CN112557383B - MnO-based 2 Copper ion colorimetric detection method of complex enzyme simulant - Google Patents
MnO-based 2 Copper ion colorimetric detection method of complex enzyme simulant Download PDFInfo
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- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 96
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N2021/775—Indicator and selective membrane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to a MnO-based catalyst 2 The colorimetric detection method and application of the copper ion of the complex enzyme simulant comprise the following steps: preparing copper ions and L-cys solutions with different concentrations; synthesis of MB and MB/Au/PANI/MnO 2 A composite material; preparing NaAC-HAC buffer solution; preparing TMB solution; optimizing conditions; and (5) colorimetric detection of copper ions. MnO-based alloy provided by the invention 2 Copper ion colorimetric detection method of complex enzyme simulant and application thereof, MB/Au/PANI/MnO 2 The composite material is used as a complex enzyme mimic, has strong catalytic performance, realizes high-sensitivity and quantitative detection of copper ions, improves the selectivity and stability of target object detection, and changes the complex enzyme mimic into doped MnO 2 The compound can be applied to detection and analysis of new targets, has strong universality, simple and convenient detection method, low cost, readily available and nontoxic raw materials, can be applied to 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 MnO 2 Copper ion colorimetric detection method of complex enzyme mimics and applicationIs used.
Background
Currently, the current state of the art commonly used in the industry is as follows:
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 participates in the formation of various biological enzymes and maintains the activity of the enzymes, so that the electron transfer and redox metabolic vital activities are normally carried out. Copper is also involved in erythropoiesis to maintain normal hematopoiesis. In addition, children's tics are closely related to copper content in the human body. However, excessive copper ion (Cu 2+ ) A number of health problems can also result, including ischemic heart disease, anemia, kidney disease, bone disease, senile dementia, prions, parkinson's disease, etc. More importantly, cu in water 2+ Too high a content may have an adverse effect on aquatic organisms. The world health organization and the U.S. environmental protection agency have established Cu in drinking water 2+ The maximum allowable limit of (2) is set to 1.3 ppm. Chinese national standards indicate that Cu in tap water 2+ Is limited to 1 mg/L. Thus, cu in the environment is monitored within an appropriate range 2+ Is of critical importance. Current detection of Cu 2+ Conventional methods of (a) typically 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 provision of specialized operators. Therefore, there is a need to design a simple quantitative detection of Cu, both biologically and environmentally 2+ Is described. The colorimetric chemical sensor is an alternative device because of 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 (Horseradish Peroxidase, HRP) is a very commonly used enzyme for H 2 O 2 Has high-efficiency catalysis effect and is widely applied to biosensing labels, such as enzyme-linked immunosorbent assay. In 2019, researchers used cotton threads as solid adsorbents to improve local Cu on the cotton threads 2+ Concentration of Cu with ascorbic acid 2+ Reduction to Cu + By observing the color change of HRP catalyzed oxidation of colorless TMB (Tetramethylbenzidine, 3', 5' -tetramethyllbenzidine) to blue oxidation state (ox TMB), cu was obtained + Has the function of inhibiting the catalytic oxidation of TMB by HRP, thereby realizing quantitative detection of Cu 2+ Compared with other analysis methods, the detection limit is 0.15 nmol/L, and the method provides a sensitive and portable online pre-concentration colorimetric detection method for Cu 2+ Is a method of (2). However. The colorimetric chemical sensor takes HRP as enzyme to catalyze reaction, and the HRP has the defects of variability, high cost, complex preparation, long reaction incubation time and the like, so that the practical application of the colorimetric chemical sensor is greatly limited. Therefore, research on the enzyme with the advantages of simple preparation, stable property, strong environmental tolerance and the like is of great significance to detection of biomolecules.
