CN110862478A - Visual heavy metal sensor based on enzymatic reaction and preparation method thereof - Google Patents
Visual heavy metal sensor based on enzymatic reaction and preparation method thereof Download PDFInfo
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- 230000000007 visual effect Effects 0.000 title claims abstract description 36
- 238000006911 enzymatic reaction Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004038 photonic crystal Substances 0.000 claims abstract description 112
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- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
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- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 6
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- ISEPWYWSHQNDEJ-UHFFFAOYSA-N 3,3-dihydroxy-2,2-dimethyl-1-phenylpropan-1-one Chemical compound OC(C(C(=O)C1=CC=CC=C1)(C)C)O ISEPWYWSHQNDEJ-UHFFFAOYSA-N 0.000 description 5
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- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
Abstract
The invention discloses a visual heavy metal sensor based on enzymatic reaction and a preparation method thereof, and solves the problems that the prior art can only detect under laboratory conditions, the instrument is expensive, the response speed is low, and the accuracy is low. The preparation method comprises the following steps: firstly, preparing ethanol pre-polymerization liquid containing a functional monomer, a cross-linking agent and an initiator, then filling the pre-polymerization liquid into gaps of photonic crystal colloidal particles, putting the photonic crystal colloidal particles into an ultraviolet lamp for polymerization, and etching by hydrofluoric acid after the polymerization is completed to obtain the visual heavy metal sensor based on enzymatic reaction. Prepared according to the aboveThe visual heavy metal sensor based on enzymatic reaction prepared by the method does not need special personnel, is simple to operate, high in sensitivity, high in response speed, cheap and portable, can be used for carrying out on-site real-time visual detection without depending on other analytical instruments, and the lowest detection limit can reach 5x10‑14g/L, and the photonic crystal sensor can be repeatedly used.
Description
Technical Field
The invention belongs to the technical field of nano functional material sensors, and relates to a visual heavy metal sensor based on enzymatic reaction and a preparation method thereof.
Background
With the progress of the industrialization level in China, the industrial system is gradually improved. Meanwhile, the industrial wastewater and the solid garbage are randomly buried, so that the natural environment is greatly polluted and damaged, and the human health is greatly threatened. Among them, heavy metal pollution is one of the most serious problems in environmental pollution. Heavy metals refer to a class of metal elements with a relative atomic density greater than 4.5g/cm3, which are mainly present in a water environment and generally include mercury (Hg), lead (Pb), copper (Cu), cadmium (Cr), and the like, which have relatively obvious biotoxicity and are not easily degraded.
Heavy metals in the water environment can finally flow to human beings through a food chain, and finally accumulate in the human body to destroy normal organ operation of the human body and even cause organ function decline, thereby harming human health. Therefore, the establishment of a method for detecting heavy metals efficiently, quickly and conveniently has important practical significance.
At present, the methods for detecting heavy metals are mature, such as an atomic absorption method, an inductively coupled plasma mass spectrometry, an ultraviolet-visible spectrophotometry, a surface enhanced Raman spectroscopy and an electrochemical analysis method. Among them, atomic absorption, ultraviolet-spectrophotometry, X-ray fluorescence spectroscopy, and surface-enhanced raman spectroscopy have been used for the detection of trace amounts of heavy metals in aqueous environments. However, these methods also have many disadvantages, such as detection only under laboratory conditions, expensive instruments, slow response speed and low accuracy. These disadvantages greatly limit the field analytical detection of heavy metals. Therefore, the development of a field visual detection technology which is rapid and sensitive to the heavy metal ions in the water environment and does not depend on a large-scale analytical instrument has important practical application value.
The photonic crystal is an ordered structure material formed by arranging two or more materials with different refractive indexes in a certain periodic sequence in space. When visible light passes through the photonic crystal, the visible light is modulated by the periodic field of the photonic crystal, and light with specific frequency is reflected, so that a bright structural color is formed. Techniques based on this particular optical property can be used to develop a variety of chemical sensors. Urease can catalyze urea to hydrolyze into bicarbonate ions, ammonium ions and hydroxide ions, and the pH responsive hydrogel photonic crystal has good response capability to acidic or alkaline ions and obvious color change in macroscopical view. When heavy metal ions exist in the solution, the heavy metal ions can inhibit the hydrolysis reaction of urease and urea, so that the pH value of a system cannot be obviously changed, and the macroscopic color of the sensor is difficult to change. Therefore, the on-site visual high-efficiency detection of the heavy metal is indirectly realized through the response of the photonic crystal sensor to the pH.
