CN113189166A - Application of nano enzyme electrode in detection of catechol - Google Patents
Application of nano enzyme electrode in detection of catechol Download PDFInfo
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- CN113189166A CN113189166A CN202010033698.2A CN202010033698A CN113189166A CN 113189166 A CN113189166 A CN 113189166A CN 202010033698 A CN202010033698 A CN 202010033698A CN 113189166 A CN113189166 A CN 113189166A
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Abstract
The application discloses an application of a nano enzyme electrode in pyrocatechol detection. The electrode substrate of the nanoenzyme electrode is modified with a metal organic framework material, and the framework of the metal organic framework material contains porphyrin rings. The nano enzyme electrode realizes the detection of catechol in a solution to be detected, has high sensitivity, high selectivity and wide linear range, and is simple to manufacture and low in cost.
Description
Technical Field
The application relates to a nano enzyme electrode, a biosensor, a preparation method and an application thereof, and belongs to the technical field of biosensors.
Background
Ortho-phenol is an important phenolic compound, is widely applied to the synthesis of chemical materials, and is a substance which has great harm to human bodies and the environment, so that the realization of quick and effective detection of the ortho-phenol is very important. The traditional pyrocatechol detection mainly comprises a high performance liquid chromatography, a fluorescence method, a spectrophotometry method and a capillary electrophoresis method, but the methods generally have the defects of long time consumption, expensive equipment, complex operation and the like. Compared with these methods, the electrochemical sensor method has attracted more and more attention by people due to its advantages of fast response, low cost, simple operation, fast analysis speed, high sensitivity, good selectivity, etc.
Many studies on the detection of catechol by electrochemical sensors have been reported. The enzyme-based sensor is a biosensor widely applied, has the advantages of high sensitivity, strong specificity, low detection limit, good selectivity, simple operation, convenience in carrying, outdoor online continuous monitoring and the like, and is a biosensor for realizing commercialization at the earliest time. Tu et al immobilized horseradish peroxidase on an agarose/carbon nanotube complex modified electrode to construct a novel amperometric biosensor for catechol detection. Shunich et al constructed enzyme-based catechol sensors based on L-ascorbic acid and tyrosinase. However, the traditional enzyme is expensive and the stability is seriously influenced by external conditions such as temperature, pH and the like, so that the traditional enzyme-based sensor is easy to inactivate in the enzyme immobilization process, and is difficult to be widely applied. With the development and mature application of nanomaterials, novel nanoenzymes have been widely used since the discovery in 2007. Metal organic framework Materials (MOFs) are porous crystalline materials formed by metal ions and organic ligands, and both PA-Tb-Cu MOF and Fe-MIL-88NH2 MOF materials have been reported to have nanoenzyme properties. MOFs have the characteristics of large specific surface area, special pore structure, high stability and richer structure. Based on these remarkable characteristics, the electrochemical sensor has wide application. However, no report is found on the current nanoenzyme electrode suitable for detecting catechol.
Disclosure of Invention
According to one aspect of the application, an application of a nano enzyme electrode in detecting catechol is provided, a metal organic framework material is modified on an electrode substrate of the nano enzyme electrode, a skeleton of the metal organic framework material contains a porphyrin ring, and due to the existence of the porphyrin ring, when the electrode is used as a working electrode, catechol in a solution to be detected can be rapidly diffused into a gap of the electrode, so that electrode current changes, and therefore detection of the catechol in the solution to be detected is achieved.
Optionally, the method specifically includes the following steps:
the nano enzyme electrode is used as a working electrode, and the working electrode is partially or completely inserted into a solution to be detected, wherein the solution to be detected comprises the catechol;
and detecting a current signal of the working electrode, and determining the concentration of catechol in the solution to be detected according to the current signal.
Optionally, the metal center of the metal-organic framework material is selected from group ivb metal elements, preferably zirconium.
