Furadantin and adriamycin TDM electrochemical sensor as well as preparation method and application thereof

Abstract

The invention discloses a nitrofurantoin and adriamycin therapeutic drug concentration monitoring (TDM) electrochemical sensor and a preparation method and application thereof.The sensor is composed of a basic electrode and a composite material modified on the surface of the electrode, the composite material takes nitrogen-doped graded porous carbon as a substrate, and gold nanoflowers are generated on the surface in situ; the method comprises the following steps: preparing a CuNC material; uniformly coating the CuNC on the surface of an electrode; gold nanoflowers are electrically reduced on the surface; the electrochemical sensor is used for detecting nitrofurantoin and adriamycin; the method has the advantages of low detection limit and high sensitivity; the potential of medical and practical application is realized; the preparation and detection are simple and feasible.

Description

Technical Field

[0001] The invention relates to the technical field of nitrofurantoin and doxorubicin TDM detection, and in particular to a nitrofurantoin and doxorubicin TDM electrochemical sensor, a preparation method and application thereof. Background Art

[0002] The broad-spectrum antibiotic nitrofurantoin belongs to the nitrofuran family. Nitrofurantoin is particularly effective against bacteria such as enteric Salmonella and Escherichia coli infections and is commonly used to treat a variety of bacterial infections in animals and humans, including tuberculosis, malaria, and urinary tract infections. Overdose of nitrofurantoin may lead to various diseases, including methemoglobinemia, hepatitis granulomas, pulmonary toxicity, autoimmune-mediated hepatitis, chronic active hepatitis, arthritis, and nephrotoxicity. Similarly, doxorubicin is an important anthraquinone antibiotic that is commonly used to treat various types of cancer, such as Hodgkin's and non-Hodgkin's lymphomas, soft tissue tumors, malignant melanomas, and bronchogenic carcinomas. Although doxorubicin can be used as an effective anticancer drug to kill tumor cells, it also has serious disadvantages such as dose-dependent and cumulative cardiotoxicity, easy to induce liver damage, bone marrow suppression, and allergy, which limits its use in medical applications. Therefore, it is very necessary to develop highly sensitive, convenient, and reliable TDM assays for nitrofurantoin and doxorubicin.

[0003] Nowadays, a variety of analytical methods have been applied to the quantification of nitrofurantoin and doxorubicin, such as liquid chromatography-mass spectrometry, high performance liquid chromatography, surface enhanced Raman scattering, immunosensors and molecular imprinting technology. However, these methods generally require complex sample pretreatment processes, are difficult and time-consuming to operate, require expensive and bulky instruments, and have poor sensitivity and selectivity. Compared with the above analytical methods, electrochemical sensors are considered to be an effective alternative due to their high selectivity, low cost, high sensitivity, portable equipment and better suitability for on-site analysis.

[0004] Copper-based MOF and its derived carbon nanocomposites have attracted wide attention in the field of electrochemistry due to their excellent electrocatalytic properties. In this patent, MOF is combined with polyvinyl pyrrolidone by a one-pot solvothermal synthesis method, followed by pyrolysis to obtain CuNC, and then gold nanoflowers are generated in situ on the surface of the modified electrode drop-coated with the material using an electrodeposition method. 2O nanoparticles greatly improve the conductivity and provide a large number of effective active sites. In addition, N doping not only provides more defects, but also the highly electronegative N changes the electronic properties of the material, thereby improving the hydrophilicity of CuNC, which is beneficial to the dispersibility of the material in water. The gold nanoflowers on the surface of CuNC and the multimodal pore size distribution of the material are conducive to improving the charge transfer between the active sites and the target molecules, enhancing its pre-enrichment effect, and realizing electrochemical signal amplification. Finally, the electrochemical sensor based on the gold nanoflowers loaded on the surface of CuNC was successfully used for the detection of nitrofurantoin and doxorubicin TDM with a lower detection limit. Summary of the invention

[0005] The purpose of the present invention is to provide a nitrofurantoin and doxorubicin TDM electrochemical sensor, a preparation method and application thereof, so as to solve the problem of complicated TDM detection of nitrofurantoin and doxorubicin.

[0006] To achieve the above object, the technical solution of the present invention is as follows: A nitrofurantoin and doxorubicin TDM electrochemical sensor comprises a base electrode, a CuNC layer is coated on the surface of the base electrode, and a gold nanoflower layer is electro-reduced outside the CuNC layer.