Disclosure of Invention
The invention aims to provide a visual heavy metal sensor based on enzymatic reaction and a preparation method thereof.
In order to achieve the above purpose, the invention provides a preparation method of a visual heavy metal sensor based on enzymatic reaction, which comprises the following steps:
firstly, preparing ethanol pre-polymerization liquid containing a functional monomer, a cross-linking agent and an initiator, then filling the pre-polymerization liquid into gaps of photonic crystal colloidal particles, putting the photonic crystal colloidal particles into an ultraviolet lamp for polymerization, and etching by hydrofluoric acid after the polymerization is completed to obtain the visual heavy metal sensor based on enzymatic reaction.
The preparation method comprises the following specific steps:
the method comprises the following steps: preparing a prepolymerization liquid containing a functional monomer, a crosslinking agent and an initiator, wherein the volume ratio of the functional monomer to the crosslinking agent to the solvent to the initiator is 1-5: 0.1-1: 5-10: 0.1, then carrying out ultrasonic treatment on the prepolymerization liquid, and refrigerating overnight;
step two: and (3) inclining the photonic crystal template by 15 degrees, then permeating the pre-polymerized liquid obtained in the step one from the edge of the photonic crystal, covering an organic glass sheet on the photonic crystal when the photonic crystal is completely permeated until the photonic crystal is transparent, then placing the photonic crystal under an ultraviolet lamp for irradiating for 3-5 hours, finally taking out the photonic crystal, etching by hydrofluoric acid, and placing the photonic crystal in water for balancing for later use, thereby obtaining the visual heavy metal sensor based on enzymatic reaction.
In the first step, the functional monomer is methacrylic acid, acrylic acid, hydroxyethyl methacrylate, methyl methacrylate or itaconic acid; the cross-linking agent is ethylene glycol dimethacrylate or N, N-methylene bisacrylamide; the solvent is ethanol, methanol, water or a mixture thereof; the initiator is 2-hydroxy-2-methyl propiophenone.
In the second step, the concentration of hydrofluoric acid is 1-4%, and the ordered units of the photonic crystals are silica colloid particles, polystyrene particles, polyacrylamide particles or polymethyl methacrylate particles.
The visual heavy metal sensor based on enzymatic reaction is prepared according to the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
compared with the traditional atomic absorption method, ultraviolet-spectrophotometry, X-ray fluorescence spectrometry and surface enhanced Raman spectrometry, the visual heavy metal sensor based on enzymatic reaction, which is prepared by the invention, does not need special personnel, is simple to operate, high in sensitivity, high in response speed, cheap and portable, can carry out on-site real-time visual detection without depending on other analytical instruments, and the minimum detection limit can reach 5X10-14g/L, and the photonic crystal sensor can be repeatedly used.
Drawings
FIG. 1 is a graph of the reflectance spectra of the sensor of example 1 before and after equilibration when placed in a blank solution.
FIG. 2 shows the sensor of example 1 placed to contain 5X10-11Reflection spectra before and after equilibrium in g/L lead ion solution.
FIG. 3 is a graph of the reflectance spectrum of the sensor of example 2 before and after equilibration when placed in a blank solution.
FIG. 4 shows the sensor of example 2 placed at 5X10-12Reflection spectra before and after equilibrium in g/L mercury ion solution.
FIG. 5 is a graph of the reflectance spectrum of the sensor of example 3 before and after equilibration when placed in a blank solution.
FIG. 6 shows the sensor of example 3 placed at 5X10-13Reflection spectra before and after equilibrium in g/L mercury ion solution.
FIG. 7 is a graph of the reflectance spectrum of the sensor of example 4 before and after equilibration when placed in a blank solution.