The use of mimetic enzymes, also known as nanoenzymes, as a biomimetic nanoenzyme for inorganic nanomaterials has attracted increasing interest in research. Bionic nano-enzymes are a class of chemically synthesized nano-materials with similar biological catalytic activity as certain natural enzymes. The nano enzyme has simpler structure and stable chemical property than natural enzyme, and has the advantages of enzyme function, mass production and low cost. In addition, the nature of the nano enzyme is a nano material, which 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 subjected to multiple designs and applications. Adding magnetic nanomaterials, e.g. Fe, to nanomaterials 3 O 4 The nano material can be effectively separated from the solution by using an external magnetic field, and can be easily recycled. However, unmodified Fe 3 O 4 Not only is easy to agglomerate and oxidize, but also is unstable in an acidic medium, thereby limiting the wide application range of the catalyst. Polyaniline (PANI) is a high-efficiency Fe 3 O 4 In recent years, PANI has been developed as a catalytic support due to its good stability of reaction conditions, non-toxicity, and low cost. Au is a metal with catalytic activity, and has the advantages of mild reaction condition, simple operation, short reaction time and reaction selectivityHigh quality. MnO (MnO) 2 The nano enzyme is artificially prepared, has good stability, a porous structure with uneven size and a specific crystal structure, and the structure is favorable for catalysis. The Magnetic Beads (MB) are anti-interference elements with high Magnetic permeability, low cost and easy use, and have the characteristics of large specific surface area, good stability, low toxicity and the like. Thus, MB, au, PANI, mnO 2 Preparation of the Complex for Cu detection 2+ Has important significance.
Cysteine (L-Cysine, L-Cys) can produce glutathione, which is the most predominant and strongest antioxidant. Glutathione is a small molecular peptide substance containing sulfhydryl, the sulfhydryl on cysteine is its active group, L-Cys and Cu 2+ Insoluble mercaptides (mercaptides) may be formed. At L-Cys and Cu 2+ After the reaction, the solution develops color in the presence of the catalytic material.
Colorimetric detection is a method for determining the content of a component to be measured by comparing (visual colorimetry) or measuring (ultraviolet-visible spectroscopy) the color depth of a solution of a colored substance based on the color reaction of a colored compound. The colorimetric detection cost is low, the operation is simple and convenient, the detection duration is short, and the visual quick qualitative detection is applicable to quick detection. Colorimetric detection is one of widely used detection methods, wherein the content of a composite material and TMB in ELISE is related to the content of an object to be detected, enzyme catalyzes a substrate to generate a colored product, the amount of the colored product is directly related to the amount of the object to be detected, and qualitative or quantitative analysis can be performed through the color shade. The enzyme catalysis efficiency is high, and the colorimetric detection sensitivity is high, so that the colorimetric detection is of great significance.
In summary, the problems of the prior art are:
(1) For detecting Cu 2+ Methods such as absorption spectroscopy, electrochemical methods, ion chromatography, which are costly, time consuming, require precision instrumentation and specialized operating technicians.
(2) Currently, used for Cu 2+ The detection has less analysis and research, and Cu 2+ Detection in biological matrix hasThe high-sensitivity detection of the low-concentration target is difficult to realize.
Disclosure of Invention
In order to solve the technical problems existing in the prior art, the invention aims to provide a MnO-based catalyst 2 Copper ion colorimetric detection method of complex enzyme simulant and application thereof, and detection range of copper ions is 1.0 multiplied by 10 2 -1.0×10 7 nM, limit of detection 0.65 nM.
In order to achieve the above purpose and achieve the above technical effects, the invention adopts the following technical scheme:
MnO-based 2 The colorimetric detection method of the copper ions of the complex enzyme mimics comprises the following steps:
s101: copper ion and L-Cys solution with different concentrations were prepared (preparation 10 2 -10 7 nmol/L Cu 2+ L-Cys solution
S102: synthesis of magnetic beads MB and MB/Au/PANI/MnO 2 Composite material
S103: preparation of NaAC-HAC buffer
S104: preparation of TMB solution
S105: condition optimization
S106: and carrying out colorimetric detection on copper ions.
Further, in step S101, cuSO is weighed 4 ·5H 2 O is prepared into a copper sulfate solution, and then diluted for a plurality of times to obtain 100 nmol/L Cu 2+ The prepared solution was stored at 4 ℃.
