CN112557383A - Based on MnO2Copper ion colorimetric detection method of complex enzyme analogue - Google Patents
Based on MnO2Copper ion colorimetric detection method of complex enzyme analogue Download PDFInfo
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 71
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 52
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Abstract
The invention is based on MnO2The copper ion colorimetric detection method of the compound enzyme simulant and the application thereof comprise the following steps: preparing copper ions with different concentrations and an L-cys solution; synthesis of MB and MB/Au/PANI/MnO2A composite material; preparing NaAC-HAC buffer solution; preparing a TMB solution; optimizing conditions; and (5) carrying out colorimetric detection on copper ions. The invention provides a MnO base2Copper ion colorimetric detection method of complex enzyme analogue and application thereof, MB/Au/PANI/MnO2The composite material is used as a composite enzyme analogue, has strong catalytic performance, realizes high-sensitivity and quantitative detection on copper ions, improves the selectivity and stability of target object detection, and changes the composite enzyme analogue into a doped MnO2The other compounds can be applied to the detection and analysis of new target objects, have strong universality, simple and convenient detection method, low cost, easily obtained raw materials and no toxicity, can be applied to the detection of actual samples, and is suitable for industrial popularization.
Description
Technical Field
The invention belongs to the technical field of colorimetric detection, and particularly relates to a colorimetric detection method based on MnO2A copper ion colorimetric detection method of a complex enzyme analogue and application thereof.
Background
Currently, the current state of the art commonly used in the industry is such that:
copper is an essential trace element of human body and plays an important role in a series of basic physiological processes and activities of human body. Copper is involved in the formation of various biological enzymes and maintains the activity of the enzymes, so that electron transfer and redox metabolic life activities are normally carried out. Copper is also involved in erythropoiesis to maintain normal hematopoiesis. In addition, childhood tics are closely related to the copper content in the human body. However, an excessive amount of copper ions (Cu)2+) It also causes a number of health problems including ischemic heart disease, anemia, kidney disease, bone disease, senile dementia, prions, parkinson's disease, etc. More importantly, Cu in water2+Too high a content may adversely affect aquatic organisms. The world health organization and the United states environmental protection agency have already treated Cu in drinking water2+The maximum allowable limit of (2) is set to 1.3 ppm. The national standard of China shows that Cu in tap water2+Is limited to a maximum concentration of 1 mg/L. Therefore, monitoring Cu in the environment in an appropriate range2+Is of critical importance. Currently detecting Cu2+The conventional methods of (2) generally use atomic absorption spectrometry, atomic fluorescence spectrometry and inductively coupled plasma mass spectrometry, but these methods are time-consuming, complicated in sample preparation, and require the presence of specialized operators. Therefore, there is a need to design a simple quantitative detection method for Cu from both biological and environmental perspectives2+The method of (1). The colorimetric chemical sensor is an alternative device due to the advantages of simple and visual operation, high selectivity, short response time and the like, can detect target ions in an aqueous medium by displaying color change, and can realize naked eye detection and field detection.
Horseradish Peroxidase (HRP) is a very commonly used enzyme for H2O2The decomposition has high-efficiency catalytic action, and is widely applied to biological sensing markers, such as enzyme-linked immunosorbent assay. In 2019, researchers take cotton threads as solid adsorbents, so that local Cu on the cotton threads is improved2+Concentration of Cu by ascorbic acid2+Reduction to Cu+By observing colorless TMB (tetramethylbenzidine, 3,3 ', 5, 5' -tetramethylbenzidine) catalyzed by HRPbenzidine) is a color change in the blue oxidation state (ox TMB), giving Cu+Has the function of inhibiting HRP catalytic oxidation TMB, thereby realizing quantitative detection of Cu2+The detection limit is 0.15nmol/L, and compared with other analysis methods, the method provides a sensitive and portable online preconcentration colorimetric detection method for detecting Cu2+The method of (1). However. The colorimetric chemical sensor takes HRP as an enzyme catalytic reaction, and the HRP has the defects of changeability, high cost, complex preparation, long reaction incubation time and the like, thereby greatly limiting the practical application of the colorimetric chemical sensor. Therefore, the research on the enzyme with the advantages of simple preparation, stable property, strong environmental tolerance and the like has important significance for detecting the biomolecule.
