CN114835913A - Colorimetric analysis method of copper-cobalt bimetallic organic framework nanoenzyme and organophosphorus colorimetric sensor thereof - Google Patents
Colorimetric analysis method of copper-cobalt bimetallic organic framework nanoenzyme and organophosphorus colorimetric sensor thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000004737 colorimetric analysis Methods 0.000 title claims abstract description 20
- 238000001514 detection method Methods 0.000 claims abstract description 31
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 24
- 239000011574 phosphorus Substances 0.000 claims abstract description 24
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- 239000011259 mixed solution Substances 0.000 claims description 13
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 9
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- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 6
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- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
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- UCDLBNQQNRQANR-UHFFFAOYSA-N 4-(4-amino-3-methylphenyl)-2,6,6-trimethylcyclohexa-2,4-dien-1-amine Chemical compound CC1(C)C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 UCDLBNQQNRQANR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a colorimetric analysis method of a copper-cobalt bimetallic organic framework nanoenzyme and an organophosphorus colorimetric sensor thereof. The CuCo-ZIF nanoenzyme synthesized by the method has a regular cubic structure, so that the CuCo-ZIF nanoenzyme has a larger specific surface area, high porosity and high stability, and the peroxidase activity of the nanoenzyme is greatly improved. And then the nano enzyme is used for constructing a colorimetric sensor for colorimetric analysis to directly and visually detect the organic phosphorus, so that the high-sensitivity detection of the organic phosphorus can be quickly, simply and visually realized, and the nano enzyme has the advantages of good stability, low detection limit, high sensitivity, good specificity and the like.
Description
Technical Field
The invention relates to the technical field of colorimetric analysis, in particular to a colorimetric analysis method of a copper-cobalt bimetallic organic framework nanoenzyme and an organophosphorus colorimetric sensor thereof.
Background
Organophosphorus pesticides are widely used in agriculture, animal husbandry, public gardens and other scenes as one of the most common pesticides. Meanwhile, the abuse of multi-occasion organophosphorus pesticides also causes pollution to water resources, fruits, vegetables and processed foods, which causes great damage to the ecological environment and human health. Therefore, it is important to detect the content of organic phosphorus in the environment efficiently and sensitively. Colorimetric sensors have attracted considerable interest in the detection of organophosphorus concentrations in samples due to their high sensitivity, rapid assay speed, high stability, and low cost. Acetylcholinesterase is commonly used in traditional organophosphorus colorimetric detection; however, acetylcholinesterase, a natural enzyme, has a very limited range of activity and interference resistance. In the prior art, a report related to direct colorimetric detection of fresh organophosphorus.
In recent years, artificial nano mimic enzymes have attracted much attention because they exhibit catalytic efficiency and enzymatic reaction kinetics similar to natural enzymes, are more stable than natural enzymes, and can still maintain high catalytic activity in a strong acid and alkali or in a larger temperature range. The Metal Organic Frameworks (MOFs) have the superior performances of high porosity, large specific surface area, high stability, adjustable pore size, special catalytic activity and the like, and are developed by extensive researchers to be used as nanoenzymes. In addition, bimetallic MOF nanoenzymes are widely used in the fields of catalysis, cancer therapy and sensors. To date, researchers have synthesized bimetallic MOF nanoenzymes of different morphologies using synthetic methods such as solvothermal methods, chemical deposition methods, ultrasound-assisted methods, and the like.
The invention combines a soft template strategy and a one-pot synthesis method, and prepares the novel copper-cobalt bimetallic organic framework nanoenzyme (CuCo-ZIF) by using copper nitrate trihydrate as a copper source and cobalt nitrate hexahydrate as a cobalt source. Application of Organic Phosphorus (OPs) to CoCu-ZIF bimetallic nanoenzyme in 3,3',5, 5-Tetramethylbenzidine (TMB) -hydrogen peroxide (H) 2 O 2 ) Inhibition of catalytic activity in the reaction. The CuCo-ZIF nano-enzyme can be in the presence of H 2 O 2 In the presence of the oxidation-accelerating TMB, an intense blue color is rapidly produced. However, in the presence of OPs, the degree to which the reaction develops blue is proportionally reduced as the concentration of OPs increases. So far, CuCo-ZIF nanoenzyme can not be used for direct organophosphorus colorimetric sensing. The CuCo-ZIF nanoenzyme prepared by the invention has excellent peroxidase activity and good stability and tolerance, and can be used for directly detecting organic phosphorus. Based on the excellent performance of the nano enzyme, the nano enzyme can be well applied to the field of colorimetric sensors.
