CN115248237A - Copper-based MOF material modified microelectrode and application thereof in superoxide anion detection - Google Patents
Copper-based MOF material modified microelectrode and application thereof in superoxide anion detection Download PDFInfo
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The application provides a copper-based MOF material modified microelectrode, which comprises the following specific preparation processes: penetrating carbon fibers into the glass capillary hole, and connecting the carbon fibers and the copper wires through silver conductive adhesive; sealing the tip of the micro-electrode with nail polish; removing pollutants on the surface of the tip of the microelectrode; and then placing the microelectrode in a suspension prepared by the copper-based MOF material to prepare the carbon fiber microelectrode wrapped by the copper-based MOF material. The MOF material prepared by using metal copper as a metal center is selected, is a copper element which imitates SOD active center and is easy to change valence, and has good catalytic O 2 ·‑ Disproportionation to O 2 And H 2 O 2 The ability of the cell to perform.
Description
Technical Field
The application relates to the technical field of new materials, in particular to a copper-based MOF material and application thereof in superoxide anion removal, a copper-based MOF material modified microelectrode and application thereof in detection of superoxide anions.
Background
O 2 ·- Belongs to active oxygenThe substance (ROS), a product of a common chemical biological reaction, such as Xanthine Oxidase (XOD) which catalyzes xanthine and O 2 And is critical to the physiological function of the organism. O is 2 ·- Involved in regulating a variety of signaling mechanisms associated with normal cellular and living functions. In order to maintain redox balance in the organism, O was measured 2 ·- And removing excess O 2 ·- Is very important. Therefore, it is designed to detect and eliminate O in biological systems 2 ·- Electrocatalytic and catalytic materials are necessary. The research is more extensive, the sensor is constructed by using biological enzyme (superoxide dismutase SOD), but because the enzyme is expensive, the enzyme can lose activity under severe conditions or long-time storage, and the enzyme activity center is easy to be covered by protein to cause the reduction of electron transfer rate, the invention has the advantages of low price, simple preparation and good stability, and the enzyme-like material is used for replacing SOD to research O in cells and living bodies 2 ·- 。
MOFs are highly ordered crystalline materials formed by coordination of metal ions with organic ligands, which have unique chemical and physical properties (including ultra-high porosity, large specific surface area, tunable structure, high thermal and chemical stability), and thus have attracted a wide range of attention in electrochemical sensors. In the organism, SOD active center has copper element which is easy to be changed in valence, so that the SOD active center has good catalytic O 2 ·- Disproportionation to O 2 And H 2 O 2 Thus, we have designed a MOF material with copper as the metal ion to achieve O 2 ·- Detection of (3).
Disclosure of Invention
The present application is directed to solving, at least to some extent, one of the technical problems in the related art.
Therefore, the application aims to provide a copper-based MOF material and application thereof in superoxide anion removal, a microelectrode modified by the copper-based MOF material and application thereof in detection of superoxide anions, wherein the copper-based MOF material takes copper as a metal center and a conductive ligand thiophene derivative 2,5-dicarboxylic acid-3,4-ethylenedioxythiophene (H) 2 L) synthesizes a copper-based metal organic framework nano material (Cu-MOF) for an organic ligand, the Cu-MOF material is modified on a Carbon Fiber Electrode (CFE) and can be used as an electrocatalyst, and the O can be treated at-0.05V 2 ·- On the other hand, cu-MOF has chemical catalytic properties similar to SOD, i.e. disproportionation and decomposition of O 2 ·- . The Cu-MOF catalyst prepared by the invention has the advantages of simple preparation method, easy operation, excellent electrocatalysis and SOD mimic enzyme performance, and realizes the elimination of O in living cells at the cell and living body level 2 ·- And (4) performing functions.
In order to achieve the purpose, the application provides a microelectrode modified by a copper-based MOF material, and the specific preparation process of the microelectrode is as follows:
penetrating carbon fibers into the glass capillary hole, and connecting the carbon fibers and the copper wires through silver conductive adhesive;
sealing the tip of the micro-electrode with nail polish;
removing pollutants on the surface of the tip of the microelectrode;
and then placing the microelectrode in a suspension prepared by the copper-based MOF material to prepare the carbon fiber microelectrode wrapped by the copper-based MOF material.