In recent years, inorganic nano materials have attracted more and more interest as a bionic nano enzyme in the research field. The bionic nano enzyme is a chemically synthesized nano material and has biological catalytic activity similar to that of some natural enzymes. The nano enzyme has a simpler structure than natural enzyme, has stable chemical properties, has the function of enzyme, and also has the advantages of batch production and low cost. In addition, the nano enzyme is essentially a nano material, has higher specific surface area and special physicochemical properties such as light, electricity, magnetism and the like, and the unique biochemical characteristics of the nano material not only enable the nano enzyme to have multiple functions, but also enable the nano enzyme to be designed and applied in multiple ways. Incorporating magnetic nanomaterials, e.g. Fe, into the nanomaterial3O4The nano material can be effectively separated from the solution by using an external magnetic field and is easy to recycle. However, unmodified Fe3O4Not only is easy to agglomerate and oxidize, but also is unstable in an acid medium, thereby limiting the wide application of the catalyst. Polyaniline (PANI) is a highly effective Fe3O4In recent years, PANI is developed as a catalytic carrier due to good stability of reaction conditions, no toxicity and low cost. The gold Au is a metal with catalytic activity, and has the characteristics of mild reaction conditions, simple operation, short reaction time, high reaction selectivity and the like. MnO2Is a nano enzyme prepared artificially, has good stability and a porous structure with uneven size, andthis configuration contributes to the catalytic action by virtue of the specific crystal structure. Magnetic Beads (MB) are an anti-interference element with high Magnetic permeability, low price and easy use, and in addition, have the characteristics of large specific surface area, good stability, low toxicity and the like. Therefore, MB, Au, PANI, MnO2Preparation of composite for detecting Cu2+Has important significance.
Cysteine (L-Cysteine, L-Cys) can produce glutathione, which is the most prominent and most powerful antioxidant. The glutathione belongs to a small molecular peptide substance containing sulfydryl, the sulfydryl on the cysteine is an active group thereof, and L-Cys and Cu2+Insoluble mercaptides (mercaptides) may be formed. In L-Cys with Cu2+After the reaction, the solution develops color in the presence of the catalytic material.
The colorimetric detection is a method of determining the content of a component to be measured by comparing (visual colorimetry) or measuring (ultraviolet-visible spectrometry) the color depth of a colored substance solution based on a color reaction of a colored compound. The colorimetric detection has low cost, simple and convenient operation, short detection time and rapid qualitative detection by naked eyes, and is suitable for rapid detection. Colorimetric detection is one of widely used detection methods, the content of a composite material and TMB in ELISE is related to the content of a substance to be detected, an enzyme catalyzes a substrate to generate a colored product, the amount of the colored product is directly related to the amount of the substance to be detected, and qualitative or quantitative analysis can be performed through the color depth. Because the enzyme catalysis efficiency is high and the colorimetric detection sensitivity is high, the colorimetric detection is of great significance.
In summary, the prior art has the following problems:
(1) for detecting Cu2+Methods such as absorption spectroscopy, electrochemical methods, ion chromatography, which are costly, time consuming, require sophisticated instrumentation and skilled personnel.
(2) At present, for Cu2+Simple analysis and research of detection are less, and Cu2+The detection in the biological matrix has certain difficulty, and the high-sensitivity detection of low-concentration target objects is difficult to realize.
Disclosure of Invention
To solve the existing problemsThe technical problem of the invention is to provide a MnO-based method2Copper ion colorimetric detection method of complex enzyme simulant and application thereof, wherein the detection range of copper ions is 1.0 multiplied by 102～1.0×107nM, limit of detection 0.65 nM.
In order to achieve the purpose and achieve the technical effect, the invention adopts the technical scheme that:
based on MnO2The copper ion colorimetric detection method of the compound enzyme simulant comprises the following steps:
s101: preparing copper ions with different concentrations and L-Cys solution (configuration 10)2-107nmol/L of Cu2+And L-Cys solution)
S102: synthesis of magnetic beads MB and MB/Au/PANI/MnO2Composite material
S103: preparing NaAC-HAC buffer solution
S104: preparing TMB solution
S105: condition optimization
S106: and carrying out colorimetric detection on the copper ions.