Disclosure of Invention
Aiming at the problems of small activity range and poor anti-interference capability of organic phosphorus colorimetric detection by utilizing natural enzyme in the prior art, the invention firstly provides the copper-cobalt bimetallic organic framework nano enzyme, and the excellent enzyme-like catalytic performance is shown by utilizing the large specific surface area, good stability and good catalytic performance of a metal-organic framework composite material interface.
The invention aims to realize the copper-cobalt bimetallic organic framework nanoenzyme, which is characterized in that Cetyl Trimethyl Ammonium Bromide (CTAB) is used as a soft template, 2-methylimidazole is used as an organic ligand, copper nitrate is used as a copper source, cobalt nitrate is used as a cobalt source, deionized water is used as a solvent to synthesize the copper-cobalt bimetallic organic framework nanoenzyme (CuCo-ZIF), and the particle size of the copper-cobalt bimetallic organic framework nanoenzyme is 450-550 nm.
The specific synthetic method of the copper-cobalt bimetallic organic framework nanoenzyme comprises the following steps:
step one, mixing a mixture of a molar ratio of 20-25: 30-35: 1, dissolving copper nitrate, cobalt nitrate and CTAB in ultrapure water, and ultrasonically vibrating the system for 10min to form solution A; dissolving 2-methylimidazole in ultrapure water according to the concentration of 0.75-0.8M, and carrying out ultrasonic vibration for 10min to form a solution B;
and secondly, adding the solution B into the solution A under the stirring state, mixing and stirring for 1 h at normal temperature, then, centrifugally separating a solid phase at 8000 rpm, washing with ethanol for three times, and finally, drying the obtained solid in a vacuum oven to obtain the copper-cobalt bimetallic organic framework nano enzyme.
Further, the concentration of copper nitrate in the solution A is 4-5 mM, and after the solution A and the solution B are mixed, the molar ratio of 2-methylimidazole, copper nitrate, cobalt nitrate and CTAB in the mixed solution is 2500-3000: 20-25: 30-35: 1.
and further, in the second step, the temperature of vacuum drying is 60-70 ℃, and the drying time is 10-12 h.
The copper-cobalt bimetallic organic framework nanoenzyme (CuCo-ZIF) is prepared by combining a soft template strategy and a one-pot synthesis method, and using copper nitrate trihydrate as a copper source and cobalt nitrate hexahydrate as a cobalt source. On one hand, the metal organic framework material has the advantages of high porosity, large specific surface area, high stability, adjustable pore diameter, special catalytic activity and the like. On the other hand, the bimetallic organic framework composite material with two metal centers has more catalytic active sites and adsorption sites. Therefore, the metal-organic framework composite material interface of the copper-cobalt nano particles synthesized by the method has large specific surface area, good stability, good catalysis, excellent enzyme-like catalysis performance, good stability and tolerance, and can be well applied to the field of colorimetric sensors based on the excellent performance of the nano enzyme.
The invention also provides a colorimetric analysis method of the organophosphorus colorimetric sensor based on the copper-cobalt bimetallic organic framework nanoenzyme, which is characterized by comprising the following steps of:
(1) ultrasonically dispersing the copper-cobalt bimetallic organic frame nanoenzyme in deionized water to obtain a uniform dispersion liquid with the dispersion concentration of 1-2 mg/mL;
(2) taking a plurality of parts of the copper-cobalt bimetallic organic framework nano enzyme dispersion liquid in the step (1), respectively adding a phosphoric acid buffer solution and quantitative volumes of organic phosphorus solutions with different concentrations, and vibrating and dispersing to obtain a uniform mixed liquid;
(3) respectively adding TMB solution and H into the mixed solution in the step (2) 2 O 2 The solutions are vibrated, dispersed and mixed uniformly, and after the reaction is carried out for 15-20 minutes at room temperature, an ultraviolet-visible spectrophotometer is used for detecting the absorbance of each solution;
(4) and (4) drawing a linear curve according to the relation between the peak value change of the absorbance of each solution in the step (3) and the corresponding concentration of the organophosphorus solution, and taking the linear curve as a standard curve for organophosphorus colorimetric detection.
