CN109851807B - Py-M-COF and electrochemical sensor and application thereof - Google Patents
Py-M-COF and electrochemical sensor and application thereof Download PDFInfo
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- CN109851807B CN109851807B CN201910025390.0A CN201910025390A CN109851807B CN 109851807 B CN109851807 B CN 109851807B CN 201910025390 A CN201910025390 A CN 201910025390A CN 109851807 B CN109851807 B CN 109851807B
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Abstract
The invention discloses a novel covalent organic framework Py-M-COF and an electrochemical sensor and application thereof.1, 3,6, 8-tetra (4-formylphenyl) pyrene is dissolved in dimethyl sulfoxide, then melamine is added to be subjected to hot bath for three days at the temperature of 180 ℃, products after the hot bath are repeatedly washed by tetrahydrofuran and ethanol and dried in an oven at the temperature of 60 ℃ to obtain Py-M-COF. The novel covalent organic framework Py-M-COF has high specific surface area and a porous framework, and can provide a large surface interface for biomolecule immobilization; aptamer chains can be attached to a COF substrate through pi-pi stacking and hydrogen bonding, and can be combined with a negatively charged aptamer through electrostatic interaction between a terminal amino functional group; the expanded pi conjugated skeleton structure can promote the transmission of charges and improve the detection sensitivity; Py-M-COF has high biological affinity to aptamer chains, has super sensitivity and selectivity to trace antibiotic detection, and has the lowest detection limit to the antibiotic enrofloxacin as 6.068 fg.mL‑1。
Description
Technical Field
The invention relates to the technical field of electrochemical sensors, in particular to a novel covalent organic framework electrochemical sensor and application thereof in detecting antibiotics.
Background
In recent years, antibiotics have been widely used in the fields of medical care, food industry, and animal husbandry to treat diseases and promote animal growth. In China, the dosage of antibiotics is incredible, which accounts for about half of the global dosage, and the antibiotics are discharged into water and soil environments in large quantities, thus seriously harming human health and ecological environment. According to the disclosure of the news, the urine of more than thousand children in Jianghe and Zhejiang hun province is detected, the urine of nearly 6 children is detected to be antibiotics, wherein, more than 2 antibiotics are detected in 1/4 children's urine, even 6 antibiotics can be detected in some urine samples, and the antibiotics only limited to livestock and poultry are also detected. If such components are present in the body for a long time, they will have an adverse effect on the growth and development of children. Due to the overuse and abuse of antibiotics, negative effects on human health and environment can be caused, such as organ toxicity, the occurrence of antibiotic-resistant bacteria, the disruption of ecological balance, and the occurrence of bacterial resistance.
Antibiotics such as Amoxicillin (Amoxicillin), Cefixime (Cefixime), Enrofloxacin (ENR), Ampicillin (ampicilin, AMP), Chlortetracycline (CTC), Oxytetracycline (OTC), Tobramycin (TOB), and the like have been widely used for the treatment of human diseases as well as the prevention and treatment of bacterial diseases in the animal and aquaculture industries. Due to its low bioavailability, only a fraction of the antibiotic can be metabolically absorbed in the animal body and the remaining antibiotic will be excreted and released into the soil, surface water and groundwater, causing serious human health risks and environmental problems. Thus, the increase of drug resistant bacteria presents a serious challenge to the health care of consumers and doctors. According to the statistics of the centers for disease control and prevention (CDC), approximately 23000 deaths that occur annually in the united states are associated with infections caused by antibiotic-resistant bacteria. Inappropriate and prophylactic use of antibiotics is common, particularly in the field of animal care, and is associated with environmental contamination by antibiotics and their metabolites. Among many antibiotics, Enrofloxacin (ENR), a fluoroquinolone antibiotic, is widely used in the animal husbandry and aquaculture industries for the prevention and treatment of bacterial diseases. Therefore, the development of portable, high-throughput and inexpensive detection systems is becoming urgent and important.