Further, in step S101, the CuSO is weighed4·5H2O, preparing into copper sulfate solution, and then diluting for several times to obtain 100nmol/L Cu2+The prepared solution is stored at 4 ℃.
Further, in step S101, L-Cys is weighed to prepare a solution of 10mL and 400. mu. mol/L, and the prepared solution is stored at 4 ℃.
Further, in step S102, the MB synthesizing step includes:
introducing nitrogen into HCl solution for 20-25min, and weighing FeCl2·4H2O and FeCl3·6H2Placing O in a round-bottom flask, adding the HCl solution introduced with nitrogen, fully stirring until the HCl solution is completely dissolved, introducing nitrogen into the mixed solution to remove oxygen for 20-25min, repeatedly introducing for several times, then rapidly adding NaOH solution, violently stirring for 2-2.1h under the protection of nitrogen, flushing for several times with secondary water until the mixed solution is neutral, placing one part at 4 ℃ for storage, and naturally drying the other part for later use.
Further, in step S102, MB/Au/PANI/MnO2Composite material compositionThe method comprises the following steps:
adding the washed magnetic beads MB into a PVP solution, shaking uniformly, adding chloroauric acid, and carrying out ultrasonic treatment for 5-6min for later use, and marking as a solution A;
aniline and HCL solution are mixed and stirred uniformly and marked as solution B;
mixing solution A and solution B, adding ammonium persulfate, shaking, standing for 2-2.1 hr, magnetically separating, cleaning, oven drying, dispersing in water, ultrasonically homogenizing, and adding KMnO4Uniformly vibrating the solution, magnetically separating and cleaning to obtain the required MB/Au/PANI/MnO2A composite material.
Further, in step S103, the preparation of the NaAC-HAC buffer solution includes:
weighing sodium acetate, diluting to 100mL, and adjusting pH to 4 with acetic acid to obtain NaAC-HAC buffer solution.
Further, in step S104, the TMB solution is ready to be prepared, and the preparation step of the TMB solution includes:
solution A: dissolving TMB in DMSO, and stirring well for later use;
and B, liquid B: citric acid added NaHPO4Stirring uniformly, and fixing the volume to 100 mL;
and then, completely adding the prepared solution A into 10mL of solution B, and uniformly performing ultrasonic treatment to obtain the needed TMB solution.
Further, in step S105, for MB/PANI/Au/MnO2Optimization of reaction volume of composite material and TMB, L-Cys and MB/PANI/Au/MnO2Optimization of composite reaction volume, Cu2+Optimization of reaction time with L-Cys, L-Cys and MB/PANI/Au/MnO2Optimization of composite material reaction time, MB/PANI/Au/MnO2Optimizing the reaction time of the composite material and TMB and optimizing the pH value of the buffer solution.
Further, in step S106, adding L-Cys solution and Cu to NaAC-HAC buffer solution2+Reaction, followed by addition of MB/PANI/Au/MnO2And adding a TMB solution into the composite material for reaction, performing colorimetric detection, and measuring absorbance.
The invention discloses a method based on MnO2Method for detecting copper ions removed by using colorimetric detection method of complex enzyme simulantThe use of MB/PAMAM/MnO as defined in claim 1 in a target2Substitution of composite materials for doped MnO2Other complexes of (a).
