CN113466300A - Preparation method of graphene modified silica sol loaded salbutamol antibody sensor - Google Patents
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Abstract
The invention relates to a preparation method of an electrochemical sensor based on graphene modified silica sol in-situ loaded salbutamol antibody. The method comprises the following steps: (1) mixing silica sol with ethanol, and adding Span-80, Tween-80 and 2-6ml of n-butanol; (2) mixing KH 550-trimethylchlorosilane and dilute hydrochloric acid, and hydrolyzing; mixing the mixed solution obtained in the step (1) and the mixed solution obtained in the step (2) to obtain modified silica sol; uniformly mixing ethanol, Span-80 and Tween-80 with deionized water in advance, and adding graphene powder and graphene quantum dots to obtain a graphene aqueous solution; dropping the prepared modified silica sol on the surface of a glassy carbon electrode, and drying to form a glue film; dropwise adding a graphene aqueous solution into the adhesive film, standing, and vacuum drying to obtain a graphene adsorption adhesive film; and continuously dropwise adding a salbutamol antibody solution into the adhesive film, and performing vacuum drying to obtain the salbutamol electrochemical sensor. The method has the advantages of simple operation, low cost, high detection sensitivity and the like.
Description
Technical Field
The invention belongs to the field of veterinary drug residue detection in food safety, and particularly relates to a preparation method of an electrochemical sensor based on graphene modified silica sol in-situ loaded salbutamol antibody.
Background
Salbutamol (SAL) is a selective beta-2 receptor agonist, has the same effect of promoting nutrient redistribution and growth as clenbuterol hydrochloride, and is added into animal feed as a growth promoter by some illegal users in animal husbandry to increase the growth rate of lean meat. According to the Ministry of agriculture No. 235, salbutamol is a banned additive and therefore cannot be detected in food (meat). The existing detection standard is GB/T22286-2008 'determination of residual quantity of various beta-receptor agonists in animal-derived food', and the detection limit of the method (high performance liquid chromatography tandem mass spectrometry) on salbutamol is 0.5 mu g/kg.
Salbutamol is mainly used at home and abroad to realize qualitative and quantitative detection by GC-MS, LC-MS, enzyme-linked immunosorbent assay (ELISA), colloidal gold labeled immunochromatography test paper strips and other technologies.
The biosensor technology is a detection method developed in recent years, and detection is performed by means of a biosensor and an external computer. At present, the sensitivity of the enzyme immunosensor can reach 0.01ng/g to the maximum, and the enzyme immunosensor is more sensitive compared with an enzyme-linked immunosorbent assay, can be used for measuring various antigen substances, is particularly suitable for measuring the contents of drugs and hormones in body fluid, and facilitates the detection work to be simpler and more efficient.
The invention utilizes the advantages of easy dispersion, large specific surface area, high loading capacity of the graphene material to electroactive substances and biomolecules, more uniform and larger distribution of electroactive sites and the like, combines the advantages of good biocompatibility, accelerated electron transmission rate and the like of the nano silica sol, prepares the composite nano material to be modified on the surface of the glassy carbon electrode, and effectively improves the sensitivity of the prepared electrochemical immunosensor. During the preparation process, parameters such as immune reaction conditions are optimized, and the sensor is at 0.1X10-7-1.5×10-7The linear relation of detecting salbutamol in a mol/L concentration range is excellent (R is 0.99), and the method can be used for detecting the target component salbutamol in an actual sample.
Disclosure of Invention
The invention aims to provide a preparation method of an electrochemical sensor based on graphene modified silica sol in-situ loaded salbutamol antibody.
The technical scheme adopted for realizing the purpose of the invention is as follows: according to the electrochemical sensor for detecting salbutamol, the KH 560-containing silica sol and the graphene solution which are prepared on the surface modification of the electrode, as the graphene has a porous structure, the salbutamol antibody is dripped on the modified electrode, so that the salbutamol antibody is coated on the graphene, and the electrochemical sensor for detecting salbutamol is obtained.