The aptamer is a single-stranded DNA or RNA molecule with a specific 3D structure screened in vitro by the SELEX method. The aptamer has the advantages of high selectivity, simplicity in synthesis, easiness in modification, good stability and the like, and is of great interest to people when being used as a recognition probe in biological detection. Recently, many analytical methods, such as luminescence spectroscopy, electrochemistry, surface plasmon resonance, and chemiluminescence, have been reported for the detection of antibiotics. However, these instrument-based methods require expensive and delicate instruments and are therefore not suitable for field applications. Researchers have reported a graphene oxide-based fluorescence sensor with a limit of detection of ENR of 3.7nM in the linear range of 5nM to 250 nM. These reported biosensor assays show relatively simple operation compared to traditional labeling methods, but they involve complicated assembly procedures and low sensitivity. The combination of the aptamer and the electrochemical detection method can construct a sensitive, rapid, simple, low-cost and effective biosensor. Electrochemical aptamer biosensors are available from two main routes, one involving covalently labeled aptamers (enzymes, metal nanoparticles and redox compounds) and the other label-free technology for detecting targets. In electrochemical sensors, ac impedance technology can be used to monitor biological recognition and changes in its electrical properties at the surface of a modified electrode. Electrochemical alternating current impedance spectroscopy (EIS) is a simple, sensitive, rapidly developed electrochemical method particularly suited for detecting signals generated by binding of an analyte to an aptamer on a sensor surface. Nanomaterials and nanocomposites have been used to increase the electroactive area, increase the loading of aptamer strands, and provide a three-dimensional structure, promote immobilization of aptamer strands, and minimize steric hindrance. Immobilization of aptamer molecules is an important step in the preparation of aptamer sensors. The most common method is to ensure sufficient stability, surface coverage of the aptamer, and maintain the same binding affinity in solution. Although various nanostructure materials and signal amplification strategies, such as gold nanoparticles, bimetallic nanoparticles, functionalized graphene, carbon nanotubes, graphene quantum dots, metal-organic frameworks, etc., have been used as sensitive membranes to construct aptamer sensors for the detection of antibiotics, it is still a challenge to find new materials with predictable structure, high specific surface area and excellent processability to effectively immobilize aptamer molecules and improve detection sensitivity.
Covalent organic backbones (COFs) are a new class of crystalline porous materials, which are composed of organic units containing only light elements (e.g., C, N, O, H and B) and are linked by strong covalent bonds. COFs are receiving increasing attention in the fields of gas storage, catalysis, photovoltaic devices, sensing and drug delivery due to their high specific surface area, ordered pore structure, tunable function, low density and mechanical strength. To date, COFs have been used to manufacture various sensing platforms, such as chemical sensors, humidity sensors, fluorescence sensors, colorimetric pH sensors, and the like, and have been used to detect nitroaromatic explosives, small organic molecules, heavy metal ions, and volatile organic compounds. According to the structural principle of COFs, an ideal biosensing platform can be constructed by reasonably designing a controllable structure. COFs with rich pi-conjugated frameworks and functional groups can act as novel matrix materials for aptamer immobilization through pi-pi stacking interactions. In addition, their two/three dimensional structure with permanent porosity can provide excellent scaffolds for charge transport and molecular diffusion on networks and improve sensitivity through signal amplification. For example, TpTta, two-dimensional ionic covalent organic nanosheets and TPA-COF synthesized as 1,3, 5-Triacyl Phloroglucinol (TP) and 4,40,400- (1,3, 5-triazine-2, 4, 6-triacyl) triphenylamine (Tta) have been used in matrix materials to construct biological platforms for selective detection of double-stranded DNA. However, most of the COFs have poor electrochemical activity, and their application as electrochemical biosensor platforms is limited. In particular, research into COF-based electrochemical sensors has not yet been matured.
Therefore, there is a need for improvement of the prior art to solve the above technical problems
Disclosure of Invention
In view of the above, the present invention provides a novel covalent organic framework that can be fabricated to become an electrochemical sensor for hypersensitivity detection of antibiotics. The method is realized by the following technical scheme:
the novel covalent organic framework Py-M-COF of the invention is prepared by the following method: 1,3,6, 8-tetra (4-formylphenyl) pyrene is dissolved in dimethyl sulfoxide, then melamine is added to be heated and bathed for three days under the temperature condition of 180 ℃, the product after the heating and bathing is repeatedly washed by tetrahydrofuran and ethanol and dried in an oven at 60 ℃ to obtain Py-M-COF.
