CN108519418B - Nano-gold-silver-three-dimensional graphene composite material modified electrode and application thereof in baicalein detection - Google Patents
Nano-gold-silver-three-dimensional graphene composite material modified electrode and application thereof in baicalein detection Download PDFInfo
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Abstract
The invention relates to a nanogold-silver-three-dimensional graphene composite material modified electrode and application thereof in baicalein detection. The preparation method of the nanogold-silver-three-dimensional graphene composite material (Au-Ag-3DGA) comprises the following steps: collecting appropriate amount of chloroauric acid (HAuCl)4) Silver nitrate (AgNO)3) And adding Graphene Oxide (GO) into water, uniformly stirring, adding a proper amount of triethylene tetramine under stirring, heating to 190 ℃, reacting for 10-12h, naturally cooling to room temperature, washing with water, and freeze-drying for 10-12h to obtain the nano gold-silver-three-dimensional graphene composite material (Au-Ag-3 DGA).
Description
Technical Field
The invention belongs to the field of nano materials and electrochemical analysis, and particularly relates to a nano gold-silver-three-dimensional graphene composite material modified electrode and application thereof in baicalein detection.
Background
Baicalein is a flavonoid compound with polyphenol hydroxyl, and is mainly derived from root of Scutellaria baicalensis Georgi, seed and stem bark of oroxylum indicum L.of Bignoniaceae, leaf of Plantago asiatica L.of Plantaginaceae, and leaf and root of comfrey. The baicalein is one of the effective components of the Shuanghuanglian oral liquid, so the baicalein has important significance for measuring the content of the baicalein. At present, the content determination method of baicalein mainly comprises three methods, namely High Performance Liquid Chromatography (HPLC), High Performance Capillary Electrophoresis (HPCE) and electrochemical means, and the two detection methods of HPLC and HPCE have the defects of troublesome and time-consuming operation, expensive instruments and consumables and the like although the results are relatively accurate. The electrochemical analysis method has the advantages of convenient and simple operation, rapidness, higher sensitivity, less time consumption and the like, and is used for analyzing and detecting the drug molecules. The invention provides a nanogold-silver-three-dimensional graphene composite material modified electrode which is high in baicalein detection sensitivity, high in stability and good in reproducibility, and the detection limit reaches 0.345nmol/L (3 sigma).
Disclosure of Invention
The invention provides a nanogold-silver-three-dimensional graphene composite material modified electrode which is characterized by comprising a substrate electrode and a nanogold-silver-three-dimensional graphene composite material (Au-Ag-3DGA) coating, wherein the substrate electrode is an ionic liquid modified carbon paste electrode (CILE).
The invention provides an electrode which is sequentially provided with a CILE substrate electrode and a nano gold-silver-three-dimensional graphene composite material (Au-Ag-3DGA) coating from inside to outside, namely an Au-Ag-3DGA/CILE electrode.
The preparation method of the nanogold-silver-three-dimensional graphene composite material (Au-Ag-3DGA) comprises the following steps: collecting appropriate amount of chloroauric acid (HAuCl)4) Silver nitrate (AgNO)3) And adding Graphene Oxide (GO) into water, uniformly stirring, adding a proper amount of triethylene tetramine under stirring, heating to 190 ℃, reacting for 10-12h, naturally cooling to room temperature, washing with water, and freeze-drying for 10-12h to obtain the nano gold-silver-three-dimensional graphene composite material (Au-Ag-3 DGA). 3-4mmol of chloroauric acid (HAuCl) per gram of Graphene Oxide (GO)4) Chloroauric acid (HAuCl)4) With silver nitrate (AgNO)3) In a molar ratio of 1: 0.8-1.0mL, preferably 0.9mL, of water is used per mg of Graphene Oxide (GO), and 40-60mL, preferably 50mL, of triethylene tetramine is used per g of Graphene Oxide (GO). The reaction is preferably carried out in a high-pressure reaction kettle, and is preferably heated to 180 ℃ for 12 hours; the water is preferably distilled or deionized water.
