CN114295587B - SPR sensor based on two-dimensional metal organic framework and preparation and application thereof - Google Patents
SPR sensor based on two-dimensional metal organic framework and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses an SPR sensor based on a two-dimensional metal organic framework, which is provided with a Cu-TCPP 2D MOF sensitization layer on a gold chip, wherein the sensitization layer is prepared by the following steps: dissolving and adding copper nitrate, trifluoroacetic acid and polyvinylpyrrolidone into a first mixed solution of N, N-dimethylformamide and ethanol to form a second mixed solution; meanwhile, dissolving TCPP in the first mixed solution, and then dropwise adding the TCPP into the second mixed solution under stirring to form a third mixed solution; carrying out ultrasonic treatment on the third mixed solution and heating; cooling to room temperature, centrifuging the obtained Cu-TCPP 2D MOF solution, washing with ethanol, and redissolving in ethanol solution for preservation; after incubating the preserved Cu-TCPP 2D MOF solution drops on the surface of the gold chip, washing the gold chip with deionized water to wash away the redundant Cu-TCPP 2D MOF solution; and then drying the gold chip by nitrogen, and fixing the Cu-TCPP 2D MOF on the surface of the gold chip to form a Cu-TCPP 2D MOF sensitization layer.
Description
Technical Field
The invention relates to an SPR sensor, in particular to an SPR sensor based on a two-dimensional metal organic framework, and preparation and application thereof.
Background
Surface Plasmon Resonance (SPR) spectroscopy is an optical technique for detecting interactions of molecules on the surface of gold films by monitoring changes in Refractive Index (RI). Compared with traditional analysis methods such as colorimetry, fluorescence method and electrochemical analysis method, the unlabeled, simple and real-time property of SPR makes it widely applied in disease diagnosis, environment and food safety supervision. The SPR signal response decays exponentially outwards in the direction perpendicular to the interface and is less sensitive to RI changes of 200nm beyond the sensing interface surface, making it difficult for existing SPR biosensors to detect macromolecular targets such as cells, bacteria and even exosomes. Detection based on the traditional sandwich method is complex in construction and requires multiple complicated operations. Therefore, it is of great importance to construct SPR sensors based on a direct method without pre-labeling and outer sandwich.
In order to meet the demand for ultrasensitive detection of trace disease biomarkers, nanomaterials have been proposed to alter the plasma sensing interface, thereby increasing the sensitivity of SPR. By flowing functionalized AuNPs (gold nanoparticles) to the surface of the sensor chip to detect human immunoglobulin G, 25-fold signal enhancement was achieved, and excellent local surface plasmon resonance formed a strong coupling effect with the surface plasmon waveform of the gold film. However, disordered distribution of nanoparticles can interfere with the optical response of surface plasmon resonance, and the bulkiness and complexity of periodic nanoparticle structures limit their practical application.
The two-dimensional material (graphene, molybdenum disulfide and the like) has larger specific surface area, high electron mobility and light absorptivity, and under the condition of no interference with interaction, the sensitized layer biomolecules for enhancing SPR signals can be constructed by the two-dimensional material, so that the sensitivity of SPR can be improved, and accurate detection is provided for trace biomarkers. Although the sensitivity of SPR sensors based on two-dimensional materials is improved, the detection accuracy and quality factor are reduced. Tunable and low-loss plasmons of graphene are of great interest, but graphene suffers from the following drawbacks that limit its direct application in SPR sensing: first, the relatively inefficient coupling between incident light and graphene plasma is detrimental to sensitive measurements of the environment outside the sensing interface. Second, graphene can generate greater damping in Surface Plasmon (SP) due to its high virtual dielectric constant, resulting in reduced detection accuracy. Third, due to the high van der waals attractive forces (5.9 kJ mol/carbon) between graphene sheets, one of the challenges in using graphene on SPR sensors is that it is prone to uncontrolled aggregation and difficult to uniformly and well disperse, and thus the modification process of such two-dimensional materials in the sensing interface is more complex. In summary, graphene alone is not the best candidate for high sensitivity detection, and its application in SPR is mainly focused on graphene-other material composite structures. For the current sensitization work of SPR sensors, there is an urgent need to find an ideal two-dimensional material with highly ordered internal structure, good photoelectric properties, excellent solubility, dispersibility and easy modification for constructing a huge latent force sensor with improved SPR performance.