1. Preparing a graphene aqueous solution:
1) under the condition of stirring in a beaker, adding 30-50g of ethanol into 5-15g of silica sol, adding 0.05-0.08g of Span-80, 0.03-0.08g of Tween-80 and 2-6ml of n-butyl alcohol by using a syringe in a dropwise adding mode, stirring for 20min at the speed of 500r/min, and then dropwise adding a proper amount of ammonia water solution under the stirring condition of 50r/min to adjust the pH value to 6.5-7.5; obtaining silica sol for later use;
2) mixing and hydrolyzing 1g of silane coupling agent KH 550-trimethylchlorosilane and 15g of dilute hydrochloric acid (0.5mol/L) mixed solution for 30 minutes in a magnetic stirring manner at the temperature of 30 ℃ according to the mass ratio of 1:15 to obtain mixed solution;
3) ultrasonically mixing the silica sol obtained in the step 1) and the mixed solution obtained in the step 2) for 10min according to the volume ratio of 15:1 to obtain modified silica sol;
4) uniformly mixing 30ml-50ml of ethanol, 0.05-0.08g of Span-80, 0.03-0.08g of Tween-80 and 100ml of deionized water in advance, performing ultrasonic treatment for 30min, adding 0.01-0.1 g of graphene powder and 0.005-0.02 g of graphene quantum dots, and uniformly performing ultrasonic treatment; obtaining a graphene aqueous solution for later use;
2. preparing a salbutamol electrochemical sensor:
1) dropping the prepared modified silica sol on the surface of a glassy carbon electrode, and drying at 80-100 ℃ for 2-4 h to enable silica sol particles to be adsorbed on the glassy carbon electrode to form a silica sol adhesive film;
2) dropwise adding the prepared graphene aqueous solution to a silica sol adhesive film on a glassy carbon electrode, standing for 0.5-1 h to enable the graphene aqueous solution to be completely soaked so that the graphene is immersed in the modified silica sol, and performing vacuum drying for 3-8 h at the temperature of 20-40 ℃ to obtain a graphene adsorption adhesive film;
3) and continuously dripping 3-12 drops of the salbutamol antibody solution on the graphene adsorption adhesive film on the glassy carbon electrode, uniformly coating by rotating at a medium speed, and then drying in vacuum for 3-8 hours at the temperature of 20-40 ℃ to obtain the salbutamol electrochemical sensor.
The salbutamol antibody (anti-SAL) is purchased from Shenzhen Huaying biotechnology Limited.
The salbutamol electrochemical sensor prepared by the preparation method is used, a three-electrode system serving as a working electrode is placed in a determination solution with a certain concentration range, and the peak current of a CV curve is recorded. And due to the excellent selectivity of the salbutamol antibody, the salbutamol antibody is only combined with salbutamol, so that the phenomenon of remarkable reduction of peak current can be generated only under the condition that the salbutamol exists, the existence of the salbutamol is confirmed, and the successful construction of the sensor is confirmed.
The method has the advantages of simple operation, low cost, high detection sensitivity and the like.
Drawings
Fig. 1 is a molecular diagram of graphene powder used in the present invention.
FIG. 2 shows the application of the sensor constructed by the invention in the concentration of 0.1X10-7-3×10-7A curve chart of the relation between the peak current and the concentration of salbutamol in a mol/L interval.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a process are given, but the scope of the present invention is not limited to the following embodiments.
In FIG. 2, the sensor constructed in example 1 of the present invention was applied to a target component of albuterol concentration of 0.1X10-7-3×10-7The peak current in the mol/L interval is related to the concentration. It can be seen that the sensor peak current has a good linear relationship with salbutamol concentration. Regression equation thereofComprises the following steps: i (mu A) ═ 9.2746-3.0115c, correlation coefficient R2＝0.9957。
Example 1
1. Preparing a graphene aqueous solution:
1) under the condition of stirring in a beaker, adding 30g of ethanol into 5g of silica sol, adding 0.05g of Span-80, 0.05g of Tween-80 and 2ml of n-butyl alcohol by using a syringe in a dropwise adding mode, stirring for 20min at the speed of 500r/min, and then dropwise adding a proper amount of ammonia water solution under the stirring condition of 50r/min to adjust the pH value to be 6.5-7.5, so as to obtain the silica sol for later use;
2) mixing and hydrolyzing 1g of KH 550-trimethylchlorosilane and 15g of dilute hydrochloric acid (0.5mol/L) in a mixed solution according to a mass ratio of 1:15 for 30 minutes at the temperature of 30 ℃ in magnetic stirring to obtain a mixed solution;
3) ultrasonically mixing the silica sol obtained in the step 1) and the mixed solution obtained in the step 2) for 10min according to the volume ratio of 15:1 to obtain modified silica sol;
4) uniformly mixing 50ml of ethanol, 0.08g of Span-80 and 0.03g of Tween-80 with 100ml of deionized water in advance, performing ultrasonic treatment for 30min, adding 0.1g of graphene powder and 0.02g of graphene quantum dots, and uniformly mixing by ultrasonic treatment to obtain a graphene aqueous solution for later use;
2. preparing a salbutamol electrochemical sensor:
1) dropping the prepared modified silica sol on the surface of a glassy carbon electrode, and drying at 100 ℃ for 2h to enable silica sol particles to be adsorbed on the glassy carbon electrode to form a silica sol adhesive film;
2) dropwise adding the prepared graphene aqueous solution to a silica sol adhesive film on a glassy carbon electrode, standing for 1h to completely soak the graphene aqueous solution, and immersing the graphene into the modified silica sol; vacuum drying at 30 deg.C for 5 hr; obtaining a graphene adsorption adhesive film;
3) continuously dripping 10 drops of salbutamol antibody solution on the graphene adsorption adhesive film on the glassy carbon electrode, uniformly coating by rotating at a medium speed, and then drying in vacuum for 5 hours at the temperature of 30 ℃ to obtain the salbutamol electrochemical sensor.