In a preferred technical scheme, the hot bath adopts an oil bath.
The invention also discloses a novel covalent organic framework electrochemical sensor which is obtained by modifying the covalent organic framework Py-M-COF on a substrate electrode.
In a preferred technical scheme, the modification method comprises the following steps:
(1) pretreatment of a substrate electrode: polishing the bare gold electrode by using 0.05m of alumina slurry, then respectively carrying out ultrasonic treatment on the bare gold electrode in a piranha solution, ethanol and water for 15 minutes, carrying out electrochemical cleaning on the bare gold electrode by using an oxidation and reduction cycle in a range of-0.2-1.6V, then washing the bare gold electrode by using ultrapure water, and drying the bare gold electrode under nitrogen, wherein the piranha solution adopts a volume ratio of H2SO4/H2O2A 3:1 solution;
(2) modification: the novel covalent organic framework Py-M-COF is prepared into 1 mg/mL-1Then dropping the aqueous suspension onto the substrate electrode pretreated in the step (1).
The invention also discloses application of the novel covalent organic framework electrochemical sensor for hypersensitive detection of antibiotics. In particular, the method is used for the hypersensitive detection of the antibiotic enrofloxacin
The invention has the beneficial effects that: the invention is novelThe covalent organic framework Py-M-COF has high specific surface area and porous framework, and can provide a large surface interface for biomolecule immobilization; aptamer chains can be attached to a COF substrate through pi-pi stacking and hydrogen bonding, and can be combined with a negatively charged aptamer through electrostatic interaction between a terminal amino functional group; the expanded pi conjugated skeleton structure can promote the transmission of charges and improve the detection sensitivity; Py-M-COF has high biological affinity to aptamer chains, has super sensitivity and selectivity to trace antibiotic detection, and has the lowest detection limit to the antibiotic enrofloxacin as 6.068 fg.mL-1。
Other advantageous effects of the present invention will be further described with reference to the following specific examples.
Drawings
The invention is further described below with reference to the following figures and examples:
FIG. 1a is a crystal structure diagram of Py-M-COF measured by PXRD method, and FIG. 1b is FT-IR spectrum of 1,3,6, 8-tetrakis (4-formylphenyl) pyrene, melamine and dimethyl sulfoxide;
FIG. 2 is a solid state of Py-M-COF13C NMR spectrum;
FIG. 3a is XPS spectra for Py-M-COF, FIG. 3b is high resolution C1s XPS spectra for Py-M-COF, FIG. 3C is high resolution N1 s XPS spectra for Py-M-COF, and FIG. 3d is high resolution O1 s XPS spectra for Py-M-COF;
FIGS. 4a, b are respectively the N2 adsorption-desorption isotherm and pore size distribution plot for Py-M-COF;
FIGS. 5a, b are SEM images of Py-M-COF, and FIGS. 5c, d are TEM images of Py-M-COF;
FIGS. 6a and b show Py-M-COF modified electrodes containing 5.0mM [ Fe (CN) ]6]3-/4-EIS graph and CV curve of ENR in 0.01M PBS (pH 7.4), FIG. 6c is aptamer concentration of different enrofloxacin, and FIG. 6d is 0.01 pg. mL-1The effect of different incubation times of enrofloxacin on EIS response, FIG. 6e is Apt of different enrofloxacin concentrationsENREIS response of/Py-M-COF/AE, FIG. 6f is Δ RctDependence on enrofloxacin concentration;
FIGS. 7a, b, c are respectively the selectivity, reproducibility and stability of the Py-M-COF-based aptamer sensor for detecting ENR;
Detailed Description
The invention is further illustrated by the following specific examples.