The invention provides an electrochemical sensing device which is characterized in that the nanogold-silver-three-dimensional graphene composite material modified electrode is used as a working electrode, and preferably an Au-Ag-3DGA/CILE electrode is used as the working electrode.
Another embodiment of the invention provides an application of the nanogold-silver-three-dimensional graphene composite modified electrode (preferably, an Au-Ag-3DGA/CILE electrode) in preparation of an electrochemical sensing device.
Another embodiment of the present invention provides a method for preparing the nanogold-silver-three-dimensional graphene composite modified electrode (preferably, Au-Ag-3DGA/CILE electrode) according to the present invention, which comprises the following steps: and (3) dripping a proper amount of gold-silver-three-dimensional graphene composite material (Au-Ag-3DGA) dispersion liquid on the surface of an ionic liquid modified carbon paste electrode (CILE), and naturally airing to obtain the nano gold-silver-three-dimensional graphene composite material modified electrode (preferably Au-Ag-3DGA/CILE electrode). Wherein gold-silver-trisThe concentration of the dispersion liquid of the graphene composite material (Au-Ag-3DGA) is 0.1-0.3mg/mL, preferably 0.2mg/mL, the dosage of the dispersion liquid of the gold-silver-three-dimensional graphene composite material (Au-Ag-3DGA) is suitable for uniformly coating the surface of an electrode, and the dosage can be reasonably selected by a person skilled in the art according to the properties of the electrode and the coating solution; the ionic liquid modified carbon paste electrode (CILE) is prepared by the following method: proper amount of graphite powder and N-1-hexylpyridine hexafluorophosphate HPPF6Putting liquid paraffin into a mortar for grinding uniformly to obtain carbon paste, filling the carbon paste into a glass electrode tube for compaction, and inserting a copper wire as a lead to obtain an ionic liquid modified carbon paste electrode, namely a CILE substrate electrode; wherein, graphite powder and HPPF6The mass ratio of (A) to (B) is 1.5-2.5: 1, preferably 2: 1; per gram of HPPF6500-700 mu L of liquid paraffin is used, and 625 mu L of liquid paraffin is preferred; the grinding time is 1.5-3.0 h; the inner diameter of the glass electrode tube is preferably 4 mm.
The invention further provides an application of the nanogold-silver-three-dimensional graphene composite material modified electrode (preferably Au-Ag-3DGA/CILE electrode) in detecting baicalein. Preferably used for detecting baicalein in serum or Shuanghuanglian oral liquid. Phosphate buffer solution with pH of 2.0 is used as supporting electrolyte in detecting baicalein.
All references to solutions herein (except where indicated) are aqueous solutions.
Compared with the prior art, the invention has the advantages that: (1) the nano gold-silver-three-dimensional graphene composite material modified electrode (preferably Au-Ag-3DGA/CILE electrode) prepared by the method has high detection sensitivity (the detection limit reaches 0.345nmol/L (3 sigma)) to baicalein, and has high stability (RSD 2.22%) and good reproducibility (RSD 4.2%); (2) when the detection sample contains inorganic metal ions, amino acids, glucose and other substances, the detection of baicalein is basically not influenced, and the method can be used for detecting the baicalein in the Shuanghuanglian oral liquid.
Drawings
Fig. 1 is SEM images (a, B) and TEM images (C, D) of the nanogold-silver-three-dimensional graphene composite;
FIG. 2 is a representation diagram of nano-Au-Ag-three-dimensional graphene composite material XRD (A) and Raman (B);
FIG. 3 is a 1X 10 in PBS buffer at pH 2.0-5A cyclic voltammetry curve (A, sweep rate of 100mV/s) and an alternating current impedance spectrogram (B) of mol/L baicalein on different modified electrodes; the working electrodes are respectively (a) CILE, (b)3DGA/CILE, (c) Au-Ag-3DGA/CILE (product c);
FIG. 4 is the DPV curves of baicalein at different concentrations on Au-Ag-3DGA/CILE electrode (from a to j: 0, 1X 10 respectively)-9,5.0×10-9,1×10-8,5.0×10-8,1×10-7,5.0×10-7,1×10-6,5.0×10-6,1×10-5mol/L); (B-D) relationship between oxidation peak current and baicalein at different concentrations.