Compared with the prior art, the invention has the beneficial effects that:
MnO2complex enzyme mimetics, i.e. MB/Au/PANI/MnO2The composite material has strong catalytic performance, can catalyze TMB to be oxidized into blue cationic free radical oxidized tetramethyl benzidine (oxidized TMB, ox TMB), can effectively inhibit the generation of cationic free radicals by L-Cys, and can reduce the cationic free radicals into colorless TMB molecules, L-Cys and Cu2+Can form insoluble mercaptide, and realize Cu by colorimetric analysis2+The quantitative detection of (2) improves Cu2+Detection sensitivity, selectivity and stability of target detection;
compared with HRP, MnO2The method has the characteristics of better chemical stability, simplicity and easiness in operation, low cost, easiness in modification and the like, and can avoid the use of biological enzymes which are high in cost, unstable and difficult to operate; by using MB/Au/PANI/MnO2Composite materials, not only for Cu2+Quantitatively detecting MB/Au/PANI/MnO2Conversion of composite materials to doped MnO2The other compounds are applied to the detection and analysis of new target objects, and have strong universality and high sensitivity;
construction of Cu by combination of nano-enzyme catalytic oxidation TMB and colorimetric analysis method2+The colorimetric analysis method for the detection object improves the analysis sensitivity and is similar to the traditional Cu method2+Compared with the detection method, the detection method avoids the defects of expensive equipment, complex pretreatment, complicated operation procedures, high toxicity and the like, is simple, convenient, efficient, low in cost, stable, easy to obtain raw materials and non-toxic, can be applied to detection of actual samples, and is suitable for industrial popularization and use.
Drawings
FIG. 1 is a flow chart of the working principle of the present invention;
FIG. 2 is a schematic diagram of the principles of the present invention;
FIG. 3 shows TMB and MB/Au/PANI/MnO at wavelength of 652nm in accordance with the present invention2Differential volume to Cu of composite reaction2+Influence graph of (2);
FIG. 4 shows TMB and MB/Au/PANI/MnO at wavelength of 652nm in accordance with the present invention2Reaction time of composite versus Cu2+Influence graph of (2);
FIG. 5 shows Cu of the present invention2+A detected selectivity experiment result graph;
FIG. 6 shows different Cu of the present invention2+Standard working curve of concentration;
FIG. 7 shows different Cu of the present invention2+UV-vis response plot of concentration.
Detailed Description
The following detailed description of the embodiments of the present invention is provided to enable those skilled in the art to more easily understand the advantages and features of the present invention, and to clearly and clearly define the scope of the present invention.
Example 1
As shown in FIGS. 1-7, a MnO based2A colorimetric detection method for copper ion of compound enzyme simulant uses copper ion Cu2+For example, the detection mechanism is as follows:
MB/PANI/MnO2the composite material is used as a composite enzyme simulant and can catalyze TMB to be oxidized into blue cation free radicals, the L-Cys can effectively inhibit the generation of the cation free radicals and reduce the cation free radicals into colorless TMB molecules, and the L-Cys and Cu2+Insoluble mercaptides can form. In L-Cys with varying concentrations of Cu2+After the reaction, the solution is in MB/PANI/MnO2The composite material and TMB become blue under the existence condition, and the absorbance value under the wavelength of 652nm changes along with the change of the concentration of the copper ions, thereby achieving the purpose of detecting the copper ions.
The invention also discloses a method based on MnO2The application of the copper ion colorimetric detection method of the compound enzyme simulant in the detection of the target object of copper ion removal is to use MB/PAMAM/MnO2Substitution of composite materials for doped MnO2The other complexes of (a) may be subjected to detection analysis of other targets.
Investigation of Cu at different concentrations2+Influence on detection and MBAnd MB/Au/PANI/MnO2Synthesis of the composite material:
(1) arrangement 102-107nmol/L of Cu2+And L-Cys solution
Weigh 0.0025g CuSO4·5H2O is prepared into 1mL and 107nmol/L copper sulfate solution. Taking 100 μ L, 107Diluting the copper sulfate solution by 10 times to obtain 106nmol/L Cu2+(ii) a Then take 100 μ L, 106Diluting by nmol/L for 10 times to obtain 105nmol/L Cu2+(ii) a According to this process 104nmol/L Cu2+、103nmol/L Cu2+、100nmol/L Cu2+。
0.00048g of L-cys was weighed out to prepare 10mL of a 400. mu. mol/L solution, and the prepared solutions were stored at 4 ℃.
(2) Magnetic beads MB and MB/Au/PANI/MnO2Synthesis of composite materials
The synthesis of MB comprises the following steps:
introducing 1.2mmol/L HCl and nitrogen for 20min, and weighing 0.29815g FeCl2·4H2O、0.81087gFeCl3·6H2Placing O in a container, adding 30mL of the HCl solution with 1.2mmol/L of nitrogen, fully stirring until the HCl solution is completely dissolved, introducing nitrogen into the mixed solution for 20min, repeatedly introducing the nitrogen for three times, then rapidly adding 30mL of NaOH with 1.25mol/L of NaOH, vigorously stirring for 2h under the protection of nitrogen, flushing the mixed solution for three times with secondary water until the mixed solution is neutral, placing one part at 4 ℃ for storage, and naturally airing the other part for later use.