FIG. 8 shows the sensor of example 4 placed at 5X10-14Reflection spectra before and after equilibrium in g/L mercury ion solution.
FIG. 9 is a graph of the reflectance spectrum of the sensor of example 5 before and after equilibration when placed in a blank solution.
FIG. 10 shows the sensor of example 5 placed at 5X10-7Reflection spectra before and after equilibrium in g/L copper ion solution.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention include, but are not limited to, the scope shown in the following examples.
The invention aims to provide a preparation method of a visual heavy metal sensor based on enzymatic reaction, which comprises the following specific steps:
the method comprises the following steps: preparing an ethanol pre-polymerization liquid containing a functional monomer, a cross-linking agent and an initiator, wherein the volume ratio of the functional monomer to the cross-linking agent to the solvent to the initiator is (1-5) to (0.1-1) to (5-10): 0.1, then placing the pre-polymerization solution into a refrigerator for refrigeration overnight after ultrasonic treatment.
Step two: and (3) inclining the photonic crystal template by 15 degrees, then permeating the pre-polymerized liquid obtained in the step one from the edge of the photonic crystal, covering an organic glass sheet on the photonic crystal when the photonic crystal is completely permeated until the photonic crystal is transparent, then placing the photonic crystal under an ultraviolet lamp for irradiating for 3-5 hours, finally taking out the photonic crystal, etching by hydrofluoric acid, and obtaining the polymer photonic crystal, and placing the polymer photonic crystal in water for balancing and standby.
In the first step, the functional monomers are methacrylic acid, acrylic acid, hydroxyethyl methacrylate, methyl methacrylate and itaconic acid; the cross-linking agent is ethylene glycol dimethacrylate or N, N-methylene bisacrylamide; the solvent is ethanol, methanol, water or a mixture thereof; the initiator is 2-hydroxy-2-methyl propiophenone.
In the second step, the concentration of the hydrofluoric acid is 1% -4%. The ordered unit of the photonic crystal is silica colloid particles, polystyrene particles, polyacrylamide particles or polymethyl methacrylate particles.
The specific monitoring steps are as follows:
adding a heavy metal solution into a urease solution, shaking up the solution after shaking up, adding the solution into a urea solution, then putting the photonic crystal sensor into the solution system, and realizing the detection of heavy metal ions by observing the color change of the sensor.
The sensor is put into the acetic acid water solution, and is balanced after the initial color of the sensor is recovered, so that the sensor can be repeatedly used.
In the monitoring step, the concentration of urea is 50 mM-200 mM, the concentration of enzyme is 1 mg/mL-10 mg/mL, and the concentration of acetic acid is 1% -15%.
Example 1
The method comprises the following steps: methacrylic acid is used as a functional monomer, ethylene glycol dimethacrylate is used as a cross-linking agent, ethanol is used as a solvent, and dihydroxyl dimethyl propiophenone is used as a photoinitiator, wherein the weight ratio of (5: 0.1: 5): 0.1 to prepare a pre-polymerization solution, and then placing the pre-polymerization solution into a refrigerator for refrigeration overnight after ultrasonic treatment.
Step two: firstly inclining the photonic crystal by 15 degrees, then permeating the pre-polymerized liquid obtained in the step one from the edge of the photonic crystal, covering an organic glass sheet on the photonic crystal when the photonic crystal is completely permeated until the photonic crystal is transparent, then placing the photonic crystal under an ultraviolet lamp for irradiating for 4 hours, finally taking out the photonic crystal, etching by 1% hydrofluoric acid, and obtaining the polymer photonic crystal, and placing the polymer photonic crystal in water to balance for later use.
Using an enzymatic reaction-based visual heavy metal sensor prepared in example 1, the blank system (water), 5x10 were separately treated-11The detection is carried out by g/L lead ion solution, and the detection steps and results are as follows.
Blank system
And (3) adding 1mL of water into 200 μ L of 2.5 mg/mL urease aqueous solution, shaking uniformly, adding the mixture into 8.8 mL of 200 mM urea aqueous solution, finally putting the photonic crystal sensor prepared in the step two into the solution system, observing the color change of the sensor, and recording the reflection spectrum before and after the balance of the sensor by a spectrometer, namely the graph 1.