Detailed Description
In order to facilitate a further understanding of the invention, the following examples are provided to illustrate it in more detail. However, these examples are only for better understanding of the present invention and are not intended to limit the scope or the principle of the present invention, and the embodiments of the present invention are not limited to the following.
Example 1
And adding chloroauric acid (0.06mmol), silver nitrate (0.06mmol) and graphene oxide (20mg) into distilled water (16mL), uniformly stirring, adding triethylene tetramine (0.8mL) under stirring, heating to 190 ℃, reacting for 10h, naturally cooling to room temperature, washing with water, and freeze-drying for 12h to obtain the nano gold-silver-three-dimensional graphene composite material (Au-Ag-3DGA, hereinafter referred to as product A).
Example 2
And adding chloroauric acid (0.08mmol), silver nitrate (0.08mmol) and graphene oxide (20mg) into deionized water (20mL), uniformly stirring, adding triethylene tetramine (1.2mL) under stirring, heating to 170 ℃, reacting for 12h, naturally cooling to room temperature, washing with water, and freeze-drying for 10h to obtain the nanogold-silver-three-dimensional graphene composite material (Au-Ag-3DGA, hereinafter referred to as product B).
Example 3
And adding chloroauric acid (0.06mmol), silver nitrate (0.06mmol) and graphene oxide (20mg) into distilled water (17.5mL), uniformly stirring, adding triethylene tetramine (1.0mL) under stirring, heating to 180 ℃, reacting for 12 hours, naturally cooling to room temperature, washing with water, and freeze-drying for 12 hours to obtain the nano gold-silver-three-dimensional graphene composite material (Au-Ag-3DGA, hereinafter referred to as product C).
The characterization results of SEM, TEM, XRD and Raman of the products A-C are consistent and are limited to space, and only the corresponding characterization results of the product C are listed in the attached drawings 1-2 of the specification of the invention.
Example 4
Adding graphene oxide (20mg) into distilled water (17.5mL), uniformly stirring, adding triethylene tetramine (1.0mL) under stirring, heating to 180 ℃, reacting for 12h, naturally cooling to room temperature, washing with water, and freeze-drying for 12h to obtain the three-dimensional graphene composite material (3DGA, hereinafter referred to as product D).
Example 5
(1) Taking 1.5g of graphite powder and 1.0g of ionic liquid HPPF6Grinding the carbon paste and 500 mu L of liquid paraffin in a mortar for 1.5h to obtain carbon paste, filling the carbon paste into a glass electrode tube with the inner diameter of 4mm, compacting, and inserting a copper wire as a lead to obtain CILE;
(2) 8-10 mu L of product A aqueous solution (0.1mg/mL) is dripped on the surface of CILE, and the modified electrode Au-Ag-3DGA/CILE (hereinafter referred to as product a) is obtained after natural air drying.
Example 6
(1) Taking 2.5g of graphite powder and 1.0g of ionic liquid HPPF6Grinding the carbon paste and 700 mu L of liquid paraffin in a mortar for 3h to obtain carbon paste, filling the carbon paste into a glass electrode tube with the inner diameter of 4mm, compacting, and inserting a copper wire as a lead to obtain CILE;
(2) and (3) dripping 8-10 mu L of aqueous solution (0.3mg/mL) of the product B on the surface of CILE, and naturally drying to obtain the modified electrode Au-Ag-3DGA/CILE (hereinafter referred to as product B).
