CN114878663A - Bimetal covalent organic framework material and electrochemical luminescence sensor and application thereof - Google Patents
Bimetal covalent organic framework material and electrochemical luminescence sensor and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation and application of functional composite materials, and provides a bimetallic Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite material, and a preparation method and application of an electrochemical luminescence sensor based on the composite material. A bimetal Zn-/Co-porphyrin covalent organic framework is grown on the surface of a carbon nano tube (MWCNTs) in situ, and a composite material integrating a common reaction accelerator and a luminophore is constructed. The bimetal Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite material is coated on a glassy carbon electrode to form a working electrode, is used for constructing a micro RNA electrochemical luminescence sensor, realizes the ultra-sensitive analysis of miR-155, and has good stability and low detection limit, wherein the detection limit is as low as 0.51 fM.
Description
Technical Field
The invention relates to the technical field of preparation and application of functional composite materials, in particular to a bimetal covalent organic framework material, an electrochemical luminescence sensor thereof and application of the bimetal covalent organic framework material in detection of MicroRNA.
Background
MicroRNA (miRNA) is endogenously expressed single-chain non-protein coding RNA and plays an important role in regulating various biological processes such as cell development, differentiation, metabolism, apoptosis and the like. In addition, some researchers have recently discovered specific miRNA sequences in tissue samples as cancer biomarkers and detected tumor-associated mirnas in serum. However, due to the characteristics of small size, high sequence homology, low abundance, easy degradation and the like, accurate and error-free detection of the miRNA is still a challenge. Therefore, the development of an accurate, sensitive and low-cost miRNA quantitative method is of great significance to biological research and clinical diagnosis.
In recent years, CuS nanoparticles, silver ion nanoparticles, and Pt nanoparticles have been used as co-reaction accelerators to construct ECL sensing systems. In particular, in the reaction with S 2 O 8 2- During the reaction, from Co 2+ Converted Co 3+ Can be converted into Co again 2 + Thus containing Co 2+ The nano material can promote more SO 4 - Generation of free radicals, thereby enhancing ECL signaling. At the same time, Co obtained 3+ Quilt H 2 O is reduced to generate a large amount of OH, and S is reduced 2 O 8 2- More SO is obtained 4 - Thus again amplifying the ECL signal. However, in these ECL systems, the emitter is associated with a strongly oxidizing intermediate SO 4 - The short distance between them results in a large energy loss and limits the efficiency of co-reaction acceleration of the co-reaction promoter on the ECL system.
Disclosure of Invention
The invention aims to provide a bimetallic Zn-/Co-porphyrin covalent organic framework composite material for detecting MicroRNA, an electrochemical luminescence sensor and application thereof.
The invention adopts the following technical scheme:
a bimetal Zn-/Co-porphyrin covalent organic framework for detecting MicroRNA is characterized in that the preparation method is as follows:
(1) adding multi-walled carbon nanotubes (MWCNTs), cobalt porphyrin (CoTAPP), zinc porphyrin (ZnTAPP), terephthalaldehyde, 1,3, 5-trimethylbenzene, absolute ethyl alcohol and acetic acid (6M) aqueous solution into a glass-resistant tube. Wherein the mass ratio of the multi-wall carbon nano tubes (MWCNTs), cobalt porphyrin (CoTAPP), zinc porphyrin (ZnTAPP) and terephthalaldehyde is 1: 1.1-1.2: 1.1-1.2: 0.8-1.0, 1,3, 5-trimethylbenzene, absolute ethyl alcohol and acetic acid (6M) aqueous solution in a volume ratio of 5: 5: 1, the volume is 50-60 mL, after ultrasonic treatment is carried out for 3 h, the tube is vacuumized to the internal pressure of 50 mTorr and is sealed by flame, and the tube is heated for 70-80 h at the temperature of 110-;
(2) the product was washed with 1, 4-dioxane, tetrahydrofuran and acetone. And drying in an oven at 50-70 ℃ for 24 h to obtain the bimetallic Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite material.
An electrochemical luminescence sensor for detecting MicroRNA comprises a glassy carbon electrode and a bimetallic Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite material coated on the glassy carbon electrode.