Accordingly, those skilled in the art have been working to develop a more sensitive SPR sensor.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention is directed to developing an SPR sensor with higher sensitivity.
In order to achieve the above purpose, the invention discloses an ultrathin M-TCP 2D MOF (metalloporphyrin two-dimensional metal organic framework) nanosheet, in particular, a Cu-TCPP 2D MOF nanosheet which has an ultrathin thickness, a highly ordered structure, a plurality of active sites on the surface, a larger specific surface area and good solubility and dispersibility is prepared. The pi-stacked electroactive porphyrin molecules of TCPP-based 2D MOFs can undergo charge transport in the MOF structure and have good electron mobility. The transient photocurrent generated by the 2D MOF under the irradiation of visible light promotes the generation of efficient photo-generated carriers, and the coupling effect between the incident light and the 2D MOF plasma is more excellent compared with graphene. In addition, cu-TCPP has good in vitro and in vivo biocompatibility due to Cu 2+ And its two-dimensional ultrathin nature, it can produce excellent near infrared light absorption, and has many advantages in SPR sensitization.
The invention firstly provides an SPR sensor based on a two-dimensional metal organic framework, which is provided with a Cu-TCPP 2D MOF sensitization layer on a gold chip, wherein the sensitization layer is prepared by the following steps:
dissolving and adding copper nitrate, trifluoroacetic acid and polyvinylpyrrolidone into a first mixed solution of N, N-dimethylformamide and ethanol to form a second mixed solution; meanwhile, dissolving TCPP in the first mixed solution, and then dropwise adding the TCPP into the second mixed solution under stirring to form a third mixed solution; carrying out ultrasonic treatment on the third mixed solution and heating; cooling to room temperature, centrifuging the obtained Cu-TCPP 2D MOF solution, washing with ethanol, and redissolving in ethanol solution for preservation;
after incubating the preserved Cu-TCPP 2D MOF solution drops on the surface of the gold chip, washing the gold chip with deionized water to wash away the redundant Cu-TCPP 2D MOF solution; and then drying the gold chip by nitrogen, and fixing the Cu-TCPP 2D MOF on the surface of the gold chip to form a Cu-TCPP 2D MOF sensitization layer.
Further, in the first mixed solution, the volume ratio of the N, N-dimethylformamide to the ethanol is 3:1; sonicating the third mixed solution for 10 minutes and heating to 80 ℃ for 3 hours; incubation is carried out on the surface of the gold chip for 30 minutes; centrifugation speed 8000r.p.m. for 10 minutes.
Further, an incubation box is provided, the incubation box comprises a first box body and a second box body which can be buckled, a gold chip is placed in the first box body, and a Cu-TCPP 2D MOF solution is dripped into the second box body; and then the first box body and the second box body are buckled, so that a gold film of the gold chip is immersed in the Cu-TCPP 2D MOF solution, the incubation box is clamped from two ends by rotating clamping jaws, and the incubation box rotates around the axis of the incubation box for centrifugal incubation.
The invention also provides a preparation method of the SPR sensor based on the two-dimensional metal organic framework, which comprises the following steps:
dissolving and adding copper nitrate, trifluoroacetic acid and polyvinylpyrrolidone into a first mixed solution of N, N-dimethylformamide and ethanol to form a second mixed solution; meanwhile, dissolving TCPP in the first mixed solution, and then dropwise adding the TCPP into the second mixed solution under stirring to form a third mixed solution; carrying out ultrasonic treatment on the third mixed solution and heating; cooling to room temperature, centrifuging the obtained Cu-TCPP 2D MOF solution, washing with ethanol, and redissolving in ethanol solution for preservation;
after incubating the preserved Cu-TCPP 2D MOF solution drops on the surface of the gold chip, washing the gold chip with deionized water to wash away the redundant Cu-TCPP 2D MOF solution; and then drying the gold chip by nitrogen, and fixing the Cu-TCPP 2D MOF on the surface of the gold chip to form a Cu-TCPP 2D MOF sensitization layer.
Further, in the first mixed solution, the volume ratio of the N, N-dimethylformamide to the ethanol is 3:1; sonicating the third mixed solution for 10 minutes and heating to 80 ℃ for 3 hours; incubation is carried out on the surface of the gold chip for 30 minutes; centrifugation speed 8000r.p.m. for 10 minutes.
