CN111781260A - Preparation method of methylene blue and carbon nanotube modified glassy carbon electrode for L-tryptophan determination and determination method of L-tryptophan - Google Patents
Preparation method of methylene blue and carbon nanotube modified glassy carbon electrode for L-tryptophan determination and determination method of L-tryptophan Download PDFInfo
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Abstract
The invention discloses a preparation method of a methylene blue and carbon nanotube modified glassy carbon electrode for L-tryptophan determination, which comprises the following steps: placing the pretreated glassy carbon electrode in 0.01-0.012 mol/L phosphate buffer solution of methylene blue, adjusting the working parameters of electrochemistry, scanning for a plurality of periods at the potential of-0.6- +1.0V at the speed of 0.05-0.06V/s, cleaning and airing to obtain a polymeric electrode; and (3) sucking and dripping the acetic acid buffer solution of chitosan uniformly mixed with the carbon nano tube on the surface of the polymeric electrode by using a microsyringe, spin-coating on the surface of the electrode, standing at normal temperature, and airing to obtain the methylene blue and carbon nano tube modified glassy carbon electrode. The invention also discloses an electrochemical determination method for L-tryptophan by using the glassy carbon electrode as a working electrode. The methylene blue and carbon nanotube modified glassy carbon electrode has good conductivity and stability, can improve the sensitivity of subsequent experimental detection, and has good reproducibility and stability.
Description
Technical Field
The invention relates to a preparation method of a glassy carbon electrode, in particular to a preparation method of a glassy carbon electrode for L-tryptophan determination and a determination method of L-tryptophan.
Background
The electrochemical sensor is a sensor which reacts with a substance to be detected to generate an electric signal, and the electric signal and the concentration of the substance to be detected are in a certain proportion relationship so as to carry out sensing detection. An electrochemical sensor generally comprises electrodes, a glassy carbon electrode is used as a Working Electrode (WE), a platinum electrode is used as an auxiliary electrode (CE), and a saturated calomel electrode is used as a Reference Electrode (RE). The electrochemical sensor has more applications in the fields of agricultural product and food safety, environmental monitoring, clinical diagnosis and the like.
At present, the detection method of L-tryptophan mainly comprises methods such as spectrophotometry, capillary electrophoresis, high performance liquid chromatography, atomic absorption spectrometry, chemiluminescence, molecular imprinting, fluorescence analysis, direct determination by using an amino acid analyzer and the like. Although the detection results of the methods are accurate, the methods have the disadvantages of complex sample treatment, expensive instruments, high requirements on operating technicians and long analysis time, and cannot be applied to the field rapid screening and determination of L-tryptophan. In the method for measuring L-tryptophan by an electrochemical method, the research of using a modified electrode is more, the used modified materials comprise Au nano particles, graphene and the like, the gold nano particles and the graphene are expensive, and the manufacturing steps of the nano materials are relatively complex.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a preparation method of a methylene blue and carbon nanotube modified glassy carbon electrode for L-tryptophan determination, and the invention aims to provide a determination method of L-tryptophan, so that the stability and the repeatability are better during electrode detection, and the L-tryptophan can be rapidly and sensitively determined.
The technical scheme of the invention is as follows: a preparation method of a methylene blue and carbon nanotube modified glassy carbon electrode for L-tryptophan determination comprises the following steps: placing the pretreated glassy carbon electrode in 0.01-0.012 mol/L phosphate buffer solution of methylene blue, adjusting the working parameters of electrochemistry, scanning for a plurality of periods at the potential of-0.6- +1.0V at the speed of 0.05-0.06V/s, cleaning and airing to obtain a polymeric electrode; and (2) sucking and dripping the acetic acid buffer solution of chitosan uniformly mixed with the carbon nano tube to the surface of the polymeric electrode by using a microsyringe, uniformly coating the acetic acid buffer solution of chitosan of the carbon nano tube on the surface of the electrode by adopting a spin-coating method, standing at normal temperature and airing to obtain the methylene blue and carbon nano tube modified glassy carbon electrode.
