was also investigated. As shown in fig. 5C, the photocurrent signal gradually increased with increasing incubation time. After more than 50 minutes, the photocurrent signal no longer changed significantly, indicating that the aptamer capturing kanamycin was saturated. Therefore, 50 minutes was chosen as the optimal incubation time. As shown in fig. 5D, the photocurrent signal increased with increasing incubation temperature, reaching a maximum at 40 ℃. When the temperature exceeds 40 ℃, the photocurrent signal decays rapidly, probably because the aptamer undergoes partial denaturation at higher temperatures. Therefore, 40 ℃ was chosen as the optimal incubation temperature.
Example 5: analytical Performance of self-enhanced PEC biosensors
The regression equation for the self-enhanced PEC biosensor was I ═ 0.064c (nM) +40.85 in the range of 0.5nM to 650nM, the correlation coefficient was 0.9998, and the detection limit was 0.1nM (S/N). The PEC biosensor has the characteristics of low detection limit and wide detection range.
Example 6: selectivity, reproducibility and stability
The selectivity of the PEC biosensor was studied by measuring 6 kanamycin analogs (ofloxacin, erythromycin, ciprofloxacin, chloramphenicol, neomycin sulfate, and streptomycin) and their photocurrent response signals with kanamycin mixtures. As shown in fig. 7A, the PEC biosensor has good selectivity for kanamycin. To measure long-term stability, the PEC biosensors were stored at 4 ℃ and 3 PEC biosensors were taken out every 5 days for measurement. As shown in fig. 7B, the photoelectric response signal of the PEC biosensor was only reduced by 5%. The result shows that the biosensor has good stability. To evaluate the reproducibility of the PEC biosensors, the photocurrent response of 5 independently prepared PEC biosensors was tested. As shown in fig. 7C, the relative standard deviation of the photocurrent signal values for the 5 PEC biosensors was 2.15%, indicating that the PEC biosensors had good reproducibility.
Example 7: determination of kanamycin in real samples
First, the fish meat is processed. The fish is purchased from local seafood markets, and 2g to 200g of fish meat, 2g to 200g of anhydrous sodium sulfate and 4mL to 40mL of ethyl acetate are mixed and then added into a centrifuge tube. Then homogenized with a meat grinder for 1 minute. After centrifugation at 6000rpm for 5 minutes, 3-30 mL of the supernatant was taken, heated at 50 ℃ and evaporated to dryness under a stream of dry nitrogen. The dried residue was dissolved in 2mL to 20mL of 0.1M phosphate buffer (pH 7.4), and kanamycin was dispersed in the sample at various concentrations for use.
Kanamycin concentration in fish meat was detected by a standard addition method and compared with the fluorescence method, as shown in Table 1, the addition concentrations of kanamycin in 1 to 5 groups were 0.20nM, 5.00nM, 20.00nM, 50.00nM and 100.00nM, respectively. The recovery rate is 95.7-105.0%, and the relative standard deviation is 1.5-4.0%. This verifies the feasibility and accuracy of PEC biosensors in actual sample analysis.
TABLE 1 determination of kanamycin content in fish samples using PEC biosensor (n ═ 9)
a nM
b Not found
c Fluorometry。
SEQUENCE LISTING
<110> Qingdao university of science and technology
<120> method for detecting kanamycin by self-enhanced photoelectrochemistry
<160> 1
<170> SIPOSequenceListing 1.0
<210> 1
<211> 21
<212> DNA
<213> aptamer
<400> 1
tgggggttga ggctaagccg a 21
Claims (1)
1. A method for detecting kanamycin by self-enhanced photoelectrochemistry comprises the following steps:
(1)Cu-MOF-NH 2 preparation of/CuSs and preparation of PEC biosensor
Firstly, processing a copper sheet; ultrasonically cleaning the copper sheet for 5 minutes respectively by using dilute hydrochloric acid, absolute ethyl alcohol and deionized water, and removing an oxide layer and stains on the surface of the copper sheet to obtain a clean copper sheet; then preparing Cu-MOF-NH 2 [ CuSs ]: dissolving 10-1358 mg of amino terephthalic acid in 2-100 mL of deionized water, adding 0.2-20 mL of 0.2M sodium hydroxide into the uniformly dissolved solution, stirring for 5 minutes, and then adding 1-100 mL of CuCl 2 ·2H 2 Stirring the O solution for 10 minutes to obtain a mixed solution; then transferring the mixed solution and the clean copper sheet into a high-pressure reaction kettle with a volume of 50-500 mL and a polytetrafluoroethylene lining, and heating for 14 hours at 50-200 ℃; naturally cooling the reaction kettle to room temperature, and then carrying out reaction on the obtained Cu-MOF-NH 2 The CuSs are washed by water and absolute ethyl alcohol and dried at the temperature of 60 ℃; then 1-100 mul of 1% CMS solution (CMS dissolved in 1% acetic acid solution) is dripped into Cu-MOF-NH 2 The surface of CuSs; drying at 50 deg.C, washing with 0.1M NaOH and deionized water for 3-5 times to obtain CMS modified Cu-MOF-NH 2 CuSs, i.e. CuSs/Cu-MOF-NH 2 (ii) CMC; then dripping 1-5% GLD solution into the modified Cu-MOF-NH 2 The CuSs/surface is reacted for 1 hour at 40 ℃, washed by deionized water and removed with GLD molecules physically adsorbed on the electrode surface to obtain GLD modified CuSs/Cu-MOF-NH 2 CMC, i.e. CuSs/Cu-MOF-NH 2 CMC/GLD; then, willDripping 1-100 mu L of 2 mu M aptamer solution on the electrodes modified with CMS and GLD, and incubating for 12 hours at 4 ℃ to obtain aptamer modified CuSs/Cu-MOF-NH 2 /CMC/GLD, PEC biosensor for kanamycin detection (CuSs/Cu-MOF-NH) 2 CMC/GLD/Ap); to detect kanamycin, different concentrations of kanamycin solution were first dropped on electrodes and then washed after 50min incubation at 40 ℃ to obtain CuSs/Cu-MOF-NH 2 Performing a photocurrent response test after performing/CMC/GLD/Ap/Kana; carrying out quantitative analysis on the clarithromycin according to the photoelectric signal;
(2) PEC measurement
In the presence of 5.0mM [ Fe (CN) ] containing 0.1M KCl 6 ] 3-/4- In solution, the Electrochemical Impedance Spectroscopy (EIS) response of the PEC biosensor was measured;
measured Cu-MOF-NH 2 /CuSs 0.1M Na 2 SO 4 The scanning range of the model Schottky curve in the solution is-0.5-0.9V, and the scanning speed is 1000 Hz;
measuring PEC signals in 0.1M phosphate buffer at pH 7.4 at a potential of 0.4V using a white LED lamp as an illumination source;
preferably, the aptamer sequence is 5' -NH 2 -(CH 2 ) 6 -TGG GGG TTG AGG CTA AGC CGA-3′。
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