Further, an incubation box is provided, the incubation box comprises a first box body and a second box body which can be buckled, a gold chip is placed in the first box body, and a Cu-TCPP 2D MOF solution is dripped into the second box body; and then the first box body and the second box body are buckled, so that a gold film of the gold chip is immersed in the Cu-TCPP 2D MOF solution, the incubation box is clamped from two ends by rotating clamping jaws, and the incubation box rotates around the axis of the incubation box for centrifugal incubation.
The invention also provides an application of the SPR sensor based on the two-dimensional metal organic framework in detecting PD-L1 exosomes, which is characterized by comprising the following steps:
dissolving and adding copper nitrate, trifluoroacetic acid and polyvinylpyrrolidone into a first mixed solution of N, N-dimethylformamide and ethanol to form a second mixed solution; meanwhile, dissolving TCPP in the first mixed solution, and then dropwise adding the TCPP into the second mixed solution under stirring to form a third mixed solution; carrying out ultrasonic treatment on the third mixed solution and heating; cooling to room temperature, centrifuging the obtained Cu-TCPP 2D MOF solution, washing with ethanol, and redissolving in ethanol solution for preservation;
after incubating the preserved Cu-TCPP 2D MOF solution drops on the surface of the gold chip, washing the gold chip with deionized water to wash away the redundant Cu-TCPP 2D MOF solution; then drying the gold chip by nitrogen, and fixing the Cu-TCPP 2D MOF on the surface of the gold chip to form a Cu-TCPP 2D MOF sensitization layer;
loading a gold chip in an SPR instrument, then flowing a peptide with the function of specifically capturing PD-L1 exosomes through the surface of the gold chip with a sensitization layer, and fixing the peptide on the surface of the gold chip through pi-pi stacking; then the PD-L1 exosome solution to be detected flows through the surface of the gold chip and is detected by an SPR instrument.
Further, in the first mixed solution, the volume ratio of the N, N-dimethylformamide to the ethanol is 3:1; sonicating the third mixed solution for 10 minutes and heating to 80 ℃ for 3 hours; incubation is carried out on the surface of the gold chip for 30 minutes; centrifugation speed 8000r.p.m. for 10 minutes.
Further, the peptide flowed over the surface of the gold chip at a flow rate of 5. Mu.L/min; the PD-L1 exosome solution to be tested flows over the gold chip surface at a flow rate of 5. Mu.L/min.
Further, an incubation box is provided, the incubation box comprises a first box body and a second box body which can be buckled, a gold chip is placed in the first box body, and a Cu-TCPP 2D MOF solution is dripped into the second box body; and then the first box body and the second box body are buckled, so that a gold film of the gold chip is immersed in the Cu-TCPP 2D MOF solution, the incubation box is clamped from two ends by rotating clamping jaws, and the incubation box rotates around the axis of the incubation box for centrifugal incubation.
The invention uses the Cu-TCPP 2D MOF which has the advantages of ultra-thin thickness, ordered structure, multiple surface active sites, large specific surface area, excellent electron mobility and light absorptivity and the like as the sensitization layer, thereby obviously improving the SPR sensitivity. According to the invention, a complex traditional sandwich is not required to be constructed, a direct SPR detection method based on a 2D MOF sensitization layer is constructed, and target analysis and detection can be carried out only by three steps of samples. The multifunctional peptide used in the invention has high specificity with the target, and the detection sample can be analyzed and detected without pretreatment.
The conception, specific structure, and technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, features, and effects of the present invention.
Drawings
FIG. 1 is an atomic force microscope image of a progressive construction of a sensing interface in a preferred embodiment of the invention;
FIG. 2 is a graph showing calibration of sensor selectivity verification and SPR angle change due to different concentrations of PD-L1 exosomes in a preferred embodiment of the present invention.
FIG. 3 is a schematic view showing the operation of the incubator according to a preferred embodiment of the present invention.
Detailed Description
The following description of the preferred embodiments of the present invention refers to the accompanying drawings, which make the technical contents thereof more clear and easy to understand. The present invention may be embodied in many different forms of embodiments and the scope of the present invention is not limited to only the embodiments described herein.
