CN109781807B - Bio-based ion imprinting sensor for detecting copper ions and preparation method thereof - Google Patents
Bio-based ion imprinting sensor for detecting copper ions and preparation method thereof Download PDFInfo
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Abstract
The invention provides a bio-based ion imprinting sensor for detecting copper ions and a preparation method thereof. The bio-based ion imprinting sensor can overcome the inherent defects of DNA such as instability of separating from a biological environment, easiness in degradation, inactivation, diffusion and aggregation and the like, has the advantages of simple preparation conditions, strong severe environment resistance, environmental friendliness, high sensitivity and strong anti-interference capability, and can realize sensitive detection of copper ions in a water system.
Description
Technical Field
The invention belongs to the field of functional materials and electrochemical sensing, and relates to a bio-based ion imprinting sensor for detecting copper ions and a preparation method thereof.
Background
With the development of the metallurgical industry and the electronic industry, a large amount of copper powder washing wastewater, electroplating wastewater and alkaline ammonia etching solution in the production process of printed circuit boards are discharged into the environment, thereby causing harm to the health of ecosystems and human beings. Copper is used as a beneficial element necessary for life, and the copper is low in toxicity, but is harmful to human bodies after excessive copper is absorbed by the human bodies. Copper element in water is gradually enriched in animals and plants through food chains, and is converted into metal organic compounds with higher toxicity, so that the copper element can easily enter human bodies through water and food. Copper, because of its high affinity for certain tissues in the human body, inhibits the activity of enzymes after binding, thereby producing toxic effects on the human body. Therefore, starting from the current situations of environment and food safety and existing key problems, a new technology suitable for rapidly and accurately detecting the content of copper ions on site is established, and the important theoretical value and practical significance are achieved for timely and effectively controlling and preventing the occurrence of food-borne diseases caused by copper pollution.
Compared with the traditional detection methods of copper ions such as an atomic absorption method, an ion chromatography method and the like, the electrochemical sensor analysis technology has the characteristics of rapidness, accuracy, high selectivity, capability of real-time and on-line detection and the like, and becomes an important development trend of heavy metal pollution detection. The sensitive functional material is a core component of an electrochemical sensor, and the structure and the physical and chemical properties of the sensitive functional material directly determine the function and the quality of the sensor.
In the process of developing the heavy metal electrochemical biosensor, a gene Probe (Probe DNA) and a Specific deoxyribozyme (Specific DNAzyme) are basically adopted as biological recognition elements. However, in practical applications, the biological macromolecules (DNA, DNAzyme) have inherent defects such as instability of being separated from the biological environment, easy degradation, inactivation, diffusion and aggregation, etc., so that the biosensor has high requirements for the use environment, is difficult to store for a long time, has high cost and is difficult to obtain an identification element, which become key factors limiting the further development of the heavy metal biosensor. Therefore, how to synthesize a stable recognition element with strong ability to resist severe environment, and having the function similar to natural antibody is a serious scientific problem for developing high-performance heavy metal biosensors.
Disclosure of Invention
The invention aims to provide a bio-based ion imprinting sensor for detecting copper ions and a preparation method thereof, which imitate a specific molecular recognition mechanism of an antibody-antigen, and prepare a novel electrochemical sensor for quickly and quantitatively detecting the copper ions by taking carboxymethyl chitosan as a functional monomer, the copper ions as template ions, glutaraldehyde as a cross-linking agent and amino functionalized graphene as a conductive reinforcing agent.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of a bio-based ion imprinting sensor for detecting copper ions is characterized by comprising the following steps:
(1) dispersing graphite oxide in distilled water through ultrasonic treatment to prepare graphite oxide dispersion liquid; adding ammonia water into the dispersion liquid, and performing ultrasonic dispersion; then placing the mixed solution into a reaction kettle for hydrothermal reaction, cooling to room temperature, carrying out suction filtration, washing with hydrochloric acid, absolute ethyl alcohol and distilled water in sequence to be neutral, and drying to obtain amino functionalized graphene;
(2) mechanically polishing glassy carbon electrode to smooth mirror surface, ultrasonically cleaning, blow-drying with nitrogen gas, and placing in electrolyte solution H2SO4Carrying out cyclic voltammetry scanning to obtain quasi-reversible cyclic voltammetry peaks, washing the electrodes with secondary distilled water, and then airing at room temperature;
(3) under the neutral condition, dissolving carboxymethyl chitosan in distilled water, and magnetically stirring at room temperature until the carboxymethyl chitosan is completely dissolved to prepare a carboxymethyl chitosan solution; adding the amino functionalized graphene prepared in the step (1) into a carboxymethyl chitosan solution, and performing ultrasonic dispersion at room temperature to obtain a carboxymethyl chitosan-amino functionalized graphene composite solution;
(4) adding a copper acetate solution into the carboxymethyl chitosan-amino functionalized graphene composite solution prepared in the step (3), adjusting the pH value to be acidic, and stirring by magnetic force to obtain a uniform mixed solution;
(5) dropwise coating the mixed solution prepared in the step (4) on the surface of the glassy carbon electrode pretreated in the step (2), and naturally airing at room temperature to obtain a modified glassy carbon electrode; placing the obtained modified glassy carbon electrode in a glutaraldehyde solution for crosslinking, taking out, and washing with an acetone/water mixed solvent; and placing the washed modified electrode in an ethylene diamine tetraacetic acid solution to wash away template ions, washing with distilled water and drying to obtain the carboxymethyl chitosan/graphene/copper ion imprinted sensor.