Further, contaminants on the surface of the tip of the micro-electrode were removed by applying a constant potential to the micro-electrode in sodium hydroxide.
Further, the concentration of the copper-based MOF material suspension is 50-800 mg/mL.
Further, the copper-based MOF material suspension is prepared by ultrasonically uniformly mixing the copper-based MOF material with 2% Nafion solution.
Further, the specific preparation method of the copper-based MOF material is as follows:
preparing a solution of 2,5-dicarboxylic acid-3,4-ethylenedioxythiophene and N, N-dimethylacetamide according to a molar ratio of 1.5 to 3.5, and dissolving copper chloride dihydrate in distilled water to obtain a substance with a mass concentration of 0.01 to 0.1 mol.L -1 The solution of (1);
and mixing the two solutions obtained after dissolution, adding the two solutions into a polytetrafluoroethylene substrate high-pressure reaction kettle, heating at high temperature to obtain Cu-MOF crystals with good crystallization, and grinding the Cu-MOF crystals to obtain the copper-based MOF material.
Further, the high-temperature heating temperature in the polytetrafluoroethylene substrate high-pressure reaction kettle is 80-150 ℃, and the heating time is 24-60 h.
An application of a microelectrode modified by a copper-based MOF material as an electrochemical sensor in detecting the concentration of superoxide anions in cells and living bodies.
Further, the application of the copper-based MOF material modified carbon fiber microelectrode in detecting the concentration of superoxide anions in cells and living bodies comprises the following specific detection processes: a three-electrode system is adopted, a Cu-MOF modified electrode is used as a working electrode, ag/AgCl is used as a reference electrode, a platinum wire is used as a counter electrode, and O is contained 2 ·- Taking 0.1M phosphate buffer solution with pH =7.5 as electrolyte, and performing timing current scanning under the working potential of-0.05V; at a specific oxygen atom 2 ·- Response currents Ip and O in the concentration range of 20-100uM (micromolar) 2 ·- The concentration is in a good linear relation, and O is obtained by responding to the numerical value of the current Ip 2 ·- And (4) concentration.
Compared with the prior art, the invention has the beneficial effects that:
(1) The MOF material prepared by using metal copper as a metal center is selected, is a copper element which imitates SOD active center and is easy to change valence, and has good catalytic O 2 ·- Disproportionating and decomposing into O 2 And H 2 O 2 The ability of the cell to perform.
(2) The Cu-MOF material synthesized by the method is simple in preparation method, high in yield and purity, and the accurate structure of the MOF can be resolved through single crystal diffraction.
(3) The Cu-MOF material prepared by the invention can be used for detecting and removing O in biological systems 2 ·- 。
Drawings
The above and/or additional aspects and advantages of the present application will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 (A) is a TEM image of a copper-based MOF material synthesized in example 1 of the present invention;
FIG. 1 (B) is an SEM image of a copper-based MOF material synthesized in example 1 of the present invention;
FIG. 1 (C) is an energy dispersive X-ray spectroscopy (EDX) of a copper-based MOF material synthesized in example 1 of the present invention;
FIG. 1 (D) is an XRD pattern and XRD pattern obtained by Diamond software fitting of the copper-based MOF material synthesized in example 1 of the present invention;
FIG. 2 (A) is an SEM image of a bare CFE in example 1 of the present invention;
FIG. 2 (B) is a SEM image of a CFE modified copper-based MOF material of example 1 of the present invention;
FIG. 3 (A) is a 20-cycle voltammogram of Cu-MOF/CFE in 0.1M PBS at a scan rate of 100mV/s in example 1 of the present invention;
FIG. 3 (B) is O in example 1 of the present invention 2 ·- Introducing cyclic voltammograms before and after PBS introduction;
FIG. 3 (C) is a bare CFE vs. O in example 1 of the present invention 2 ·- Cyclic voltammograms of (a);