Optionally, the backbone contains at least one of tetra (4-carboxyphenyl) porphyrin, tetra-phenyl porphyrin, tetra (4-hydroxyphenyl) porphyrin;
optionally, the preparation method of the metal-organic framework material comprises the following steps:
reacting a mixed solution containing a ligand, a connecting agent and a zirconium source to obtain the metal organic framework material;
wherein the ligand is a compound containing a porphyrin ring; the compound containing porphyrin ring is selected from at least one of tetra (4-carboxyphenyl) porphyrin, tetra-phenyl porphyrin and tetra (4-hydroxyphenyl) porphyrin;
the connecting agent is an aromatic compound with carboxyl;
the aromatic compound with carboxyl is selected from at least one of benzoic acid and p-methyl benzoic acid.
Alternatively, the solvent of the mixed solution is preferably DMF.
Optionally, the electrode substrate may be a glassy carbon electrode, a gold electrode, a platinum electrode, or other conductive electrodes.
Optionally, the metal-organic framework material is fixed on the electrode substrate through a film forming matter;
optionally, the film forming material is selected from at least one of chitosan, bovine serum albumin and perfluorinated sulfonic acid proton membrane;
optionally, the mass ratio of the metal organic framework material to the film forming material is 0.02-1.5: 10, preferably 0.03-0.08: 10, and the amount of the film forming material is 0.001-0.1 g/electrode substrate.
Optionally, Ag/AgCl electrode, non-aqueous phase Ag/Ag+The electrode, the saturated calomel electrode and the mercury/mercurous sulfate electrode are used as reference electrodes.
In one embodiment, the metal-organic framework material is PCN222, which is used for detecting catechol. Alternatively, PCN222 is a typical mesoporous MOF material consisting essentially of Zr6+And the detection probe is connected with a tetra (4-carboxyl phenyl) porphyrin (TCPP) ligand, and the catechol is detected by using the prepared high-porosity PCN222 nano material modified electrode. The results show that the sensor based on PCN222 has good repeatability, sensitivity and detection limit.
Optionally, the fixing the metal-organic framework material on the electrode substrate by a film forming material specifically includes:
dissolving a film forming material and the metal organic framework material in an organic solvent to obtain a coating;
dripping the coating on the electrode substrate, and drying;
the organic solvent is at least one of NN-dimethylformamide, methanol, ethanol and acetonitrile.
The beneficial effects that this application can produce include:
(1) the nano enzyme electrode provided by the application has high sensitivity, selectivity and wide linear range when used for detecting catechol, and is simple to manufacture and low in cost.
(2) The application provides a simple, convenient, economic and stable method for detecting catechol, and can be widely applied to the fields of environment and food safety.
(3) The detection line of the nano enzyme electrode to pyrocatechol provided by the application can reach 10 mu mol L-1。
Drawings
FIG. 1 is a reaction scheme of example 1;
FIG. 2 is a graph showing the color change before and after the reaction in example 1;
FIG. 3 is a representation of PCN222 synthesized in example 1, wherein FIGS. 3A and 3B are SEM images of PCN222 and FIGS. 3C and 3D are TEM images of PCN 222;
FIG. 4A is a UV/Vis spectrum and FIG. 4B is a Fourier Infrared spectrum of PCN222 synthesized in example 1;
FIG. 5A is a cyclic voltammogram of the GC electrode matrix, chitosan/GC, and the chitosan-PCN 222/GC electrode prepared in example 2; FIG. 5B is a plot of cyclic voltammetry for the chitosan-PCN 222/GC electrode and GC electrode matrix prepared in examples 2, 3 and 4; FIG. 5C is a graph of the trend of peak current with PCN222 concentration; FIG. 5D is a cyclic voltammogram at different scan speeds; FIG. 5E is a graph of current intensity versus scan speed;
FIG. 6 shows a chitosan-PCN 222/GC sensor pair of 10. mu. molL-1A graph of the electrical response of catechol and other phenols of (a);
fig. 7A is a graph of current as a function of catechol concentration and fig. 7B is a calibration curve of steady state current versus catechol concentration.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the starting materials in the examples of the present application were all purchased commercially, wherein:
chitosan was purchased from sigma; n, N-Dimethylamide (DMF) (ACS Spectroscopy grade, 99.8%), benzoic acid (BA, 99.5%) and zirconium oxychloride octahydrate (ZrOCl)2·8H2O, 98%) was purchased from alatin; tetrakis (4-carboxyphenyl) porphyrin (TCPP) (97.0%) was purchased from TCI; deionized water is drinking water with 18.2M omega of resistance; glassy Carbon (GC) was purchased from model CHI103 of chenhua corporation, shanghai.