Further, in the step (1), the concentration of the graphite oxide solution is 5-8 mg/mL; the concentration of ammonia water is 20%; the volume ratio of the graphite oxide dispersion liquid to the ammonia water is 1: 1-1: 3; the hydrothermal reaction temperature is 150-180 ℃, and the reaction time is 5-6 h.
Further, in the step (2), the diameter of the glassy carbon electrode is 3 mm; al for glassy carbon electrode2O3Mechanically polishing the powder to a smooth mirror surface, Al2O3The particle size of the powder is 1.0 μm, 0.3 μm or 0.05 μm; the ultrasonic cleaning time is 2-3 min.
Further, the electrolyte solution H in the step (2)2SO4The concentration of (A) is 1.0 mol/L; the scanning speed of the cyclic voltammetry is 100mV/s, and the scanning range is-0.3 to + 1.5V.
Further, in the step (2), the quasi-reversible cyclic voltammetry peak: peak current ratio was 1:1, the peak potential difference is less than 90 mV.
Further, in the step (3), the concentration of the carboxymethyl chitosan solution is 0.5 wt.% to 0.8 wt.%; the mass ratio of the amino functionalized graphene to the carboxymethyl chitosan is 1: 1-1: 1.4.
Further, in the step (4), the concentration of the copper acetate solution is 5 wt.%; the pH values of the mixed solutions are respectively 4.9-5.3; the mass ratio of the amino functionalized graphene to the carboxymethyl chitosan is 1: 1-1: 1.4; the volume ratio of the carboxymethyl chitosan-amino functionalized graphene composite solution to the copper acetate solution is 1: 1-1: 1.5.
Further, in the step (5), the concentration of the glutaraldehyde is 25 vol.%, and the crosslinking time is 1-3 h; the concentration of the ethylene diamine tetraacetic acid disodium solution is 0.5mol/L, and the elution time is 2-4 h.
The bio-based ion imprinting sensor for detecting copper ions, which is prepared by the preparation method, has a large number of coordination atoms O, N and abundant chelating groups such as hydroxyl, amino and carboxyl, enhances the affinity to metal ions, has an ordered microporous three-dimensional network structure, and improves the selective recognition capability of the sensor to copper ions.
As a novel preparation method of sensitive functional materials, the ion imprinting technology has the advantages of good selectivity, strong chemical stability and reusability, and becomes an important direction in the field of heavy metal detection. The ion imprinting technology is characterized in that ions are used as a template, the ions are combined with a functional monomer or a coordination monomer to form a chelate through the actions of static electricity, covalence, coordination and the like, and the template ions are removed after cross-linking polymerization to obtain the rigid imprinted polymer material which has a specific spatial structure and can selectively identify heavy metal ions. The invention adopts the ion imprinting technology to specifically synthesize the plastic antibody for specifically identifying the copper ions, utilizes the strong metal chelating capacity formed by the carboxymethyl chitosan and the copper ions, improves the stability, the conductivity and the mechanical property of the material by mixing the amino functionalized graphene, and realizes the high-efficiency selective detection of the heavy metal pollutants with low concentration, high toxicity and difficult degradation in the complex water environment.