FIG. 4 is a graph of Cu-MOF/CFE vs. 20 to 100 μ M O at-0.05V (vs. Ag/AgCl) potential in example 1 of the present invention 2 ·- Ampere response graph of (1), O per addition 2 ·- The concentration is 20 mu M;
FIG. 5 is a graph of Cu-MOF/CFE vs. O at-0.05V (vs. Ag/AgCl) potential in example 1 of the present invention 2 ·- The test chart of (1) selectivity and anti-interference performance on other substances, wherein in the test chart, 20 mu M AA, 5 mu M DA, 5 mu M5-HT and 5 mu M H are respectively added at different times in the experimental process 2 O 2 20 μ M UA and 10 μ M O 2 ·- ；
FIG. 6 (A) is a graph showing the amperometric recording of O released by Hela cells at a potential of-0.05V (vs. Ag/AgCl) for Cu-MOF/CFE in example 1 of the present invention 2 ·- Wherein the insets are bright field micrographs of Cu-MOF/CFE and microinjection tubes on Hela cell clusters;
FIG. 6 (B) is a graph of Cu-MOF/CFE recording Fe at-0.05V (vs. Ag/AgCl) in example 1 of the present invention 2+ Stimulation of rat cerebral cortex to release O 2 ·- The microinjection rate is 2.5 muL/min, and the stimulation is carried out at 1300s, 1500s and 1700s respectively, and lasts for 20s each time;
FIG. 6 (C) shows the release of O by Cu-MOF/CFE under stimulation with zymosan A at-0.05V (vs. Ag/AgCl) in example 1 of the present invention 2 ·- Current response of (d);
FIG. 6 (D) is a graph showing the detection of Fe by Cu-MOF/CFE at-0.05V (vs. Ag/AgCl) in example 1 of the present invention 2+ Stimulation of rat cerebral cortex to release O 2 ·- Current response of (d);
FIG. 7 is an experiment in which Cu-MOF is observed to scavenge intracellular ROS under a fluorescence microscope and a corresponding bright field microscope in example 1 of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1:
in this example, copper-based MOF materials were prepared according to the following method, and used to modify microelectrodes, and the obtained microelectrodes were applied to detection of superoxide anions in cells and living bodies, while copper-based MOF materials were used to remove superoxide anions in cells, the detailed preparation method and application were as follows:
the preparation method of the copper-based MOF material (Cu-MOF) comprises the following specific preparation processes:
34.1mg of H 2 L (conductive ligand thiophene derivative 2,5-dicarboxylic acid-3,4-ethylenedioxythiophene) was dissolved in 5mL of N, N-Dimethylacetamide (DMA) while 46.04mg of CuCl was added 2 ·2H 2 O dissolved in 10mL H 2 O is in; and then mixing the two solutions, adding the mixed solutions into a polytetrafluoroethylene substrate high-pressure reaction kettle with the specification of 20mL, heating the mixture at 90 ℃ for 48 hours to obtain well-crystallized Cu-MOF, and grinding the well-crystallized Cu-MOF into Cu-MOF powder in an agate mortar.
The structure of the prepared Cu-MOF material is characterized, and the specific characterization result is as follows:
the Transmission Electron Microscope (TEM) and SEM images of the Cu-MOF are shown in FIG. 1 (A) and FIG. 1 (B), and the synthesized Cu-MOF is seen to be rectangular plate-shaped and has the size of 60-200 nm.
FIG. 1 (C) is the corresponding energy dispersive X-ray spectroscopy (EDX) of the copper-based MOF material, showing that the prepared Cu-MOF consists of C, O, S and Cu element, without any other elements.
FIG. 1 (D) is an XRD pattern of the copper-based MOF material and an XRD pattern obtained by fitting Diamond software, wherein the synthesized Cu-MOF material has a series of sharp diffraction peaks on the XRD pattern, and is the same as a Cu-MOF simulation model (Database Identifier IHONOK, position Number 1040717, cambridge crystalline Data Centre), which shows that the Cu-MOF with the same crystal structure is successfully synthesized, the average grain size is calculated to be about 76.2nm by a Scherrer formula, and the morphology Data size of the Cu-MOF is combined, which shows that perfect Cu-MOF crystals are formed in the hydrothermal reaction process, and each rectangular nanosheet can be considered to be a single-crystal nanomaterial.
