An electrochemiluminescence sensor for detecting fluoride ions and its application method

Abstract

The present invention relates to an electrochemiluminescence sensor for detecting fluoride ions and an application method thereof. Firstly, calcium peroxide nanoparticles are synthesized, and then a layer of silicon dioxide shell is in situ wrapped around the calcium peroxide nanoparticles. ‑ The reaction between calcium peroxide and silica etches the silica shell, causing the calcium peroxide nanoparticles wrapped in the silica shell to be exposed to the aqueous solution. Calcium peroxide is used to react with water to generate H2O2 as a co-reactant in electrochemiluminescence. The luminescent agent luminol is added, and a certain range of cyclic voltammetric signals are applied through an electrochemical workstation using a three-electrode system. The luminescence intensity is recorded by a chemiluminescence analyzer to achieve the F in water. ‑ Specific detection.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical sensing and relates to an electrochemiluminescence sensor for detecting fluoride ions and an application method thereof. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention, and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.

[0003] Fluoride is a trace element necessary for the human body, but high concentrations of fluoride intake are very harmful to the human body. It can cause chronic and acute fluoride poisoning symptoms, reduce the body's immune system, and excessive fluoride can also cause animals to have low blood pressure or even anemia, affecting their growth and development. High fluoride exposure in cells can cause mitochondrial oxidative damage, reduce the rate of the mitochondrial respiratory chain, and thus lead to mitochondrial dysfunction. At the same time, the irreversible pollution and damage caused by fluoride compounds in the environment are becoming more and more obvious. Constructing a sensitive and fast F - Detection methods are crucial for public health and environmental safety. Traditional fluoride ion analysis methods include ion chromatography, selective electrode method, fluorine reagent colorimetry and fluorescent probe method. Although the above methods have good sensitivity and selectivity, they cannot be effectively promoted due to the need for expensive instruments. Therefore, the construction of F-detection methods with good selectivity, high sensitivity, convenience, speed and low cost has received more and more attention. Summary of the invention

[0004] The present invention provides an electrochemiluminescence sensor for detecting fluoride ions and an application method thereof. Silicon dioxide microspheres are prepared to encapsulate calcium peroxide nanoparticles. HF is used to specifically etch silicon dioxide to gradually etch the silicon dioxide shell, thereby exposing the encapsulated calcium peroxide nanoparticles. The exposed calcium peroxide nanoparticles can react with water to generate H 2 O 2 , H 2 O 2 As H 2 O 2 -luminol is a co-reactant in the electrochemiluminescence system. It is connected to the electrochemical workstation through a traditional three-electrode system and a certain positive voltage is applied to excite H 2 O 2 -Luminol electrochemiluminescence system, based on the electrochemiluminescence intensity, can detect F in water - Detection.

[0005] In a first aspect of the present invention, an electrochemiluminescence sensor for detecting fluoride ions is provided, which comprises a composite material of calcium peroxide nanoparticles wrapped in silicon dioxide, an electrochemiluminescence detection cell and a working electrode.

[0006] Furthermore, the working electrode is a glassy carbon electrode with a diameter of 5 mm.

[0007] Furthermore, the preparation method of the silica-coated calcium peroxide nanoparticle composite material comprises the following steps:

[0008] (1) Synthesizing calcium peroxide nanoparticles using a coprecipitation method;

[0009] (2) dispersing the obtained calcium peroxide nanoparticles into a silicon dioxide precursor solution to prepare a silicon dioxide-coated calcium peroxide nanoparticle composite material.

[0010] Furthermore, the preparation process of the calcium peroxide nanoparticles is as follows: first, a sodium hyaluronate aqueous solution of appropriate concentration is prepared and stirred evenly, then a calcium chloride aqueous solution of appropriate concentration is prepared, the prepared calcium chloride aqueous solution and the sodium hyaluronate aqueous solution are stirred and mixed, a sodium hydroxide solution is added and stirred, and then H 2 O 2 The reaction was stirred at room temperature, and after the reaction was completed, the mixture was washed with water by centrifugation and finally freeze-dried to obtain light yellow calcium peroxide powder.

