CN109374706B - Method for detecting trace amount of carbalkoxy by using cubic Ia3d structure mesoporous carbon CMK-8 direct electrochemical sensor - Google Patents
Method for detecting trace amount of carbalkoxy by using cubic Ia3d structure mesoporous carbon CMK-8 direct electrochemical sensor Download PDFInfo
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- CN109374706B CN109374706B CN201811365014.8A CN201811365014A CN109374706B CN 109374706 B CN109374706 B CN 109374706B CN 201811365014 A CN201811365014 A CN 201811365014A CN 109374706 B CN109374706 B CN 109374706B
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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Abstract
The invention relates to a method for measuring trace amount of carbalkoxy by using a direct electrochemical sensor of cubic Ia3d structure mesoporous carbon CMK-8. According to the invention, a glassy carbon electrode is modified by adopting the mesoporous carbon CMK-8 with the cubic Ia3d structure, and the constructed sensor is used for directly measuring the carbalkoxy. When the concentration of the carbalkoxy is in the range of 0.5nM to 500.0nM, the electrochemical signal response and the carbalkoxy concentration have a good linear relation, and the detection limit of the method is 74.4 pM. The method obviously improves the sensitivity of the kappa oxygen detection, and is easy to automate for the detection of the low-concentration kappa oxygen.
Description
Technical Field
The invention belongs to the technical field of novel functional materials and electrochemical sensing detection, relates to a method for detecting trace amount of carba oxygen, and particularly relates to a method for detecting trace amount of carba oxygen by using a cubic Ia3d structure mesoporous carbon CMK-8 direct electrochemical sensor.
Background
Carbadox (CBX for short) is a traditional quinoxaline medicine, and the medicine is a chemically synthesized special animal medicine, has a broad-spectrum antibacterial effect, can promote the growth and development of animals such as pigs, chickens, cows, sheep, rabbits and the like, can improve the conversion rate of feed, and is widely applied to aquaculture and poultry breeding such as pigs, chickens and the like. However, many toxicology reports indicate that carbalkoxy is genotoxic, mutagenic and carcinogenic. When the feed additive is added into the feed, the feed additive can obviously remain in the body after being eaten by animals, and has very serious harm to the health of human bodies. Therefore, even though our country is a large country for the use of such drugs, there has been a clear regulation that prohibits the use of carbadox. However, due to the obvious effects of increasing lean meat percentage and the like, the situation of illegal addition and use still exists, and therefore, the establishment of a simple, convenient and effective kappa oxygen detection method is particularly important.
At present, most reports of kappa oxygen detection methods are provided, and an immunological method, a liquid chromatography, a gas chromatography-tandem mass spectrometry, a liquid chromatography-tandem mass spectrometry and the like are mainly provided. China also provides a national standard method for detecting the carbachol oxygen. The most common method is liquid chromatography-tandem mass spectrometry, but the method has complicated steps when processing an actual sample, has high requirements on detection instruments and is not simple enough. The electrochemical detection is efficient and rapid, has high selectivity and high sensitivity, has relatively low requirements on instruments, and is widely applied to various detections, but the literature report of electrochemical determination of the carba oxygen is rare.
The mesoporous material is a porous material with the aperture between 2.0nm and 50.0nm, and the mesoporous carbon is a non-silicon-based mesoporous material. It has a large surface area (up to 2500 m)2Per g) and pore volume (2.25 cm)3In terms of/g). In 1999, Ryoo et al firstly synthesized ordered mesoporous carbon molecular sieve CMK-1 by using a template method. Thereafter, various ordered mesoporous carbons were synthesized successively. Ordered mesoporous carbon has some more excellent properties: the pore channel structure is regular and highly ordered, the pore size distribution is narrow and can be regulated and controlled within a certain range, the specific surface area is large, the conductivity is good, and the pore channel has good thermal stability and certain hydrothermal stability. Because of its excellent performance, mesoporous carbon is used as an electrode modification material to be applied more and more widely in electrochemical catalysis and sensors. The use of mesoporous carbon CMK-3 is currently the most widely used, while the use of mesoporous carbon CMK-8 of the structure of cubic Ia3d is less.