(II) the preparation process of the microelectrode modified by the copper-based MOF material comprises the following steps:
drawing a glass capillary tube by using a P-97 type drawing instrument, wherein the set parameters are as follows: HEAT 560, PULL 55, VEL 95, TIME200, P200;
cutting the tip of the capillary tube by a scalpel blade, penetrating carbon fiber with the diameter of 30 mu m into the hole, connecting the carbon fiber and the copper wire by silver conductive adhesive, and sealing the tip of the electrode by nail polish to avoid the phenomenon of siphonage generated when the electrode is immersed in solution and influence on electrochemical measurement;
immersing a microelectrode (CFE) in ethanol to remove nail polish on the surface of carbon fiber, and after drying the surface of the microelectrode, applying a constant potential of 1.5V (vs. Ag/Cl) in 0.1M NaOH for 80s to remove pollutants on the surface of the CFE tip;
uniformly mixing Cu-MOF powder (300 mg/mL) with Nafion accounting for 2 percent, and soaking the CFE in the solution to obtain the Cu-MOF modified carbon fiber microelectrode (Cu-MOF/CFE).
The characterization results of the morphology and the electrochemical performance of the carbon fiber microelectrode modified by the copper-based MOF material are as follows:
in fig. 2 (a), a SEM image of a bare CFE is shown, and fig. 2 (B) is a SEM image of Cu-MOF/CFE, and compared with fig. 2 (a), it is clearly seen that in fig. 2 (B), there are densely-distributed rectangular sheet-shaped Cu-MOFs on the surface of the carbon fiber, which indicates that with the aid of Nafion, cu-MOF can be successfully modified on the CFE, and lays a foundation for subsequent electrochemical experiments.
FIG. 3 (A) is a cyclic voltammogram of Cu-MOF/CFE in 0.1M PBS for 20 consecutive cycles, and it can be seen from this graph that the reduction peak at-0.2V is attributed to Cu II Reduction to Cu 0 The reproducible voltammogram also shows that the Cu-MOF is stable in CFE and is suitable for further in vivo living cell analysis application.
FIG. 3 (B) is a graph in which O is 2 ·- The cyclic voltammograms before and after introduction of PBS, wherein in FIG. 3 (B), the curve of PBS is the cyclic voltammogram of Cu-MOF/CFE in 0.1M PBS, the curve of PBS + XOD is the cyclic voltammogram of PBS containing 1. Mu.L XOD, the curve of PBS + XOD + 400. Mu.M Xanthine is the cyclic voltammogram of PBS containing 1. Mu.L XOD and 400. Mu.M Xanthine, and the graph shows that O is 2 ·- When PBS is introduced, a obvious reduction peak appears at about-0.05V in Cu-MOF/CFE;
also as a control, we tested bare CFE versus O 2 ·- See in particular FIG. 3 (C) (where PBS is the cyclic voltammogram of naked CFE and PBS + XOD + 400. Mu.M Xanthine is the cyclic voltammogram of naked CFE containing 1. Mu.L XOD and 400. Mu.M Xanthine), no significant reduction peak was found at-0.05V, indicating that O 2 ·- Is the reason of the reduction peak generated by the Cu-MOF/CFE, and the results show that the Cu-MOF/CFE can be used for detecting O 2 ·- In vivo analysis and cell analysis applications.
We use the chronoamperometryStudy of Cu-MOF/CFE vs. O 2 ·- The electrochemical sensing performance of the Cu-MOF/CFE shows good linear response (as shown in figure 4) and correlation coefficient (R) in the concentration range of 20-100 mu M 2 ) 0.962, with a minimum detection limit of 5.18 μ M (signal-to-noise ratio = 3); as shown in FIG. 5, the selectivity of Cu-MOF/CFE is characterized, and the sensor is used for detecting AA, DA, UA, 5-HT and H in actual physiological concentration when a constant voltage of-0.05V is applied 2 O 2 The response is far lower than 10 mu M O 2 ·- Indicating that Cu-MOF/CFE is expected to be applied to living cells and in vivo analysis.