When no heavy metal exists in the system, urease catalyzes urea hydrolysis, so that the pH value of the system is obviously changed, and it can be observed from figure 1 that the reflection peak position moves from initial 546 nm to 622 nm when the photonic crystal sensor is balanced, the reflection peak position moves by 76nm altogether, and macroscopically the reflection peak position changes from green to deep red.
-11Lead ion solution
1mL of 5X10-10Adding the g/L lead ion aqueous solution into 200 mu L2.5 mg/mL urease aqueous solution, shaking up, adding the solution into 8.8 mL200 mM urea aqueous solution, and finally putting the photonic crystal sensor prepared in the step two into the solution system, wherein the lead ion concentration of the solution system is 5x10-11g/L, the sensor color change was observed and the reflectance spectra before and after its equilibrium were recorded by the spectrometer, fig. 2.
Photonic crystal sensor detecting 5x10-11In g/L lead ion, the change of the pH value of the system is reduced due to the inhibition effect of the lead ion on the enzymatic reaction, and it can be observed from figure 2 that the position of the reflection peak of the photonic crystal sensor is shifted from initial 546 nm to 611 nm, and the total shift is 65 nm. Compared with the blank system (i.e. FIG. 1, a total shift of 76 nm), the shift is reduced by 11nm, and the color at equilibrium is also changed from dark red to light red, thereby realizing the 5x10 color pair-11And (5) detecting the visual response of the g/L lead ions.
Example 2
The method comprises the following steps: methacrylic acid is used as a functional monomer, ethylene glycol dimethacrylate is used as a cross-linking agent, ethanol is used as a solvent, and dihydroxyl dimethyl propiophenone is used as a photoinitiator, wherein the weight ratio of (5: 0.5: 5): 0.1 is prepared into a prepolymerization liquid, and then the prepolymerization liquid is placed into a refrigerator for refrigeration overnight after ultrasonic treatment.
Step two: firstly inclining the photonic crystal by 15 degrees, then permeating the pre-polymerized liquid obtained in the step one from the edge of the photonic crystal, covering an organic glass sheet on the photonic crystal when the photonic crystal is completely permeated until the photonic crystal is transparent, then placing the photonic crystal under an ultraviolet lamp for irradiating for 4 hours, finally taking out the photonic crystal, etching by 1% hydrofluoric acid, and obtaining the polymer photonic crystal, and placing the polymer photonic crystal in water to balance for later use.
Using an enzymatic reaction-based visual heavy metal sensor prepared in example 2, the blank system (water), 5x10 were separately treated-12And g/L mercury ion solution is detected, and the detection steps and results are as follows.
Blank system
And (3) adding 1mL of water into 200 μ L of 2.5 mg/mL urease aqueous solution, shaking uniformly, adding the mixture into 8.8 mL of 200 mM urea aqueous solution, finally putting the photonic crystal sensor prepared in the step (II) into the solution system, observing the color change of the sensor, and recording the reflection spectrum before and after the balance of the sensor by a spectrometer, namely the graph is shown in figure 3.
When no heavy metal exists in the system, urease catalyzes urea hydrolysis, so that the pH value of the system is obviously changed, and it can be observed from figure 3 that the reflection peak position is shifted from initial 544 nm to 615 nm and is shifted by 71nm altogether when the photonic crystal sensor is balanced, and macroscopically, the reflection peak position is changed from green to deep red.
-12Mercury ion solution
1mL of 5X10-11Adding the g/L mercury ion aqueous solution into 200 mu L2.5 mg/mL urease aqueous solution, shaking up, adding the solution into 8.8 mL200 mM urea aqueous solution, and finally putting the photonic crystal sensor prepared in the step two into the solution system, wherein the mercury ion concentration of the solution system is 5x10-12g/L, the sensor color change was observed and the reflectance spectra before and after its equilibrium were recorded by the spectrometer, fig. 4.