[0007] A method for preparing a nitrofurantoin and doxorubicin TDM electrochemical sensor, the preparation method comprising the following steps: Step 1: Evenly apply the CuNC aqueous suspension on the surface of the base electrode and dry it to obtain a modified electrode; wherein the concentration of the CuNC aqueous suspension is 3-5 mg / mL, and the coating amount of the CuNC aqueous suspension is 0.022-0.067 mL / cm 2 .

[0008] Step 2: placing the modified electrode in a tetrachloroauric acid solution for electroreduction so that the surface of the modified electrode is covered with a gold nanoflower layer, thereby obtaining a nitrofurantoin and doxorubicin TDM electrochemical sensor.

[0009] As a further improvement, the base electrode is a 3 mm diameter glassy carbon electrode.

[0010] As a further improvement, the tetrachloroauric acid solution is a 2-4 mg / mL tetrachloroauric acid aqueous solution.

[0011] As a further improvement, the conditions for the electro-reduction are: the reduction voltage is -0.2-0.4 volts and the time is 200-400 seconds.

[0012] As a further improvement, the preparation method of CuNC is as follows: 1.1) Weigh 850-900 parts by mass of copper nitrate trihydrate, 250-350 parts by mass of PVP, and 400-450 parts by mass of trimesic acid; 1.2) Dissolve copper nitrate trihydrate and PVP in solvent 1 to obtain mixture A; Dissolving trimesic acid in solvent 1 to obtain mixture B; 1.3) Mix the mixtures A and B evenly and transfer them to a high-pressure reactor. The temperature is controlled at 80-120°C and the reaction is carried out for 20-25 hours to obtain MOF. 1.4) MOF is calcined at 800°C for 2 hours under a nitrogen atmosphere; after the reaction is cooled, the product is collected and ground to obtain CuNC.

[0013] As a further improvement, the solvent 1 is a DMF solution, and the water content in the DMF solution is 5-20%.

[0014] A use of the above-mentioned nitrofurantoin and doxorubicin TDM electrochemical sensor is characterized in that the nitrofurantoin and doxorubicin TDM electrochemical sensor is used to detect the concentration of nitrofurantoin or doxorubicin in a solution.

[0015] A further improvement is that when detecting the concentration of nitrofurantoin or doxorubicin in a solution, the pH of the solution is 5-9, and the incubation time of the nitrofurantoin and doxorubicin TDM electrochemical sensors in the aqueous solution is 20-30 minutes; the solution is one of PBS buffer solution, Hac-NaAc buffer solution, HCl buffer solution, aqueous solution or blood.

[0016] In a further improvement, the solution is a PBS buffer solution.

[0017] The advantages of the present invention are as follows: 1. In the present invention, gold nanoflowers and CuNC are used to construct the sensor sensing interface. Nitrofurantoin and doxorubicin are made into standard samples of different concentrations. The standard samples are co-incubated with the nitrofurantoin and doxorubicin TDM electrochemical sensors to obtain a standard curve with the concentration of nitrofurantoin and doxorubicin as the horizontal coordinate and the electrochemical signal intensity as the vertical coordinate, thereby realizing the quantitative detection of the concentration of nitrofurantoin and doxorubicin. Not only does it have strong catalytic and conductive abilities, but when used, the sample can be directly incubated with the nitrofurantoin and doxorubicin TDM sensor to obtain the detection result. Compared with the detection method in the prior art, the sensor of the present invention can be directly used without the steps of grinding, preparing a suspension, etc., and the preparation and detection are simple and easy.

[0018] 2. The detection range of the sensor for nitrofurantoin in the present invention is 8*10 -9 -3.5*10 -7 M, the minimum detection limit is 1.405 nM (equivalent to 0.335 ng / mL); the detection range of the sensor for doxorubicin is 10 -8 -1.5*10 -6M, the minimum detection limit is 1.278 nM (equivalent to 0.729 ng / mL); it can be seen that the sensor prepared by the present invention has an ultra-low detection limit; it has high sensitivity and a low detection limit.

[0019] 3. The nitrofurantoin and doxorubicin TDM electrochemical sensor provided by the present invention has cyclic voltammetry curves and Nyquist curves characterized as follows: Figure 2 As shown, it is proved that the TDM electrochemical sensor of nitrofurantoin and doxorubicin has strong electrochemical detection performance. The CuNC loaded with gold nanoflowers catalyzes the reaction between nitrofurantoin and doxorubicin, and then electron transfer occurs to generate sensitive current signals, which has high sensitivity for TDM detection of nitrofurantoin and doxorubicin.