(III) applying the Cu-MOF/CFE prepared in the way to detecting O in cells and living bodies 2 ·- The specific detection process is as follows:
for monitoring O in real time 2 ·- The Hela cells were released and cultured in the incubator for two days or more to form cell clusters. Prior to electrochemical measurements, the cell culture broth was replaced with PBS without any protein to prevent contamination of the electrodes. It has been reported in the literature that under zymosan A stimulation, a large amount of O is released from the active cell cluster 2 ·- . As shown in FIGS. 6 (A), 6 (B), 6 (C) and 6 (D), to contain O 2 ·- Taking a phosphate buffer solution with the pH value of 0.1M and 7.5 as an electrolyte, and performing timing current scanning at the working potential of-0.05V; at a specific oxygen atom 2 ·- Response currents Ip and O in the concentration range of 20-100 mu M (micromolar) 2 ·- The concentration shows good linear relation, and the O is obtained by corresponding current measurement 2 ·- Concentration; microelectrodes and microinjection tubes for stimulation are placed close to each other on a cluster of living cells, for stimulating and detecting the release of O from the cells 2 ·- 585s A sharp current drop signal is present, which indicates that O is stimulated by zymosan A 2 ·- Is released in large quantities. O detected on the surface of the electrode 2 ·- The local maximum concentration is about 20 μ M, which is probably due to the vigorous metabolism of cancer cells and the massive biochemical reactions inside the cells. Due to O 2 ·- Diffused into the solution and the current gradually returned to the base level prior to stimulation. Thin and thinThe results of cellular experiments show that the Cu-MOF/CFE has the function of detecting O in real time at the cellular level 2 ·- The ability of the cell to perform.
In-vivo detection of O for testing prepared Cu-MOF/CFE sensor 2 ·- The performance of the compound is detected by an amperometric method by implanting the compound into the cerebral cortex of SD rats and Fe is used 2+ Stimulation to produce O 2 ·- Then to O therein 2 ·- Concentration detection, specific detection conditions and method and application of Cu-MOF/CFE in detecting O in cells 2 ·- The detection method and conditions are the same, and O is obtained by corresponding current measurement 2 ·- Concentration, as shown in FIG. 6 (B), fe was injected with a micro-syringe pump at a rate of 2.5. Mu.L/min in 1300s, 1500s and 1700s, respectively 2+ The rapid decrease of current indicates the production of O in the rat brain 2 ·- (ii) a Then, the current value returns to the baseline because of O 2 ·- May spread throughout the brain region or be decomposed by other protective reducing agents such as AA, GSH, etc. These results indicate that Cu-MOF/CFE can also be successfully applied in vivo experiments. The diversity, adjustability and other excellent properties of the Cu-MOF can expand the application of the MOF in bioanalysis and open up a new path for the design of an electrode interface.
(IV) the Cu-MOF material prepared by the method is used for eliminating O in cells 2 ·- The specific process comprises the following steps:
the Cu-MOF dispersion and Hela cells in the culture medium were incubated for 24 hours, experiments were performed under a fluorescence microscope, and the green fluorescence generated by the reaction of ROS and DCFH-DA was observed. In addition, incubation of cells with β -Lap for 6 hours resulted in the production of large amounts of Reactive Oxygen Species (ROS).
Referring to FIG. 7, (where (E) is a control experiment showing Hela cells without any ROS-initiating and scavenging agents, (F) cells incubated with Cu-MOF, (G) cells incubated with DCFH-DA, (H) cells incubated with DCFH-DA and Cu-MOF), it is noted that there is greenish fluorescence in the untreated cells, where the greenish fluorescence may be derived from ROS indigenous to Hela cells. After incubation with Cu-MOF, the fluorescence intensity decreased. And after the treatment of beta-Lap, the green fluorescence is obviously enhanced, and the large amount of ROS in cells is shown. However, little green fluorescence was observed after β -Lap treatment of Cu-MOF incubated cells, i.e. there were few ROS in the system. These experiments with changes in intracellular ROS concentration, as reflected by fluorescence intensity, provide strong evidence that the Cu-MOF has an excellent ability to scavenge intracellular ROS.