[0011] Furthermore, the concentration of the sodium hyaluronate aqueous solution is 1 mg / mL-10 mg / mL; the concentration of the calcium chloride aqueous solution is 1 mol / L-5 mol / L.

[0012] The volume ratio of the sodium hyaluronate aqueous solution to the calcium chloride aqueous solution is 2-5.

[0013] The concentration of the sodium hydroxide solution is 0.1 mol / L-1 mol / L, and the dosage is 2.5 mL-10 mL.

[0014] The reaction time is 10min-60min.

[0015] The volume ratio of hydrogen peroxide to sodium hyaluronate aqueous solution is 0.02-0.05; the mass concentration thereof is 30%.

[0016] Furthermore, the preparation process of the silica-encapsulated calcium peroxide nanoparticle composite material of the present invention is as follows: calcium peroxide nanoparticles and polyvinyl pyrrolidone are dispersed in a mixed solution of water and ethanol, stirred and dispersed evenly, then an ammonia solution is added and continued to be stirred, and finally tetraethyl orthosilicate is added and continued to be stirred for reaction, and finally centrifuged and washed with ethanol, and then dried to obtain the silica-encapsulated calcium peroxide nanoparticle composite material.

[0017] Furthermore, the dosage of calcium peroxide nanoparticles and polyvinyl pyrrolidone is 2mg-10mg and 25mg-100mg respectively.

[0018] The amount of water and ethanol mixed solution used is 20mL-50mL, and the volume ratio is 1:2.

[0019] The amount of ammonia solution used is 1 mL-3 mL, and the mass concentration is 10%-25%.

[0020] The amount of tetraethyl orthosilicate used is 50 μL-200 μL.

[0021] The reaction time is 4h-6h.

[0022] A second aspect of the present invention provides an application method of an electrochemiluminescence sensor for detecting fluoride ions, comprising the following steps:

[0023] The calcium peroxide nanoparticle composite material wrapped with silicon oxide is dispersed in a F-containing - The solution after the reaction was added to the electrochemical luminescence detection cell, and then luminol was added to mix evenly. The three electrodes were inserted into the electrochemical workstation, and a certain voltage was applied through the electrochemical workstation to stimulate the reaction, and the luminescence intensity was recorded to realize the detection of F. - Quantitative.

[0024] Furthermore, the amount of the silica-wrapped calcium peroxide nanoparticle composite material is 5 mg-20 mg.

[0025] The heating reaction temperature is 40°C-70°C, and the reaction time is 15min-60min.

[0026] The amount of the mixed solution used is 300 μL-800 μL.

[0027] The dosage of luminol is 10μL-30μL; the concentration of luminol is 30-80mmol / L.

[0028] The voltage scanning range is 0V-1.0V.

[0029] Beneficial effects of the present invention:

[0030] 1.F - Preparation method of electrochemiluminescent sensor, using the reaction between calcium peroxide and water to generate H in situ 2 O 2 As a co-reactant in the electrochemiluminescence system, it avoids the introduction of co-reactants in the traditional electrochemiluminescence system and reduces the detection cost.

[0031] 2. Use F - Corrosion reaction to silicon dioxide, improving the resistance to F - The selectivity of F in water samples can be achieved - High specificity, high sensitivity and rapid detection.

[0032] 3. Electrochemiluminescence detection method of the present invention - The operation is fast and simple, and the reaction and results are automatically completed and recorded by the instrument, avoiding the influence of subjective factors and ensuring good repeatability, which is convenient for on-site detection. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] The drawings in the specification, which constitute a part of the present application, are used to provide further understanding of the present application. The illustrative embodiments of the present application and their descriptions are used to explain the present application and do not constitute improper limitations on the present application.

[0034] Figure 1 Schematic diagram of electrochemiluminescence sensor.

[0035] Figure 2 Schematic diagram of the working principle of electrochemiluminescence sensor for detecting F-. DETAILED DESCRIPTION

[0036] It should be noted that the following detailed descriptions are exemplary and are intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0037] Example 1

[0038] An electrochemiluminescence fluoride ion detection sensor comprises a silicon dioxide-wrapped calcium peroxide nanoparticle composite material, an electrochemiluminescence detection cell and a working electrode.