Further, the phosphoric acid buffer solution is composed of 0.1M Na 2 HPO 4 Solution and 0.1M and NaH 2 PO 4 The solution is mixed, and the pH of the mixed solution is 4-4.5; the volume ratio of the copper-cobalt bimetallic organic framework nano enzyme dispersion liquid to the phosphoric acid buffer solution to the organic phosphorus solution is as follows: 20-25: 12-16: 1;
further, in the step (3), the TMB solution with the concentration of 20 mM is added into the mixed solution with the volume of 11.0-11.5% of the volume of the mixed solution in the step 2, and the H is added 2 O 2 The solution concentration was 1M, 1/10 was added in a volume of TMB solution, the H 2 O 2 The concentration of the solution is 1M, and the volume is 0.02 mL; the reaction time is 15min and H 2 O 2 The concentration of the solution is 1M, and the volume is 0.2 mL; the volume was 0.02 mL.
The detection principle of the colorimetric analysis method of the organophosphorus colorimetric sensor based on the copper-cobalt bimetallic organic framework nanoenzyme is as follows: by utilizing the inhibiting effect of Organic Phosphorus (OPs) on the catalytic activity of the CoCu-ZIF bimetallic nanoenzyme in a TMB-hydrogen peroxide reaction system, the CuCo-ZIF nanoenzyme can have H 2 O 2 In the presence of the oxidation-accelerating TMB, an intense blue color is rapidly produced. However, in the presence of OPs, the degree to which the reaction develops blue is proportionally reduced as the concentration of OPs increases. Compared with the natural enzyme colorimetric detection, the method has the following beneficial effects: the colorimetric sensor prepared by the invention does not need to rely on acetylcholinesterase, avoids inactivation, is simple to operate, has good anti-interference performance, uses the nano enzyme with good stability, is not easy to inactivate, and can be used for real-time and direct visual sensitive detection; compared with the similar direct colorimetric detection of organophosphorus, the copper-cobalt bimetallic organic framework nanoenzyme used in the invention has simpler preparation, lower detection limit and larger linear range.
Drawings
FIG. 1 is an electron microscope image of Cu-Co bimetallic organic framework nanoenzyme prepared in example 1.
FIG. 2 is a schematic diagram of the principle of the organophosphorus colorimetric sensor and colorimetric analysis method of the copper-cobalt bimetallic organic framework nanoenzyme of the present invention.
Fig. 3 is a diagram illustrating the feasibility study of the organophosphorus colorimetric analysis method of the copper-cobalt bimetallic organic framework nanoenzyme in this example 3.
FIG. 4 is a linear curve of the colorimetric detection of the Cu-Co bimetallic organic framework nanoenzyme in example 3 for organophosphorus standard samples of known concentrations.
FIG. 5 is a linear plot of colorimetric detection of known concentrations of organophosphorus (dichlorvos) standards for the copper-cobalt bimetallic organic framework nanoenzymes of example 5.
FIG. 6 is a linear curve of the colorimetric detection of organophosphorus standard sample based on cobalt-zinc bimetallic organic framework nanoenzyme in example 6.
Detailed Description
Example 1
In this example, the copper-cobalt bimetallic organic framework nanoenzyme is prepared first.