MB/Au/PANI/MnO2The composite material synthesis steps comprise:
adding 1mL of the washed MB into PVP solution (0.1g of PVP +10mL of water), placing in a constant-temperature oscillator, shaking for 1h, and dropwise adding 2mL of HAuCl with the mass fraction of 1%4Performing ultrasonic treatment for 5min, and marking as solution A for later use;
stirring and mixing 0.3mL of aniline and 10mL of 1mol/L HCl uniformly, and marking as a solution B;
mixing the solution A and the solution B, adding 0.18g of ammonium persulfate, oscillating for 1 hour, standing for 2 hours, then carrying out magnetic separation, washing precipitates for 1-2 times by using ethanol, and drying at 50-60 ℃;
taking 5mg of the dried productDispersing in 5mL water, ultrasonic treating, adding 5mg KMnO4Oscillating for 1h, performing magnetic separation, washing the precipitate for 1-2 times, and filling the precipitate into a 2mL centrifuge tube to obtain MB/Au/PANI/MnO2Composite material, subsequently the synthesized MB/Au/PANI/MnO2The composite material is diluted by four times to obtain MB/Au/PANI/MnO for experiments2The composite material is prepared by taking MB/Au/PANI/MnO for experiments each time2The composite material is uniformly mixed for 25 s.
(3) Preparation of buffer solution
8.3g of sodium acetate (NaAC) was weighed out, diluted to 100mL, and adjusted to pH 4 with 1.75mol/L of acetic acid (HAC) to obtain 0.6mol/L, pH ═ 4 NaAC-HAC buffer.
Example 2
The preparation steps of the TMB solution comprise:
the TMB solution is ready for use.
Solution A: dissolving 0.0143g of TMB in 100 mu L of DMSO, and uniformly stirring for later use;
and B, liquid B: 24.3mL of 0.1mol/L citric acid was added with 5.7mL of 0.2mol/L NaH2PO4Stirring uniformly, and fixing the volume to 100 mL;
and then completely adding the prepared solution A into 10mL of solution B, and uniformly performing ultrasonic treatment to obtain a 6mmol/L TMB solution for experiments, and storing the solution at 4 ℃ in a dark place.
Example 3
Cu2+Colorimetric detection of (2):
s101: weigh 0.0025g CuSO4·5H2O is prepared into 1mL and 107nmol/L copper sulfate solution. Taking 100 μ L, 107Diluting the copper sulfate solution at nmol/L by 10 times to obtain 106nmol/L Cu2+(ii) a Taking 100 μ L, 106Diluting by nmol/L for 10 times to obtain 105nmol/L Cu2+(ii) a According to this process 104nmol/L Cu2+、103nmol/L Cu2+、102nmol/L Cu2+。
0.00048g of L-cys was weighed out to prepare 10mL of a 400. mu. mol/L solution, and the prepared solutions were stored at 4 ℃.
S102: the synthesis of MB comprises the following steps:
introducing 1.2mmol/L HCl into 30mL of the solution for 20min, and weighing 0.29815g FeCl2·4H2O、0.81087g FeCl3·6H2Placing O in a container, adding 30mL of the HCl solution with 1.2mmol/L of nitrogen, fully stirring until the HCl solution is completely dissolved, introducing nitrogen into the mixed solution for 20min, repeatedly introducing the nitrogen for three times, then rapidly adding 30mL of NaOH with 1.25mol/L of NaOH, vigorously stirring for 2h under the protection of nitrogen, flushing the mixed solution for three times with secondary water until the mixed solution is neutral, placing one part at 4 ℃ for storage, and naturally airing the other part for later use.
