CN110308142B - Tetracycline flexible gold-like foil electrochemical luminescence sensor and preparation method and detection method thereof - Google Patents
Tetracycline flexible gold-like foil electrochemical luminescence sensor and preparation method and detection method thereof Download PDFInfo
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- 229960002180 tetracycline Drugs 0.000 title claims abstract description 59
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- 235000019364 tetracycline Nutrition 0.000 title claims abstract description 59
- 150000003522 tetracyclines Chemical class 0.000 title claims abstract description 59
- 238000001514 detection method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000004020 luminiscence type Methods 0.000 title claims abstract description 10
- 239000011888 foil Substances 0.000 title claims description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 25
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 19
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 229910052697 platinum Inorganic materials 0.000 claims abstract description 5
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- 239000002105 nanoparticle Substances 0.000 claims description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
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Abstract
The invention provides a tetracycline flexible gold foil electrochemical luminescence sensor, a preparation method and a detection method thereof. Then, using electrostatic attraction to make positive terpyridyl ruthenium (Ru (bpy)3 2+) The tetracycline is loaded on a gold foil-like electrode and is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum electrode is used as an auxiliary electrode to form a three-electrode system, and the tetracycline is detected by an electrochemiluminescence method. The linear range of detection of the method is 1.0 multiplied by 10‑9～1.0×10‑4mol/L, detection limit of 3.7X 10‑10mol/L, the sensor prepared by the invention has simple manufacturing process, low cost and high sensitivity for detecting tetracycline.
Description
Technical Field
The invention belongs to the technical field of environmental monitoring, and particularly relates to a flexible gold foil electrode (AuNPs @ BC/Ru (bpy)) loaded by terpyridyl ruthenium3 2+) An electrochemiluminescence assay for detecting tetracycline as a working electrode.
Background
Tetracycline is a representative antibiotic, and is mainly used for treating infections caused by clinical pathogenic bacteria such as mycoplasma pneumonia infection, genitourinary tract infection, early cholera, epidemic typhus and the like. Because of its excellent bactericidal effect, tetracycline is widely used in the aquaculture industry and is recognized by the chinese department of agriculture as an animal feed additive. However, excessive use of tetracycline results in serious residues of antibiotics in animal feed, which poses serious safety problems for humans eating animal food. Therefore, there is a need to develop a sensitive and accurate method for detecting tetracycline in environments, foods and drugs.
Commonly used tetracycline detection methods include microbial detection, high performance liquid chromatography, liquid chromatography/mass spectrometry, thin layer chromatography, enzyme linked immunosorbent assay, capillary electrophoresis, electrochemical methods, fluorescence spectroscopy, chemiluminescence, and the like. Although each method has its advantages and disadvantages, sensitivity, specificity, rapidity, miniaturization of the instrument, and low cost remain goals to be achieved.
Electrochemiluminescence is an analytical method for producing light emission based on electrochemical reaction contact. Its advantages are high sensitivity, wide detection range, simple instrument, etc. and it has become a powerful means for electrochemical analysis and test.
Although the electrochemiluminescence method for detecting tetracycline has been developed to some extent, how to further improve the sensitivity, reduce the cost and simplify the process becomes a key factor for large-area application and popularization in real life. The bacterial cellulose membrane is taken as a material with the advantages of compact reticular structure, large specific surface area, simple manufacture, low cost, environmental friendliness and the like, and is widely applied to various fields at present. By utilizing the characteristics of the bacterial cellulose membrane, the loading capacity of the luminophor terpyridyl ruthenium can be effectively improved, so that the detection sensitivity is improved.
Disclosure of Invention
The invention aims to provide preparation of a tetracycline flexible gold-like foil electrochemical luminescence sensor and a method for detecting tetracycline with high sensitivity and low cost.
In order to achieve the purpose, the invention provides the following scheme: a method for detecting tetracycline with high sensitivity and low cost specifically relates to preparation of a flexible gold foil electrode by using a bacterial cellulose membrane, loading of terpyridyl ruthenium, preparation of tetracycline standard solutions with different concentrations, drawing of a standard curve and detection of an actual sample. Further, the detection method specifically comprises the following steps:
(1) flexible gold foil-like electrode prepared from bacterial cellulose membrane
The area is 2cm2Soaking a (1cm multiplied by 2cm) purified bacterial cellulose membrane in 30-60 mL of 30 nm-containing gold nanoparticle solution, shaking for 36-48 h without needing to useAnd drying to obtain the flexible gold foil electrode.