Further, in step S101, L-Cys was weighed to prepare a 10. 10 mL. Mu. Mol/L solution, and the prepared solution was stored at 4 ℃.
Further, in step S102, the synthesizing step of MB includes:
introducing nitrogen into HCl solution for 20-25 min, and weighing FeCl 2 ·4H 2 O and FeCl 3 ·6H 2 Placing O in a round bottom flask, adding above HCl solution with nitrogen gas, stirring thoroughly to dissolve, introducing nitrogen gas into the mixed solution to deoxidize for 20-25 min, repeatedly introducing several times, then rapidly adding NaOH solution, vigorously stirring under nitrogen protection for 2-2.1 h, washing with secondary water several times to neutrality, one partThe components are preserved at 4 ℃ for standby, and the other components are naturally dried for standby.
Further, in step S102, MB/Au/PANI/MnO 2 The synthesis steps of the composite material comprise:
adding the washed magnetic beads MB into PVP solution, shaking uniformly, adding chloroauric acid, and performing ultrasonic treatment for 5-6min for later use, and marking as solution A;
mixing aniline and HCL solution, stirring uniformly, and marking as solution B;
mixing solution A and solution B, adding ammonium persulfate, shaking, standing for 2-2.1-h, magnetically separating, cleaning, oven drying, dispersing in water, ultrasonic homogenizing, adding KMnO 4 The solution is vibrated evenly, magnetically separated and washed to obtain the required MB/Au/PANI/MnO 2 A composite material.
Further, in step S103, the preparation step of the NaAC-HAC buffer solution includes:
weighing sodium acetate, diluting to constant volume to 100 mL, and regulating pH to 4 with acetic acid to obtain NaAC-HAC buffer solution.
Further, in step S104, the TMB solution is to be prepared for use, and the preparation steps of the TMB solution include:
and (3) solution A: dissolving TMB in DMSO, and uniformly stirring for later use;
and (2) liquid B: citric acid added NaHPO 4 Stirring uniformly, and fixing the volume to 100 mL;
and then adding all the prepared solution A into 10 mL of solution B, and carrying out ultrasonic homogenization to obtain the required TMB solution.
Further, in step S105, the MB/PANI/Au/MnO 2 Optimization of reaction volume of composite material and TMB, L-Cys and MB/PANI/Au/MnO 2 Optimization of reaction volume of composite material, cu 2+ Optimization of reaction time with L-Cys, L-Cys and MB/PANI/Au/MnO 2 Optimization of composite material reaction time, MB/PANI/Au/MnO 2 And (3) optimizing the reaction time of the composite material and TMB, and optimizing the pH of a buffer solution.
Further, in step S106, naAC-HAC buffer is added with L-Cys solution and Cu 2+ Reaction followed by addition of MB/PANI/Au/MnO 2 Adding TMB solution into the composite material for reaction, and performing colorimetric detectionAnd measuring absorbance.
The invention discloses a MnO-based catalyst 2 Application of copper ion colorimetric detection method of complex enzyme mimics in detection of target object for removing copper ions, and MB/PAMAM/MnO 2 Replacement of composite material with doped MnO 2 Is a complex of a different type.
Compared with the prior art, the invention has the beneficial effects that:
MnO 2 complex enzyme mimics, i.e., MB/Au/PANI/MnO 2 The composite material has strong catalytic performance, can catalyze TMB to be oxidized into blue cationic free radical oxidized tetramethyl benzidine (ox TMB), and can effectively inhibit the generation of cationic free radical to reduce the cationic free radical into colorless TMB molecules, and the L-Cys and Cu 2+ Insoluble thiolates can be formed to effect Cu by colorimetric analysis 2+ Is quantitatively detected, cu is improved 2+ Detection sensitivity, selectivity and stability of target detection;
compared with HRP, mnO 2 The method has the characteristics of good chemical stability, simple operation, low cost, easy modification and the like, and can avoid using high-cost unstable biological enzymes which are difficult to operate; by using MB/Au/PANI/MnO 2 Composite material not only can be used for Cu 2+ The MB/Au/PANI/MnO can also be quantitatively detected 2 The composite material is replaced by doped MnO 2 The complex is applied to detection and analysis of new targets, and has strong universality and high sensitivity;
combination of nano enzyme catalytic oxidation TMB and colorimetric analysis method for constructing Cu 2+ The new colorimetric analysis method for the detection object improves the analysis sensitivity and is compared with the traditional Cu 2+ Compared with the detection method, the method has the advantages of avoiding the defects of expensive equipment, complex pretreatment, complex operation procedure, high toxicity and the like, along with simplicity, high efficiency, low cost, stability, readily available raw materials and no toxicity, can be applied to actual sample detection, and is suitable for industrial popularization and use.
