CN110511744B - Preparation method and application of phosphorescent quantum dot imprinted material - Google Patents

Preparation method and application of phosphorescent quantum dot imprinted material Download PDF

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CN110511744B
CN110511744B CN201910781767.5A CN201910781767A CN110511744B CN 110511744 B CN110511744 B CN 110511744B CN 201910781767 A CN201910781767 A CN 201910781767A CN 110511744 B CN110511744 B CN 110511744B
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何瑜
宋功武
周建刚
葛伊莉
周吉
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Hubei University
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Abstract

The invention provides a preparation method and application of a phosphorescent quantum dot imprinted material, which comprises the following steps: 1) mixing L-cysteine and MnCl2And ZnSO4Mixing the aqueous solutions, adjusting pH with alkaline solution, stirring at room temperature while introducing inert gas to allow L-cysteine and Mn2+And Zn2+Fully complexing; adding Na by syringe2S, continuously reacting the aqueous solution, aging, then settling the quantum dots by absolute ethyl alcohol, and centrifugally separating to obtain water-soluble room-temperature phosphorescent Mn: ZnS quantum dots; 2) adding L-cysteine into water-soluble room-temperature phosphorescent Mn: ZnS quantum dots to protect the Mn: ZnS quantum dots, and adding a virtual template to obtain a mixed solution; stirring the mixed solution at room temperature, dropwise adding silicate ester, and stirring vigorously; then adjusting the pH value with alkali liquor; continuously stirring the solution of the system; washing with ethanol and water to remove the virtual template molecules to obtain solid double virtual fragments SiO2The @ Mn: ZnS phosphorescent quantum dot imprinted material is a molecular imprinted material with the functions of enriching and removing algal toxins.

Description

Preparation method and application of phosphorescent quantum dot imprinted material
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method and application of a phosphorescent quantum dot imprinted material.
Background
The fluorescence test method is seriously interfered by background and scattered light, is not beneficial to measuring actual biological samples and environmental samples, and room temperature phosphorescence sensing has many advantages compared with fluorescence sensing and becomes an important detection mode. Because the traditional phosphorescence quantum dot sensor can not specifically identify the target object, the quantum dot and the molecular imprinting technology are combined, so that the selectivity is improved to a great extent.
The molecular imprinting can synthesize materials with specific selective recognition sites, and the materials have good practical value. The molecular imprinting material is simple to prepare, has the advantages of good selectivity, stable chemical property, low cost and the like, and is widely applied to chemical sensing, photodegradation, separation and solid-phase extraction. Traditional methods of molecular imprinting involve complexation of functional monomers and molecular templates, followed by cross-linking of the monomers and removal of the template, thereby forming complementary recognition sites of similar size and shape to the template for detection of molecular analytes having similar structures. Although convenient, conventional methods suffer from several drawbacks, including incomplete template removal, leakage of toxic template molecules, low binding capacity, and poor accessibility. Therefore, to overcome these disadvantages, surface fragment imprinting is used, in which only a part of the target analyte molecule or a fragment having a similar structure is used as a molecular template to form recognition sites on the surface of the synthetic material or in a position close to the surface, thereby facilitating removal of the template.
At present, molecular imprinting is used for research on Microcystins (MCs) less frequently, and MC-LR is generally adopted as a template to prepare a molecular imprinting polymer. Because MCs have complex structures, a plurality of varieties and high toxicity and cost, and the risk of template leakage also exists, the MCs are not easy to be directly used as molecular templates, and the difficulty of the research is that how to select cheap and easily-obtained alternative templates.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a preparation method of a double-virtual-segment phosphorescent quantum dot imprinted material, so as to prepare the molecularly imprinted material with the functions of enriching and removing algal toxins.