HT7700 Transmission Electron Microscope (TEM) (Hitachi, Japan), SU8220 Scanning Electron Microscope (SEM) (Hitachi, Japan), ultraviolet/visible spectrophotometer (UV/Vis) (Jena, Germany), Fourier transform Infrared Spectrophotometer (FTIR) (Shimadzu, Japan), 4-20R high-speed centrifuge (Hennuo instruments), DF-II high-temperature oil bath (white Tower New treasure Instrument works, jin Tan), SB-5200DTN ultrasonic cleaning machine (Ningbo Xinzhi Biotech), CHI 660B electrochemical workstation (Shanghai Chenghua instruments, Ltd.).
Example 1PCN222 Synthesis
50mg of TCPP, 150mg of zirconium oxychloride octahydrate and 2.8g of benzoic acid are dissolved in 50mL of DMF containing 1% (volume concentration) of deionized water, the mixture is subjected to ultrasonic treatment at 25 ℃ for 10min to be uniformly mixed, then the mixture is transferred into an oil bath kettle at 90 ℃ to react for 4h, and after the reaction is finished, the mixture is centrifuged at 13000rpm/min for 30min and washed with DMF for 3 times to obtain the target product PCN 222. The reaction mechanism of example 1 is shown in FIG. 1, and the color change is shown in FIG. 2, wherein FIG. 2a shows that the reaction system is green before the reaction, and FIG. 2b shows that the reaction system is purple after the reaction.
Example 2
Polishing Glassy Carbon (GC) on chamois leather with 0.35 μm polished aluminum powder for 6min, ultrasonic cleaning the polished GC with deionized water and absolute ethyl alcohol for 3 times, and placing the GC in 1mol L-1The sulfuric acid solution is prepared by cyclic voltammetry at a potential of 0-1.7V to 0.1Vs-1Scanning for 30 times at the scanning speed, ultrasonically cleaning and airing to obtain the GC electrode matrix. The PCN222 obtained in example 1 was dissolved in water by sonication to give a concentration of 50mgL-1Dissolving chitosan in water to obtain a chitosan solution with the mass concentration of 1%, and mixing the obtained PCN222 solution and the chitosan solution according to the volume ratio of 1: 1 to obtain a PCN222 and chitosan mixed solution, dripping 6 mu L of the PCN222 and chitosan mixed solution on a GC electrode substrate, and naturally airing at normal temperature to obtain the chitosan-PCN 222/GC electrode.
Example 3
The preparation method is essentially the same as that of example 2, except that the concentration of the PCN222 solution is 1gL-1。
Example 4
The preparation method was substantially the same as in example 2, except that the concentration of the PCN222 solution was 500mgL-1。
Characterization of PCN222
The surface morphology, size and microstructure of the PCN222 nanoparticles synthesized in example 1 were characterized by Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM), in which the target product PCN222 prepared in example 1 was dissolved in 20ml dmmf. As shown in FIG. 3, the PCN222 is substantially elliptical in shape, approximately 400nm in size, and relatively uniform in size. The cell heights of PCN222 are distributed along the length axis [111] of PCN 222.