Drawings
FIG. 1 is a flow chart of the working principle of the invention;
FIG. 2 is a schematic diagram of the present invention;
FIG. 3 shows TMB and MB/Au/PANI/MnO at a wavelength of 652nm according to the present invention 2 Different volumes of composite material reaction versus Cu 2+ Is a graph of the influence of (1);
FIG. 4 shows TMB and MB/Au/PANI/MnO at a wavelength of 652nm according to the present invention 2 Reaction time of composite vs. Cu 2+ Is a graph of the influence of (1);
FIG. 5 is a Cu of the present invention 2+ A detected selective experimental result graph;
FIG. 6 shows different Cu's of the present invention 2+ Standard working curve graph of concentration;
FIG. 7 shows different Cu's of the present invention 2+ Concentration UV-vis response curve.
Detailed Description
The following embodiments of the present invention are described in detail so that the advantages and features of the present invention may be more readily understood by those skilled in the art, thereby making a clearer and more definite definition of the scope of the present invention.
Example 1
As shown in fig. 1-7, a MnO-based composition 2 Copper ion colorimetric detection method of complex enzyme simulant by using copper ion Cu 2+ The detection is taken as an example, and the action mechanism is as follows:
MB/PANI/MnO 2 the composite material is used as a complex enzyme mimic, can catalyze TMB to oxidize into blue cationic free radicals, and the L-Cys can effectively inhibit the generation of the cationic free radicals, so that the cationic free radicals are reduced into colorless TMB molecules, and the L-Cys and Cu 2+ Insoluble mercaptides may be formed. At L-Cys with Cu at different concentrations 2+ After the reaction, the solution was prepared in MB/PANI/MnO 2 The composite material and TMB become blue under the existence condition, and the absorbance value at 652nm wavelength changes along with the change of the copper ion concentration, thereby achieving the purpose of detecting copper ions.
The invention also discloses a MnO-based catalyst 2 Application of copper ion colorimetric detection method of complex enzyme mimics in detection of target object for removing copper ions, and MB/PAMAM/MnO 2 Replacement of composite material with doped MnO 2 Can be used for detecting and analyzing other targets.
Investigation of Cu at different concentrations 2+ Influence on detection and MB/Au/PANI/MnO 2 Synthesis of composite materials:
(1) Configuration 10 2 -10 7 nmol/L Cu 2+ L-Cys solution
Weighing 0.0025 g CuSO 4 ·5H 2 O is formulated into 1mL, 10 7 nmol/L copper sulfate solution. Taking 100 mu L, 10 7 nmol/L copper sulfate solution, diluted 10 times to obtain 10 6 nmol/L Cu 2+ The method comprises the steps of carrying out a first treatment on the surface of the Taking 100 mu L and 10 6 nmol/L dilution 10 times to 10 5 nmol/L Cu 2+ The method comprises the steps of carrying out a first treatment on the surface of the Preparation 10 according to this method 4 nmol/L Cu 2+ 、10 3 nmol/L Cu 2+ 、100 nmol/L Cu 2+ 。
0.00048g of L-cys were weighed out and prepared as 10 mL. Mu. Mol/L solutions, which were stored at 4 ℃.