Synthesizing the copper-cobalt bimetallic organic framework nanoenzyme by a soft template one-pot method, namely taking a reactor A, and mixing the reactor A and the nanoenzyme according to a molar ratio of 20: 30: 1, respectively weighing copper nitrate trihydrate, cobalt nitrate hexahydrate and CTAB, then weighing ultrapure water according to the concentration of 0.045mmol/mL of the copper nitrate trihydrate, putting the components into a reactor A, and ultrasonically mixing for 10min to obtain a light pink solution A after uniformly mixing; preparing a solution B of 2-methylimidazole and ultrapure water according to the concentration of 0.79M in another reactor B, and then preparing a reaction product by mixing 2-methylimidazole and copper nitrate trihydrate according to the molar ratio of 2750: 20, dropping the solution A into the reactor B, rapidly stirring at normal temperature for 1 hour, standing for 15min after reaction, centrifuging the solution at 8000 rpm, washing with anhydrous ethanol for 3 times, and finally washing at 60% o And (3) drying for 12 h under the condition of C in vacuum to obtain CuCo-ZIF nano enzyme particles.
As shown in fig. 1, which is an electron microscope image of the copper-cobalt bimetallic organic frame nanoenzyme of this embodiment, it can be clearly seen from fig. 1a and 1b that the copper-cobalt bimetallic organic frame nanoenzyme is cubic, has a particle size of about 500 nm, and is uniformly dispersed.
Example 2
Synthesizing the copper-cobalt bimetallic organic framework nanoenzyme by a soft template one-pot method, namely taking a reactor A, and mixing the reactor A and the nanoenzyme according to a molar ratio of 25: 35: 1, respectively weighing copper nitrate trihydrate, cobalt nitrate hexahydrate and CTAB, then weighing ultrapure water according to the concentration of 0.04mmol/mL of the copper nitrate trihydrate, putting the components into a reactor A, and ultrasonically mixing for 10min to obtain a light pink solution A after uniformly mixing; preparing a solution B of 2-methylimidazole and ultrapure water according to the concentration of 0.75M in another reactor B, and mixing the solution B with 2-methylimidazole and copper nitrate trihydrate according to the molar ratio of 2500: 25, dropping the solution A into the reactor B, rapidly stirring at normal temperature for 1 hr, standing for 15min after reaction, centrifuging the solution at 8000 rpm, washing with anhydrous ethanol for 3 times, and finally 70 o Vacuum drying for 10 h under the condition of C to obtain the CuCo-ZIF nano-enzyme particles of the embodiment.
Example 3
In this embodiment, the principle schematic diagram of the organophosphorus colorimetric sensor of the copper-cobalt bimetallic organic framework nanoenzyme and the colorimetric analysis method shown in fig. 2 is used to study the colorimetric analysis method of the organophosphorus colorimetric sensor, using the copper-cobalt bimetallic organic framework nanoenzyme prepared in example 1 as an active ingredient.
In the embodiment, 1 mg of the prepared copper-cobalt bimetallic organic framework nanoenzyme is ultrasonically dispersed in 1 mL of deionized water to obtain a uniform dispersion liquid; then, 0.2 mL of the dispersion was added to 0.1M Na 2 HPO 4 And NaH 2 PO 4 The pH value of PBS is 4, a known concentration of 0.1 mL of methylpyrimidine phosphorus (organic phosphorus) solution is added, and uniform mixed solution is obtained by shaking and dispersing; finally, 0.2 mL of 20 mM TMB solution and 0.02 mL of 10M H 2 O 2 Adding the solution into the mixed solution in sequence, vibrating, dispersing and mixing uniformly, reacting for 15min at room temperature, and detecting the absorbance of the solution at 652 nm by using an ultraviolet-visible spectrophotometer; the reaction and detection procedure was repeated using 0.1 mL of organophosphorus (pirimiphos-methyl) solutions of various known concentrations.