[0020] 4. The preparation method of the electrochemical detection nanoprobe of the present invention is simple and easy, and has low cost. In addition, the sensor film material is a MOF-based derivative material and can be preserved for a long time. Therefore, the sensor of the present invention has the possibility of large-scale production and has the potential for medical and practical applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 The schematic diagram of the preparation process of the electrochemical TDM electrochemical sensor for nitrofurantoin and doxorubicin of the present invention and its use for detecting nitrofurantoin and doxorubicin; Figure 2 The scanning electron microscope image and element mapping image of CuNC loaded with gold nanoflowers of the present invention; Figure 3 is the X-ray diffraction pattern of CuNC of the present invention; Figure 4 is the X-ray photon energy diagram of CuNC of the present invention; Figure 5 This is the specific surface area and pore size analysis diagram of CuNC of the present invention; Figure 6 The cyclic voltammetry curve and Nyquist impedance diagram of the TDM electrochemical sensor of nitrofurantoin and doxorubicin of the present invention are shown in FIG. a a is the cyclic voltammetry curve, b is the Nyquist impedance diagram; Figure 7 : The cyclic voltammetry curve of the nitrofurantoin and doxorubicin TDM electrochemical sensor of the present invention in a PBS solution containing nitrofurantoin and doxorubicin; the bare glassy carbon electrode group shows two obvious reduction signals, which are the reduction peaks of nitrofurantoin and doxorubicin ( Figure 7 a), while with CuNC ( Figure 7 b) and gold nanoflowers ( Figure 7 (c) The reduction signals of furantoin and doxorubicin modified by the glassy carbon electrode gradually increase. When the gold nanoflowers are electro-reduced on the CuNC surface, the reduction signal response of the sensor to furantoin and doxorubicin reaches the highest level.

[0022] Figure 8 Response diagram of incubation time, pH, CuNC volume, electroreduction time, electroreduction voltage and buffer solution of the nitrofurantoin and doxorubicin TDM electrochemical sensor of the present invention; Fig. 9 Response diagrams of nitrofurantoin and doxorubicin at different scanning rates of the nitrofurantoin and doxorubicin TDM electrochemical sensor of the present invention; Fig.10 The electric signal of the nitrofurantoin and doxorubicin TDM electrochemical sensor of the present invention is as follows: -9 -3.5*10 -7 M) and doxorubicin (10 -8 -1.5*10 -6 M) Trend diagram of the change of signal intensity when added respectively; Fig.11 The electric signal of the nitrofurantoin and doxorubicin TDM electrochemical sensor of the present invention changes with nitrofurantoin (10 -8 -3*10 -7 M) and doxorubicin (5*10 -8 -1.5*10 -6 M) Trend graph of signal intensity changes when adding simultaneously; Fig.12 The anti-interference ability test graph and repeatability test graph of the nitrofurantoin and doxorubicin TDM electrochemical sensors after adding different interfering substances in the present invention; DETAILED DESCRIPTION

[0023] In order to facilitate the understanding of the present invention, the present invention will be described more fully below with reference to the relevant drawings. The preferred embodiments of the present invention are shown in the drawings. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thorough and comprehensive.

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification are only for describing specific implementation purposes and are not intended to limit the present invention. Example

[0025] A nitrofurantoin and doxorubicin TDM electrochemical sensor comprises a base electrode and the CuNC and electro-reduced gold nanoflowers. The preparation method comprises the following steps: Step 1: preparing MOF by hydrothermal synthesis; Step 2, calcining the MOF to obtain CuNC; Step 3, evenly coating CuNC on the surface of the glassy carbon electrode; Step 4: electro-reducing the gold nanoflowers in a tetrachloroauric acid solution using the modified electrode obtained in step 3; obtaining a TDM electrochemical sensor for furantoin and doxorubicin.

[0026] In this embodiment, step one specifically includes the following steps: 875 mg of copper nitrate trihydrate and 300 mg of PVP were dissolved in 20 mL of DMF solution and stirred for 10 minutes to obtain mixture A; Trimesic acid was also dissolved in 10 mL of DMF solution and stirred for five minutes to obtain mixture B; Mixtures A and B were mixed evenly, transferred to a polytetrafluoroethylene high-pressure reactor, the temperature was controlled at 80° C., and reacted for 24 hours.