The preparation method of the electrochemical luminescence sensor for detecting MicroRNA comprises the following steps:
(1) the Glassy Carbon Electrode (GCE) is pretreated. 4-6 mu L of bimetal Zn-/Co-porphyrin covalent organic framework composite material is dropped on the surface of a pretreated polished Glassy Carbon Electrode (GCE) and dried in a dark place at room temperature;
(2) 9-11. mu.L glutaraldehyde (2.5 wt%, GA) was dropped onto the electrode surface and incubated for 40-60 min. In the process, the bimetal Zn-/Co-porphyrin covalent organic framework/multi-wall carbon nano tube composite material is modified through a classical GA coupling reaction. Placing the modified polished Glassy Carbon Electrode (GCE) in an H1 solution (10 mu L) with the concentration of 2 mu M at 3-5 ℃ for incubation for 11-13H, and lightly washing with ultrapure water to remove unbound H1;
(3) after washing, nonspecific active sites were removed with 9-11. mu.L of 2 mM 6-Mercaptohexanol (MCH). Modifying the H1 fixed on the surface of the electrode by using 9-11 mu L H2 (2 mu M) and miRNA-155 mixed solution with different concentrations, then incubating for 1-3H under the condition of 37 ℃, and then washing to remove unbound chains;
(4) adding 9-11 mL of a solution containing 0.10M K into an ECL detection unit 2 S 2 O 8 In PBS (0.1M, pH 7.4), the ECL response was measured. The scanning voltage is set to-1.7-0V, the scanning speed is 0.1V/s, and the high voltage of the photomultiplier is 850V.
Compared with the prior art, the invention has the beneficial effects that:
the bimetal Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite material has larger structureSpecific surface area, can fix a large amount of hairpin structure H1, combines excellent ECL performance and a cyclic amplification strategy, and has the concentration of miRNA-155 of 1.0 multiplied by 10 -13 M is increased to 1.0X 10 -5 M, ECL intensity is gradually reduced, and the linear relation with the logarithm value of miRNA-155 concentration is good. The ECL biosensor realizes the ultra-sensitive analysis of miR-155, and the detection limit is as low as 0.51 fM. The strategy provides a new approach for establishing a high-efficiency ECL electrochemiluminescence sensor, and has huge clinical diagnosis potential.
Drawings
FIG. 1 is a transmission electron microscope image of a bimetallic Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite;
FIG. 2 is a high resolution transmission electron microscope image of a bimetallic Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite;
FIG. 3 is a spectrum of XPS measurement;
FIG. 4 is a Fourier transform infrared spectrum of a pristine multiwall carbon nanotube and bimetallic Zn-/Co-porphyrin covalent organic framework/multiwall carbon nanotube composite;
FIG. 5 is an ECL response plot for electrochemiluminescence sensors of different concentrations of miRNA-155;
FIG. 6 is a graph of the linear dependence of ECL intensity on the logarithm of miRNA-155 concentration;
FIG. 7 is a schematic diagram of the specificity of ECL electrochemiluminescence sensors for different interfering substances;
FIG. 8 is a schematic of the stability of an ECL electrochemiluminescence sensor;
FIG. 9 is a graphical representation of long term storage stability of ECL electrochemiluminescence sensors.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the present invention, but the present invention is not limited to the following embodiments, and various modifications and changes can be made in the details of the present description based on different viewpoints and applications without departing from the spirit of the present invention.
It is to be understood that the terminology used in the examples is for the purpose of describing particular embodiments, and is not intended to limit the scope of the present invention, as methods in the following examples without specification to particular conditions are generally in accordance with conventional conditions, or with conditions suggested by the various manufacturers.
When examples are given for ranges of values, it is understood that unless otherwise defined herein, both endpoints of each range of values and any value therebetween can be selected and unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and are described in the specification of the present invention, and any methods, apparatus, and materials similar or equivalent to those described in the examples of the present invention may be used to practice the present invention.