The gold nanoparticles are gold nanoparticles with negative charges, the particle size is 30nm, the volume of the solution is 30-60 mL, and the concentration is 1.404 mmol/L.
(2) Preparation of flexible gold foil electrode loaded with terpyridyl ruthenium
Adding the flexible gold foil electrode obtained in the step (1) into 30-60 mL of 1.0 multiplied by 10-4Standing the solution of the terpyridyl ruthenium in mol/L for 12-24 h, and drying the solution at 60 ℃ to obtain the flexible gold foil electrode loaded with the terpyridyl ruthenium.
(3) Preparation of tetracycline standard solutions with different concentrations
0.1mol/L Phosphate Buffer Solution (PBS) containing 0.05mol/L Triethanolamine (TEOA) at pH 7.0 was prepared, and 1.0X 10 was prepared using phosphate buffer solution-3The mol/L tetracycline solution is mixed with 1.0X 10-3The tetracycline solution of mol/L is diluted by the buffer solution to prepare a series of concentration ranges of 5.0 × 10-10～1.0×10-4And (3) a tetracycline standard solution in mol/L. Electrochemiluminescence sensor for detecting tetracycline
(4) Drawing of standard curve
Accurately measuring 20.0mL of tetracycline standard solution prepared in the step (3) as a solution to be detected, and carrying out quantitative analysis on AuNPs @ BC/Ru (bpy)3 2+The electrode is used as a working electrode, the Ag/AgCl electrode is used as a reference electrode, the platinum electrode is used as an auxiliary electrode to form a traditional three-electrode system, cyclic voltammetry scanning is carried out within the range of an electrochemical window from 0V to 1.5V, the high voltage of a photomultiplier tube is 800V, the scanning speed is 100mV/s, a potential-luminous intensity curve is recorded, the linear relation between the luminous intensity difference before and after tetracycline addition and the tetracycline concentration logarithm value is established, and a corresponding linear regression equation is obtained.
(5) Detection of actual samples
And (4) carrying out pretreatment and then adjusting the pH value in the actual sample detection, carrying out detection according to the method in the step (4), and substituting the obtained luminous intensity response value into the abscissa corresponding to the standard curve obtained in the step (4) to obtain the concentration of tetracycline.
After the technical scheme is adopted, the invention has the following advantages:
(1) according to the invention, the bacterial cellulose membrane is selected as a substrate material for manufacturing the flexible gold-like foil electrode, the surface of the bacterial cellulose membrane is provided with a large number of hydroxyl groups, a large number of gold nanoparticles can be stably adsorbed, and the gold-like foil electrode which is smooth and has good conductivity can be obtained after drying. And the bacterial cellulose membrane material has very strong adsorption capacity and good self-stability.
(2) The invention selects the bacterial cellulose membrane as the substrate material for manufacturing the flexible gold-like foil electrode, has a natural compact reticular structure and a large specific surface area, the flexible gold-like foil electrode can be directly used as the electrode without modification, and compared with the traditional electrode, the invention can obviously improve the loading capacity of the luminescent agent terpyridyl ruthenium, thereby improving the sensitivity, and the detection sensitivity can reach 0.37 nmol/L.
(3) The invention selects the bacterial cellulose membrane as the substrate material of the flexible gold foil electrode, and has the advantages of simple manufacture, low cost, environmental protection and the like.
(4) The invention selects gold nano particles with negative electricity to manufacture the flexible gold foil electrode, and compared with the traditional electrode, the flexible gold foil electrode can simply and stably load the luminescent agent terpyridyl ruthenium with positive electricity by utilizing the electrostatic attraction effect.
(5) The invention selects the flexible gold foil electrode loaded with terpyridyl ruthenium as the electrochemical luminescence sensor to detect tetracycline, has quick response, realizes the quick detection of tetracycline, and only needs a few minutes in the detection process of each sample.
(6) The invention selects the flexible gold foil electrode loaded by terpyridyl ruthenium, detects the tetracycline by an electrochemiluminescence method, has the advantages of stable signal and high sensitivity, and has the concentration of the tetracycline of 1.0 multiplied by 10-9～1.0×10-4The light intensity difference value and the tetracycline concentration logarithm value in the mol/L range form a good linear relation, and the detection Limit (LOD) reaches 3.7 multiplied by 10-10mol/L。
Drawings
FIG. 1 is a photograph and scanning electron microscope of a terpyridyl ruthenium loaded flexible gold-like foil electrode.