Introduction of material sources: 1,3,6, 8-tetrakis (4-formylphenyl) pyrene (TFPy), melamine and dimethyl sulfoxide (DMSO) were purchased from Aladdin reagents, Inc. (Shanghai, China). Enrofloxacin (ENR), aptamer, tetracycline, kanamycin (Kana), Tobramycin (TOB), streptomycin, Oxytetracycline (OTC), and human serum were purchased from Solarbio bioengineering, inc (beijing). KH2PO4, Na2HPO4 & 12H2O, KCl, NaCl, K3[ Fe (CN)6] and K4[ Fe (CN)6] & H2O were ordered by the national Chemicals Co., Ltd. (Beijing). All chemical reagents used were analytical reagent grade and were used without further purification. All solutions were prepared in ultrapure water (. gtoreq.18.2 M.OMEGA.cm). The targeting aptamer sequence is as follows: ENR targeting aptamer (AptENR): 5 '-CCC ATC AGG-GTG-CTA GGC-TACAC GGT TCG GCT CTC TGA GCC CGG GTT ATT TCA GGG-GGA-3'.
Preparation and characterization of novel covalent organic framework Py-M-COF
6mg of TFPy was dissolved in 6mL of DMSO. 10mg of melamine were then added to the above mixture in an oil bath (180 ℃ C.) for three days. And repeatedly washing the product with tetrahydrofuran and ethanol for multiple times, and then drying in an oven at 60 ℃ to obtain the novel covalent organic framework Py-M-COF.
The crystal structure of the synthesized PY-M COF was determined by PXRD method using X-ray diffractometer model D/Max-2500, Cu target ka ray (λ 0.15406nm) for powder X-ray diffraction (PXRD). As shown in fig. 1a, the PXRD pattern of the sample shows three distinct peaks at 5.9 °, 6.8 ° and 14.2 °, and the d-spacings thereof can be calculated according to bragg's law as 14.97nm, 13.03nm and 6.25nm, respectively. FIG. 1b shows FT-IR spectra of TFPY, melamine and Py-M-COF using a Bruker TENSOR27 spectrometer (at 4 cm)-132 scans) was analyzed for chemical composition by fourier transform infrared spectroscopy (FT-IR). The characteristic peak at 1698cm-1 is due to the C ═ O stretch band of tfpyp (curve i), while the peaks at 3469, 3419 and 3336cm-1 are due to the N-H stretch vibration of melamine (curve ii). FT-IR spectrum of Py-M-COF (curve iii) at 1654cm-1The C ═ N vibrational band is shown, indicating successful condensation of tfpye and melamine through imine bond formation. Meanwhile, the characteristic peaks at 3420 and 1698cm-1 were respectively attributed to N-H stretching vibration and C ═ O stretching vibration, indicating the presence of terminal amino and aldehyde groups in Py-M-COF.
By passing13The chemical structure of Py-M-COF was further confirmed by C NMR,13c NMR spectra were recorded on a Bruker Avance 400MHz spectrometer at 8000Hz at ambient temperature. As shown in fig. 2, solid state 13C NMR: δ 166.4(C ═ N), 190.1, 155.9, 145.4, 144.3, 132.4, 130.1, 126.8, 125.3, 123.1, 122.4 ppm. These results indicate the formation of a C ═ N bond, demonstrating the successful synthesis of Py-M-COF.
In addition, the chemical structure of Py-M-COF was also characterized by XPS spectroscopy, with X-ray photoelectron spectroscopy (XPS) data collected on an ESCLAB 250Xi spectrometer (Thermo Fisher Science, Manchester, UK) with an Al K α X-ray source (1486.6eV photons). In FIG. 3a, XPS spectra of Py-M-COF show three intensity peaks at 284.6, 399.5 and 531.6eV, respectively, for C1s, N1 s, and O1 s. The analysis of the composition of the sample shows that the surface element composition of the sample is: carbon (65.91%), nitrogen (16.79%) and oxygen (17.3%). The high resolution C1s spectrum of Py-M-COF (fig. 3b) can be decomposed into four peaks, C-N at 283.8eV, C-C/C-H at 284.6eV, C-N at 285.5eV, C-O at 287.4eV and pi-pi at 290.6eV, respectively. The N1 s spectrum (fig. 3C) can be fitted to two peaks centered at 399.1 and 400.3eV, assigned to N-C/N-H and N ═ C, respectively. The O1 s XPS spectrum of Py-M-COF (fig. 3d) showed only the O ═ C peak corresponding to 531.6 eV. These results indicate that imine linkages (C ═ N) are formed in Py-M-COF and that carbon-and nitrogen-containing groups (i.e., -NH2) are present.