In order to achieve the above objects, in a basic embodiment, the present invention provides a method for preparing a phosphorescent quantum dot imprinted material, comprising the steps of:
1) mixing L-cysteine and MnCl2And ZnSO4Mixing the aqueous solutions, adjusting pH to 10-12 with alkaline solution, stirring at room temperature while introducing inert gas to make L-cysteine and Mn2+And Zn2+Fully complexing; adding Na by syringe2Continuously reacting the S aqueous solution for 15-30 min; then, at the temperature of 30-80 ℃, placing the reaction solution in the air atmosphere, and aging for 1-10 h; after aging, using absolute ethyl alcohol to settle the quantum dots, and carrying out centrifugal separation to obtain water-soluble room-temperature phosphorescent Mn: ZnS quantum dots;
2) adding L-cysteine into water-soluble room-temperature phosphorescent Mn: ZnS quantum dots to protect the Mn: ZnS quantum dots, and then adding a virtual template to obtain a mixed solution; stirring the mixed solution at room temperature for 20-40min, adding silicate ester dropwise, and stirring vigorously for 8-15 min; then adjusting the pH value to 7-12 with alkali liquor; continuously stirring the solution of the system for 20-30 h; washing with ethanol and water to remove the virtual template molecules to obtain solid double virtual fragments SiO2The material is a phosphorescent quantum dot imprinted material with @ Mn: ZnS.
In a preferred embodiment, in step 1), the L-cysteine, MnCl2And ZnSO4The molar ratio of the aqueous solution is 40-120: 1-10: 10-100.
In a preferred embodiment, in step 1), the pH of the solution is adjusted to 11 with a base solution.
In a preferred embodiment, in step 1), the inert gas is introduced for 20 to 40 min.
In a preferred embodiment, in step 2), the adding of the virtual template is: adding an aqueous solution of the first virtual template and an ethanol solution containing the second virtual template.
In a preferred embodiment, in step 2), the first virtual template is selected from the group consisting of phenylalanine, tyrosine, lysine and arginine.
In a preferred embodiment, in step 2), the second virtual template is n-propanol, n-butane, acetone, and pentylbenzene.
In a preferred embodiment, in step (2), the base is NaOH, ammonia, Na2CO3And NaHCO3。
In a preferred embodiment, in step (2), the silicates are tetraethoxysilane, tetrapropoxysilane, dimethyldichlorosilane, and tributylaminomethylsilane.
The invention also aims to provide the application of the phosphorescent quantum dot printing material prepared by the method, and the phosphorescent quantum dot printing material is applied to microcystin solution for enriching and detecting microcystin.
In a preferred embodiment, the method of application comprises: firstly, preparing a blotting material solution with the concentration of 1-10 mg/mL; preparing a series of microcystin standard solutions by using PBS (PBS buffer solution with pH value of 7.4 and 0.01M); and (3) putting 2mL of imprinting material solution into a cuvette, adding 10 mu L of prepared microcystin standard solution, shaking uniformly, standing for 5-60min, and performing room-temperature phosphorescence test.
Through the technical scheme, the method provided by the invention adopts the virtual fragment as the molecular template, reduces the toxicity and cost in the synthesis process, has specificity and high sensitivity, can identify the potentials of a series of similar substances, and provides a new thought for detecting MCs.
Drawings
Fig. 1 is an XRD spectrum of the imprinted material prepared in example 1 of the present invention.
FIGS. 2a-2b are XPS spectra of blotting materials prepared in example 1 of the invention.
FIGS. 3a-3b are TEM spectra of imprinted materials prepared in example 3 of the present invention.
FIG. 4 is a graph showing the effect of detecting microcystin by using the blotting material prepared in example 1 of the present invention.
FIG. 5 is a graph showing the effect of detecting microcystin by using the blotting material prepared in example 2 of the present invention.
Detailed Description
In order to better understand the technical solutions, the technical solutions of the present application are described in detail with specific embodiments below, and it should be understood that the specific features in the embodiments and examples of the present application are detailed descriptions of the technical solutions of the present application, but not limitations of the technical solutions of the present application, and the technical features in the embodiments and examples of the present application may be combined with each other without conflict. It should be understood that the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The embodiment of the invention provides a preparation method of a double-virtual-segment phosphorescent quantum dot imprinted material, so that the molecular imprinting with the functions of enriching and clearing algal toxins is prepared, the toxicity and the cost in the synthesis process are reduced, and the double-virtual-segment phosphorescent quantum dot imprinted material has the advantages of specificity and high sensitivity.