The measurement method and steps for detecting PD-LI exosomes using a Cu-TCPP 2D MOF-based SPR sensor in this example are as follows:
(1) Synthesis of Cu-TCPP 2D MOF:
a mixed solution of 12mLN, N-Dimethylformamide (DMF) and ethanol (V: V=3:1) was added to a 20mL bottle, and then copper nitrate (3.6 mg,0.015 mmol), trifluoroacetic acid (1.0M. Times.10. Mu.L), polyvinylpyrrolidone (PVP, 10.0 mg) were added thereto to dissolve. Meanwhile, TCPP (4.0 mg,0.005 mmol) was dissolved in a mixed solution of 4ml dmf and ethanol (V: v=3:1), and then added dropwise to the above mixed solution with stirring. After that, the mixed solution was sonicated for 10 minutes and heated to 80 ℃ for 3 hours. After heating was stopped, the solution was cooled to room temperature and the resulting red-violet Cu-TCPP 2D MOF solution was centrifuged at 8000r.p.m. for 10 minutes and washed twice with ethanol. Finally, the obtained Cu-TCPP 2D MOF was redissolved in 10ml of ethanol solution and stored at 4 ℃.
(2) SPR sensor performance analysis
Different refractive index measurements were analyzed, including deionized water and 1-16.7wt% sodium chloride solution (ri= 1.33330, 1.33500, 1.33675, 1.34170, 1.34986, 1.36370). 300 mu of sodium chloride solution with different mass fractions was flowed to the gold chips and rinsed with deionized water. The SPR angular displacement is measured and collected throughout the monitoring process. The SPR signal changes of bare gold chips and two-dimensional MOF-modified gold chips were compared using the same concentrations of multifunctional peptide and exosomes.
(3) Construction of SPR sensor chip for detecting PD-L1 exosomes
50. Mu.L of 2DMOF nanosheet solution of appropriate concentration was dropped onto the surface of the treated gold chip. After 30 minutes incubation, the gold chips were rinsed with deionized water to wash away excess 2DMOF nanoplatelet solution. The gold chip was again dried with nitrogen and the two-dimensional MOF nanoplatelets were fixed on the gold chip surface. The modified gold chip was fixed in the SPR instrument. Then 300. Mu.L of 100. Mu.g/mL of a peptide having an antipollution function and a specific capturing function of PD-L1 exosomes was flowed over the surface of the 2DMOF nanoplatelet at a flow rate of 5. Mu.L/min, and the peptide was immobilized on the surface of the gold chip by pi-pi stacking. Then 300. Mu.L of PD-L1 exosomes capable of binding specifically to peptides were flowed over the gold chip surface at a flow rate of 5. Mu.L/min. The buffer solution for baseline was deionized water and the entire sampling process was performed under the monitoring of the SPR instrument.
SPR monitors PD-L1 exosomes:
the adopted PD-L1 exosome concentrations are respectively as follows: 10 4 、5×10 4 、10 5 、5×10 5 、10 6 、5×10 6 exosomes/mL.
Test conditions: SPR measurements of PD-L1 exosomes of different concentrations were performed using an SPR instrument at room temperature.
Referring to the drawings, FIG. 1 is an atomic force microscope image of a stepwise construction of a sensing interface. Gold chips (a), 2D MOF-modified chips (B), 2D images of the sensing interface of the exosomes (C) and cross-sectional thickness maps were characterized by atomic force microscopy, respectively. The two-dimensional MOF was decorated on a flat smooth bare gold chip and the layered structure of Cu-TCPP was again confirmed by atomic force microscopy. The morphology structure of the bare gold chip shows good uniformity, and the roughness is 5nm. As is clear from fig. 1B, the MOF is a two-dimensional platelet structure, relatively uniform in morphology, and approximately 10nm thick (minus 5nm roughness of the bare die). And then, the sensing interface for capturing the exosomes is characterized, so that the presence of the exosomes with the wavelength of 120nm on the 2D MOF can be clearly observed, and the successful construction of the sensing interface is shown.