N with liquid nitrogen at a temperature of 77K using a Micromeritics ASAP 2010 instrument2Adsorption-desorption isotherm testing. Py-M-COF showed adsorption-desorption isotherms with N2 form IV (FIG. 4a), reflecting the characteristics of its mesoporous structure. The Brunauer-Emmett-Teller (BET) surface area of the COF was 495m2 g-1, and the total pore volume was 0.62cm3 g-1. The pore size distribution calculated by the Barrett-Joyner-Halenda (BJH) method showed a narrow distribution centered at 3.9nm (FIG. 4b)This also indicates the mesostructure of Py-M-COF.
And (3) characterizing the appearance of the sample by using SEM and TEM, and characterizing the surface appearance of the synthesized sample by using JSM-6490LV field emission scanning electron microscope (FE-SEM, Japan) and JEOL JEM-2100 high-resolution Transmission Electron Microscope (TEM) of a 200kV field emission gun. As shown in FIGS. 5a and 5b, Py-M-COF showed irregular large particles. The sample has rough surface, and convex and blocky nano particles are gathered on the surface. TEM images of Py-M-COF (FIGS. 5c and 5d) illustrate that the large particles consist of multiple layers of nanoplatelets. The two-dimensional nanosheet structure of the COF imparts high charge carrier mobility to the material as well as rich anchoring sites for immobilization of biomolecules.
Construction of two, Py-M-COF base aptamer electrochemical sensor and electrochemical measurement thereof
Bare gold electrodes (AE) 3 mm in diameter were cleaned prior to use. AE was polished with 0.05m alumina slurry and then separately in piranha solution (v/v,3: 1H)2SO4/H2O2) Ethanol and water for 15 minutes. Then, at 0.5M H2SO4And performing electrochemical cleaning on AE in an oxidation and reduction cycle within the range of-0.2-1.6V, then washing with ultrapure water, and drying under nitrogen.
Mixing 0.242g KH2PO4,1.445g Na2HPO4·12H2O,0.200g KCl and 8.003g NaCl were mixed to prepare phosphate buffered saline (PBS, 0.01M, pH 7.4). Before use, 1.650g K was dissolved in 1LPBS3Fe(CN)6And 2.111g K4Fe(CN)6An electrolyte solution is prepared. Aptamer (1. mu.M), ENR (1 mg. multidot.mL) were prepared in PBS-1) The stock solutions were stored at 4 ℃, human serum was diluted 1000-fold with 0.01M PBS solution (pH 7.4) and spiked with different amounts of ENR for application analysis
To prepare an aptamer sensor based on Py-M-COF, 10.0L of Py-M-COF in water suspension (1 mg. mL)-1) Drop on pretreated bare AE (Py-M-COF/AE). Subsequently, the modified AE was soaked in an aptamer solution of ENR at 4 ℃ for 2 hours, rinsed thoroughly with PBS, and incubated at mild N2Drying with air flowDrying to complete AptENRConstruction of the/Py-M-COF/AE aptamer sensor.
Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS) tests were performed on a CHI 660E electrochemical workstation. The electrochemical measurement adopts a traditional three-electrode system, and comprises a bare electrode or a modified AE electrode as a working electrode, Ag/AgCl (3mol KCl) as a reference electrode, and a platinum wire as an auxiliary electrode. In the presence of 5mM [ Fe (CN)6]3-/4-In PBS solution (pH 7.4,0.01mol) at a scanning speed of 50 mV. multidot.s-1CV testing was performed in the range of-0.2V to 0.8V. EIS test was carried out in a frequency range of 0.01Hz to 100kHz under the condition that the open circuit potential was 0.22V, and the amplitude was 5 mV. EIS spectra were analyzed using the ZView2 software obtained from Scribner Associates Incorporated. The software utilizes a non-linear least squares fit to determine the parameters of the elements in the equivalent circuit.