The embodiment of the invention mainly comprises the following steps: a preparation method of a phosphorescent quantum dot imprinted material comprises the following steps:
1) mixing L-cysteine and MnCl2And ZnSO4Mixing the aqueous solutions, adjusting pH to 10-12 with alkaline solution, stirring at room temperature while introducing inert gas to make L-cysteine and Mn2+And Zn2+Fully complexing; adding Na by syringe2Continuously reacting the S aqueous solution for 15-30 min; then at 30-80 deg.CAging the reaction solution for 1-10h in an air atmosphere; after aging, using absolute ethyl alcohol to settle the quantum dots, and carrying out centrifugal separation to obtain water-soluble room-temperature phosphorescent Mn: ZnS quantum dots;
2) adding L-cysteine into water-soluble room-temperature phosphorescent Mn: ZnS quantum dots to protect the Mn: ZnS quantum dots, and then adding a virtual template to obtain a mixed solution; stirring the mixed solution at room temperature for 20-40min, adding silicate ester dropwise, and stirring vigorously for 8-15 min; then adjusting the pH value to 7-12 by using alkali liquor; continuously stirring the solution of the system for 20-30 h; washing with ethanol and water to remove the virtual template molecules to obtain solid double virtual fragments SiO2The @ Mn: ZnS phosphorescent quantum dot imprinted material.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the examples of the present invention are commercially available or can be prepared by an existing method.
Example 1
The preparation method of the phosphorescent quantum dot imprinted material in the embodiment 1 of the invention comprises the following steps:
in a 100mL three-necked flask, 25mL of 0.02 mol/L-cysteine and 3mL of 0.01mol/L MnCl were added2And 5mL of 0.1mol/L ZnSO4Adjusting pH of the aqueous solution to 11 with 1mol/L NaOH, magnetically stirring at room temperature while introducing nitrogen for 30min to make L-cysteine and Mn2+And Zn2+And (4) fully complexing. 5mL of 0.1mol/L Na was added via syringe2And (5) continuously reacting the S aqueous solution for 20 min. Then, the solution was aged for 5 hours at 50 ℃ under an air atmosphere. And then, precipitating the quantum dots by using absolute ethyl alcohol with the same volume, centrifugally separating, collecting solids, and drying in vacuum at room temperature for 24 hours to obtain the water-soluble room-temperature phosphorescent quantum dots.
32mL of 3mg/mL L-cysteine protected Mn: ZnS quantum dots were added to a round bottom flask, 5mL of an aqueous tyrosine solution and 5mL of an ethanol solution containing n-butane were added. The mixed solution was stirred at room temperature for 30min, 0.5mL of tetraethoxysilane was added dropwise each time, vigorously stirred for 10min, and then adjusted to pH 8 with NaOH. The solution of the system was stirred continuously for 24 h. Final imprinting material and molecular polymerizationThe compound was washed with ethanol and water to remove the dummy template molecule. Vacuum drying at room temperature to obtain solid double-virtual-segment SiO2The material is a phosphorescent quantum dot imprinted material with @ Mn: ZnS.
The molecular imprinting material provided by the embodiment of the invention is applied to microcystin solution to enrich and detect microcystin.
The detection method comprises the following steps: first, a blotting material solution was prepared at a concentration of 5 mg/mL. A series of microcystin standard solutions were prepared with PBS buffer (pH 7.40.01M). And (3) putting 2mL of imprinting material solution into a cuvette, adding 10 mu L of microcystin prepared standard solution, shaking uniformly, standing for 30min, and carrying out room-temperature phosphorescence test.
In the phosphorescence mode, phosphorescence spectrum is recorded under excitation wavelength of 305nm, changes of the concentration of the algae toxin are monitored through changes of phosphorescence intensity, emission wavelength is 591nm, voltage is set at 900V, and the slit widths of excitation and emission are 15 nm and 20nm respectively.
As shown in FIG. 4, the phosphorescent quantum dot imprinted material in example 1 conforms to a linear equation within the concentration range of the phycotoxin of 0.125-0.225nM, and satisfactory detection effects can be obtained.