As shown in FIG. 3, the method is based on the above colorimetric detection method of this example to carry out the organophosphorus colorimetric analysis of Cu-Co bimetallic organic frame nanoenzymeFeasibility study of analytical method. Colorimetric analysis studies of the four test solutions were performed separately. The absorbance curves for different concentrations of organophosphorous solution in PBS buffered solution of 0.1M pH =4.0 are shown in fig. 3A. Curve a is CuCo-ZIF nanoenzyme in TMB-H in the absence of organic phosphorus 2 O 2 Absorbance curve in the system. Curve d is TMB-H in the absence of both organophosphorus and CuCo-ZIF nanoenzymes 2 O 2 Absorbance curve of the system. Curves b and c show that the CuCo-ZIF nanoenzyme is present in TMB-H at an organic phosphorus concentration of 60 nM and 3. mu.M, respectively 2 O 2 Absorbance curve in the system. It can be seen that the absorbance at 652 nm is greatly increased for curve a compared to curve d, while the absorbance at 652 nm is successively decreased for curves b and c compared to curve a, but still greater than curve d. Shows that the CuCo-ZIF nano enzyme can greatly promote H 2 O 2 The oxidation process of the TMB is hindered when organic phosphorus exists, and the inhibition effect is more obvious when the concentration of the organic phosphorus is higher. Each cuvette in fig. 3B is a schematic representation of the actual color development of the absorbance detection solution corresponding to each absorbance curve of fig. 3A, wherein the blue color of the detection solution in cuvette a is darkest, the colors of cuvettes B and c become lighter as the concentration of surface phosphorus increases, and the three samples in cuvette d are substantially colorless and transparent. By combining the data, the prepared organophosphorus colorimetric detection based on the copper-cobalt bimetallic organic framework nanoenzyme can be proved to be feasible.
FIG. 4 is a linear plot of a fixed volume of standard organophosphorus (pirimiphos-methyl) samples at different known concentrations according to the analysis method described in the second paragraph of this example, and as described in Table 1. Analytical testing of 22 different known concentrations of organophosphorus (pirimiphos-methyl) as described in table 1, the specific concentration values and the corresponding absorbance values are described in table 1, where the concentration is in μ M.
TABLE 1
As shown in FIG. 4A, the absorbance curves of the solutions measured by the organic phosphorus concentration value and the ultraviolet spectrophotometer shown in Table 1 are plotted by using different known concentration values as abscissa, and subtracting the absorbance value at 652 nM of the solution at the organic phosphorus concentration shown in FIG. 4A from the absorbance value at 652 nM of the solution in the absence of organic phosphorus to obtain an absorbance difference (Δ A), and using each Δ A value as ordinate, a standard curve shown in FIG. 4B is obtained, and according to the aforementioned analytical measurement and the standard curve shown in FIG. 4B, it can be seen that the corresponding Δ A linearly increases with the organic phosphorus concentration, the linear ranges reach 0.0006 μ M to 0.03 μ M and 0.03 μ M to 3 μ M, and the CuCo-ZIF nanoenzyme has a higher activity in this concentration range and a better linear response range to organic phosphorus, and the detection Limit (LOD) can be as low as 0.151 nM, particularly, higher detection sensitivity can be exhibited in the range of the bottom concentration of 0.0006 μ M to 0.03 μ M, the activity of the organic nano enzyme is stronger.
Example 4
To examine the reliability of the practical application of the nanoenzyme sensor of example 3, the colorimetric detection method of example 3 was used to perform the spiking detection of the actual samples, and the spiking concentration of the organophosphorus in each sample is shown in Table 2. Compared with the content detection method of the prior reference method, the relative error of the method detection is less than 10 percent, which shows that the sensor can accurately detect the content of organic phosphorus in an actual sample, and the method is shown in Table 2:
TABLE 2 measurement of organophosphorous (pirimiphos-methyl) by spiking
Example 5
The embodiment is an organophosphorus (dichlorvos) colorimetric analysis method based on copper-cobalt bimetallic organic framework nanoenzyme, which comprises the following steps:
ultrasonically dispersing 1 mg of copper-cobalt bimetallic organic framework nanoenzyme (CuCo-ZIF nanoenzyme obtained in example 2) in 1 mL of deionized water to obtain uniform dispersion liquid; then, 0.2 mL of the dispersion was added to a pH of 4.5 over 0.1M Na 2 HPO 4 And NaH 2 PO 4 Adding 0.1 mL of dichlorvos solution with different known concentrations into the phosphoric acid buffer solution, and vibrating and dispersing to obtain a mixtureMixing the mixture evenly; finally, 0.2 mL of 20 mM TMB solution and 0.02 mL of 10M H 2 O 2 And sequentially adding the solution into the mixed solution, oscillating, dispersing and uniformly mixing, reacting at room temperature for 15min, and detecting the absorbance of the solution at 652 nm by using an ultraviolet-visible spectrophotometer. In this example, each known concentration of dichlorvos solution and the corresponding absorbance values are shown in table 3.