The salbutamol antibody described in this example was purchased from Shenzhen Huaying Biotechnology GmbH.
Detection of salbutamol:
the salbutamol electrochemical sensor prepared by the preparation method of the embodiment is used for placing a three-electrode system serving as a working electrode in a determination solution with a certain concentration range, and recording the peak current of a CV curve. And due to the excellent selectivity of the salbutamol antibody, the salbutamol antibody is only combined with salbutamol, so that the phenomenon of remarkable reduction of peak current can be generated only under the condition that the salbutamol exists, the existence of the salbutamol is confirmed, and the successful construction of the sensor is confirmed.
The sensor constructed in the embodiment is applied to the detection of the target component salbutamol in an actual sample, and the actual concentration range of the detection is 0.1X10-7-1.5×10-7The linearity of clenbuterol hydrochloride antibody was good when measured over the mol/L concentration range (R ═ 0.9957), as shown in fig. 2.
Example 2
1. Preparing a graphene aqueous solution:
1) adding 3g of ethanol into 15g of silica sol under the stirring condition in a beaker, adding 0.06g of Span-80, 0.03g of Tween-80 and 4ml of n-butyl alcohol by using a syringe in a dropwise adding mode, stirring for 20min under the condition of 500r/min, and then dropwise adding a proper amount of ammonia water solution under the stirring condition of 50r/min to adjust the pH value to 7.5 to obtain the silica sol for later use;
2) mixing and hydrolyzing 1g of KH 550-trimethylchlorosilane and 15g of dilute hydrochloric acid (0.5mol/L) in a mixed solution according to a mass ratio of 1:15 for 30 minutes at the temperature of 30 ℃ in magnetic stirring to obtain a mixed solution;
3) ultrasonically mixing the silica sol obtained in the step 1) and the mixed solution obtained in the step 2) for 10min according to the volume ratio of 15:1 to obtain modified silica sol;
4) uniformly mixing 50ml of ethanol, 0.08g of Span-80 and 0.03g of Tween-80 with 100ml of deionized water in advance, performing ultrasonic treatment for 30min, adding 0.05g of graphene powder and 0.02g of graphene quantum dots, and uniformly mixing by ultrasonic treatment to obtain a graphene aqueous solution for later use;
2. preparing a salbutamol electrochemical sensor:
1) dropping the prepared modified silica sol on the surface of a glassy carbon electrode, and drying at 80 ℃ for 4h to enable silica sol particles to be adsorbed on the glassy carbon electrode to form a silica sol adhesive film;
2) dropwise adding the prepared graphene aqueous solution to a silica sol adhesive film on a glassy carbon electrode, standing for 0.5h to ensure that the graphene is completely soaked in the modified silica sol; vacuum drying for 3h at 40 ℃ to obtain a graphene adsorption adhesive film;
3) and continuously dripping 8 drops of the salbutamol antibody solution on the graphene adsorption adhesive film on the glassy carbon electrode, uniformly coating by rotating at a medium speed, and then drying in vacuum for 8 hours at the temperature of 20 ℃ to obtain the salbutamol electrochemical sensor.
The sensor constructed in the embodiment is applied to the detection of the target component salbutamol in an actual sample, and the actual concentration range of the detection is 0.1X10-7-1.5×10-7The linear relation of clenbuterol hydrochloride antibody is good when the concentration range of mol/L is detected (R is 0.9975).