Example 1 preparation method of bimetallic Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite material
1.1
(1) Multiwall carbon nanotubes (10 mg), cobalt porphyrin (11 mg), zinc porphyrin (11 mg), terephthalaldehyde (8 mg), 1,3, 5-trimethylbenzene (25 mL), absolute ethanol (25 mL), and aqueous acetic acid (6M, 5 mL) were mixed in a glass-resistant tube. After 3 h of sonication, the tube was then evacuated to an internal pressure of 50 mTorr, flame sealed and heated at 110 ℃ for 70 h. Subsequently, the product was collected by centrifugation sequentially with 1, 4-dioxane, tetrahydrofuran and acetone. Finally, drying in an oven at 70 ℃ for 24 hours to obtain the expected bimetallic Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite material;
(2) the obtained product is comprehensively characterized, and fig. 1 and fig. 2 are transmission electron microscope and high-resolution transmission electron microscope images of the bimetallic Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite material respectively, and show the crystal structure and morphology of the composite material. High resolution transmission electron microscopy images of bimetallic Zn-/Co-porphyrin covalent organic framework/multiwall carbon nanotube composites have lattice fringes with d-spacing of 0.35 nm, corresponding to the (002) plane of multiwall carbon nanotubes (MWCNTs). The high-resolution transmission electron microscope image also shows that the multi-walled carbon nanotube is modified by the organic framework nanosheet, and the thickness of the coating is about 0.75 nm; as shown in FIG. 3, an XPS measurement spectrogram shows that C, N, O, Zn and Co elements coexist in the structure of the bimetal Zn-/Co-porphyrin covalent organic framework/multi-wall carbon nanotube composite material. As shown in FIG. 4, the Fourier transform infrared spectrogram shows that COF-366-Zn/Co new characteristic peaks are also found at 1338, 1172, 997 and 794 cm-1 in the bimetallic Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite material compared with the original MWCNTs, and the COF-366-Zn/Co derivative is successfully attached to the surface of the MWCNTs
1.2
(1) Multiwall carbon nanotubes (10 mg), cobalt porphyrin (11.5 mg), zinc porphyrin (11.5 mg), terephthalaldehyde (9 mg), 1,3, 5-trimethylbenzene (25.5 mL), absolute ethanol (25.5 mL), and aqueous acetic acid (6M, 5.1 mL) were mixed in a glass-resistant tube. After 3 h of sonication, the tube was then evacuated to an internal pressure of 50 mTorr, flame sealed and heated at 115 ℃ for 73 h. Subsequently, the product was collected by centrifugation sequentially with 1, 4-dioxane, tetrahydrofuran and acetone. Finally, drying in an oven at 60 ℃ for 24 hours to obtain the expected bimetallic Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite material;
(2) the solid product obtained was fully characterized: the results were in accordance with 1.1
1.3
(1) Multiwall carbon nanotubes (10 mg), cobalt porphyrin (12 mg), zinc porphyrin (12 mg), terephthalaldehyde (10 mg), 1,3, 5-trimethylbenzene (26 mL), absolute ethanol (26 mL), and aqueous acetic acid (6M, 5.2 mL) were mixed in a glass-resistant tube. After 3 h of sonication, the tube was then evacuated to an internal pressure of 50 mTorr, flame sealed and heated at 130 ℃ for 80 h. Subsequently, the product was collected by centrifugation sequentially with 1, 4-dioxane, tetrahydrofuran and acetone. Finally, drying in an oven at 60 ℃ for 24 hours to obtain the expected bimetallic Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite material;
(2) the solid product obtained was fully characterized: the results were in agreement with 1.1.
Example 2 electrochemiluminescence sensor preparation of MicroRNA
(1) The Glassy Carbon Electrode (GCE) is pretreated. Then, 5 mu L of the bimetallic Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite material is dropped on the surface of the polished GCE which is pretreated, and the polished GCE is dried in a dark place at room temperature;
(2) mu.L glutaraldehyde (2.5 wt%, GA) was dropped onto the electrode surface and incubated for 50 min. In the process, the bimetal Zn-/Co-porphyrin covalent organic framework/multi-wall carbon nano tube composite material is modified through a classical GA coupling reaction. The modified GCE was incubated in 2. mu.M H1 solution (10. mu.L) at 4 ℃ for 12H, and gently washed with ultrapure water to remove unbound H1;
(3) after washing, nonspecific active sites were removed with 9. mu.L of 2 mM 6-Mercaptohexanol (MCH). Modifying the H1 fixed on the surface of the electrode by using 9 mu L H2 (2 mu M) and miRNA-155 mixed solution with different concentrations, then incubating for 2H at 37 ℃, and then washing to remove unbound strands, thus obtaining the electrochemiluminescence sensor of MicroRNA.