FIG. 2 is a calibration graph of SPR angle change caused by sensor selectivity verification and PD-L1 exosomes at different concentrations. It is well known that a variety of interfering substances exist in the blood environment, such as impurity proteins, ascorbic acid, glutathione, glucose, and the like. The recognition domain in the peptide (FHYQRDTPKSYN) has been shown to have strong binding capacity to PD-L1 with a dissociation constant (KD) of 0.51. Mu.M. Whether the peptide recognition domain can specifically capture the PD-L1 ectodomain which is highly expressed on the exosome is one of key parts of an accurate and sensitive blood environment exosome sensor. Fig. 2A, B records signal changes caused by interfering substances (GSH, AA, glu, BSA) in the blood and by exosomes flowing across the surface of the SPR sensor chip. Four interferences compared to 97m ° signal change caused by target PD-L1 exosomesThe average value of the SPR signal change caused by the substance was only 7m DEG, -1m DEG, 8m DEG and 15m DEG, respectively, and p values of less than 0.01 indicate that the difference was extremely remarkable. It can be seen that the four interfering substances do not have a significant effect on the SPR sensor. These results confirm that the manufactured sensor has excellent specificity for exosomes. In order to verify the linear relationship between the amount of the detection substance and the signal response of the SPR sensor, the adopted PD-L1 exosome concentrations were respectively: 10 4 、5×10 4 、10 5 、5×10 5 、10 6 、5×10 6 exosomes/mL. Fig. 2C, D is a linear fit of the SPR curve and resulting data for signal changes caused by gradient concentration targets flowing across the sensor chip surface. The SPR angular displacement increases with the increase of the PD-L1 exosome concentration, and the SPR angular change has good linear relation with the logarithm of the PD-L1 exosome concentration. The linear equation is Δθ=0.0324 lgC Exo 0.11984, the linear correlation coefficient is 0.989, the detection limit is 16.7 exosomes/mL, and the detection requirements are met.
As shown in fig. 3, in order to fix the two-dimensional MOF nano-sheet on the surface of the gold film 3 of the gold chip 4 faster and more tightly, the incubation time is saved, and an incubation box is provided, which comprises a first box body 1 and a second box body 2 that can be buckled. And then a gold chip 4 is placed in the first box body 1, and 2DMOF nanosheet solution 5 is dripped into the second box body 2. Then the first box body 1 and the second box body 2 are buckled, so that the gold film 3 of the gold chip 4 is immersed in the 2DMOF nanosheet solution, the incubation box is clamped from two ends through the rotary clamping jaw 6 and is rotated around the axis of the incubation box to perform centrifugal incubation, and the two-dimensional MOF nanosheets in the 2DMOF nanosheet solution are deposited and fixed on the surface of the gold film 3 of the gold chip 4 more quickly and more tightly.
The invention uses Cu-TCPP 2D MOF which has the advantages of ultra-thin thickness, ordered structure, multiple surface active sites, large specific surface area, excellent electron mobility and light absorptivity and the like as the sensitization layer, thereby obviously improving SPR sensitivity. The method constructs a direct SPR detection method based on the 2D MOF sensitization layer, uses the multifunctional peptide to integrate multiple functions of anchoring the 2D MOF, preventing interface nonspecific adsorption, specifically capturing PD-L1 exosomes and the like, can omit complex and tedious interface construction, and can perform target analysis and detection only by 3 steps. The method has high specificity, selectivity, simplicity and sensitivity, and can detect trace PD-L1 exosomes. The constructed simple and rapid SPR sensor chip has good expandability and broad prospect, and the method provides a new platform for clinically detecting some trace target biomolecules.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention without requiring creative effort by one of ordinary skill in the art. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (7)
1. The SPR sensor based on the two-dimensional metal organic framework is characterized in that a Cu-TCPP 2D MOF sensitization layer is arranged on a gold chip, wherein the sensitization layer is prepared through the following steps:
dissolving and adding 0.015mM copper nitrate, 1.0 M trifluoroacetic acid and 10.0 mg polyvinylpyrrolidone into 12mL of a first mixed solution of N, N-dimethylformamide and ethanol in a volume ratio of 3:1 to form a second mixed solution; meanwhile, 0.005mM of TCPP is dissolved in the first mixed solution, and then is added into the second mixed solution dropwise under stirring to form a third mixed solution; sonicating the third mixed solution for 10 minutes and heating to 80 ℃ for 3 hours; cooling to room temperature, centrifuging the obtained Cu-TCPP 2D MOF solution at 8000r.p.m. for 10 minutes, washing with ethanol, redissolving in 10ml ethanol solution and preserving at 4 ℃;
after incubating the preserved Cu-TCPP 2D MOF solution drops on the surface of the gold chip, washing the gold chip with deionized water to wash away the redundant Cu-TCPP 2D MOF solution; and then drying the gold chip by nitrogen, and fixing the Cu-TCPP 2D MOF on the surface of the gold chip to form a Cu-TCPP 2D MOF sensitization layer.