MB/Au/PANI/MnO2The composite material synthesis steps comprise:
adding 1ml of the washed MB into PVP solution (0.1g of PVP +10ml of water), oscillating the shaking table for 1h, adding 2ml of 1% chloroauric acid, and carrying out ultrasonic treatment for 5min for later use, wherein the solution is marked as solution A;
0.3ml aniline, 10ml and 1M HCl, and the mixture is mixed and stirred evenly and marked as solution B;
mixing the solution A and the solution B, simultaneously adding 0.18g of ammonium persulfate, oscillating for 1h, standing for 2h, performing magnetic separation, cleaning for 1-2 times by using ethanol, drying and weighing at the temperature of 50-60 ℃, dispersing 5mg of the product in 5ml of water, performing ultrasonic homogenization, and adding 5mg of KMnO4Oscillating for 1h, magnetically separating, and washing for 1-2 times to obtain the required MB/Au/PANI/MnO2A composite material.
S103: the preparation method of the NaAC-HAC buffer solution comprises the following steps:
8.3g of sodium acetate (NaAC) was weighed out, diluted to 100mL, and adjusted to pH 4 with 1.75mol/L of acetic acid (HAC) to obtain 0.6mol/L, pH ═ 4 NaAC-HAC buffer.
S104: the preparation steps of the TMB solution comprise:
the TMB solution is ready for use.
Solution A: dissolving 0.0143g of TMB in 100 mu L of DMSO, and uniformly stirring for later use;
and B, liquid B: 24.3mL of 0.1mol/L citric acid was added with 5.7mL of 0.2mol/L NaH2PO4Stirring uniformly, and fixing the volume to 100 mL;
and then completely adding the prepared solution A into 10mL of solution B, and uniformly performing ultrasonic treatment to obtain a 6mmol/L TMB solution for experiments, and storing the solution at 4 ℃ in a dark place.
S105: optimizing conditions:
MB/PANI/Au/MnO2optimization of reaction volume of composite material and TMB, L-Cys and MB/PANI/Au/MnO2Optimization of reaction volume, Cu2+Optimization of reaction time with L-Cys, L-Cys and MB/PANI/Au/MnO2Optimization of composite material reaction time, MB/PANI/Au/MnO2Optimizing the reaction time of the composite material and TMB and optimizing the pH value of the buffer solution.
FIG. 3 shows TMB and MB/Au/PANI/MnO at wavelength of 652nm in accordance with the present invention2Differential volume to Cu of composite reaction2+The results show the magnitude of the absorbance signal versus TMB and MB/Au/PANI/MnO2The volume of the composite reaction is linearly related, the correlation coefficient is 0.9817, and the larger the volume, the larger the signal value.
FIG. 4 shows TMB and MB/Au/PANI/MnO at wavelength of 652nm in accordance with the present invention2Reaction time of composite versus Cu2+The results show that the absorbance signal is not substantially affected by the reaction time.
S106: for Cu2+And (3) carrying out selective detection:
under the best optimization condition, taking a concentration (1mM) of copper ions and other ions (magnesium ions, iron ions, zinc ions, sodium ions, calcium ions, cadmium ions, potassium ions and manganese ions) which are 10 times of the copper ions in a linear range, and using the system to react (L-Cys, MB/PANI/MnO/manganese dioxide ions)2Material and TMB) and detecting the absorbance value of the material, wherein the ultraviolet scanning wavelength range is 200-800 nm.
The results shown in fig. 5 show that the detection method of the present invention has good selectivity for copper ions under the interference of magnesium ions, iron ions, zinc ions, sodium ions, calcium ions, cadmium ions, potassium ions, and manganese ions.
FIG. 6 shows Cu of different2+Standard working curve of concentration, fig. 7 is different Cu2+Concentration UV-vis response plot, the magnitude of the absorbance signal increases with increasing copper ion concentration.
The parts of the invention not specifically described can be realized by adopting the prior art, and the details are not described herein.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. Based on MnO2The copper ion colorimetric detection method of the compound enzyme simulant is characterized by comprising the following steps:
s101: arrangement 102-107nmol/L of Cu2+And L-Cys solution
S102: synthesis of magnetic beads and MB/Au/PANI/MnO2Composite material
S103: preparing NaAC-HAC buffer solution
S104: preparing TMB solution
S105: condition optimization
S106: and carrying out colorimetric detection on the copper ions.