(2) Magnetic beads MB and MB/Au/PANI/MnO 2 Synthesis of composite materials
The synthesis steps of MB include:
30 mL mmol/L HCl is taken and nitrogen is introduced for 20 min, 0.29815 g FeCl is weighed 2 ·4H 2 O、0.81087 g FeCl 3 ·6H 2 Placing O in a container, adding 30 mL mmol/L HCl solution with nitrogen introduced therein and fully stirring until the solution is completely dissolved, introducing nitrogen into the mixed solution for 20 min, repeatedly introducing three times, then rapidly adding 30 mL mol/L NaOH and 1.25 mol/L NaOH, vigorously stirring for 2 h under the protection of nitrogen, flushing with secondary water for three times until the solution is neutral, placing one part of the solution at 4 ℃ for standby, and naturally airing the other part of the solution for standby.
MB/Au/PANI/MnO 2 The synthesis steps of the composite material comprise:
adding 1ml of the washed MB into PVP solution (0.1 g PVP+10 ml water), oscillating with a constant temperature oscillator to 1 h, and dripping 2 mL mass percent of 1% HAuCl 4 Ultrasonic for 5min for later use, and marking as a solution A;
0.3 mL aniline and 10 mL 1 mol/L HCl are stirred and mixed uniformly and marked as solution B;
mixing the solution A and the solution B, adding 0.18-g ammonium persulfate, oscillating for 1-h, standing for 2-h, performing magnetic separation, washing the precipitate with ethanol for 1-2 times, and drying at 50-60 ℃;
dispersing dried product 5 mg in 5 mL water, ultrasonic treating, adding 5 mg KMnO 4 Performing magnetic separation after oscillating 1 h, washing the precipitate for 1-2 times, and loading into a centrifuge tube of 2 mL to obtain MB/Au/PANI/MnO 2 Composite material, then the synthesized MB/Au/PANI/MnO 2 Diluting the composite material four times to obtain MB/Au/PANI/MnO for experiment 2 Composite material, MB/Au/PANI/MnO for each experiment 2 The composite materials are uniformly mixed 25 to s.
(3) Buffer solution preparation
Sodium acetate (NaAC) 8.3, g was weighed, diluted to a constant volume of 100 mL, and pH was adjusted to 4 with 1.75 mol/L acetic acid (HAC) to give 0.6 mol/L, pH =4 NaAC-HAC buffer.
Example 2
The preparation steps of the TMB solution comprise:
the TMB solution is ready to use.
And (3) solution A: 0.0143 Dissolving g TMB in 100 mu L DMSO, and uniformly stirring for later use;
and (2) liquid B: 24.3 5.7. 5.7 mL, 0.2 mol/L NaH are added to the solution of mL and 0.1 mol/L citric acid 2 PO 4 Stirring uniformly, and fixing the volume to 100 mL;
and then adding all the prepared solution A into 10 mL of solution B, carrying out ultrasonic homogenization to obtain 6 mmol/L TMB solution for experiments, and preserving at 4 ℃ in a dark place.
Example 3
Cu 2+ Colorimetric detection of (c):
s101: weighing 0.0025 g CuSO 4 ·5H 2 O is formulated into 1mL, 10 7 nmol/L copper sulfate solution. Taking 100 mu L, 10 7 nmol/L copper sulfate solution, diluted 10 times to obtain 10 6 nmol/L Cu 2+ The method comprises the steps of carrying out a first treatment on the surface of the Taking 100 mu L, 10 6 nmol/L dilution 10 times to 10 5 nmol/L Cu 2+ The method comprises the steps of carrying out a first treatment on the surface of the Preparation 10 according to this method 4 nmol/L Cu 2+ 、10 3 nmol/L Cu 2+ 、10 2 nmol/L Cu 2+ 。
0.00048g of L-cys were weighed out and prepared as 10 mL. Mu. Mol/L solutions, which were stored at 4 ℃.