[0039] (1) The preparation process of the calcium peroxide nanoparticles of the present invention is as follows: first, 25 mg of sodium hyaluronate is weighed and dispersed into 5 mL of secondary water, and ultrasonically mixed to obtain a transparent solution; 0.555 g of calcium chloride is weighed and dissolved in 2 mL of secondary water; the prepared calcium chloride aqueous solution is added dropwise to the sodium hyaluronate aqueous solution under stirring, and stirred for 30 min until the mixture is uniform; 0.1 g of sodium hydroxide is weighed and dispersed into 5 mL of secondary water; the prepared sodium hydroxide solution is transferred into the mixed solution of sodium hyaluronate and calcium chloride and continued to stir; 200 μL of 30% H2O is pipetted with a pipette; 2 O 2 The above mixed solution was added, stirred and reacted at room temperature for 30 minutes. After the reaction was completed, the mixture was centrifuged at 10,000 rpm for 30 minutes, washed with secondary water for 3 times, and finally freeze-dried to obtain light yellow calcium peroxide particle powder.

[0040] (2) The preparation process of the composite material of calcium peroxide nanoparticles wrapped with silicon dioxide of the present invention is as follows: 10 mL of secondary water and 20 mL of ethanol are placed in a round-bottom flask, stirred and mixed evenly, 10 mg of the calcium peroxide powder prepared above is weighed and evenly dispersed in the mixed solution of water and ethanol, then 50 mg of polyvinyl pyrrolidone (average molecular weight 240000) is weighed and continued to stir for 10 min to mix evenly, 2 mL of 25% ammonia water is measured by a pipette and added to the solution and stirred for 5 min, 100 μL of tetraethyl orthosilicate is added to the solution and the reaction is continued for 5 h. The target product can be obtained by centrifugation washing and drying at 80°C.

[0041] (4) F - The analysis and testing process is as follows (eg Figure 1 , Figure 2 As shown in the figure): First, 10 mg of the above-obtained silica-wrapped nanoparticles-calcium peroxide nanoparticle composite material was dispersed into 10 mL of F-containing - The aqueous solution was placed at 60°C for 30 minutes. 500 μL of the reaction solution was taken into a 96-well microplate with a pipette. The 96-well plate was placed in a dark box of a chemiluminescence analyzer. 20 μL of 50 mmol / L luminol was added to initiate the reaction. A cyclic voltammetry voltage signal was applied to the three electrodes with a scanning range of 0.2V-0.8V and a scanning rate of 100mV / s to stimulate the electrochemiluminescence reaction. The luminescence signal intensity was recorded by the chemiluminescence detector, and a working curve was drawn. The intensity was analyzed to achieve the F - Quantitative detection of.

[0042] Example 2

[0043] An electrochemiluminescence fluoride ion detection sensor comprises a silicon dioxide-wrapped calcium peroxide nanoparticle composite material, an electrochemiluminescence detection cell and a working electrode.

[0044] (1) The preparation process of the calcium peroxide nanoparticles of the present invention is as follows: first, 50 mg of sodium hyaluronate is weighed and dispersed into 5 mL of secondary water, and ultrasonic mixing is performed to obtain a transparent solution. 1.11 g of calcium chloride is weighed and dissolved in 2 mL of secondary water, and the prepared calcium chloride aqueous solution is added dropwise to the sodium hyaluronate aqueous solution under stirring, and stirred for 30 minutes until the mixture is uniform. 0.1 g of sodium hydroxide is weighed and dispersed into 5 mL of secondary water, and the prepared sodium hydroxide solution is transferred into the mixed solution of sodium hyaluronate and calcium chloride and continued to stir. 200 μL of 30% H2O is pipetted with a pipette. 2 O 2 The above mixed solution was added, stirred and reacted at room temperature for 30 minutes. After the reaction was completed, the mixture was centrifuged at 10,000 rpm for 30 minutes, washed with secondary water for 3 times, and finally freeze-dried to obtain light yellow calcium peroxide particle powder.