The electrochemical sensor is a sensor for detecting a target object based on the principle of electrochemical reaction, and takes an electrode as a sensor conversion element, a material modified on the electrode as a sensitive element, the sensitive element is contacted with ions or molecules of a detected object to generate chemical reaction or change, the conversion element directly or indirectly converts the reaction or change into an electric signal, and the relationship between chemical quantities such as the concentration and the composition of the target object and an output electric signal is established, so that the quantitative detection of the target object is realized. The electrochemical sensor has the advantages of high sensitivity, good selectivity, simple operation, rapid detection, easy miniaturization, capability of carrying out online monitoring even in vivo analysis in a complex system and the like, is an active research field in electroanalytical chemistry, and has been widely applied to the aspects of clinical examination, food and drug analysis, environmental monitoring, life science and the like.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a method for detecting trace amount of carbalkoxy by using a direct electrochemical sensor of the cubic Ia3d structure mesoporous carbon CMK-8, and the method can be used for detecting the trace amount of carbalkoxy with high sensitivity by using the amplification effect of the cubic Ia3d structure mesoporous carbon CMK-8.
The invention relates to a method for detecting trace amount of carbalkoxy by using a direct electrochemical sensor of cubic Ia3d structure mesoporous carbon CMK-8, which comprises the following steps:
A. and (3) processing the gold electrode:
washing the gold electrode (phi is 3mm) with secondary deionized water, polishing and grinding with gamma-alumina polishing powder of 0.05 μm, washing with water again, and air drying for later use;
B. preparing a cubic Ia3d structure mesoporous carbon CMK-8 dispersion liquid:
accurately weighing a certain amount of mesoporous carbon CMK-8 powder with a cubic Ia3d structure, dispersing with DMF, and performing ultrasonic treatment for 1h to obtain uniformly dispersed mesoporous carbon dispersion liquid of 4 mg/mL;
C. and (3) a cubic Ia3d structure mesoporous carbon CMK-8 modified electrode:
uniformly dripping a proper amount of the mesoporous carbon CMK-8 dispersion liquid with the cubic Ia3d structure on the treated gold electrode by using a microsyringe, placing under an infrared lamp for drying, and airing to room temperature for later use;
D. construction of the electrochemical sensor:
placing the modified electrode in a certain concentration of Na3PO4The buffer solution was scanned to stability via differential pulse voltammetry. Then constant potential enrichment is carried out under magnetic stirring at 1000rpm, the potential interval is-0.3V-0.7V, and the enrichment time is 10-35 min.
E. Detection of carbalkoxy:
electrochemical testing employs a three-electrode system: the working electrode is a cubic Ia3d structure mesoporous carbon CMK-8 modified electrode, the counter electrode is a hollow titanium rod, and the reference electrode is a saturated calomel electrode; electrochemical test in home-made electrolytic cellCarrying out the steps of (1); the volume of the self-made electrolytic cell is 25mL, the volume of the loaded electrolyte is 20mL in each test, and an electromagnetic stirrer is used for stirring. The electrolyte is Na3PO4And (4) buffering the solution, adjusting the pH value by using NaOH, and introducing high-purity nitrogen for 5min before use to fully remove dissolved oxygen in the buffer solution.
According to a further feature of the electrochemical sensor of the present invention, the dispersion of mesoporous carbon CMK-8 having the structure of Ia3d in step C is used in an amount of 4. mu.L.
According to a further feature of the electrochemical sensor of the present invention, in the step D, Na is contained in the electrolytic cell3PO4The pH of the buffer solution was 7.0.
According to a further feature of the electrochemical sensor of the present invention, in the step D, the enrichment potential is 0.3V.
According to a further feature of the electrochemical sensor of the present invention, in the step D, the enrichment time is 25 min.
The electrochemical sensor for detecting the trace amount of the carba oxygen overcomes the defects of complicated method, complicated steps and the like in the prior art when the carba oxygen is detected, better improves the detection sensitivity, and is easy to automate for the detection of the trace amount of the carba oxygen.
Drawings
FIG. 1 is a differential pulse voltammogram of different electrodes, in which (a) a bare electrode and (b) a cubic Ia3d structure mesoporous carbon CMK-8 modified electrode. The inset is an enlarged view of the bare electrode.