Photonic crystal sensor detecting 5x10-12In g/L of mercury ions, the mercury ions have an inhibiting effect on enzymatic reaction, so that the pH change of the system is reduced, and it can be observed from FIG. 4 that the reflection peak position of the photonic crystal sensor is shifted from initial 544 nm to 550 nm, and is shifted by 5nm altogether. The shift was reduced by 66 compared to the blank (FIG. 3, a total shift of 71 nm)nm, the color at equilibrium also changes from light red to green, thus realizing the 5x10 color pair-12And (5) detecting the visual response of the g/L mercury ions.
Example 3
The method comprises the following steps: firstly, taking acrylic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linking agent, ethanol as a solvent, and dihydroxyl dimethyl propiophenone as a photoinitiator, wherein the weight ratio of acrylic acid to ethylene glycol dimethacrylate to ethanol is 5:0.1: 5:0.1 to prepare a pre-polymerization solution, and then placing the pre-polymerization solution into a refrigerator for refrigeration overnight after ultrasonic treatment.
Step two: firstly inclining the photonic crystal by 15 degrees, then permeating the pre-polymerized liquid obtained in the step one from the edge of the photonic crystal, covering an organic glass sheet on the photonic crystal when the photonic crystal is completely permeated until the photonic crystal is transparent, then placing the photonic crystal under an ultraviolet lamp for irradiating for 4 hours, finally taking out the photonic crystal, etching by 1% hydrofluoric acid, and obtaining the polymer photonic crystal, and placing the polymer photonic crystal in water to balance for later use.
Using an enzymatic reaction-based visual heavy metal sensor prepared in example 3, the blank system (water), 5X10 were separately treated-13And g/L mercury ion solution is detected, and the detection steps and results are as follows.
Blank system
And (3) adding 1mL of water into 200 μ L of 2.5 mg/mL urease aqueous solution, shaking up, adding the mixture into 8.8 mL of 200 mM urea aqueous solution, finally putting the photonic crystal sensor prepared in the step two into the solution system, observing the color change of the sensor, and recording the reflection spectrum before and after the balance by a spectrometer, namely the graph of FIG. 5.
When no heavy metal exists in the system, urease catalyzes urea hydrolysis, so that the pH value of the system is obviously changed, and it can be observed from figure 5 that the reflection peak position is shifted from initial 540 nm to 722 nm when the photonic crystal sensor is balanced, the reflection peak position is shifted to 82nm altogether, and the reflection peak position is changed from green to deep red macroscopically.
-13Mercury ion solution
1mL of 5X10-12Adding the mercury ion water solution of g/L into urease water solution of 200 mu L and 2.5 mg/mL, shaking up, adding into 200 mM urea of 8.8 mLPutting the photonic crystal sensor prepared in the second step into a solution system, wherein the concentration of mercury ions in the solution system is 5x10-13g/L, the sensor color change was observed and the reflectance spectra before and after its equilibrium were recorded by the spectrometer, i.e. fig. 6.
Photonic crystal sensor detecting 5x10-13In g/L of mercury ions, the mercury ions have an inhibiting effect on enzymatic reaction, so that the pH change of the system is reduced, and it can be observed from FIG. 6 that the position of the reflection peak of the photonic crystal sensor is shifted from initial 540 nm to 615 nm, and is shifted by 71nm altogether. Compared to the blank system (FIG. 5, total shift of 82 nm), the shift was reduced by 11nm, and the color at equilibrium was also changed from dark red to light red, thus achieving a 5 × 10 color pair-13And (5) detecting the visual response of the g/L mercury ions.
Example 4
The method comprises the following steps: firstly, taking itaconic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linking agent, ethanol as a solvent, and dihydroxy dimethyl propiophenone as a photoinitiator, wherein the weight ratio of itaconic acid to ethylene glycol dimethacrylate to ethanol is 5:0.5: 5:0.1 to prepare a pre-polymerization solution, and then placing the pre-polymerization solution into a refrigerator for refrigeration overnight after ultrasonic treatment.