Example 2:
in this example, the copper-based MOF material used in example 1 can be prepared as follows:
34.1mg of H 2 L was dissolved in 5mL of N, N-Dimethylacetamide (DMA) while 92.08mg of CuCl was added 2 ·2H 2 O dissolved in 10mL H 2 O is in; the two solutions were mixed and added to a teflon-lined autoclave with a specification of 20mL, and heated at 90 ℃ for 48h. Well-crystallized Cu-MOF was then obtained and then ground in an agate mortar to Cu-MOF powder.
Example 3:
in this example, the copper-based MOF material used in example 1 can be prepared as follows:
34.1mg of H 2 L was dissolved in 10mL of N, N-Dimethylacetamide (DMA) while 46.04mg of CuCl was added 2 ·2H 2 O dissolved in 10mL H 2 And O, mixing the two solutions, adding the mixture into a polytetrafluoroethylene substrate high-pressure reaction kettle with the specification of 20mL, and heating the mixture for 48 hours at 90 ℃. Well-crystallized Cu-MOF was then obtained and then ground in an agate mortar to Cu-MOF powder.
Example 4:
in this example, the copper-based MOF material used in example 1 can be prepared as follows:
34.1mg of H 2 L was dissolved in 5mL of N, N-Dimethylacetamide (DMA) while 46.04mg of CuCl was added 2 ·2H 2 O dissolved in 10mL H 2 And O, mixing the two solutions, adding the mixed solution into a polytetrafluoroethylene substrate high-pressure reaction kettle with the specification of 20mL, and heating the kettle at the temperature of 120 ℃ for 48 hours. Then obtaining Cu-MOF with good crystallization, and then adding the Cu-MOF into agateGrinding into Cu-MOF powder in a mortar.
Example 5:
in this example, the copper-based MOF material modified microelectrode of example 1 can be prepared as follows:
drawing a glass capillary tube by using a P-97 type drawing instrument, cutting the tip of the capillary tube by using a scalpel blade, penetrating carbon fibers with the diameter of 30 mu m into the hole, connecting the carbon fibers and copper wires by using silver conductive adhesive, sealing the tip of an electrode by using nail polish, and removing the nail polish on the surface of the carbon fibers by using ethanol;
a constant potential of 1.5V (vs. ag/Cl) was applied in 0.1M NaOH for 80s to remove contaminants from the CFE tip surface. Uniformly mixing Cu-MOF powder (600 mg/mL) with Nafion accounting for 2 percent, and soaking the CFE in the solution to obtain the Cu-MOF modified carbon fiber microelectrode (Cu-MOF/CFE).
It should be noted that, in the description of the present application, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. In addition, in the description of the present application, "a plurality" means two or more unless otherwise specified.
Any process or method descriptions in flow charts or otherwise described herein may be understood as representing modules, segments, or portions of code which include one or more executable instructions for implementing specific logical functions or steps of the process, and the scope of the preferred embodiments of the present application includes other implementations in which functions may be executed out of order from that shown or discussed, including substantially concurrently or in reverse order, depending on the functionality involved, as would be understood by those reasonably skilled in the art of the present application.
In the description herein, reference to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Although embodiments of the present application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present application, and that variations, modifications, substitutions and alterations may be made to the above embodiments by those of ordinary skill in the art within the scope of the present application.
Claims (8)
1. A copper-based MOF material modified microelectrode is characterized in that the specific preparation process of the microelectrode is as follows:
penetrating carbon fibers into the glass capillary hole, and connecting the carbon fibers and the copper wires through silver conductive adhesive;
sealing the tip of the micro-electrode with nail polish;
removing pollutants on the surface of the tip of the microelectrode;
and then placing the microelectrode in a suspension prepared by the copper-based MOF material to prepare the carbon fiber microelectrode wrapped by the copper-based MOF material.
2. The copper-based MOF material modified microelectrode of claim 1, wherein the contaminant on the surface of the tip of the microelectrode is removed by applying a constant potential to the microelectrode in sodium hydroxide.
3. The copper-based MOF material modified microelectrode of claim 1, wherein the concentration of the suspension of copper-based MOF material is from 50 to 800mg/mL.