FIG. 2 is a graph of cyclic voltammetric luminescence in phosphate buffered solutions containing different concentrations of tetracycline.
From fig. 2, a standard curve of the difference of the luminescence intensity of the terpyridyl ruthenium-loaded flexible gold-like foil electrode before and after adding tetracycline with different concentrations and the log value of tetracycline concentration can be obtained.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
The bacterial cellulose membrane used in this example was obtained in the laboratory by a conventional culture method using Acetobacter xylinum.
Other reagents and instruments used in this example are commercially available.
The invention is described in more detail below with reference to the following examples:
example (b):
(1)AuNPs@BC/Ru(bpy)3 2+preparation of the electrodes
The purified bacterial cellulose membrane was cut into small pieces (about 1X 2cm)2) (purification means that the membrane is soaked in NaOH solution and heated to remove bacteria, then the bacterial cellulose membrane is soaked in 30mL of gold nanoparticle solution with negative charge and the concentration of the gold nanoparticle solution is 1.404mmol/L, and the gold nanoparticle solution is shaken for 36-48 h, so that AuNPs @ BC can be obtained without drying.
AuNPs @ BC was immersed in 30mL of 1.0X 10-4mol/L Ru(bpy)3 2+Soaking in the solution for 24h, and drying at 60 ℃ to obtain AuNPs @ BC/Ru (bpy)3 2+An electrode;
for the convenience of detection, the dried film was adhered to a platinum wire with a conductive adhesive, and the upper part of the electrode was covered with an insulating tape by 1X 1cm2The membrane of (2) is used for reaction.
(2) Drawing of standard curve
With AuNPs @ BC/Ru (bpy)3 2+The electrode is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum electrode is used as an auxiliary electrode to form a traditional three-electrode system, 0.1mol/L PBS buffer solution with pH of 7.0 and 0.05mol/L TEOA is used as a blank solution to detect the luminous intensity, and the three-electrode system is placed in a series of tetracycline concentrations (0, 5 multiplied by 10)-10mol/L、1×10-9mol/L、5×10-9mol/L、1×10-8mol/L、1×10-7mol/L、1×10-6mol/L、1×10-5mol/L、2×10-5mol/L、5×10-5mol/L、1×10-4mol/L, corresponding to the range from a to k) of buffer solution with pH value of 7.0 in figure 2, in the electrochemical window range of 0 to 1.5V, the photomultiplier high pressure is 800V, the scanning speed is 100mV/s, cyclic voltammetry scanning is carried out, ECL curves are recorded, the linear relation between the luminous intensity difference before and after adding tetracycline and the tetracycline concentration logarithm value is established, the linear regression equation is that y is 437.9x +4320.5, the regression coefficient is 0.926, and the detection range of the linear regression equation is 1.0 multiplied by 10-9～1.0×10-4mol/L, detection limit of 3.7X 10-10mol/L。
(3) Detection of samples
And (3) filtering a water sample in the pool, adjusting the pH to 7.0 by using 0.1mol/L PBS (phosphate buffer solution) containing 0.05mol/L TEOA, using 20mL of the obtained solution for electrochemical luminescence detection, testing the sample solution according to the electrochemical test method same as the step (2), calculating the concentration of tetracycline in the sample to be detected by using a linear regression equation corresponding to the standard curve obtained in the step (2) according to the obtained difference value of the luminescence intensity values, and obtaining the result shown in Table 1.
TABLE 1 determination of water samples in an artificial fish farm
As shown in Table 1, the samples were tested in parallel for 3 times, the relative standard deviation was less than 5.0%, and the recovery rate of the spiked standard ranged from 98% to 105%. Experimental results show that the method is feasible for detecting the tetracycline in the water sample of the pond by electrochemical luminescence.
The above embodiments are only for illustrating the invention, but not for limiting the invention, and those skilled in the art can make corresponding adjustments and modifications without departing from the scope of the invention, so that all technical solutions formed by equivalent substitutions or equivalent modifications belong to the protection scope of the invention.