The invention has the advantages that the bio-based material is light in weight, loose in volume and poor in selectivity, the invention fully utilizes the coordinating group of carboxymethyl chitosan through the structural design of the composite material, adopts the ion imprinting and the hybrid method to solve the compatibility and specificity of the material, and constructs the sensing material which has excellent performance and is used for detecting heavy metal ions.
The preparation method of the bio-based ion imprinting sensor for detecting copper ions, which is disclosed by the invention, is simple, green and environment-friendly, has the characteristics of low cost, high sensitivity, good stability and strong anti-interference capability, and has a potential application prospect in the fields of food safety and environmental monitoring.
Drawings
Fig. 1 is a schematic preparation flow diagram of a preparation method of a bio-based ion imprinting sensor for detecting copper ions according to the present invention.
Fig. 2 is a surface topography of a bio-based ion imprinting sensor for detecting copper ions according to the present invention.
FIG. 3 shows the DPV response peak current intensity and Cu of the bio-based ion imprinted sensor for detecting copper ions according to the present invention2+Linear dependence of concentration.
Detailed Description
For further illustration of the objects and technical advantages of the present invention, the present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto. It should be understood that the following specific examples are illustrative only and are not intended to limit the scope of the invention. The invention belongs to the protection scope based on the embodiments and any combination of the invention.
Example 1
The preparation method of the bio-based ion imprinting sensor for detecting copper ions is shown in figure 1.
(1) Dispersing 350mg of graphite oxide in 40mL of distilled water through ultrasonic treatment, adding 40mL of 20% ammonia water into the graphite oxide, and continuing ultrasonic dispersion for 0.5 h; then the mixed solution is put into a reaction kettle for hydrothermal reaction for 5 hours at 160 ℃; and cooling to room temperature, carrying out suction filtration, washing with 45 mass percent hydrochloric acid, absolute ethyl alcohol and distilled water in sequence to be neutral, and drying to obtain the amino functionalized graphene.
(2) The glassy carbon electrode with the diameter of 3mm has the granularity of 1.0 mu mAl2O3Mechanically polishing the powder to a smooth mirror surface, ultrasonically cleaning with secondary distilled water for 2min for three times, ultrasonically cleaning with anhydrous ethanol and secondary distilled water for 3min, blow-drying with nitrogen, and adding 1.0mol/L electrolyte solution H2SO4And performing cyclic voltammetry scanning to obtain quasi-reversible cyclic voltammetry peaks, wherein the cyclic voltammetry scanning speed is 100mV/s, the scanning range is-0.3 to +1.5V, and the peak current ratio is 1:1. and (3) a quasi-reversible cyclic voltammetry peak with the peak potential difference smaller than 90mV, washing the electrode by using secondary distilled water, and airing at room temperature.
(3) Dissolving 100mg of carboxymethyl chitosan in 20ml of distilled water, magnetically stirring at room temperature until the carboxymethyl chitosan is completely dissolved, adding 100mg of amino functionalized graphene into the carboxymethyl chitosan solution, and performing ultrasonic dispersion at room temperature to obtain the carboxymethyl chitosan-amino functionalized graphene composite solution.
(4) Adding 20ml of 5% copper acetate solution into the carboxymethyl chitosan-amino functionalized graphene composite solution, adjusting the pH to 5, and magnetically stirring to obtain a uniform mixed solution;
(5) dripping the mixed solution prepared in the step (4) on the surface of the glassy carbon electrode pretreated in the step (2), and naturally airing at room temperature; placing the obtained modified glassy carbon electrode in a 25% glutaraldehyde solution for crosslinking for 2h, taking out, and washing with an acetone/water mixed solvent; and (3) placing the washed modified electrode in 0.5mol/L disodium ethylene diamine tetraacetate solution for elution for 2 hours, washing away template ions, washing with distilled water and drying to obtain the carboxymethyl chitosan/graphene/copper ion imprinting sensor.