As shown in FIG. 4A, the ultraviolet-visible absorption spectrum of PCN222 shows a typical absorption peak of porphyrin-type MOFs, the main peak is 435nm, and the absorption peaks of 4Q bands are 500-700 nm. PCN222 was further characterized by FTIR spectroscopy. As shown in FIG. 4B, the absorption peaks of the macrocyclic skeleton appear at 1710, 1659, 1558 and 1416cm respectively-1The O-H stretching peak appears at 1000cm-1The absorption peak of benzene ring in TCPP appears at 871cm-1And 780cm-1。
Characterization of Chitosan-PCN 222/GC electrodes
At 5mmol L-1In the potassium ferricyanide solution, cyclic voltammetry measurements were performed on the GC electrode substrate, the chitosan/GC (same as the chitosan-PCN 222/GC electrode in example 2, except that no PCN222 was added) and the chitosan-PCN 222/GC electrode prepared in example 2, respectively. As shown in FIG. 5A, the difference in the potentials at the redox peak locations of the GC electrode substrates (indicated by bare in FIG. 5) is approximately equal to 65mV, indicating that the electrode GC electrode substrates have been completely cleaned by a sulfuric acid solution. Comparing chitosan/GC (denoted chitosan in FIG. 5) with the GC electrode matrix (denoted pcn222+ chitosan in FIG. 5) it can be seen that the peak is instead reduced when chitosan is modified on the electrode, since chitosan blocks [ Fe (CN) ] in potassium ferricyanide solution6]3-/4The ions are transferred to the electrode surface. When the chitosan-PCN 222 is modified on the electrode, the current is significantly increased, which proves the high conductivity of the PCN222, and at the same time, the pore structure is further strengthened because it has a special pore structure allowing ions in the solution to pass through. These porous structures and interconnecting channels allow for rapid ion transfer in the electrolyte, which is desirable for enhancing electrochemical studentsThe transduction ability of the biosensor is very important.
Cyclic voltammetry measurements of the chitosan-PCN 222/GC electrodes and GC electrode matrices prepared in examples 2, 3, and 4 are shown in FIG. 5B. The chitosan-PCN 222/GC electrodes prepared in examples 2, 3 and 4 are represented by PCN222(50 μ g), PCN222(1mg) and PCN222(500 μ g), respectively, in fig. 5. the peak current versus PCN222 concentration curve (fig. 5C) shows that the peak current is rather reduced with increasing PCN222 concentration, which indicates that the amount of PCN222 has a significant effect on the sensitivity. When the mass ratio of the PCN222 to the chitosan is 0.03-0.08: 10, the sensitivity is optimal. The effect of sweep rate on peak current was then further explored using cyclic voltammetry between 100mV and 600mV, as shown in FIGS. 5C, 5D and 5E, showing a clear linear increase in peak current versus sweep rate, indicating [ Fe (CN)6]3-/4Adsorption on chitosan-PCN 222/GC was controlled by the sweep rate.
Example 5 Chitosan-PCN 222/GC sensor
The embodiment provides a chitosan-PCN 222/GC sensor, which comprises a working electrode, a reference electrode and an auxiliary electrode, wherein the working electrode is provided by embodiments 2-4, the reference electrode is an Ag/AgCl electrode, a platinum wire is an auxiliary electrode, a three-electrode system is formed, when the chitosan-PCN 222/GC sensor is used for measurement, part or all of the working electrode is inserted into a solution to be measured, a current signal of the working electrode is detected, and the concentration of a compound containing phenolic hydroxyl in the solution to be measured is determined according to the current signal.