S102: the synthesis steps of MB include:
30 mL mmol/L HCl is taken and nitrogen is introduced for 20 min, 0.29815 g FeCl is weighed 2 ·4H 2 O、0.81087 g FeCl 3 ·6H 2 Placing O in a container, adding 30 mL mmol/L HCl solution with nitrogen introduced therein and fully stirring until the solution is completely dissolved, introducing nitrogen into the mixed solution for 20 min, repeatedly introducing three times, then rapidly adding 30 mL mol/L NaOH and 1.25 mol/L NaOH, vigorously stirring for 2 h under the protection of nitrogen, flushing with secondary water for three times until the solution is neutral, placing one part of the solution at 4 ℃ for standby, and naturally airing the other part of the solution for standby.
MB/Au/PANI/MnO 2 The synthesis steps of the composite material comprise:
adding 1ml of the washed MB into PVP solution (0.1 g PVP+10 ml water), oscillating a shaking table 1 h, adding 2 ml of 1% chloroauric acid, and performing ultrasonic treatment for 5min for later use, and marking as solution A;
0.3 mixing and stirring well ml of aniline+ ml and 1M HCL, and marking as a solution B;
mixing solution A and solution B, adding ammonium persulfate 0.18 g, oscillating 1 h, standing 2 h, magnetically separating, washing with ethanol 1-2 times, oven drying at 50-60deg.C, weighing, dispersing 5 mg above product in 5 ml water, ultrasound homogenizing, adding 5 mg KMnO 4 Oscillating 1 h, magnetically separating, washing with water for 1-2 times to obtain the required MB/Au/PANI/MnO 2 A composite material.
S103: the preparation steps of the NaAC-HAC buffer solution comprise:
sodium acetate (NaAC) 8.3, g was weighed, diluted to a constant volume of 100 mL, and pH was adjusted to 4 with 1.75 mol/L acetic acid (HAC) to give 0.6 mol/L, pH =4 NaAC-HAC buffer.
S104: the preparation steps of the TMB solution comprise:
the TMB solution is ready to use.
And (3) solution A: 0.0143 Dissolving g TMB in 100 mu L DMSO, and uniformly stirring for later use;
and (2) liquid B: 24.3 5.7. 5.7 mL, 0.2 mol/L NaH are added to the solution of mL and 0.1 mol/L citric acid 2 PO 4 Stirring uniformly, and fixing the volume to 100 mL;
and then adding all the prepared solution A into 10 mL of solution B, carrying out ultrasonic homogenization to obtain 6 mmol/L TMB solution for experiments, and preserving at 4 ℃ in a dark place.
S105: condition optimization:
MB/PANI/Au/MnO 2 optimization of reaction volume of composite material and TMB, L-Cys and MB/PANI/Au/MnO 2 Optimization of reaction volume, cu 2+ Optimization of reaction time with L-Cys, L-Cys and MB/PANI/Au/MnO 2 Optimization of composite material reaction time, MB/PANI/Au/MnO 2 And (3) optimizing the reaction time of the composite material and TMB, and optimizing the pH of a buffer solution.
FIG. 3 shows TMB and MB/Au/PANI/MnO at a wavelength of 652nm according to the present invention 2 Different volumes of composite material reaction versus Cu 2+ The results show that the absorbance signal magnitude is related to TMB and MB/Au/PANI/MnO 2 The volume of the composite material reaction is linearly related, the correlation coefficient is 0.9817, and the larger the volume is, the larger the signal value is.
FIG. 4 shows TMB and MB/Au/PANI/MnO at a wavelength of 652nm according to the present invention 2 Reaction time of composite vs. Cu 2+ The results show that the absorbance signal is substantially unaffected by the reaction time.
S106: for Cu 2+ And (3) carrying out selective detection:
under the optimal conditions, taking copper ions with a concentration (1 mM) in a linear range and other ions (magnesium ions, iron ions, zinc ions, sodium ions, calcium ions, cadmium ions, potassium ions and manganese ions) in an amount which is 10 times that of the copper ions, and using a system reaction (L-Cys, MB/PANI/MnO) 2 The material and TMB) and detecting the absorbance value, 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 different Cu 2+ Concentration standard working curve, FIG. 7 shows different Cu 2+ UV-vis response of concentrationThe magnitude of the absorbance signal should be plotted to increase with increasing copper ion concentration.