[0045] (2) The preparation process of the composite material of calcium peroxide nanoparticles wrapped with silicon dioxide of the present invention is as follows: 10 mL of secondary water and 20 mL of ethanol are placed in a round-bottom flask, stirred and mixed evenly, 2 mg of the calcium peroxide powder prepared above is weighed and evenly dispersed in the mixed solution of water and ethanol, then 25 mg of polyvinyl pyrrolidone (average molecular weight 240000) is weighed and continued to stir for 10 min to mix evenly, 1 mL of 25% ammonia water is measured by a pipette and added to the solution and stirred for 5 min, 50 μL of tetraethyl orthosilicate is added to the solution and the reaction is continued for 5 h. The target product can be obtained by centrifugation washing and drying at 80°C.

[0046] (4) F - The analysis and testing process is as follows (eg Figure 1 , Figure 2 As shown in the figure): First, 10 mg of the above-obtained silica-wrapped nanoparticles-calcium peroxide nanoparticle composite material was dispersed into 10 mL of F-containing - The aqueous solution was placed at 60°C for 30 minutes. 500 μL of the reaction solution was taken into a 96-well microplate with a pipette. The 96-well plate was placed in a dark box of a chemiluminescence analyzer. 20 μL of 50 mmol / L luminol was added to initiate the reaction. A cyclic voltammetry voltage signal was applied to the three electrodes with a scanning range of 0.2V-0.8V and a scanning rate of 100mV / s to stimulate the electrochemiluminescence reaction. The luminescence signal intensity was recorded by the chemiluminescence detector, and a working curve was drawn. The intensity was analyzed to achieve the F - Quantitative detection of.

[0047] Example 3

[0048] An electrochemiluminescence fluoride ion detection sensor comprises a silicon dioxide-wrapped calcium peroxide nanoparticle composite material, an electrochemiluminescence detection cell and a working electrode.

[0049] (1) The preparation process of the calcium peroxide nanoparticles of the present invention is as follows: first, 5 mg of sodium hyaluronate is weighed and dispersed into 5 mL of secondary water, and ultrasonically mixed to obtain a transparent solution; 0.222 g of calcium chloride is weighed and dissolved in 2 mL of secondary water; the prepared calcium chloride aqueous solution is added dropwise to the sodium hyaluronate aqueous solution under stirring, and stirred for 30 minutes until the mixture is uniform; 0.1 g of sodium hydroxide is weighed and dispersed into 5 mL of secondary water; the prepared sodium hydroxide solution is transferred into the mixed solution of sodium hyaluronate and calcium chloride and continued to stir; 200 μL of 30% H2O is pipetted by a pipette; 2 O 2The above mixed solution was added, stirred and reacted at room temperature for 30 minutes. After the reaction was completed, the mixture was centrifuged at 10,000 rpm for 30 minutes, washed with secondary water for 3 times, and finally freeze-dried to obtain light yellow calcium peroxide particle powder.

[0050] (2) The preparation process of the composite material of calcium peroxide nanoparticles wrapped with silicon dioxide of the present invention is as follows: 10 mL of secondary water and 20 mL of ethanol are placed in a round-bottom flask, stirred and mixed evenly, 10 mg of the calcium peroxide powder prepared above is weighed and evenly dispersed in the mixed solution of water and ethanol, then 100 mg of polyvinyl pyrrolidone (average molecular weight 240000) is weighed and continued to stir for 10 min to mix evenly, 3 mL of 25% ammonia water is measured by a pipette and added to the solution and stirred for 5 min, 200 μL of tetraethyl orthosilicate is added to the solution and the reaction is continued for 5 h. The target product can be obtained by centrifugation washing and drying at 80°C.

[0051] (4) F - The analysis and testing process is as follows (eg Figure 1 , Figure 2 As shown in the figure): First, 20 mg of the above-obtained silica-wrapped nanoparticles-calcium peroxide nanoparticle composite material was dispersed into 10 mL of F-containing - The aqueous solution was placed at 60°C for 30 minutes. 500 μL of the reaction solution was taken into a 96-well microplate with a pipette. The 96-well plate was placed in a dark box of a chemiluminescence analyzer. 30 μL of 50 mmol / L luminol was added to initiate the reaction. A cyclic voltammetric voltage signal was applied to the three electrodes with a scanning range of 0.2V-0.8V and a scanning rate of 100mV / s to stimulate the electrochemiluminescence reaction. The luminescence signal intensity was recorded by the chemiluminescence detector, and a working curve was drawn. The intensity was analyzed to achieve the F - Quantitative detection of.