[0027] After the reaction is cooled, the product is collected, transferred to a centrifuge tube, and weighed and quantified after vacuum drying to obtain MOF.

[0028] In this embodiment, step 2 specifically includes the following steps: 1000 mg of MOF was placed in a porcelain boat, transferred to a tube furnace, and calcined at 800 °C for 2 h under a nitrogen atmosphere; After the reaction was cooled, the product was collected and ground using an agate mortar for 5 minutes to obtain CuNC.

[0029] In this embodiment, in step 3, the concentration of the CuNC aqueous suspension is 3 mg / mL.

[0030] In this embodiment, step 4 specifically includes the following steps: Installing the modified electrode obtained in step 3 into a three-electrode system; The electrode was immersed in a 3 mg / mL aqueous solution of tetrachloroauric acid; The gold nanoflowers were electroreduced using chronoamperometry at a voltage of -0.4 V for 400 s to obtain the TDM electrochemical sensors for nitrofurantoin and doxorubicin.

[0031] The performance of the sensor prepared in this example was tested, and the results were as follows: The preparation and detection of the nitrofurantoin and doxorubicin TDM electrochemical sensor Figure 1 As shown, the nitrofurantoin and doxorubicin TDM electrochemical sensor includes a base electrode as well as the CuNC and electro-reduced gold nanoflowers.

[0032] like Figure 2 As shown in the ab SEM images in Fig. 1, CuNC is evenly distributed on the electrode surface. Figure 2 From the ce, we can see that the surface-reduced gold nanoflowers were successfully prepared and evenly distributed; like Figure 3As shown, the X-ray photoelectron spectroscopy shows the presence of corresponding copper and nitrogen elements in the synthesized CuNC.

[0033] like Figure 4 As shown, the prepared CuNC has a microporous-mesoporous-macroporous structure with a high specific surface area; like Figure 5 As shown, the X-ray diffraction patterns of CuNC are consistent with those of Cu standard card and Cu 2 The standard calorimeter of O showed consistent peaks, proving the successful synthesis of CuNC.

[0034] like Figure 6 As shown, Figure 6 Figure a is a cyclic voltammetry curve commonly used in the characterization of electrochemical properties. By comparing the strength of the redox signal peaks of different modified electrodes in potassium ferrocyanide solutions with the same concentration, the performance of the electrochemical sensor can be preliminarily judged. Figure 6 b is the EIS impedance spectrum, which is usually used to illustrate the surface impedance of the prepared electrochemical sensor. The impedance strength can be intuitively explained by comparing the radius of the arc segment in the impedance diagram. It can be simply understood that the larger the radius of the arc segment, the greater the material impedance. Figure 6 As can be seen from Figure b, the nitrofurantoin and doxorubicin TDM electrochemical sensor has strong conductivity and good electrochemical performance; the nitrofurantoin and doxorubicin TDM electrochemical sensor prepared by the present invention can be used for sensitive detection of nitrofurantoin and doxorubicin.

[0035] like Figure 7 As shown, by comparing the cyclic voltammetry curves of different modified electrodes in the same PBS solution of nitrofurantoin and doxorubicin, the nitrofurantoin and doxorubicin TDM electrochemical sensor prepared by the present invention has good electrocatalytic activity for nitrofurantoin and doxorubicin.

[0036] like Figure 8 As shown in Figure a, the effects of incubation time of 1 min, 5 min, 10 min, 15 min, 20 min, 25 min and 30 min on the signal intensity of the electrochemical sensor were studied. As the incubation time increased to 20 min, the electrochemical signal intensity reached a peak. This result shows that the TDM sensor for nitrofurantoin and doxorubicin has better sensitivity for the detection of nitrofurantoin and doxorubicin when the incubation time is 20 min.

[0037] like Figure 8As shown in b, the effects of pH values ​​of 5, 6, 7, 8 and 9 on the signal intensity of the electrochemical sensor were studied. When pH < 7, the detection sensitivity of the nitrofurantoin and doxorubicin TDM electrochemical sensor gradually decreased with the decrease of pH; on the contrary, when pH > 7, the detection sensitivity of this nitrofurantoin and doxorubicin TDM electrochemical sensor gradually decreased with the increase of pH. This result shows that the nitrofurantoin and doxorubicin TDM sensor has better sensitivity for the detection of nitrofurantoin and doxorubicin under the condition of pH 7.