The prepared bio-based ion imprinting sensor for detecting copper ions has a large amount of coordination atoms O, N and abundant chelating groups such as hydroxyl, amino and carboxyl, enhances the affinity to metal ions, has an ordered microporous three-dimensional network structure, and improves the selective recognition capability of the sensor on the copper ions. Fig. 2 shows a scanning electron micrograph of the surface of the sensor electrode, which has a dense, rough, porous surface structure. FIG. 3 shows the results for Cu2+Increases with increasing concentration at 2.0X 10-9～9.0×10-7The peak current and the concentration thereof in the mol/L concentration range have good linear relation, and the linear equation is ip(μA)＝0.04775+0.288c(mol/L)(R20.9957) and c is Cu in the equation2+Concentration of (a), (b), (c), (d)pThe reduction peak current value obtained by differential pulse voltammetry.
Example 2
(1) Dispersing 350mg of graphite oxide in 40mL of distilled water through ultrasonic treatment, adding 40mL of 20% ammonia water into the graphite oxide, and continuing ultrasonic dispersion for 0.5 h; then the mixed solution is put into a reaction kettle for hydrothermal reaction for 6 hours at 160 ℃; and cooling to room temperature, carrying out suction filtration, washing with 45 mass percent hydrochloric acid, absolute ethyl alcohol and distilled water in sequence to be neutral, and drying to obtain the amino functionalized graphene.
(2) The glassy carbon electrode with the diameter of 3mm has the granularity of 1.0 mu mAl2O3Mechanically polishing the powder to a smooth mirror surface, ultrasonically cleaning with redistilled water for 3min each time, repeating the steps for three times, ultrasonically cleaning with absolute ethyl alcohol and redistilled water for 3min, blow-drying with nitrogen, and then putting into 1.0mol/L electrolyte solution H2SO4And performing cyclic voltammetry scanning to obtain quasi-reversible cyclic voltammetry peaks, wherein the cyclic voltammetry scanning speed is 100mV/s, the scanning range is-0.3 to +1.5V, and the peak current ratio is 1:1, quasi-reversible cyclic voltammetric peaks with a peak potential difference of less than 90mV, adding distilled waterAnd (5) washing the electrode, and then drying at room temperature.
(3) Dissolving 100mg of carboxymethyl chitosan in 20ml of distilled water, magnetically stirring at room temperature until the carboxymethyl chitosan is completely dissolved, adding 140mg of amino functionalized graphene into the carboxymethyl chitosan solution, and performing ultrasonic dispersion at room temperature to obtain the carboxymethyl chitosan-amino functionalized graphene composite solution.
(4) Adding 30ml of 5% copper acetate solution into the carboxymethyl chitosan-amino functionalized graphene composite solution, adjusting the pH to 5, and magnetically stirring to obtain a uniform mixed solution;
(5) dripping the mixed solution prepared in the step (4) on the surface of the glassy carbon electrode pretreated in the step (2), and naturally airing at room temperature; placing the obtained modified glassy carbon electrode in a 25% glutaraldehyde solution for crosslinking for 3h, taking out, and washing with an acetone/water mixed solvent; and (3) placing the washed modified electrode in 0.5mol/L disodium ethylene diamine tetraacetate solution for elution for 3 hours, washing away template ions, washing with distilled water and drying to obtain the carboxymethyl chitosan/graphene/copper ion imprinting sensor.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (9)
1. A preparation method of a bio-based ion imprinting sensor for detecting copper ions is characterized by comprising the following steps:
(1) dispersing graphite oxide in distilled water through ultrasonic treatment to prepare graphite oxide dispersion liquid; adding ammonia water into the dispersion liquid, and performing ultrasonic dispersion; then placing the mixed solution into a reaction kettle for hydrothermal reaction, cooling to room temperature, carrying out suction filtration, washing with hydrochloric acid, absolute ethyl alcohol and distilled water in sequence to be neutral, and drying to obtain amino functionalized graphene;
(2) mechanically polishing glassy carbon electrode to smooth mirror surface, ultrasonically cleaning, blow-drying with nitrogen gas, and placing in electrolyte solution H2SO4Carrying out cyclic voltammetry scanning to obtain quasi-reversible cyclic voltammetry peaks, washing the electrodes with secondary distilled water, and then airing at room temperature;
(3) under the neutral condition, dissolving carboxymethyl chitosan in distilled water, and magnetically stirring at room temperature until the carboxymethyl chitosan is completely dissolved to prepare a carboxymethyl chitosan solution; adding the amino functionalized graphene prepared in the step (1) into a carboxymethyl chitosan solution, and performing ultrasonic dispersion at room temperature to obtain a carboxymethyl chitosan-amino functionalized graphene composite solution;
(4) adding a copper acetate solution into the carboxymethyl chitosan-amino functionalized graphene composite solution prepared in the step (3), adjusting the pH value to be acidic, and stirring by magnetic force to obtain a uniform mixed solution;
(5) dropwise coating the mixed solution prepared in the step (4) on the surface of the glassy carbon electrode pretreated in the step (2), and naturally airing at room temperature to obtain a modified glassy carbon electrode; placing the obtained modified glassy carbon electrode in a glutaraldehyde solution for crosslinking, taking out, and washing with an acetone/water mixed solvent; and placing the washed modified electrode in an ethylene diamine tetraacetic acid solution to wash away template ions, washing with distilled water and drying to obtain the carboxymethyl chitosan/graphene/copper ion imprinted sensor.