During the electrochemical measurement, the aptamer sensor was immersed in different concentrations of ENR solutions to determine the sensitivity and detection limit (denoted ENR/Apt) of the aptamer sensor to the analyteENRPy-M-COF/AE). The selectivity of the aptamer sensor was determined by incubation with tetracycline, kanamycin (Kana), TOB, Na +, K +, streptomycin, and OTC at room temperature. The reproducibility was evaluated by five aptamer sensors prepared independently. For stability evaluation, aptamer sensors were stored at 4 ℃ for 15 days and EIS measurements were taken daily. The suitability of the aptamer sensor was verified with human serum.
FIG. 6a shows EIS plots and ENR detection process for an aptamer sensor based on Py-M-COF modified electrodes. Using solution resistance (Rs), charge transfer resistance (R)ct) An equivalent circuit consisting of a Constant Phase Element (CPE) and a warburg impedance (W) simulates the EIS spectrum (inset in fig. 6 a). Bare AE shows a small semicircle (R) at high frequenciesct0.102kohm), a linear portion (curve i) is displayed at low frequencies. R of Py-M-COF/AE when Py-M-COF is modified to the surface of AEctThe value rises slightly to 0.129kohm (curve ii), which means on the electrode surface [ Fe (CN)6]3-/4-The electron transfer rate of the redox probe is relatively high. Fixing aptamer chain (Apt) on surface of Py-M-COF modified electrodeENR) After that, a semicircle was observedIncreased in diameter (R)ct0.239kohm) (curve iii) due to the negatively charged aptamer to negatively charged [ fe (cn))6]3-/4-The electron transfer is further hindered by electrostatic repulsion between the redox probes. In addition, when the concentration is 0.01 pg.mL-1R of the electrode after incubation in concentration target ENR moleculesctThe value further increases to 0.460kohm (curve iv) because the bio-molecular layer hinders the transfer of charge to the electrode surface. CV was also used to characterize the different steps of detection of ENR by the Py-M-COF aptamer sensor. As shown in FIG. 6b, [ Fe (CN)6]3-/4-The peak oxidation and reduction currents at Py-M-COF/AE (curve ii) are less than the peak redox current at bare AE (curve i), indicating that Py-M-COF decreases the electron transfer rate. For AptENRPy-M-COF/AE (curve iii) and ENR/AptENRthe/Py-M-COF/AE (curve iv) shows a significant reduction in current due to the barrier effect of the aptamer chain and the ENR molecular layer on electron transfer. The EIS and CV results confirm that the proposed aptamer sensor has an effective sensitivity to ENR. This is probably due to the fact that the two-dimensional Py-M-COF has an extended pi-conjugated backbone, a high specific surface area and a microporous structure, giving more anchoring sites suitable for the immobilization of aptamers. Therefore, the synthesized Py-M-COF is expected to be an effective sensing platform for measuring ENR.
Operating conditions such as aptamer concentration and target incubation time can affect the electrochemical signal and sensitivity of the analyte determination. R in aptamer immobilization as shown in FIG. 6cctThe values gradually increased with increasing ENR aptamer concentration, indicating that more aptamer chains are anchored at the surface of the Py-M-COF sensitive layer. RctThe value reached a high value at 100nM and then tended to stabilize, which means that the aptamer immobilized on Py-M-COF/AE was saturated. Furthermore, Apt increases with the incubation time in the target ENR solutionENRR of/Py-M-COF/AE sensorctThe value reached maximum response at 0.4h, then dropped slightly to a steady value at 1h as the PBS was thoroughly rinsed (fig. 6 d). Therefore, an ENR aptamer concentration of 100nM and ENR molecules incubation for 1h was chosen as the optimal condition in further measurements.