[0038] like Figure 8 As shown in Figure c, the effect of CuNC drop volume on the signal intensity of the TDM electrochemical sensor for nitrofurantoin and doxorubicin was studied. When the drop volume was less than 4 μL, the detection sensitivity of the TDM electrochemical sensor for nitrofurantoin and doxorubicin decreased with the decrease of volume; on the contrary, when the drop volume was greater than 4 μL, the detection sensitivity of the TDM electrochemical sensor for nitrofurantoin and doxorubicin decreased with the increase of volume. This result shows that the TDM electrochemical sensor for nitrofurantoin and doxorubicin has better sensitivity when 4 μL CuNC is drop-coated on the surface.

[0039] like Figure 8 As shown in Figure d, the effect of the electroreduction time of gold nanoflowers on the detection sensitivity of the TDM electrochemical sensor for nitrofurantoin and doxorubicin was studied. When the electroreduction time was 400 seconds, the detection sensitivity of the TDM electrochemical sensor for nitrofurantoin and doxorubicin reached the highest level.

[0040] like Figure 8 As shown in Figure e, the relationship between the detection sensitivity of the TDM electrochemical sensor for nitrofurantoin and doxorubicin and the electroreduction voltage of the gold nanoflowers was studied. When the reduction voltage was -0.4 volts, the TDM electrochemical sensor for nitrofurantoin and doxorubicin had a higher detection sensitivity.

[0041] like Figure 8 As shown in f, the effects of Hac-NaAc, PBS and HCl buffer on the response intensity of the TDM electrochemical sensor for nitrofurantoin and doxorubicin were studied. The results showed that the TDM electrochemical sensor for nitrofurantoin and doxorubicin in PBS solution had higher sensitivity to nitrofurantoin and doxorubicin.

[0042] like Fig. 9 As shown, the electrochemical responses of nitrofurantoin and doxorubicin on the surface of the nitrofurantoin and doxorubicin TDM electrochemical sensor changed with the change of the scan rate. Fig. 9 Figure b shows that the reduction current of nitrofurantoin is linearly correlated with the logarithm of the scan rate, while the reduction current of doxorubicin is linearly correlated with the scan rate. This indicates that nitrofurantoin is diffusion-controlled on the electrode surface, while doxorubicin is adsorption-controlled.

[0043] The quantitative detection of nitrofurantoin and doxorubicin using the nitrofurantoin and doxorubicin TDM electrochemical sensor includes the following steps: Weigh nitrofurantoin powder and dilute it with DMF: water (1:1) to prepare a 1 mM concentration stock solution; at the same time, weigh doxorubicin powder and dilute it with water to prepare a 1 mM concentration stock solution; dilute the nitrofurantoin stock solution and doxorubicin stock solution with PBS at different ratios to obtain standard solutions of nitrofurantoin and doxorubicin coexisting at different concentrations, and incubate them with nitrofurantoin and doxorubicin TDM electrochemical sensors as test samples for 20 min, with 3 replicates for each concentration, and record the electrochemical signal intensity value, as shown in the following figure. Fig.10 As shown in the figure, the electrochemical signal intensity increases with the increase of nitrofurantoin and doxorubicin concentrations. In addition, a standard curve was drawn with nitrofurantoin concentration as the horizontal axis and electrochemical signal intensity as the vertical axis. Fig.11 b, has a good linear relationship R 2 =0.9995, LOD = 1.405 nM; with doxorubicin concentration as the horizontal axis and electrochemical affinity as the vertical axis, a standard curve was drawn for 11 days, which had a good linear relationship R 2 =1.278, LOD=1.278 nM. Conclusion: The linear range of nitrofurantoin detection is 8*10 -9 -3.5*10 -7 M, LOD was 1.405 nM; the linear range of detection for doxorubicin was 10 -8 -1.5*10 -6 M, LOD is 1.278 nM. This sensor system has a wide linear range and extremely low detection limit; it has good reproducibility in repeated experiments.

[0044] A quantitative analysis was performed on the simultaneous changes in the concentrations of nitrofurantoin and doxorubicin. Fig.12 , the concentration of doxorubicin added was five times that of nitrofurantoin. As the concentrations of nitrofurantoin and doxorubicin increased, their respective electrochemical signals increased simultaneously, showing excellent linear relationships: I of nitrofurantoin = 0.06022 C + 3.3339 (R 2 =0.9982); I of doxorubicin = 0.5828 C + 4.4270 (R 2 =0.9988). These results indicate that the present nitrofurantoin and doxorubicin TDM electrochemical sensor can be used for sensitive detection of nitrofurantoin and doxorubicin.