2. The preparation method according to claim 1, wherein in the step (1), the concentration of the graphite oxide solution is 5-8 mg/mL; the concentration of ammonia water is 20%; the volume ratio of the graphite oxide dispersion liquid to the ammonia water is 1: 1-1: 3; the hydrothermal reaction temperature is 150-180 ℃, and the reaction time is 5-6 h.
3. The production method according to claim 1, wherein in the step (2), the glassy carbon electrode has a diameter of 3 mm; al for glassy carbon electrode2O3Mechanically polishing the powder to a smooth mirror surface, Al2O3The particle size of the powder is 1.0 μm, 0.3 μm or 0.05 μm; the ultrasonic cleaning time is 2-3 min.
4. The method according to claim 1, wherein in the step (2), electricity is suppliedElectrolyte solution H2SO4The concentration of (A) is 1.0 mol/L; the scanning speed of the cyclic voltammetry is 100mV/s, and the scanning range is-0.3 to + 1.5V.
5. The method according to claim 1, wherein the quasi-reversible cyclic voltammetry peaks in step (2): peak current ratio was 1:1, the peak potential difference is less than 90 mV.
6. The preparation method according to claim 1, wherein in the step (3), the concentration of the carboxymethyl chitosan solution is 0.5 wt.% to 0.8 wt.%; the mass ratio of the amino functionalized graphene to the carboxymethyl chitosan is 1: 1-1: 1.4.
7. The method according to claim 1, wherein in the step (4), the concentration of the copper acetate solution is 5 wt.%; the pH values of the mixed solutions are respectively 4.9-5.3; the mass ratio of the amino functionalized graphene to the carboxymethyl chitosan is 1: 1-1: 1.4; the volume ratio of the carboxymethyl chitosan-amino functionalized graphene composite solution to the copper acetate solution is 1: 1-1: 1.5.
8. The preparation method according to claim 1, wherein in the step (5), the glutaraldehyde concentration is 25 vol.%, and the crosslinking time is 1-3 h; the concentration of the ethylene diamine tetraacetic acid disodium solution is 0.5mol/L, and the elution time is 2-4 h.
9. A bio-based ion imprinted sensor for detecting copper ions prepared by the preparation method of any one of claims 1 to 8.
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Non-Patent Citations (4)
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| A glassy carbon electrode modified with amino-functionalized graphene oxide and molecularly imprinted polymer for electrochemical sensing of bisphenol A;Dadkhah, Sahar et al.;《Microchimica Acta》;20160321;第183卷(第6期);全文 * |
| Highly sensitive and selective ion-imprinted polymers based on one-step electrodeposition of chitosan-graphene nanocomposites for the determination of Cr(VI);Wu, Shuping et al.;《Carbohydrate Polymers》;20180424;第195卷;全文 * |
| Ion-imprinted carboxymethyl chitosan–silica hybrid sorbent for extraction of cadmium from water samples;Lü, Haixia et al.;《International Journal of Biological Macromolecules》;20130208;第56卷;全文 * |
| Protective effects of ion-imprinted chitooligosaccharides as uranium-specific chelating agents against the cytotoxicity of depleted uranium in human kidney cells;Zhang, Xiao-fei et al.;《Toxicology》;20110527;第286卷(第1期);第76至83页 * |
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