Example 7
(1) Taking 1.6g of graphite powder and 0.8g of ionic liquid HPPF6Grinding the carbon paste and 500 mu L of liquid paraffin in a mortar for 2.0h to obtain carbon paste, filling the carbon paste into a glass electrode tube with the inner diameter of 4mm, compacting, and inserting a copper wire as a lead to obtain CILE;
(2) and (3) dripping 8-10 mu L of aqueous solution (0.2mg/mL) of the product C on the surface of CILE, and naturally drying to obtain the modified electrode Au-Ag-3DGA/CILE (hereinafter referred to as product C).
Example 8
(1) Taking 1.6g of graphite powder and 0.8g of ionic liquid HPPF6Grinding the carbon paste and 500 mu L of liquid paraffin in a mortar for 2.0h to obtain carbon paste, filling the carbon paste into a glass electrode tube with the inner diameter of 4mm, compacting, and inserting a copper wire as a lead to obtain CILE;
(2) 8-10 mu L of aqueous solution (0.2mg/mL) of the product D is dripped on the surface of CILE, and the modified electrode 3DGA/CILE (hereinafter referred to as product D) is obtained after natural drying.
Example 9 study of the electrochemical behavior of baicalein on CILE, products c-d
In 0.1mol/LpH 2.0.0 PBS buffer solution, 1.0 × 10 was investigated by cyclic voltammetry-5The electrochemical behavior of mol/L baicalein on different electrodes (CILE, products c-d) is shown in FIG. 3. On CILE (curve a), baicalein has a pair of redox peaks at 0.436V and 0.420V, and Ipa and Ipc are respectively 1.574 muA and 0.964 muA, which indicates that the baicalein can realize direct electrochemistry on the surface of CILE. Curve b is the electrochemical behavior curve of baicalein on 3DGA/CILE (product d), Epa and Epc are respectively at 0.436V and 0.431V, Ipa and Ipc are respectively at 2.198 μ A and 2.060 μ A, and are 1.40 times and 2.14 times of peak current on CILE, which indicates that the existence of 3DGA is favorable for the electron transfer of an electrode interface and can improve the electrochemical signal of baicalein. The curve c is the electrochemical behavior curve of baicalein on Au-Ag-3DGA/CILE (product c), Epa and Epc are respectively positioned at 0.443V and 0.425V, Ipa and Ipc are respectively 6.668 muA and 4.282 muA, the values are respectively 3.03 times and 2.08 times of 3DGA/CILE and are 4.24 times and 4.44 times of CILE, which indicates that the existence of Au-Ag-3DGA obviously improves the electron transfer rate of baicalein on the surface of a modified electrode and the electrode performance, and probably is due to the beneficial effects of high surface area, high conductivity and synergistic effect of Au-Ag-3 DGA.
Example 10 Linear Range and detection Limit
In PBS buffer solution with pH of 2.0, the relation between the oxidation peak current and the concentration of baicalein was examined by DPV method (sweep rate of 0.05-0.90V/s)Fig. 4A is an overlay of a portion of a representative DPV curve. The result shows that the DPV oxidation peak current of the baicalein is 1 multiplied by 10-9～1×10-8mol/L (FIG. 4B), 1X 10-8～1×10-7mol/L (FIG. 4C) and 1X 10-7～1×10-5The mol/L (FIG. 4D) shows good linear relationship in the three concentration ranges, and the linear regression thereof is respectively as follows: ipa (μ a) ═ 177.66C (μmol/L) +0.684(n ═ 7, γ ═ 0.995), Ipa (μ a) ═ 47.47C (μmol/L) +2.14(n ═ 6, γ ═ 0.993), Ipa (μ a) ═ 2.81C (μmol/L) +6.99(n ═ 11, γ ═ 0.995), and the detection limit is 0.345nmol/L (3 σ).