[0052] The above description is only the preferred embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. An electrochemiluminescence sensor for detecting fluoride ions, characterized in that: The electrochemiluminescence fluoride ion detection sensor comprises a calcium peroxide nanoparticle composite material wrapped in silicon dioxide, an electrochemiluminescence detection cell and a working electrode; The preparation method of the silicon dioxide-wrapped calcium peroxide nanoparticle composite material comprises the following steps: (1) Synthesis of calcium peroxide nanoparticles using a coprecipitation method; (2) dispersing the obtained calcium peroxide nanoparticles into a silicon dioxide precursor solution to prepare a silicon dioxide-coated calcium peroxide nanoparticle composite material; The preparation process of the calcium peroxide nanoparticles is as follows: first, a sodium hyaluronate aqueous solution of appropriate concentration is prepared and stirred evenly, then a calcium chloride aqueous solution of appropriate concentration is prepared, the prepared calcium chloride aqueous solution and the sodium hyaluronate aqueous solution are stirred and mixed, a sodium hydroxide solution is added and stirred, and then H2O2 is added and stirred at room temperature for reaction, after the reaction is completed, the light yellow calcium peroxide powder is obtained by centrifugal washing and finally freeze-drying; The concentration of the sodium hyaluronate aqueous solution is 1 mg / mL - 10 mg / mL; the concentration of the calcium chloride aqueous solution is 1 mol / L - 5 mol / L; The volume ratio of the sodium hyaluronate aqueous solution to the calcium chloride aqueous solution is 2-5; The concentration of sodium hydroxide solution is 0.1 mol / L - 1 mol / L, and the amount used is 2.5 mL - 10 mL; The volume ratio of hydrogen peroxide to sodium hyaluronate aqueous solution is 0.02-0.05; wherein the mass concentration of hydrogen peroxide is 30%; The reaction time is 10 min - 60 min.

2. The electrochemiluminescence fluoride ion sensor according to claim 1, characterized in that: The working electrode is a glassy carbon electrode with a diameter of 5 mm.

3. The electrochemiluminescence fluoride ion sensor according to claim 1, characterized in that: Calcium peroxide nanoparticles and polyvinyl pyrrolidone are dispersed in a mixed solution of water and ethanol, stirred and dispersed evenly, then an ammonia solution is added and stirring is continued, finally tetraethyl orthosilicate is added and stirring reaction is continued, finally centrifuged and washed with ethanol, and then dried to obtain a silica-coated calcium peroxide nanoparticle composite material.

4. The electrochemiluminescence fluoride ion sensor according to claim 3, characterized in that: The dosage of calcium peroxide nanoparticles and polyvinylpyrrolidone was 2 mg - 10 mg and 25 mg - 100 mg, respectively; The amount of water and ethanol mixed solution used is 20 mL - 50 mL, and the volume ratio is 1:2; The amount of ammonia solution is 1 mL - 3 mL, and the mass concentration is 10% - 25%; The amount of ethyl orthosilicate used is 50 μL - 200 μL; The reaction time is 4 h - 6 h.

5. An application method of the electrochemiluminescence sensor for detecting fluoride ions according to any one of claims 1 to 4, characterized in that: The calcium peroxide nanoparticle composite material wrapped with silicon oxide is dispersed in a F-containing - The solution after the reaction was added to the electrochemical luminescence detection cell, and then luminol was added to mix evenly. The three electrodes were inserted into the electrochemical workstation, and a certain voltage was applied through the electrochemical workstation to stimulate the reaction, and the luminescence intensity was recorded to realize the detection of F. - Quantitative.

6. The application method according to claim 5, characterized in that: The amount of the silica-wrapped calcium peroxide nanoparticle composite material is 5 mg to 20 mg.

7. The application method according to claim 5, characterized in that: The heating reaction temperature is 40 ℃ - 70 ℃, and the reaction time is 15 min - 60 min.

8. The application method according to claim 5, characterized in that: The amount of the mixed solution is 300 μL - 800 μL; the amount of luminol is 10 μL - 30 μL; the concentration of luminol is 30-80 mmol / L; the voltage scanning range is 0 V -1.0 V.

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