TABLE 3
| |
1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| Concentration of | 0.006 | 0.03 | 0.09 | 0.15 | 0.3 | 1.5 | 2.1 | 2.4 | 3 |
| Absorbance of the solution | 2.6 | 2.5365 | 2.485 | 2.438 | 2.4 | 1.631 | 1.255 | 1.039 | 0.489 |
The method of fig. 4 is plotted in example 3, and a linear curve for detecting the standard sample of organophosphorus (dichlorvos) is plotted as shown in fig. 5 according to the peak absorbance corresponding to the dichlorvos solution of each concentration. In this example, the linear range of organophosphorus (dichlorvos) detection is 0.006. mu.M to 3. mu.M, and the limit of detection (LOD) is 1.32 nM. Therefore, the organophosphorus colorimetric sensor based on the copper-cobalt bimetallic organic framework nanoenzyme has good detectability to dichlorvos, and the actual organophosphorus pesticide detection application range is wide.
Example 6 (comparative example)
In this embodiment, a cobalt-zinc bimetallic organic framework nanoenzyme is prepared first, and then an organophosphorus colorimetric sensor and a colorimetric analysis method based on the cobalt-zinc bimetallic organic framework nanoenzyme are performed.
Firstly, an organophosphorus colorimetric sensor for preparing cobalt-zinc bimetallic organic framework nanoenzyme and a colorimetric analysis method are prepared, and the method comprises the following steps: 1.455 g of cobalt nitrate hexahydrate and 1.487 g of zinc nitrate hexahydrate were dissolved in 4 mL of deionized water. Then, it was mixed with 40 mL of a 1.25 mM aqueous solution of 2-methylimidazole, sonicated for 5min, and allowed to stand at room temperature for 6 hours. And after the reaction is finished, centrifuging the solution at 8000 rpm for 15min, washing the solution for 3 times by using absolute ethyl alcohol, and finally drying the solution at 50 ℃ for 12 h to obtain the CoZn-ZIF nano enzyme.
Then ultrasonically dispersing the 1 mg of cobalt-zinc bimetallic organic framework nano-enzyme in 1 mL of deionized water to obtain uniform dispersion liquid; then, 0.2 mL of the dispersion was added to 0.1M Na 2 HPO 4 And NaH 2 PO 4 Adding 0.1 mL of organic phosphorus solution with known concentration into phosphoric acid buffer solution with pH value of 4, and vibrating and dispersing to obtain uniform mixed solution; finally, 0.2 mL of 20 mM TMB solution and 0.02 mL of 10M H 2 O 2 And sequentially adding the solution into the mixed solution, oscillating, dispersing and mixing uniformly, reacting at room temperature for 15min, and detecting the absorbance of the solution at 652 nm by using an ultraviolet-visible spectrophotometer to obtain a linear curve for detecting the organophosphorus standard sample as shown in FIG. 6.
As can be seen from the analysis of FIG. 6, the linear range of the standard organophosphorus sample detected based on the cobalt-zinc bimetallic organic framework nanoenzyme is 0.15 μ M-4 μ M, and the detection Limit (LOD) is 61 nM, compared with example 3 (the linear ranges are 0.0006 μ M-0.03 μ M and 0.03 μ M-3 μ M, and the detection limit is 0.151 nM), the organophosphorus colorimetric sensor based on the copper-cobalt bimetallic organic framework nanoenzyme has a wider linear range and higher sensitivity.