Example 2
The embodiment 2 of the invention provides a preparation method of a phosphorescent quantum dot imprinted material, which comprises the following steps:
in a 100mL three-necked flask, 40mL of 0.02 mol/L-cysteine and 2mL of 0.01mol/L MnCl were added2And 8mL of 0.1mol/L ZnSO4Adjusting pH of the aqueous solution to 11 with 1mol/L NaOH, magnetically stirring at room temperature while introducing nitrogen for 30min to make L-cysteine and Mn2+And Zn2+And (4) fully complexing. 8mL of 0.1mol/L Na was added by syringe2And (5) continuously reacting the S aqueous solution for 20 min. Then, the solution was aged for 7 hours at 80 ℃ under an air atmosphere. And then, precipitating the quantum dots by using absolute ethyl alcohol with the same volume, centrifugally separating, collecting solids, and drying in vacuum at room temperature for 24 hours to obtain the water-soluble room-temperature phosphorescent quantum dots.
Adding 45mL of 3mg/mL L-cysteine protected Mn: ZnS quantum dots into a round-bottom flask, and adding 5mL of benzeneAlanine in water, 5mL ethanol solution with n-propanol. The mixed solution was stirred at room temperature for 30min, 0.5mL of tetrapropoxysilane was added dropwise each, vigorously stirred for 10min, and then adjusted to pH 8 with ammonia. The solution of the system was stirred continuously for 24 h. Finally, the imprinting material and the molecular polymer are washed by ethanol and water to remove the virtual template molecules. Vacuum drying at room temperature to obtain solid double-virtual-segment SiO2The material is a phosphorescent quantum dot imprinted material with @ Mn: ZnS.
The molecular imprinting material provided by the embodiment of the invention is applied to microcystin solution to enrich and detect microcystin. The method comprises the following steps:
first, a blotting material solution was prepared at a concentration of 5 mg/mL. A series of microcystin standard solutions were prepared with PBS buffer (pH 7.40.01M). And (3) putting 2mL of imprinting material solution into a cuvette, adding 10 mu L of microcystin prepared standard solution, shaking uniformly, standing for 30min, and carrying out room-temperature phosphorescence test.
In the phosphorescence mode, phosphorescence spectrum is recorded under excitation wavelength of 305nm, changes of the concentration of the algae toxin are monitored through changes of phosphorescence intensity, emission wavelength is 591nm, voltage is set at 900V, and the slit widths of excitation and emission are 15 nm and 20nm respectively.
As shown in FIG. 5, the phosphorescent quantum dot blotting material of example 2 conforms to the linear equation within the concentration range of the phycotoxin of 0.05-0.175nM, and the detection can obtain satisfactory results.
Example 3
The preparation method of the phosphorescent quantum dot imprinted material in the embodiment 3 of the invention comprises the following steps:
in a 100mL three-necked flask, 60mL of 0.02 mol/L-cysteine and 10mL of 0.01mol/L MnCl were added2And 10mL of 0.1mol/L ZnSO4Aqueous solution of 1mol/L NaHCO3Adjusting the pH value of the solution to 12, magnetically stirring at room temperature while introducing nitrogen for 40min to allow L-cysteine and Mn2+And Zn2+And (4) fully complexing. 5mL of 0.1mol/L Na was added by syringe2And (5) continuously reacting the S aqueous solution for 30 min. Then, the solution was aged at 30 ℃ for 10 hours in an air atmosphere. Then with an equal volumeAnd (3) precipitating the quantum dots by using absolute ethyl alcohol, carrying out centrifugal separation, collecting solids, and carrying out vacuum drying at room temperature for 24 hours to obtain the water-soluble room-temperature phosphorescent quantum dots.
50mL of 3mg/mL L-cysteine protected Mn: ZnS quantum dots were added to a round-bottom flask, and 5mL of an aqueous solution of lysine and 5mL of an ethanol solution containing pentylbenzene were added. Stirring the mixed solution at room temperature for 40min, dropwise adding 0.5mL of dimethyldichlorosilane, vigorously stirring for 15min, and adding NaHCO3The pH was adjusted to 12. The solution of the system was stirred continuously for 30 h. Finally, the imprinting material and the molecular polymer are washed by ethanol and water to remove the virtual template molecules. Vacuum drying at room temperature to obtain solid double-virtual-segment SiO2The material is a phosphorescent quantum dot imprinted material with @ Mn: ZnS.