Step two: firstly inclining the photonic crystal by 15 degrees, then permeating the pre-polymerized liquid obtained in the step one from the edge of the photonic crystal, covering an organic glass sheet on the photonic crystal when the photonic crystal is completely permeated until the photonic crystal is transparent, then placing the photonic crystal under an ultraviolet lamp for irradiating for 4 hours, finally taking out the photonic crystal, etching by 1% hydrofluoric acid, and obtaining the polymer photonic crystal, and placing the polymer photonic crystal in water to balance for later use.
Using an enzymatic reaction-based visual heavy metal sensor prepared in example 4, the blank system (water), 5X10 were separately treated-13And g/L mercury ion solution is detected, and the detection steps and results are as follows.
Blank system
And (3) adding 1mL of water into 200 μ L of 2.5 mg/mL urease aqueous solution, shaking up, adding the mixture into 8.8 mL of 200 mM urea aqueous solution, finally putting the photonic crystal sensor prepared in the step two into the solution system, observing the color change of the sensor, and recording the reflection spectrum before and after the balance by a spectrometer, namely the graph of fig. 7.
When no heavy metal exists in the system, urease catalyzes urea hydrolysis, so that the pH value of the system is obviously changed, and it can be observed from figure 7 that the reflection peak position moves from initial 542 nm to 628 nm when the photonic crystal sensor is balanced, the reflection peak position moves by 86nm altogether, and macroscopically the reflection peak position changes from green to deep red.
-14Mercury ion solution
1mL of 5X10-13Adding the g/L mercury ion aqueous solution into 200 mu L2.5 mg/mL urease aqueous solution, shaking up, adding the solution into 8.8 mL200 mM urea aqueous solution, and finally putting the photonic crystal sensor prepared in the step two into the solution system, wherein the mercury ion concentration of the solution system is 5x10-14g/L, the sensor color change was observed and the reflectance spectra before and after its equilibrium were recorded by the spectrometer, i.e. fig. 8.
Photonic crystal sensor detecting 5x10-14In g/L of mercury ions, the mercury ions have an inhibiting effect on enzymatic reaction, so that the pH change of the system is reduced, and it can be observed from FIG. 8 that the position of the reflection peak of the photonic crystal sensor is shifted from initial 542 nm to 626 nm, and is shifted by 82nm altogether. Compared to the blank system (FIG. 7, total shift 86 nm), the shift was reduced by 4nm, and there was essentially no change in color at equilibrium, indicating that the mercury ion was 5X10-14And g/L is the lowest detection limit of the sensor.
Example 5
The method comprises the following steps: firstly, taking itaconic acid as a functional monomer, ethylene glycol dimethacrylate as a cross-linking agent, ethanol as a solvent, and dihydroxy dimethyl propiophenone as a photoinitiator, wherein the weight ratio of itaconic acid to ethylene glycol dimethacrylate to ethanol is 5:0.5: 5: 0.2 to prepare a pre-polymerization solution, and then placing the pre-polymerization solution into a refrigerator for refrigeration overnight after ultrasonic treatment.
Step two: firstly inclining the photonic crystal by 15 degrees, then permeating the pre-polymerized liquid obtained in the step one from the edge of the photonic crystal, covering an organic glass sheet on the photonic crystal when the photonic crystal is completely permeated until the photonic crystal is transparent, then placing the photonic crystal under an ultraviolet lamp for irradiating for 4 hours, finally taking out the photonic crystal, etching by 1% hydrofluoric acid, and obtaining the polymer photonic crystal, and placing the polymer photonic crystal in water to balance for later use.
Using an enzymatic reaction-based visual heavy metal sensor prepared in example 5, the blank system (water), 5x10 were separately treated-7The detection is carried out by g/L copper ion solution, and the detection steps and results are as follows.
Blank system
And (3) adding 1mL of water into 200 μ L of 2.5 mg/mL urease aqueous solution, shaking up, adding the mixture into 8.8 mL of 200 mM urea aqueous solution, finally putting the photonic crystal sensor prepared in the step two into the solution system, observing the color change of the sensor, and recording the reflection spectrum before and after the balance by a spectrometer, namely the graph of FIG. 9.