Example 3
1. Preparing a graphene aqueous solution:
1) under the condition of stirring in a beaker, adding 40g of ethanol into 8g of silica sol, adding 0.06g of Span-80, 0.06g of Tween-80 and 4ml of n-butyl alcohol by using a syringe in a dropwise adding mode, stirring for 20min at the speed of 500r/min, and then dropwise adding a proper amount of ammonia water solution under the stirring condition of 50r/min to adjust the pH to be 6.5; obtaining silica sol for later use;
2) mixing and hydrolyzing 1g of KH 550-trimethylchlorosilane and 15g of dilute hydrochloric acid (0.5mol/L) in a mixed solution according to a mass ratio of 1:15 for 30 minutes at the temperature of 30 ℃ in magnetic stirring to obtain a mixed solution;
3) ultrasonically mixing the silica sol obtained in the step 1) and the mixed solution obtained in the step 2) for 10min according to the volume ratio of 15:1 to obtain modified silica sol;
4) uniformly mixing 50ml of ethanol, 0.05g of Span-80, 0.08g of Tween-80 and 100ml of deionized water in advance, performing ultrasonic treatment for 30min, adding 0.5g of graphene powder and 0.01g of graphene quantum dots, and performing ultrasonic mixing uniformly; obtaining a graphene aqueous solution for later use;
2. preparing a salbutamol electrochemical sensor:
1) dropping the prepared modified silica sol on the surface of a glassy carbon electrode, and drying at 80-100 ℃ for 4h to enable silica sol particles to be adsorbed on the glassy carbon electrode to form a silica sol adhesive film;
2) dropwise adding the prepared graphene aqueous solution to a silica sol adhesive film on a glassy carbon electrode, standing for 1h to enable the graphene aqueous solution to be completely soaked so as to enable the graphene to be soaked in the modified silica sol; vacuum drying at 20 deg.C for 8 hr; obtaining a graphene adsorption adhesive film;
3) and continuously dripping 3-12 drops of the salbutamol antibody solution on the graphene adsorption adhesive film on the glassy carbon electrode, uniformly coating by rotating at a medium speed, and then drying in vacuum for 8 hours at the temperature of 20 ℃ to obtain the salbutamol electrochemical sensor.
The sensor constructed in the embodiment is applied to the detection of the target component salbutamol in an actual sample, and the actual concentration range of the detection is 0.1X10-7-1.5×10-7The linearity of clenbuterol hydrochloride antibody was well detected in the mol/L concentration range (R ═ 0.9948).
Claims (4)
1. A preparation method of a graphene modified silica sol loaded salbutamol antibody sensor is characterized by comprising the following steps:
preparing a graphene aqueous solution:
1) under the condition of stirring in a beaker, adding 30-50g of ethanol into 5-15g of silica sol, adding 0.05-0.08g of Span-80, 0.03-0.08g of Tween-80 and 2-6ml of n-butyl alcohol by using a syringe in a dropwise adding mode, stirring for 20min at the speed of 500r/min, and then dropwise adding a proper amount of ammonia water solution under the stirring condition of 50r/min to adjust the pH =6.5-7.5, so as to obtain the silica sol for later use;
2) mixing and hydrolyzing 1g of silane coupling agent KH 550-trimethylchlorosilane and 15g of dilute hydrochloric acid with the concentration of 0.5mol/L according to the mass ratio of 1:15 to obtain a mixed solution;
3) ultrasonically mixing the silica sol obtained in the step 1) and the mixed solution obtained in the step 2) for 10min according to the volume ratio of 15:1 to obtain modified silica sol;
4) uniformly mixing 30ml-50ml of ethanol, 0.05-0.08g of Span-80, 0.03-0.08g of Tween-80 and 100ml of deionized water in advance, performing ultrasonic treatment for 30min, adding 0.01-0.1 g of graphene powder and 0.005-0.02 g of graphene quantum dots, and performing ultrasonic mixing uniformly to obtain a graphene aqueous solution for later use;
preparing a salbutamol electrochemical sensor:
1) dropping the prepared modified silica sol on the surface of a glassy carbon electrode, and drying to form a silica sol adhesive film;
2) dropwise adding the prepared graphene aqueous solution to a silica sol adhesive film on a glassy carbon electrode, standing for 0.5-1 h, and performing vacuum drying to obtain a graphene adsorption adhesive film;
3) and continuously dripping 3-12 drops of salbutamol antibody solution onto the graphene adsorption adhesive film on the glassy carbon electrode, uniformly coating by rotating at a medium speed, and performing vacuum drying to obtain the salbutamol electrochemical sensor.
2. The method for preparing the graphene modified silica sol loaded salbutamol antibody sensor according to claim 1, wherein the mixture is obtained by mixing and hydrolyzing for 30 minutes under the condition of 30 ℃ in magnetic stirring.
3. The preparation method of the graphene modified silica sol loaded salbutamol antibody sensor according to claim 1, wherein the drying is carried out at a temperature of 80-100 ℃ for 2-4 h.
4. The preparation method of the graphene modified silica sol loaded salbutamol antibody sensor according to claim 1, wherein the vacuum drying is carried out at a temperature of 20-40 ℃ for 3-8 h.
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