Example 11 Selectivity
The DPV method (in PBS buffer solution with pH of 2.0, sweep speed of 0.05-0.90V/s) is adopted for the experiment to treat coexisting substance pairs of part of common inorganic metal ions, amino acids and the like at 1.0 multiplied by 10-5The influence of the mol/L baicalein measurement was examined, and the experimental results are shown in Table 1. The data in the table show that the existence of common substances has no obvious influence on the determination of the baicalein, which indicates that the Au-Ag-3DGA/CILE (product c) has good selectivity on the determination of the baicalein.
TABLE 1 interfering substance pairs 1.0X 10-5Effect of mol/L baicalein detection
EXAMPLE 12 measurement of Shuanghuanglian oral liquid sample
In order to test the practical application capability of the method, the method is used for measuring the content of baicalein in the Shuanghuanglian oral liquid. The low concentration determination experimental procedure method is as follows: the Shuanghuanglian oral liquid is diluted by 5 ten thousand times by PBS buffer solution with the pH value of 2.0, the concentration of the baicalein is measured according to a standard addition method, and the recovery rate is between 97.0 and 106.0 percent as shown in the table 2. The high concentration determination experimental procedure method is as follows: the Shuanghuanglian oral liquid is diluted by 1 ten thousand times by using PBS buffer solution with the pH value of 2.0, and then the concentration of the baicalein is measured according to a standard addition method, and the recovery rate is between 95.3 and 104.5 percent as shown in the table 3. The relative standard deviation of the sample detection is less than 5 percent, which shows that the method has better determination result for the practical sample of the baicalein.
Table 2 content and recovery of baicalein in shuanghuanglian in low concentration zone (n ═ 3)
TABLE 3 baicalein content and recovery in Shuanghuanglian in high concentration interval (n ═ 3)
EXAMPLE 13 stability and reproducibility of the electrodes
Au-Ag-3DGA/CILE is added at 1 × 10-5After the continuous scanning is carried out in the baicalein solution of mol/L for 30 circles, the peak current is reduced to 97.8 percent of the initial current, and after the continuous scanning is carried out for 70 circles, the peak current is reduced to 95.6 percent of the initial current, which indicates that the modified electrode has better stability. For 1 × 10-5The mol/L baicalein is parallelly determined for 10 times, the RSD value is 2.22%, and the products a-c are respectively utilized for 1 × 10-5The RSD of the baicalein solution of mol/L is 4.2 percent, which indicates that the electrode has good stability and reproducibility.
Claims (2)
1. The application of a nanogold-silver-three-dimensional graphene composite material modified electrode in detecting baicalein, wherein the nanogold-silver-three-dimensional graphene composite material modified electrode comprises a substrate electrode, a nanogold-silver-three-dimensional graphene composite material (Au-Ag-3DGA) coating, and the substrate electrode is an ionic liquid modified carbon paste electrode (CILE); the preparation method of the nanogold-silver-three-dimensional graphene composite material (Au-Ag-3DGA) comprises the following steps: collecting appropriate amount of chloroauric acid (HAuCl)4) Silver nitrate (AgNO)3) Adding Graphene Oxide (GO) into water, stirring uniformly, adding a proper amount of triethylene tetramine under stirring, heating to 190 ℃ for reaction at the temperature of 170 ℃ for 10-12h, naturally cooling to room temperature, washing with water, and freeze-drying for 10-12h to obtain the nano gold-silver-three-dimensional graphene composite material (Au-Ag-3DGA), wherein 3-4mmol of chloroauric acid (HAuCl) is used per gram of Graphene Oxide (GO)4) Chloroauric acid (HA)uCl4) With silver nitrate (AgNO)3) In a molar ratio of 1: 1, using 0.8-1.0mL of water per mg of Graphene Oxide (GO) and 40-60mL of triethylene tetramine per gram of Graphene Oxide (GO), reacting in a high-pressure reaction kettle, heating to 180 ℃, and reacting for 12 hours; the water is selected from distilled water or deionized water.
2. The use of claim 1, wherein the use is for detecting the content of baicalein in Shuanghuanglian oral liquid.
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