Example 4
The embodiment 4 of the invention provides a preparation method of a phosphorescent quantum dot imprinted material, which comprises the following steps:
in a 100mL three-necked flask, 20mL of 0.02 mol/L-cysteine and 1mL of 0.01mol/L MnCl were added2And 1mL of 0.1mol/L ZnSO4Adjusting pH of the aqueous solution to 10 with 1mol/L ammonia water, magnetically stirring at room temperature while introducing nitrogen for 20min to make L-cysteine and Mn2+And Zn2+And (4) fully complexing. Then 8mL of 0.1mol/L Na was added by syringe2And (5) continuously reacting the S aqueous solution for 15 min. Then, the solution was aged at 80 ℃ for 1 hour under an air atmosphere. And then, precipitating the quantum dots by using absolute ethyl alcohol with the same volume, performing centrifugal separation, collecting solids, and performing vacuum drying at room temperature for 20 hours to obtain the water-soluble room-temperature phosphorescent quantum dots.
45mL of 3mg/mL L-cysteine protected Mn: ZnS quantum dots are added into a round-bottom flask, and 5mL of arginine aqueous solution and 5mL of n-propanol-containing ethanol solution are added. The mixed solution was stirred at room temperature for 20min, 0.5mL of tetrapropoxysilane was added dropwise each, stirred vigorously for 8min, and then adjusted to pH 7 with ammonia. The solution of the system was stirred continuously for 20 h. Finally, the imprinting material and the molecular polymer are washed by ethanol and water to remove the virtual template molecules. Vacuum drying at room temperature to obtain solid double-virtual-segment SiO2@ Mn: ZnS phosphorescence quantum dot blottingA material.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (6)

1. A preparation method of a phosphorescent quantum dot imprinted material is characterized by comprising the following steps: the method comprises the following steps:
1) mixing L-cysteine and MnCl2And ZnSO4Mixing the aqueous solutions, adjusting pH to 10-12 with alkaline solution, stirring at room temperature while introducing inert gas to make L-cysteine and Mn2+And Zn2+Fully complexing; adding Na by syringe2S, continuously reacting for 15-30min with the aqueous solution; then, at the temperature of 30-80 ℃, putting the reaction solution in the air atmosphere, and aging for 1-10 h; after aging, using absolute ethyl alcohol to settle the quantum dots, and carrying out centrifugal separation to obtain water-soluble room-temperature phosphorescent Mn: ZnS quantum dots;
2) adding L-cysteine into water-soluble room-temperature phosphorescent Mn: ZnS quantum dots to protect the Mn: ZnS quantum dots, and adding a virtual template to obtain a mixed solution; stirring the mixed solution at room temperature for 20-40min, adding silicate ester dropwise, and stirring vigorously for 8-15 min; then adjusting the pH value to 7-12 by using alkali liquor; continuously stirring the solution of the system for 20-30 h; washing with ethanol and water to remove the virtual template molecules to obtain solid double virtual fragments SiO2The material is a phosphorescent quantum dot imprinting material with the material of @ Mn: ZnS;
in the step 1), the L-cysteine and the MnCl are added2And ZnSO4The molar ratio of the aqueous solution is 40-120: 1-10: 10-100;
in step 2), adding the virtual template comprises: adding an aqueous solution of the first virtual template and an ethanol solution containing the second virtual template; the first virtual template is phenylalanine, tyrosine, lysine or arginine, and the second virtual template is n-propanol, n-butane or pentylbenzene.
2. The preparation method of the phosphorescent quantum dot printing material according to claim 1, wherein the preparation method comprises the following steps: in the step 1), the pH value of the solution is adjusted to 11 by using the alkali liquor.
3. The preparation method of the phosphorescent quantum dot printing material according to claim 1, wherein the preparation method comprises the following steps: in the step 1), inert gas is introduced for 20-40 min.
4. The preparation method of the phosphorescent quantum dot printing material according to claim 1, wherein the preparation method comprises the following steps: in the step 2), the alkali is NaOH, ammonia water or Na2CO3Or NaHCO3。
5. The preparation method of the phosphorescent quantum dot printing material according to claim 1, wherein the preparation method comprises the following steps: in the step 2), the silicate is tetraethoxysilane or tetrapropoxysilane.
6. Use of a phosphorescent quantum dot imprinted material prepared according to the method of any of claims 1 to 5, characterized in that: the phosphorescent quantum dot blotting material is applied to microcystin solution for enriching and detecting microcystin.
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