Claims (9)
1. A tetracycline flexible gold-like foil electrochemical luminescence sensor is characterized in that: adsorbing gold nanoparticles with negative electricity on a bacterial cellulose membrane to obtain a flexible gold foil electrode, and loading terpyridyl ruthenium on the flexible gold foil electrode to obtain a terpyridyl ruthenium-loaded flexible gold foil electrode (AuNPs @ BC/Ru (bpy))3 2+) An electrochemiluminescence sensor for detecting tetracycline.
2. A method for preparing the tetracycline flexible gold-like foil electrochemiluminescence sensor according to claim 1, wherein the method comprises the following steps:
(1) preparation of flexible gold-like foil electrode (AuNPs @ BC)
Soaking the purified bacterial cellulose membrane in a gold nanoparticle solution with negative electricity, shaking to enable the gold nanoparticles to be fully mixed with the bacterial cellulose membrane, and adsorbing the gold nanoparticles onto the bacterial cellulose membrane to obtain a flexible gold-like foil electrode (AuNPs @ BC);
(2) flexible gold foil electrode loaded with terpyridyl ruthenium (AuNPs @ BC/Ru (bpy))3 2+) Preparation of
Placing the flexible gold foil electrode obtained in the step (1) in a terpyridyl ruthenium solution, standing and adsorbing to ensure that the terpyridyl ruthenium is filled in a space network of the flexible gold foil electrode, and drying at 60 ℃ to obtain the flexible gold foil electrode (AuNPs @ BC/Ru (bpy))3 2+）。
3. The method for preparing the tetracycline flexible gold-like foil electrochemiluminescence sensor according to claim 2, wherein: the gold nanoparticles in the step (1) are negatively charged gold nanoparticles with the particle size of 30 nm; the shaking time is 36-48 h.
4. The method for preparing the tetracycline flexible gold-like foil electrochemiluminescence sensor according to claim 2, wherein: the concentration of the terpyridyl ruthenium solution in the step (2) is 1.0 multiplied by 10-4 mol/L, and the adsorption time is 12-24 h.
5. A method for detecting tetracycline by electrochemiluminescence using the sensor of claim 1 or the sensor prepared by the method of any one of claims 2-4, wherein:
flexible gold foil electrode loaded with terpyridyl ruthenium (AuNPs @ BC/Ru (bpy))3 2+) And the Ag/AgCl electrode is used as a working electrode, the platinum electrode is used as an auxiliary electrode, and a three-electrode system is formed for performing electrochemiluminescence detection on tetracycline.
6. The method for detecting tetracycline according to claim 5, wherein: the method comprises the following specific steps:
(1) preparation of tetracycline standard solutions with different concentrations
Preparing Phosphate Buffer Solution (PBS) containing Triethanolamine (TEOA), and preparing 1.0 × 10 with the buffer solution-3The mol/L tetracycline solution is mixed with 1.0X 10-3The mol/L tetracycline solution is diluted with buffer solution to prepare a series of concentrations ranging from 5.0 × 10-10 ~ 1.0× 10-4A tetracycline standard solution of mol/L;
(2) drawing of standard curve
Accurately measuring the tetracycline standard solution prepared in the step (1) as a solution to be detected, and taking AuNPs @ BC/Ru (bpy)3 2+The electrode is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum electrode is used as an auxiliary electrode to form a traditional three-electrode system, cyclic voltammetry scanning is carried out within the range of an electrochemical window from 0V to 1.5V, the high voltage of a photomultiplier tube is 800V, the scanning speed is 100mV/s, a potential-luminous intensity curve is recorded, the linear relation between the luminous intensity difference before and after tetracycline addition and the tetracycline concentration logarithm value is established, and a corresponding linear regression equation is obtained;
(3) actual sample detection
And (3) carrying out pretreatment and pH adjustment on the actual sample detection, carrying out detection according to the method in the step (2), and calculating the concentration of tetracycline according to the linear regression equation in the step (2).
7. The method for detecting tetracycline by electrochemiluminescence according to claim 6, wherein: the concentration of the phosphoric acid buffer solution in the step (1) is 0.1mol/L, and the pH value is 7.0.
8. The method for detecting tetracycline by electrochemiluminescence according to claim 6, wherein: the concentration of the triethanolamine in the step (1) in the phosphoric acid buffer solution is 0.05 mol/L.
9. The method for detecting tetracycline by electrochemiluminescence according to claim 6, wherein: the detection limit of the tetracycline concentration is 3.7 multiplied by 10-10 mol/L。
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