2. The MnO-based composition of claim 12The copper ion colorimetric detection method of the compound enzyme simulant is characterized in that in the step S101, CuSO is weighed4·5H2O, preparing into copper sulfate solution, and then diluting for several times to obtain 100nmol/L Cu2 +The prepared solution is stored at 4 ℃.
3. The MnO-based composition of claim 12The copper ion colorimetric detection method of the complex enzyme simulant is characterized in that in the step S101, L-Cys is weighed to prepare 10mL of 400 mu mol/L solution, and the prepared solution is stored at 4 ℃.
4. The MnO-based composition of claim 12The copper ion colorimetric detection method of the compound enzyme simulant is characterized in that in the step S102, the magnetic bead synthesis step comprises the following steps:
introducing nitrogen into HCl solution for 20-25min, and weighing FeCl2·4H2O and FeCl3·6H2Placing O in a round-bottom flask, adding the HCl solution which is introduced with nitrogen, and fully stirring until the solution is finishedDissolving completely, introducing nitrogen into the mixed solution to remove oxygen for 20-25min, repeatedly introducing for several times, rapidly adding NaOH solution, stirring vigorously under nitrogen protection for 2-2.1h, washing with secondary water for several times to neutrality, preserving one part at 4 deg.C, and naturally air drying the other part for use.
5. The MnO-based composition of claim 12The copper ion colorimetric detection method of the compound enzyme simulant is characterized in that in the step S102, MB/Au/PANI/MnO2The composite material synthesis steps comprise:
adding the washed MB into a PVP solution, shaking uniformly, adding chloroauric acid, and carrying out ultrasonic treatment for 5-6min for later use, and marking as a solution A;
aniline and HCL solution are mixed and stirred uniformly and marked as solution B;
mixing solution A and solution B, adding ammonium persulfate, shaking, standing for 2-2.1 hr, magnetically separating, cleaning, oven drying, dispersing in water, ultrasonically homogenizing, and adding KMnO4Uniformly vibrating the solution, magnetically separating and cleaning to obtain the required MB/Au/PANI/MnO2A composite material.
6. The MnO-based composition of claim 12The copper ion colorimetric detection method of the compound enzyme simulant is characterized in that in the step S103, the preparation step of the NaAC-HAC buffer solution comprises the following steps:
weighing sodium acetate, diluting to 100mL, and adjusting pH to 4 with acetic acid to obtain NaAC-HAC buffer solution.
7. The MnO-based composition of claim 12The copper ion colorimetric detection method of the compound enzyme simulant is characterized in that in the step S104, a TMB solution is prepared for use, and the preparation step of the TMB solution comprises the following steps:
solution A: dissolving TMB in DMSO, and stirring well for later use;
and B, liquid B: citric acid added NaHPO4Stirring uniformly, and fixing the volume to 100 mL;
and then, completely adding the prepared solution A into 10mL of solution B, and uniformly performing ultrasonic treatment to obtain the needed TMB solution.
8. The MnO-based composition of claim 12The copper ion colorimetric detection method of the compound enzyme simulant is characterized in that in the step S105, MB/PANI/Au/MnO is subjected to color matching2Optimization of reaction volume of composite material and TMB, L-Cys and MB/PANI/Au/MnO2Optimization of composite reaction volume, Cu2+Optimization of reaction time with L-Cys, L-Cys and MB/PANI/Au/MnO2Optimization of composite material reaction time, MB/PANI/Au/MnO2Optimizing the reaction time of the composite material and TMB and optimizing the pH value of the buffer solution.
9. The MnO-based composition of claim 12The copper ion colorimetric detection method of the compound enzyme simulant is characterized in that in the step S106, NaAC-HAC buffer solution is taken, and L-Cys solution and Cu are added2+Reaction, followed by addition of MB/PANI/Au/MnO2And adding a TMB solution into the composite material for reaction, performing colorimetric detection, and measuring absorbance.
10. Based on MnO2The application of the copper ion colorimetric detection method of the compound enzyme simulant in the detection of the target object for removing the copper ions is characterized in that the MB/PAMAM/MnO in the claim 12Substitution of composite materials for doped MnO2Other complexes of (a).
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