4. The copper-based MOF material modified microelectrode of claim 1 or 3, wherein the suspension of copper-based MOF material is prepared by ultrasonically and uniformly mixing the copper-based MOF material with a 2% solution of Nafion.
5. The copper-based MOF material modified microelectrode of any of claims 1 to 3, wherein the copper-based MOF material is prepared by a specific method comprising:
preparing a solution of 2,5-dicarboxylic acid-3,4-ethylenedioxythiophene and N, N-dimethylacetamide according to a molar ratio of 1.5 to 3.5, and dissolving copper chloride dihydrate in distilled water to obtain a substance with a mass concentration of 0.01 to 0.1 mol.L -1 The solution of (1);
and mixing the two solutions obtained after dissolution, adding the two solutions into a polytetrafluoroethylene substrate high-pressure reaction kettle, heating at high temperature to obtain Cu-MOF crystals with good crystallization, and grinding the Cu-MOF crystals to obtain the copper-based MOF material.
6. The copper-based MOF material modified microelectrode of claim 5, wherein the polytetrafluoroethylene substrate high pressure reaction kettle is heated at a temperature of 80 to 150 ℃ for 24 to 60 hours.
7. Use of the copper-based MOF material modified microelectrode of claim 1 as an electrochemical sensor for detecting the concentration of superoxide anions in cells and living organisms.
8. The application of the copper-based MOF material modified carbon fiber microelectrode in detecting the concentration of superoxide anions in cells and living bodies is characterized in that the specific detection method is as follows: a three-electrode system is adopted, a Cu-MOF modified electrode is used as a working electrode, ag/AgCl is used as a reference electrode, a platinum wire is used as a counter electrode, and O is contained 2 ·- Taking a phosphate buffer solution with the pH value of 0.1M and 7.5 as an electrolyte, and performing timing current scanning at the working potential of-0.05V; at a specific oxygen atom 2 ·- Response currents Ip and O within the concentration range 2 ·- The concentration is in a good linear relation, and O is obtained by responding to the numerical value of the current Ip 2 ·- And (4) concentration.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370943A (en) * | 2014-11-03 | 2015-02-25 | 南开大学 | Preparation method and application of [Cu2(HL)2(Mu2-OH)2(H2O)5] |
| CN107478697A (en) * | 2017-07-27 | 2017-12-15 | 华中科技大学 | Rime shape metal organic frame composite micro-electrode and in-situ preparation method and application |
| CN109406600A (en) * | 2018-09-19 | 2019-03-01 | 新乡医学院 | It is a kind of can be in the production method of body real-time detection hydrogen peroxide microelectrode |
| CN110726762A (en) * | 2019-08-30 | 2020-01-24 | 南京理工大学 | Application of copper-based three-dimensional metal organic framework material in enzyme simulation |
-
2021
- 2021-04-28 CN CN202110469893.4A patent/CN115248237B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370943A (en) * | 2014-11-03 | 2015-02-25 | 南开大学 | Preparation method and application of [Cu2(HL)2(Mu2-OH)2(H2O)5] |
| CN107478697A (en) * | 2017-07-27 | 2017-12-15 | 华中科技大学 | Rime shape metal organic frame composite micro-electrode and in-situ preparation method and application |
| CN109406600A (en) * | 2018-09-19 | 2019-03-01 | 新乡医学院 | It is a kind of can be in the production method of body real-time detection hydrogen peroxide microelectrode |
| CN110726762A (en) * | 2019-08-30 | 2020-01-24 | 南京理工大学 | Application of copper-based three-dimensional metal organic framework material in enzyme simulation |
Non-Patent Citations (1)
| Title |
|---|
| RAJESH SEENIVASAN 等: "Nanotechnology for Electroanalytical Biosensors of Reactive Oxygen and Nitrogen Species", 《THE CHEMICAL RECORD》, pages 886 - 901 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116251624A (en) * | 2023-05-15 | 2023-06-13 | 四川大学 | Method for preparing SOD artificial enzyme and improving activity of Mn-based enzyme-imitating SOD |
| CN116251624B (en) * | 2023-05-15 | 2023-07-07 | 四川大学 | Method for preparing SOD artificial enzyme and improving activity of Mn-based enzyme-imitating SOD |
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