2. The SPR sensor based on the two-dimensional metal organic framework, as claimed in claim 1, wherein an incubation box is provided, the incubation box comprises a first box body and a second box body which can be buckled, a gold chip is firstly placed in the first box body, and a Cu-TCPP 2D MOF solution is dripped into the second box body; and then the first box body and the second box body are buckled, so that a gold film of the gold chip is immersed in the Cu-TCPP 2D MOF solution, the incubation box is clamped from two ends by rotating clamping jaws, and the incubation box rotates around the axis of the incubation box for centrifugal incubation.
3. The preparation method of the SPR sensor based on the two-dimensional metal organic framework is characterized by comprising the following steps of:
dissolving and adding 0.015mM copper nitrate, 1.0 M trifluoroacetic acid and 10.0 mg polyvinylpyrrolidone into 12mL of a first mixed solution of N, N-dimethylformamide and ethanol in a volume ratio of 3:1 to form a second mixed solution; meanwhile, 0.005mM of TCPP is dissolved in the first mixed solution, and then is added into the second mixed solution dropwise under stirring to form a third mixed solution; sonicating the third mixed solution for 10 minutes and heating to 80 ℃ for 3 hours; after cooling to room temperature, the resulting Cu-TCPP 2D MOF solution was centrifuged at 8000r.p.m. for 10 minutes, washed with ethanol, redissolved in 10ml ethanol solution and stored at 4 ℃;
after incubating the preserved Cu-TCPP 2D MOF solution drops on the surface of the gold chip, washing the gold chip with deionized water to wash away the redundant Cu-TCPP 2D MOF solution; and then drying the gold chip by nitrogen, and fixing the Cu-TCPP 2D MOF on the surface of the gold chip to form a Cu-TCPP 2D MOF sensitization layer.
4. The preparation method of the SPR sensor based on the two-dimensional metal organic framework, as claimed in claim 3, wherein an incubation box is provided, the incubation box comprises a first box body and a second box body which can be buckled, a gold chip is firstly placed in the first box body, and a Cu-TCPP 2D MOF solution is dripped into the second box body; and then the first box body and the second box body are buckled, so that a gold film of the gold chip is immersed in the Cu-TCPP 2D MOF solution, the incubation box is clamped from two ends by rotating clamping jaws, and the incubation box rotates around the axis of the incubation box for centrifugal incubation.
5. Use of a two-dimensional metal organic framework based SPR sensor as claimed in claim 1 for detecting PD-L1 exosomes, comprising the steps of:
loading a gold chip in an SPR instrument, then flowing a peptide with the function of specifically capturing PD-L1 exosomes through the surface of the gold chip with a sensitization layer, and fixing the peptide on the surface of the gold chip through pi-pi stacking; then the PD-L1 exosome solution to be detected flows through the surface of the gold chip and is detected by an SPR instrument.
6. The use of a two-dimensional metal organic framework based SPR sensor as claimed in claim 5 for detecting PD-L1 exosomes, wherein the peptide is flowed over the surface of the gold chip at a flow rate of 5 μl/min; the PD-L1 exosome test solution was flowed over the gold chip surface at a flow rate of 5 . Mu.L/min.
7. The use of the SPR sensor based on the two-dimensional metal organic framework in detecting PD-L1 exosomes according to claim 6, wherein an incubation box is provided, the incubation box comprises a first box body and a second box body which can be buckled, a gold chip is placed in the first box body, and a Cu-TCPP 2D MOF solution is dripped in the second box body; and then the first box body and the second box body are buckled, so that a gold film of the gold chip is immersed in the Cu-TCPP 2D MOF solution, the incubation box is clamped from two ends by rotating clamping jaws, and the incubation box rotates around the axis of the incubation box for centrifugal incubation.
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