Further, the amount of the acetic acid buffer solution of chitosan dropwise added and mixed with the carbon nano tube is 8-12 mug calculated by the weight of the carbon nano tube.
Further, the pretreatment of the glassy carbon electrode comprises the steps of polishing and grinding the glassy carbon electrode by using aluminum oxide polishing powder, and cleaning the glassy carbon electrode by ultrasonic cleaning in nitric acid, absolute ethyl alcohol and pure water respectively.
Further, the acetic acid buffer solution of chitosan is prepared by adding chitosan powder into 1-1.5% acetic acid buffer solution, uniformly stirring, and then carrying out ultrasonic treatment, wherein the ratio of the chitosan powder to the acetic acid buffer solution is 5-6 g: 1L.
Further, the concentration of the carbon nano tubes in the acetic acid buffer solution of the chitosan mixed with the carbon nano tubes is 0.9-1.0 g/L.
A method for measuring L-tryptophan comprises the steps of using a methylene blue and carbon nano tube modified glassy carbon electrode prepared by the method as a working electrode, using a platinum electrode as an auxiliary electrode and using a saturated calomel electrode as a reference electrode, measuring blank phosphate buffer solution and phosphate buffer solution added with different amounts of L-tryptophan in an electrochemical method to obtain a standard equation of response current related to the concentration of L-tryptophan, then measuring a solution to be measured containing L-tryptophan to obtain a response current value, and substituting the response current value into a standard curve equation to obtain the corresponding L-tryptophan content.
Further, when the electrochemical method is used for measuring, the pH value of the phosphate buffer solution is 5-7, the potential is set to-0.6- +1.0V, and the temperature is controlled to be 25-30 ℃.
Compared with the prior art, the method has the advantages that the one-step method is used for directly polymerizing the pretreated electrode, the operation is simple and convenient, the prepared methylene blue and carbon nanotube modified glassy carbon electrode has strong conductivity, large specific surface area, high detection sensitivity, strong anti-interference performance and stability, and when the L-tryptophan is measured, the concentration of the L-tryptophan with the lowest detection limit is 2 × 10-6mol/L。
Drawings
Fig. 1 is a cyclic voltammogram of a glassy carbon electrode at different modification stages.
FIG. 2 is a plot of cyclic voltammetry of L-tryptophan at a bare glassy carbon electrode and an electrode of the invention.
FIG. 3 is a diagram illustrating response current when the amount of carbon nanotubes is different.
FIG. 4 is a diagram illustrating response currents of different pH values of the detection system.
FIG. 5 is a diagram illustrating response current of the detection system at different temperatures.
FIG. 6 is a cyclic voltammogram of different concentrations of L-tryptophan at the electrodes of the examples.
FIG. 7 is a graph showing the relationship between the response current value and the L-tryptophan concentration.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto.
The reagents and instruments involved in the embodiment of the invention are as follows:
the instrument comprises the following steps: glassy carbon electrodes (shanghai yuanmaoelectronics limited), CHI760E electrochemical workstation (shanghai meiieelectric practical ltd), JT-410HT type cleaning ultrasonic wave (shenzhen cleaning ultrasonic wave ltd), microsyrinths (shanghai guang zhengzhen medical instrument ltd), electronic balances (mettler-toduli instrument (shanghai) ltd), laboratory pH meters (mettler-toduli instrument (shanghai) ltd), and digital display temperature-controlled water baths (shanghai potyoto electric instruments factory).
Reagent: carbon nanotubes (Shenzhen nanometer gang Co., Ltd.), methylene blue (Tianjin Shenyuan chemical reagent Co., Ltd.), L-tryptophan (Ji Biotech Co., Ltd.), chitosan (Kuer chemical technology Co., Ltd.), potassium ferricyanide (Tianjin Mao chemical reagent factory), sodium acetate (Jiangsu Qiangsheng high performance chemical reagent Co., Ltd.), glacial acetic acid (Shanghai Ling Peak chemical reagent Co., Ltd.), disodium hydrogen phosphate (Tianjin City Beichen squar reagent factory), potassium dihydrogen phosphate (Tianjin Deng chemical reagent Co., Ltd.), sodium chloride (Tianjin Body chemical reagent Co., Ltd.), potassium chloride (Tianjin Shuchen chemical reagent factory), all the above reagents are analytically pure, and the experimental water is secondary distilled water.