Example 3 electrochemiluminescence sensor Performance testing of MicroRNA
(1) Quantitative detection of a bimetal Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube/K2S 2O8 system on miRNA-155: with the concentration of miRNA-155 from 1.0X 10 -13 M is increased to 1.0X 10 -5 M, ECL intensity gradually decreased. FIG. 5 is a graph of ECL response of an electrochemiluminescence sensor with miRNA-155 at different concentrations, and it can be seen from FIG. 6 that the ECL intensity is in a good linear relationship with the logarithmic value of the miRNA-155 concentration;
(2) selectivity test of ECL electrochemiluminescence sensors: three different mirnas, including miRNA-141, let-7a, and miRNA-21, were used as interfering substances. FIG. 7 is a schematic diagram of the selection of ECL electrochemiluminescence sensor specificity for different interfering substances, showing that the interference is negligible and that the ECL immunoassay has good specificity;
(3) stability test of ECL electrochemiluminescence sensors: the electrode was scanned for 20 cycles with a Relative Standard Deviation (RSD) of 0.29%, and fig. 8 is a graph illustrating the stability of the ECL electrochemiluminescence sensor, showing that the electrode was stable under constant scanning. FIG. 9 is a graph showing long term storage stability, where the response drops to around 98% of the initial response when the immunosensor is stored at 4 ℃ for 3 weeks, indicating that the ECL electrochemiluminescence sensor has acceptable long term stability.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
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Claims (4)
1. A preparation method of a bimetallic Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite material is characterized by comprising the following steps:
(1) adding multi-walled carbon nanotubes (MWCNTs), cobalt porphyrin (CoTAPP), zinc porphyrin (ZnTAPP), terephthalaldehyde, 1,3, 5-trimethylbenzene, absolute ethyl alcohol and acetic acid (6M) aqueous solution into a glass-resistant tube, wherein the mass ratio of the multi-walled carbon nanotubes (MWCNTs), the cobalt porphyrin (CoTAPP), the zinc porphyrin (ZnTAPP) and the terephthalaldehyde is 1: 1.1-1.2: 1.1-1.2: 0.8-1.0, 1,3, 5-trimethylbenzene, absolute ethyl alcohol and acetic acid (6M) aqueous solution in a volume ratio of 5: 5: 1 (volume 50-60 mL), after 3 hours of ultrasonic treatment, vacuumizing the tube to the internal pressure of 50 mTorr and sealing the flame, and heating for 70-80 hours at 110-130 ℃;
(2) and washing the product with 1, 4-dioxane, tetrahydrofuran and acetone in sequence, and drying in an oven at 50-70 ℃ for 24 h to obtain the bimetallic Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite material.
2. An electrochemiluminescence sensor for detecting MicroRNA, comprising: the surface of the pretreated polished Glassy Carbon Electrode (GCE) is coated with a bimetal Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite material.
3. The electrochemiluminescence sensor for detecting MicroRNA of claim 2, wherein the preparation method comprises:
(1) coating 4-6 mu L of bimetallic Zn-/Co-porphyrin covalent organic framework/multi-walled carbon nanotube composite material on the surface of a pretreated polished Glassy Carbon Electrode (GCE), and drying in a dark place at room temperature;
(2) dripping 8-12 mu L of glutaraldehyde (2.5 wt%, GA) on the surface of the electrode, incubating for 40-60 min, modifying the bimetal Zn-/Co-porphyrin covalent organic framework/multi-wall carbon nanotube composite material, placing the modified Glassy Carbon Electrode (GCE) in an H1 solution (8-12 mu L) with the concentration of 2 mu M at 3-5 ℃, incubating for 11-13H, and slightly washing with ultrapure water to remove unbound H1;
(3) removal of non-specific active sites with 8-12. mu.L of 2 mM 6-Mercaptohexanol (MCH);
(4) the electrode surface immobilized H1 was modified with 8-12 μ L H2 (2 μ M) and mixed miRNA-155 solutions of different concentrations, incubated at 36-38 ℃ for 1-3H, and washed to remove unbound strands.
4. The use of an electrochemiluminescence sensor for detecting MicroRNA according to claim 2, wherein the ultrasensitive analysis of miRNA-155 is achieved in the range of 0.10 pM to 10 μ M with a detection limit of 0.51 fM.
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