Example 6 biosensor for detection of catechol content
Catechol is an important chemical synthetic material, but has great harm to human body, so that the realization of quick and effective detection of catechol is particularly important. Based on the chitosan-PCN 222/GC sensor prepared in example 5, the catechol content was measured by chronoamperometry. In the optimization of the working potential, 0.1V (relative to Ag/AgCl) was chosen as the constant working potential, since the background current was small. When a working potential is applied, the surface of the working electrode is charged and the material modifying the surface of the working electrode is activated. The charge transfer process of PCN222 corresponds to a selective reaction,allowing ions of a particular species to adsorb on the surface. To study the selectivity of the chitosan-PCN 222/GC sensor, 10. mu.L of catechol, bisphenol A, phenol, and nonylphenol were added to 8mL of 50mmol L-1Different liquids to be detected are obtained from the PBS solution, and the liquids to be detected are respectively tested by adopting a chitosan-PCN 222/GC sensor, as shown in figure 6, except catechol, other phenols can not generate obvious electric signal response. This indicates that PCN222 has good selectivity for catechol.
FIG. 7A is a time-current curve of the chitosan-PCN 222/GC sensor for detecting catechol. The concentration of the solution is 50mmol L per 50s to 8mL-110 mu L of catechol is added into the PBS solution and stirred evenly. The response time of the chitosan-PCN 222/GC sensor to catechol, i.e., the time taken for the steady state current to reach 95%, was 4s, and the rapid response of the chitosan-PCN 222/GC sensor was probably due to the rapid diffusion of catechol in the external solution into the pores of the PCN 222. Figure 7B is a calibration curve of current with catechol concentration. The chitosan-PCN 222/GC sensor has a wide linear range of 10-70 mu M and a signal sensitivity of 15.42mAcm-1M-1. This indicates that PCN222 can improve signal sensitivity.
The detection line is the main parameter of the biosensor, and the detection line of the chitosan-PCN 222/GC biosensor for catechol can reach 10 mu molL-1。
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. The application of the nano enzyme electrode in detecting catechol is characterized in that a metal organic framework material is modified on an electrode substrate of the nano enzyme electrode, and the skeleton of the metal organic framework material contains porphyrin rings.
2. The use according to claim 1, characterized in that it comprises in particular the following steps:
the nano enzyme electrode is used as a working electrode, and the working electrode is partially or completely inserted into a solution to be detected, wherein the solution to be detected comprises the catechol;
and detecting a current signal of the working electrode, and determining the concentration of catechol in the solution to be detected according to the current signal.
3. The use of claim 1, wherein the backbone comprises at least one of tetra (4-carboxyphenyl) porphyrin, tetra-phenyl porphyrin, tetra (4-hydroxyphenyl) porphyrin.
4. Use according to claim 1, wherein the metal-organic framework material is fixed on the electrode substrate by means of a film former.
5. The use according to claim 4, wherein the membrane forming material is at least one selected from the group consisting of chitosan, bovine serum albumin, and perfluorosulfonic proton membrane.
6. The use according to claim 4, wherein the mass ratio of the metal organic framework material to the film former is 0.02-1.5: 10.
7. The use according to claim 6, wherein the mass ratio of the metal organic framework material to the film former is 0.03-0.08: 10.
8. The use according to claim 4, wherein the amount of the film-forming material is 0.001 to 0.1 g/electrode substrate.
9. Use according to claim 1, wherein the metal organic framework material is PCN 222.
10. The nanoenzyme electrode application as claimed in claim 2, wherein the nanoenzyme electrode is prepared from Ag/AgCl electrode and non-aqueous phase Ag/Ag+The electrode, the saturated calomel electrode and the mercury/mercurous sulfate electrode are used as reference electrodes.
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| CN115073756A (en) * | 2021-10-28 | 2022-09-20 | 中国人民解放军国防科技大学 | Metal organic framework nano material and preparation method thereof, and composite material loaded with metal organic framework nano material and preparation method thereof |
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| CN115073756A (en) * | 2021-10-28 | 2022-09-20 | 中国人民解放军国防科技大学 | Metal organic framework nano material and preparation method thereof, and composite material loaded with metal organic framework nano material and preparation method thereof |
| CN115073756B (en) * | 2021-10-28 | 2023-09-12 | 中国人民解放军国防科技大学 | Metal-organic framework nano material and preparation method thereof, composite material loaded with metal-organic framework nano material and preparation method thereof |
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