Pretreating a glassy carbon electrode: the method comprises the following steps of adhering clean flannelette to a glass sheet, dipping a small amount of distilled water on the flannelette, properly wetting, pouring a proper amount of aluminum oxide polishing powder to prepare turbid liquid, and putting a glassy carbon electrode on the turbid liquid to perform polishing and grinding treatment. Washed clean and respectively put in HNO3(1: 1, V/V), absolute ethyl alcohol and pure water, rinsing with water, scanning the polished glassy carbon electrode in 10mmol/L potassium ferricyanide solution by adopting cyclic voltammetry, and controlling the detected peak difference between the upper peak and the lower peak within 80 mV.
Electropolymerization of methylene blue: firstly, adjusting electrochemical working parameters in 0.01mol/L methylene blue buffer solution (pH is 5.0), scanning for 40 periods at the potential of-0.6 to +1.0V and at the speed of 0.05V/s, and polymerizing the methylene blue on the surface of the electrode to form a layer of film. And washing the polymerized glassy carbon electrode with secondary distilled water, and airing for later use. The one-step method is adopted to directly polymerize the pretreated electrode, and the method is simple to operate, convenient and good in effect.
Modification of a working electrode: preparing a chitosan solution: 0.5g of chitosan powder is weighed, dissolved in 100ml of 1 percent acetic acid buffer solution, stirred evenly and then placed in an ultrasonic cleaner for ultrasonic treatment for 30 minutes to obtain the chitosan solution with the texture like water. Taking 10ml of 5% chitosan solution, adding 0.01g of carbon nano tubes into the chitosan solution, properly mixing the chitosan solution and the carbon nano tubes, placing the mixture in an ultrasonic cleaner for 2 hours of ultrasound to ensure that the carbon nano tubes are uniformly distributed in the solution, sucking 12 mu L of the solution by a microsyringe and dripping the solution on the surface of a polymethylene blue electrode, uniformly coating the carbon nano tube solution on the surface of the electrode by adopting a spin coating method, standing the electrode at normal temperature for 6-8 hours, and airing the electrode to be modified for later use.
And (3) determination: white, red and green wires in the electrochemical workstation are respectively connected with the reference electrode, the auxiliary electrode and the glassy carbon electrode (working electrode). In the experiment, the electrochemical performance of the glassy carbon electrode is characterized by using cyclic voltammetry, and a PBS buffer solution (phosphate buffered saline solution) with the pH of 7.4, which is prepared in advance, is used as a detection base solution.
And (3) processing of a sample: taking out 350mg compound amino acid capsule, grinding the particulate matter in the capsule, adding into PBS buffer solution with 245ml pH5, heating in water bath at 100 deg.C, and stirring until the particulate matter is completely dissolved. The obtained sample solution was stored in a brown bottle at low temperature for use.
Referring to fig. 1, curves a, b, and c are cyclic voltammograms of a bare electrode, a polymeric methylene blue electrode, and a carbon nanotube-modified electrode in a blank PBS buffer (pH 6.0), respectively. The background current of the curve b is slightly increased compared with that of the curve a, the background current of the curve c is obviously increased, and the curve c shows good stability, which indicates that the glassy carbon electrode modified by the polymethylene blue/carbon nano tube has good conductivity and stability, and can improve the sensitivity of subsequent experimental detection.
Referring to FIG. 2, the curve a and the curve b are respectively 1 × 10-4The electrochemical behavior of mol/L-tryptophan on the bare glass carbon electrode and the electrode of the carbon nanotube modified in the example. On the bare electrode, the oxidation peak of L-tryptophan appeared at 0.70V (curve a); on the modified electrode, the oxidation peak current value of the L-tryptophan is obviously improved, the peak current is increased by about 6 times, and the peak potential is negatively shifted to 0.65V (curve b), which shows that the electrochemical sensor modified by the polymethylene blue/carbon nano tube can efficiently catalyze and oxidize the L-tryptophan. The modified glassy carbon electrode has obviously enhanced conductivity and simultaneouslyThe nano-particle has a large specific surface area, can effectively enrich more target objects, and can promote the rapid transfer of electrons, thereby greatly improving the detection sensitivity.