Fig. 2 is a standard absorption curve of a sensor according to the present invention.
Fig. 3 is a graph of the selectivity of the sensor according to the invention. In the figure, the horizontal axis shows the added substances, and the interfering substances such as urea, uric acid, hypoxanthine, ascorbic acid, inosine and the like are arranged from left to right in sequence.
Detailed Description
Example 1: construction of the electrochemical sensor for detecting trace amount of carba oxygen according to the present invention
The invention relates to a method for detecting trace amount of carbalkoxy by using a direct electrochemical sensor of cubic Ia3d structure mesoporous carbon CMK-8, which comprises the following steps:
(1) and (3) processing the gold electrode:
washing the gold electrode (phi is 3mm) with secondary deionized water, polishing and grinding with gamma-alumina polishing powder of 0.05 μm, washing with water again, and air drying for later use;
(2) preparing a cubic Ia3d structure mesoporous carbon CMK-8 dispersion liquid:
accurately weighing a certain amount of mesoporous carbon CMK-8 powder with a cubic Ia3d structure, dispersing with DMF, and performing ultrasonic treatment for 1h to obtain a uniformly dispersed mesoporous carbon dispersion liquid of 4 mg/mL.
(3) And (3) a cubic Ia3d structure mesoporous carbon CMK-8 modified electrode:
and (3) uniformly dripping a proper amount of the cubic Ia3d structure mesoporous carbon CMK-8 dispersion liquid on the treated gold electrode by using a microsyringe, placing under an infrared lamp for drying, and airing to room temperature for later use.
(4) Construction of the electrochemical sensor:
placing the modified electrode in a certain concentration of Na3PO4The buffer solution was scanned to stability via differential pulse voltammetry. Then constant potential enrichment is carried out under magnetic stirring at 1000rpm, the potential interval is-0.3V-0.7V, and the enrichment time is 10-35 min.
(5) Detection of carbalkoxy:
electrochemical testing employs a three-electrode system: the working electrode is a cubic Ia3d structure mesoporous carbon CMK-8 modified electrode, the counter electrode is a hollow titanium rod, and the reference electrode is a saturated calomel electrode. Electrochemical tests were performed in a home-made electrolytic cell. The volume of the self-made electrolytic cell is 25mL, the volume of the loaded electrolyte is 20mL in each test, and an electromagnetic stirrer is used for stirring. The electrolyte is Na3PO4And (4) buffering the solution, adjusting the pH value by using NaOH, and introducing high-purity nitrogen for 5min before use to fully remove dissolved oxygen in the buffer solution.
Example 2: the invention relates to differential pulse voltammetry characterization of an electrochemical sensor for detecting trace amount of carba oxygen
And (3) observing the electrochemical reaction of the carbachol oxygen on the bare electrode and the mesoporous carbon CMK-8 modified electrode with the cubic Ia3d structure by adopting a differential pulse voltammetry method. As shown in FIG. 1, the peak current of 2 μ M kappa oxygen was 0.46 μ A on the bare electrode (curve a), whereas the peak current reached 233.4 μ A (curve a) with modification of the cubic Ia3d structure mesoporous carbon CMK-8 (curve b), with a 507-fold increase in peak current over the bare electrode. And it is obvious from fig. 2 that the baseline of the curve b is obviously shifted down compared with the baseline of the curve a, which shows that CMK-8 has a large specific surface area and can effectively increase the signal.
Example 3: linear range and detection limit experiments
Based on the strong electrocatalytic effect of the cubic Ia3d structure mesoporous carbon CMK-8 modified electrode on the electrochemical reduction of the carbalkoxy, the ultrasensitive electrochemical detection method of the carbalkoxy can be established, when the carbalkoxy is in the concentration range of 0.1nM to 500.0nM, the electrochemical signal response and the carbalkoxy concentration have a good linear relation (see figure 2), the linear regression equation is-I (mu A) ═ 0.503 × C (nmol/L) -0.128, R ═ 0.997, and the detection limit is 74.4 pM..
Example 4: influence of interfering substances
Selectivity experiments this experiment was done by comparing the peak current ratio (I/I) of the sensors0) As shown in FIG. 3, when the carbalkoxy concentration was 100nM, no interference was observed with any interferents such as urea, uric acid, hypoxanthine, ascorbic acid, inosine, and the like at 100-fold concentrations.