When no heavy metal exists in the system, urease catalyzes urea hydrolysis, so that the pH value of the system is obviously changed, and it can be observed from figure 9 that the reflection peak position is shifted from initial 547 nm to 622 nm when the photonic crystal sensor is balanced, the reflection peak position is shifted by 75nm altogether, and macroscopically, the reflection peak position is changed from green to deep red.
-7Copper ion solution
1mL of 5X10-6Adding the g/L copper ion aqueous solution into 200 mu L2.5 mg/mL urease aqueous solution, shaking up, adding the mixture into 8.8 mL200 mM urea aqueous solution, and finally putting the photonic crystal sensor prepared in the step two into the solution system, wherein the copper ion concentration of the solution system is 5x10-7g/L, the sensor color change was observed and the reflectance spectra before and after its equilibrium were recorded by the spectrometer, i.e. fig. 10.
Photonic crystal sensor detecting 5x10-7In g/L of copper ions, the pH change of the system is reduced due to the inhibition effect of the copper ions on the enzymatic reaction, and it can be observed from FIG. 6 that the position of the reflection peak of the photonic crystal sensor is shifted from 547 nm to 589 nm, and is shifted by 42 nm altogether. Compared to the blank system (FIG. 1, total shift of 75 nm), the shift is reduced by 33nm, the color at equilibrium changes from deep red to orange, thus achieving a color contrast of 5 × 10-7And g/L visual response detection of copper ions.
After the detection of the above embodiment is finished, the sensor is put into 5% acetic acid aqueous solution, and the sensor is balanced after the initial color is recovered, so that the sensor can be used repeatedly.
Claims (5)
1. A preparation method of a visual heavy metal sensor based on enzymatic reaction is characterized by comprising the following steps:
firstly, preparing ethanol pre-polymerization liquid containing a functional monomer, a cross-linking agent and an initiator, then filling the pre-polymerization liquid into gaps of photonic crystal colloidal particles, putting the photonic crystal colloidal particles into an ultraviolet lamp for polymerization, and etching by hydrofluoric acid after the polymerization is completed to obtain the visual heavy metal sensor based on enzymatic reaction.
2. The preparation method of the visual heavy metal sensor based on enzymatic reaction according to claim 1, wherein the visual heavy metal sensor comprises:
the method specifically comprises the following steps:
the method comprises the following steps: preparing a prepolymerization liquid containing a functional monomer, a crosslinking agent and an initiator, wherein the volume ratio of the functional monomer to the crosslinking agent to the solvent to the initiator is 1-5: 0.1-1: 5-10: 0.1, then carrying out ultrasonic treatment on the prepolymerization liquid, and refrigerating overnight;
step two: and (3) inclining the photonic crystal template by 15 degrees, then permeating the pre-polymerized liquid obtained in the step one from the edge of the photonic crystal, covering an organic glass sheet on the photonic crystal when the photonic crystal is completely permeated until the photonic crystal is transparent, then placing the photonic crystal under an ultraviolet lamp for irradiating for 3-5 hours, finally taking out the photonic crystal, etching by hydrofluoric acid, and placing the photonic crystal in water for balancing for later use, thereby obtaining the visual heavy metal sensor based on enzymatic reaction.
3. The preparation method of the visual heavy metal sensor based on enzymatic reaction according to claim 2, wherein the visual heavy metal sensor comprises:
in the first step, the functional monomer is methacrylic acid, acrylic acid, hydroxyethyl methacrylate, methyl methacrylate or itaconic acid; the cross-linking agent is ethylene glycol dimethacrylate or N, N-methylene bisacrylamide; the solvent is ethanol, methanol, water or a mixture thereof; the initiator is 2-hydroxy-2-methyl propiophenone.
4. The preparation method of the visual heavy metal sensor based on enzymatic reaction as claimed in claim 3, wherein the visual heavy metal sensor comprises:
in the second step, the concentration of hydrofluoric acid is 1-4%, and the ordered units of the photonic crystals are silica colloid particles, polystyrene particles, polyacrylamide particles or polymethyl methacrylate particles.
5. An enzymatic reaction-based visual heavy metal sensor manufactured by the manufacturing method of claims 1-4.
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