Respectively sucking 5-15 mul of carbon nanotube solution with the concentration of 1mg/mL and the step length of 1 mul by using a micro-sampling needle, dripping the solution on the surface of a polymethylene blue electrode, modifying the electrode, and respectively performing cyclic voltammetry on the modified electrode to obtain 1 × 10-4The corresponding response current value is obtained by measuring the L-tryptophan in mol/L, and the result is shown in FIG. 3 by plotting the amount of the carbon nano tube and the response current value: when the amount of the carbon nanotubes is 5-12 μ g, the current response value gradually increases with the increase of the amount of the carbon nanotubes. The current response value is not changed greatly and gradually decreases when the current response value is 12-15 mu g.
Referring to FIG. 4, when the pH of the detection system is in the range of 3 to 6, the response current value increases with the increase of pH, and no obvious oxidation peak appears when the pH is 3 or 4; the pH value is in the range of 6-9, and the response current value is gradually reduced along with the increase of the pH value. When the pH is too low, a pair of lone electrons on the nitrogen atom in the amine group will react with H+The combination is not beneficial to forming nitrogen positive free radicals, so that the oxidation reaction is more difficult, and an oxidation peak is difficult to appear during cyclic voltammetry scanning; when the pH is too high, the amount of OH in the aqueous solution is too high-Oxygen evolution reaction is easy to occur on the electrode, thereby affecting the stability of the detection system.
A water bath is adopted to heat the detection system, the temperature range is controlled to be 20-70 ℃, and the temperature gradient is set to be 1 × 10 to the concentration every 10 DEG C-4The detection is carried out by using L-Trp solution of mol/L, as shown in the figure 5: at the temperature of 20-50 ℃, the response current value of the L-Trp on the modified electrode is increased along with the rise of the temperature; when the temperature exceeded 50 ℃, the response current value began to gradually decrease. May affect the stability of the glassy carbon electrode due to too high temperature
L-tryptophan determination: setting the potential to be-0.6 to +1.0V, adopting a PBS (phosphate buffer solution) with the pH value of 5-7 at the room temperature of 25-30 ℃, and respectively measuring the modified glassy carbon electrode in a blank PBS buffer solution and a PBS buffer solution added with different amounts of L-tryptophan to obtain a standard response current related to the concentration of the L-tryptophanQuasi-equation cyclic voltammogram As shown in FIG. 6, an oxidation peak was observed at 0.65V, and the oxidation peak current value was gradually increased with the increase of L-tryptophan concentration at 1 × 10-5～1.2×10-3The standard curve is shown in figure 7, the linear relation equation is that I is 15.02+70.12C, the correlation coefficient R is 0.9891, and the L-tryptophan concentration with the lowest detection limit is 2 × 10-6mol/L. And detecting the L-tryptophan in the compound amino acid capsule by using a glassy carbon electrode, and substituting the obtained response current value into a standard curve equation to obtain the corresponding L-tryptophan content.
Dissolving compound amino acid capsule (each capsule contains L-tryptophan 5mg) with PBS buffer solution with pH of 6.0 to obtain solution containing L-tryptophan 1 × 10-4The mol/L mixed amino acid solution was detected by a modified electrode, and the response current value was measured to be 22.3. mu.A, and the value was substituted into the standard equation to calculate the concentration to be 1.03 × 10-4mol/L. The accuracy was calculated to be 97%, indicating that this method has good accuracy.