The part of the invention which is not specifically described is only required to adopt the prior art, and is not described in detail herein.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (1)
1. MnO-based 2 The colorimetric detection method for the copper ions of the complex enzyme mimics is characterized by comprising the following steps of:
s101: configuration 10 2 -10 7 nmol/L Cu 2+ An L-Cys solution;
s102: synthetic magnetic beads and MB/Au/PANI/MnO 2 A composite material;
s103: preparing NaAC-HAC buffer solution;
s104: preparing TMB solution;
s105: optimizing conditions;
s106: colorimetric detection is carried out on copper ions;
in step S101, cuSO is weighed 4 ·5H 2 O is prepared into a copper sulfate solution, and then diluted for a plurality of times to obtain 100 nmol/L Cu 2+ The prepared solution is preserved at 4 ℃;
in the step S101, L-Cys is weighed to prepare 10 mL and 400 mu mol/L solution, and the prepared solution is stored at 4 ℃;
in step S102, the step of synthesizing the magnetic beads includes:
introducing nitrogen into HCl solution for 20-25 min, and weighing FeCl 2 ·4H 2 O and FeCl 3 ·6H 2 Placing O in a round bottom flask, adding above HCl solution, stirring thoroughly to dissolve, introducing nitrogen into the mixed solution to remove oxygen for 20-25 min, repeatedly introducing several times, rapidly adding NaOH solution, vigorously stirring under nitrogen protection for 2-2.1 h, washing with secondary water several times to neutrality, and storing at 4deg.CNaturally airing a part of the mixture for standby;
in step S102, MB/Au/PANI/MnO 2 The synthesis steps of the composite material comprise:
adding the washed MB into PVP solution, shaking uniformly, adding chloroauric acid, and performing ultrasonic treatment for 5-6min for later use, and marking as solution A;
mixing aniline and HCL solution, stirring uniformly, and marking as solution B;
mixing solution A and solution B, adding ammonium persulfate, shaking, standing for 2-2.1-h, magnetically separating, cleaning, oven drying, dispersing in water, ultrasonic homogenizing, adding KMnO 4 The solution is vibrated evenly, magnetically separated and washed to obtain the required MB/Au/PANI/MnO 2 A composite material;
in step S103, the preparation step of the NaAC-HAC buffer solution comprises the following steps:
weighing sodium acetate, diluting to constant volume to 100 mL, and regulating pH to 4 with acetic acid to obtain NaAC-HAC buffer solution;
in step S104, the TMB solution is ready to be prepared, and the preparation steps of the TMB solution include:
and (3) solution A: dissolving TMB in DMSO, and uniformly stirring for later use;
and (2) liquid B: citric acid added NaHPO 4 Stirring uniformly, and fixing the volume to 100 mL;
then adding all the prepared solution A into 10 mL of solution B, and carrying out ultrasonic homogenization to obtain a required TMB solution;
in step S105, for MB/PANI/Au/MnO 2 Optimization of reaction volume of composite material and TMB, L-Cys and MB/PANI/Au/MnO 2 Optimization of reaction volume of composite material, cu 2+ Optimization of reaction time with L-Cys, L-Cys and MB/PANI/Au/MnO 2 Optimization of composite material reaction time, MB/PANI/Au/MnO 2 Optimizing the reaction time of the composite material and TMB and the pH of a buffer solution;
in step S106, naAC-HAC buffer solution is taken, L-Cys solution and Cu are added 2+ Reaction followed by addition of MB/PANI/Au/MnO 2 Adding TMB solution into the composite material for reaction, performing colorimetric detection, and measuring absorbance;
MB/PANI/Au/MnO 2 the composite material has strong catalytic performance and catalysisOxidation of TMB to blue cationic radical, tetramethyl benzidine oxide, and L-Cys is effective in inhibiting the formation of cationic radicals, which are reduced to colorless TMB molecules, L-Cys and Cu 2+ Formation of insoluble thiolates, cu was achieved by colorimetric analysis 2+ The detection range of copper ions was 1.0X10 2 -1.0×10 7 nM, limit of detection 0.65 nM.
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