[0045] Anti-interference experiments, repeatability and stability experiments were carried out on the nitrofurantoin and doxorubicin TDM electrochemical sensors: like Fig.12a. After adding protein-precipitated serum to the standard sample, the electrochemical signal does not decay, indicating that the prepared electrochemical sensor has excellent anti-interference performance; the repeatability and stability test results of the sensor are shown in Fig.12 (b-c), Five groups of different sensors were tested five times and showed good repeatability and stability.

[0046] Table 1

[0047] Table 1 shows the contents of nitrofurantoin and doxorubicin and the recovery rates in standard serum samples measured by the nitrofurantoin and doxorubicin TDM electrochemical sensors of the present invention.

[0048] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A nitrofurantoin and doxorubicin TDM electrochemical sensor, characterized in that: The invention comprises a basic electrode, the surface of the basic electrode is coated with a CuNC layer, and the outer surface of the CuNC layer is electrically reduced with a gold nanoflower layer.

2. A method for preparing a nitrofurantoin and doxorubicin TDM electrochemical sensor, characterized in that: The preparation method comprises the following steps: Step 1: Evenly apply the CuNC aqueous suspension on the surface of the base electrode and dry it to obtain a modified electrode; wherein the concentration of the CuNC aqueous suspension is 3-5 mg / mL, and the coating amount of the CuNC aqueous suspension is 0.022-0.067 mL / cm 2 ; Step 2: placing the modified electrode in a tetrachloroauric acid solution for electroreduction so that the surface of the modified electrode is covered with a gold nanoflower layer, thereby obtaining a nitrofurantoin and doxorubicin TDM electrochemical sensor.

3. The method for preparing the nitrofurantoin and doxorubicin TDM electrochemical sensor according to claim 2, characterized in that: The base electrode is a 3 mm diameter glassy carbon electrode.

4. The method for preparing the nitrofurantoin and doxorubicin TDM electrochemical sensor according to claim 2, characterized in that: The tetrachloroauric acid solution is a 2-4 mg / mL tetrachloroauric acid aqueous solution.

5. The method for preparing the nitrofurantoin and doxorubicin TDM electrochemical sensor according to claim 2, characterized in that: The conditions for the electroreduction are: reduction voltage of -0.2 to -0.4 volts and time of 200 to 400 seconds.

6. The method for preparing the nitrofurantoin and doxorubicin TDM electrochemical sensor according to claim 2, characterized in that: The preparation method of CuNC is as follows: 1.1) Weigh 850-900 parts by mass of copper nitrate trihydrate, 250-350 parts by mass of PVP, and 400-450 parts by mass of trimesic acid; 1.2) Dissolve copper nitrate trihydrate and PVP in solvent 1 to obtain mixture A; Dissolving trimesic acid in solvent 1 to obtain mixture B; 1.3) Mix the mixtures A and B evenly and transfer them to a high-pressure reactor. The temperature is controlled at 80-120°C and the reaction is carried out for 20-25 hours to obtain MOF. 1.4) MOF is calcined at 800°C for 2 hours under a nitrogen atmosphere; after the reaction is cooled, the product is collected and ground to obtain CuNC.

7. The method for preparing the nitrofurantoin and doxorubicin TDM electrochemical sensor according to claim 5, characterized in that: The solvent 1 is a DMF solution, and the water content in the DMF solution is 5-20%.

8. Use of the nitrofurantoin and doxorubicin TDM electrochemical sensor according to any one of claims 1 to 6, characterized in that: The nitrofurantoin and doxorubicin TDM electrochemical sensor is used to detect the concentration of nitrofurantoin or doxorubicin in a solution.

9. Use of the nitrofurantoin and doxorubicin TDM electrochemical sensor according to claim 8, characterized in that: When detecting the concentration of nitrofurantoin or doxorubicin in a solution, the pH of the solution is 5-9, and the incubation time of the nitrofurantoin and doxorubicin TDM electrochemical sensors in the aqueous solution is 20-30 minutes; the solution is one of PBS buffer solution, Hac-NaAc buffer solution, HCl buffer solution, aqueous solution or blood.

10. Use of the nitrofurantoin and doxorubicin TDM electrochemical sensor according to claim 9, characterized in that: The solution is a PBS buffer solution.

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