In addition, an interference test, stability and reproducibility test was carried out at a concentration of 1 × 10-4The determination was carried out by adding the interfering substance to a solution of L-tryptophan in mol/L at a concentration of 1 × 10 in 10ml-4Nicotinic acid, L-tyrosine, L-cystine, L-leucine, L-aspartic acid and lysine with tryptophan concentration of 100 times are respectively added into the L-tryptophan solution in mol/L for determination, and the results show that other amino acids have no influence on the determination of the L-tryptophan except the L-tyrosine, the electrode of the embodiment is placed in a blank PBS buffer solution for circular scanning until the electrode is stable, and then the determination is carried out at 1 × 10-4The value of the response current was recorded for a mol/L solution of L-tryptophan 5 parts of 1 × 10 were again measured in parallel in the same procedure-4The response current values detected six times for the mol/L-tryptophan solution were recorded as 22.3. mu.A, 22.0. mu.A, 22.8. mu.A, 22.0. mu.A, 22.1. mu.A and 21.8. mu.A, respectively, with a relative standard deviation RSD of 1.58%, and the same concentration (1 × 10) was measured after the electrode was left to stand for 15 days-4mol/L) was again measured, and the response current value was 20.3, which was 91.6% of the initial value.
Claims (7)
1. A preparation method of a methylene blue and carbon nanotube modified glassy carbon electrode for L-tryptophan determination is characterized by comprising the following steps: placing the pretreated glassy carbon electrode in 0.01-0.012 mol/L phosphate buffer solution of methylene blue, adjusting the working parameters of electrochemistry, scanning for a plurality of periods at the potential of-0.6- +1.0V at the speed of 0.05-0.06V/s, cleaning and airing to obtain a polymeric electrode; and (2) sucking and dripping the acetic acid buffer solution of chitosan uniformly mixed with the carbon nano tube to the surface of the polymeric electrode by using a microsyringe, uniformly coating the acetic acid buffer solution of chitosan of the carbon nano tube on the surface of the electrode by adopting a spin-coating method, standing at normal temperature and airing to obtain the methylene blue and carbon nano tube modified glassy carbon electrode.
2. The method for preparing a methylene blue and carbon nanotube modified glassy carbon electrode for L-tryptophan determination according to claim 1, wherein the amount of the acetic acid buffer solution dropwise added with the chitosan mixed with the carbon nanotubes is 8-12 μ g calculated by the weight of the carbon nanotubes.
3. The method for preparing a methylene blue and carbon nanotube modified glassy carbon electrode for L-tryptophan determination according to claim 1, wherein the pretreatment of the glassy carbon electrode comprises polishing and grinding the glassy carbon electrode by using aluminum oxide polishing powder, and ultrasonically cleaning the glassy carbon electrode in nitric acid, absolute ethyl alcohol and pure water respectively after the glassy carbon electrode is washed clean.
4. The method for preparing the methylene blue and carbon nanotube modified glassy carbon electrode for L-tryptophan determination according to claim 1, wherein the preparation of the acetic acid buffer solution of chitosan comprises the steps of adding chitosan powder into 1-1.5% of the acetic acid buffer solution, uniformly stirring, and then carrying out ultrasonic treatment, wherein the ratio of the chitosan powder to the acetic acid buffer solution is 5-6 g: 1L.
5. The method for preparing the methylene blue and carbon nanotube modified glassy carbon electrode for L-tryptophan determination according to claim 4, wherein the concentration of carbon nanotubes in the acetic acid buffer solution of chitosan mixed with carbon nanotubes is 0.9-1.0 g/L.
6. A method for measuring L-tryptophan is characterized in that a methylene blue and carbon nanotube modified glassy carbon electrode prepared by the method in any one of the meanings of claims 1 to 5 is used as a working electrode, a platinum electrode is used as an auxiliary electrode, a saturated calomel electrode is used as a reference electrode, measurement is carried out in a blank phosphate buffer solution and a phosphate buffer solution added with different amounts of L-tryptophan by an electrochemical method to obtain a standard equation of the response current related to the concentration of the L-tryptophan, then a solution to be measured containing the L-tryptophan is measured to obtain a response current value, and the response current value is substituted into a standard curve equation to obtain the corresponding content of the L-tryptophan.
7. The method of measuring L-tryptophan according to claim 6, wherein the pH of the phosphate buffer solution is 5 to 7, the potential is set to-0.6 to +1.0V, and the temperature is controlled to 25 to 30 ℃ in the electrochemical measurement.
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Application publication date: 20201016 |