Example 5: determination of actual samples
After the actual sample is treated, the extract is taken and subjected to electrochemical measurement, and the measurement results are shown in table 1. As can be seen from Table 1, the recovery rate of the process is 89.75% -105.38%, and the relative standard deviation is 9.87-4.23%.
Table 1: and (5) adding a standard to the actual sample to obtain a detection result (n is 5).
| Standard concentration (nM) | Recovery (%) | |
| 50 | 89.75 | 9.87 |
| 100 | 105.38 | 5.81 |
| 200 | 98.7 | 4.23 |
Claims (5)
1. A method for detecting trace amount of carbalkoxy by using a direct electrochemical sensor of cubic Ia3d structural mesoporous carbon CMK-8 is characterized by comprising the following steps:
A. and (3) processing the gold electrode:
washing the gold electrode with secondary deionized water, polishing and grinding with 0.05 μm gamma-alumina polishing powder, washing with water again, and air drying;
B. preparing a cubic Ia3d structure mesoporous carbon CMK-8 dispersion liquid:
accurately weighing a certain amount of mesoporous carbon CMK-8 powder with a cubic Ia3d structure, dispersing with DMF, and performing ultrasonic treatment for 1h to obtain uniformly dispersed mesoporous carbon dispersion liquid of 4 mg/mL;
C. and (3) a cubic Ia3d structure mesoporous carbon CMK-8 modified electrode:
uniformly dripping a proper amount of the mesoporous carbon CMK-8 dispersion liquid with the cubic Ia3d structure on the treated gold electrode by using a microsyringe, placing under an infrared lamp for drying, and airing to room temperature for later use;
D. construction of the electrochemical sensor:
placing the modified electrode in a certain concentration of Na3PO4Scanning the buffer solution to be stable through differential pulse voltammetry; then carrying out constant potential enrichment under magnetic stirring at 1000rpm, wherein the potential interval is-0.3V-0.7V, and the enrichment time is 10-35 min;
E. detection of carbalkoxy:
electrochemical testing employs a three-electrode system: the working electrode is a cubic Ia3d structure mesoporous carbon CMK-8 modified electrode, the counter electrode is a hollow titanium rod, and the reference electrode is a saturated calomel electrode; the electrochemical test is carried out in a self-made electrolytic cell; the volume of the self-made electrolytic cell is 25mL, and the volume of the electrolyte is loaded during each testStirring the solution by using an electromagnetic stirrer, wherein the volume is 20 mL; the electrolyte is Na3PO4And (4) buffering the solution, adjusting the pH value by using NaOH, and introducing high-purity nitrogen for 5min before use to fully remove dissolved oxygen in the buffer solution.
2. The method of claim 1, wherein: in the step C, the using amount of the cubic Ia3d structure mesoporous carbon CMK-8 dispersion liquid is 4 mu L.
3. The method of claim 1, wherein: in the step D, Na is contained in the electrolytic cell3PO4The pH of the buffer solution was 7.0.
4. The method of claim 1, wherein: in the step D, the enrichment potential is 0.3V.
5. The method of claim 1, wherein: in the step D, the enrichment time is 25 min.
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| CN201811365014.8A CN109374706B (en) | 2018-11-16 | 2018-11-16 | Method for detecting trace amount of carbalkoxy by using cubic Ia3d structure mesoporous carbon CMK-8 direct electrochemical sensor |
| JP2019166741A JP6684381B1 (en) | 2018-11-16 | 2019-09-13 | Method for detecting trace carbadox using direct electrochemical sensor with mesoporous carbon CMK-8 having cubic Ia3d structure |
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| CN110988071B (en) * | 2019-12-20 | 2022-06-21 | 肇庆学院 | Application of graphitized hydroxyl multi-walled carbon nanotube @ cubic Ia3d structured mesoporous carbon electrochemical sensor in detection of thiamethoxam |
| CN110988074B (en) * | 2019-12-20 | 2021-12-21 | 肇庆学院 | CoCu @ cubic Ia3d structure mesoporous carbon electrochemical sensor and application thereof in detection of trace cyadox |
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