Claims (7)
1. The copper-cobalt bimetallic organic framework nanoenzyme is characterized in that Cetyl Trimethyl Ammonium Bromide (CTAB) is used as a soft template, 2-methylimidazole is used as an organic ligand, copper nitrate is used as a copper source, cobalt nitrate is used as a cobalt source, and deionized water is used as a solvent to synthesize the copper-cobalt bimetallic organic framework nanoenzyme (CuCo-ZIF), wherein the particle size of the CuCo-ZIF is 450-550 nm.
2. The copper-cobalt bimetallic organic framework nanoenzyme as claimed in claim 1, characterized in that the specific synthetic method of the copper-cobalt bimetallic organic framework nanoenzyme comprises the following steps:
step one, mixing a mixture of a molar ratio of 20-25: 30-35: 1, dissolving copper nitrate, cobalt nitrate and CTAB in ultrapure water, and ultrasonically vibrating the system for 10min to form solution A; dissolving 2-methylimidazole in ultrapure water according to the concentration of 0.75-0.8M, and carrying out ultrasonic vibration for 10min to form a solution B;
and secondly, adding the solution B into the solution A under the stirring state, mixing and stirring for 1 h at normal temperature, then, centrifugally separating a solid phase at 8000 rpm, washing with ethanol for three times, and finally, drying the obtained solid in a vacuum oven to obtain the copper-cobalt bimetallic organic framework nano enzyme.
3. The copper-cobalt bimetallic organic framework nanoenzyme as in claim 2, wherein the copper nitrate in the solution A is copper nitrate trihydrate with a concentration of 4-5 mM, the cobalt nitrate is cobalt nitrate hexahydrate, and after the solution A and the solution B are mixed, the molar ratio of 2-methylimidazole, copper nitrate, cobalt nitrate and CTAB in the mixed solution is 2500-3000: 20-25: 30-35: 1.
4. the copper-cobalt bimetallic organic framework nanoenzyme as in claim 2, wherein in the second step, the temperature of vacuum drying is 60-70 ℃ and the drying time is 10-12 h.
5. A colorimetric analysis method of an organophosphorus colorimetric sensor based on copper-cobalt bimetallic organic framework nanoenzyme is characterized by comprising the following steps:
(1) ultrasonically dispersing the copper-cobalt bimetallic organic framework nanoenzyme as defined in any one of claims 1 to 4 in deionized water to obtain a uniform dispersion liquid with a dispersion concentration of 1 to 2 mg/mL;
(2) taking a plurality of parts of the copper-cobalt bimetallic organic framework nano enzyme dispersion liquid in the step (1), respectively adding a phosphoric acid buffer solution and quantitative volumes of organic phosphorus solutions with different concentrations, and vibrating and dispersing to obtain a uniform mixed liquid;
(3) respectively adding TMB solution and H into the mixed solution in the step (2) 2 O 2 The solutions are vibrated, dispersed and mixed uniformly, and after the reaction is carried out for 15-20 minutes at room temperature, an ultraviolet-visible spectrophotometer is used for detecting the absorbance of each solution;
(4) and (4) drawing a linear curve according to the relation between the peak value change of the absorbance of each solution in the step (3) and the corresponding concentration of the organophosphorus solution, and taking the linear curve as a standard curve for organophosphorus colorimetric detection.
6. A colorimetric method in accordance with claim 5, wherein in the step (2), the phosphate buffer solution is composed of 0.1M Na 2 HPO 4 Solution and 0.1M and NaH 2 PO 4 The solution is mixed, and the pH of the mixed solution is 4-4.5; the volume ratio of the copper-cobalt bimetallic organic framework nano enzyme dispersion liquid to the phosphoric acid buffer solution to the organic phosphorus solution is as follows: 20-25: 12-16: 1.
7. the colorimetric method according to claim 5, wherein the concentration of the TMB solution in the step (3) is 20 mM, and the H is added in an amount of 11.0 to 11.5% by volume based on the volume of the mixture in the step 2 2 O 2 The solution concentration was 1M, 1/10 was added in a volume of TMB solution, the H 2 O 2 The concentration of the solution is 1M, and the volume is 0.02 mL; the reaction time is 15min and H 2 O 2 The concentration of the solution is 1M, and the volume is 0.2 mL; the volume was 0.02 mL.
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