To study AptENRQuantitative analysis of ENR Properties/Py-M-COF/AEThus, EIS measurement was carried out. As shown in FIG. 6e, the EIS curve semicircular diameter increases with increasing ENR concentration. In the range of 0.01 to 2000 pg.mL-1In a wide range of (FIG. 6f), Δ RctValue (Δ R)ct＝Rct，ENR-Rct，Apt) Is proportional to the logarithm of the ENR concentration, where R isct，ENRAnd Rct，AptAre respectively AptENRR before and after incubation of/Py-M-COF/AE with ENRctThe value is obtained. The corresponding linear regression equation is Δ Rct(kohm)＝0.375+0.128Log CENR(pg·mL-1) Coefficient of correlation (R)2) Is 0.994. At a signal-to-noise ratio (S/N) of 3, the limit of detection (LOD) can be calculated to be 6.068 fg. multidot.mL-1This means that the Py-M-COF based aptamer sensors have a high sensitivity for ENR assays. These results indicate that Py-M-COF can be used as an effective biosensing platform for ultrasensitive detection of antibiotics. Our results show that the efficient measurement of ENR has a larger detection range and lower LOD than previously reported (table 1).
TABLE 1
The selectivity, reproducibility and stability of the sensor were further investigated. The concentration of the mixture is 100 pg/mL-1Tetracycline, Kana, TOB, Na+、K+Antibiotics such as streptomycin and OTC to detect AptENRPy-M-COF/AE vs ENR (10 pg. mL)-1) The specificity of (A). As shown in fig. 7a, negligible signal response was obtained in the perturbed samples, indicating good selectivity of the aptamer sensor. To investigate the reproducibility of the sensor, 5 modified electrodes were independently prepared under the same conditions. Detection 0.01 pg. mL-1Δ R of ENRctThe Relative Standard Deviation (RSD) of the values was 1.25% (fig. 7b), indicating that the electrochemical aptamer sensors prepared were reproducible. The storage stability of the sensor was evaluated by continuously measuring the electrochemical signal of the sensor for 15 days, and when the test was not performed, the modified electrode was stored in a refrigerator at 4 ℃. As shown in FIG. 7c, Δ RctThe value response remains almost a stable value, which means that the biosensor has good stability. The result shows that the developed aptamer sensor has good selectivity, high reproducibility and excellent stability for detecting ENR.
Application of tri-Py-M-COF-based aptamer electrochemical sensor
The feasibility of the proposed aptamer sensor was evaluated by detecting ENR in serum using standard addition methods. As shown in Table 2, the recovery rate of ENR is 101-112.4%, and all the recovery rates are within an acceptable range. The RSD range of ENR is 1.52-4.58%. Therefore, the constructed Py-M-COF-based electrochemical aptamer sensor has good recovery rate and potential for detecting antibiotic residues in biological fluid.
TABLE 2
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (4)
1. Use of a covalent organic framework electrochemical sensor, characterized in that the covalent organic framework is prepared by a method comprising: dissolving 1,3,6, 8-tetra (4-formylphenyl) pyrene in dimethyl sulfoxide, adding melamine, carrying out hot bath for three days at the temperature of 180 ℃, repeatedly washing the product after the hot bath by tetrahydrofuran and ethanol, drying in an oven at the temperature of 60 ℃ to obtain a Py-M-COF covalent organic skeleton, and modifying the prepared Py-M-COF covalent organic skeleton on a substrate electrode to obtain an electrochemical sensor on the electrode, wherein the electrochemical sensor is used for hypersensitive detection of antibiotics.
2. Use of a covalent organic framework electrochemical sensor according to claim 1, characterized in that: the hot bath is an oil bath.
3. Use of a covalent organic framework electrochemical sensor according to claim 1, characterized in that: the modification method comprises the following steps:
(1) pretreatment of a substrate electrode: polishing the bare gold electrode by using 0.05m of alumina slurry, then respectively carrying out ultrasonic treatment on the bare gold electrode in a piranha solution, ethanol and water for 15 minutes, carrying out electrochemical cleaning on the bare gold electrode by using an oxidation and reduction cycle in a range of-0.2-1.6V, then washing the bare gold electrode by using ultrapure water, and drying the bare gold electrode under nitrogen, wherein the piranha solution adopts a volume ratio of H2SO4/H2O2A 3:1 solution;
(2) modification: the covalent organic backbone Py-M-COF was formulated to 1 mg. mL-1Then dropping the aqueous suspension onto the substrate electrode pretreated in the step (1).
4. Use of a covalent organic framework electrochemical sensor according to claim 1, characterized in that: is used for the hypersensitivity detection of the antibiotic enrofloxacin.
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