CN114324513A - Poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-walled carbon nanotube modified electrode, preparation method and application - Google Patents
Poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-walled carbon nanotube modified electrode, preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 39
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-walled carbon nanotube modified electrode, a preparation method and application, which belong to the technical field of glassy carbon electrodes and comprise the following steps: polishing the surface of a glassy carbon electrode, cleaning, dropwise adding a Shewanella MR-1/multi-walled carbon nanotube composite material solution on the surface, drying, taking the electrode as a working electrode, placing the electrode in a chloroauric acid aqueous solution, depositing nanogold by constant potential through a time-current method, taking the electrode as the working electrode, performing cyclic voltammetry scanning in an L-phenylalanine solution, cleaning, and drying to obtain the poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-walled carbon nanotube modified electrode. The electrode prepared by the invention has the characteristics of good catalysis effect on baicalein, high sensitivity, high detection speed and the like. The electrode is combined with cyclic voltammetry scanning and differential pulse voltammetry to quantitatively detect baicalein, and the electrode has the advantages of high sensitivity, high response speed, strong response signal and the like.
Description
Technical Field
The invention relates to the technical field of glassy carbon electrodes, in particular to a poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-wall carbon nanotube modified electrode, a preparation method and application.
Background
Baicalein (BAI) is a commonly used Chinese medicine, and is present in some plants such as leaves of Scutellaria baicalensis Georgi, leaves and roots of Leptospermum scoparium, and the like. Has the effects of clearing heat, eliminating dampness, purging pathogenic fire, removing toxic substances, etc. The molecular structure of the compound belongs to flavonoid substances. The BAI obtained by tests has a plurality of special functions, including the effects of resisting oxidation, scavenging free radicals, preventing and treating fatty liver, resisting tumor, resisting allergy and diminishing inflammation, so that the BAI is of great importance for the research of BAI. BAI detection means mainly comprises a capillary electrophoresis method, a High Performance Liquid Chromatography (HPLC), a combined technology, a static injection chemiluminescence method, an ultraviolet spectrophotometry and the like. The measurement operation is complex, the required instruments and equipment are expensive, and the detection cost is high.
Disclosure of Invention
The invention aims to provide a poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-walled carbon nanotube modified electrode, a preparation method and application, wherein the modified electrode has the characteristics of high sensitivity, high detection speed and the like, and is combined with cyclic voltammetry and differential pulse voltammetry to carry out electrochemical behavior research on baicalein and realize quantitative detection on the baicalein and I of the baicaleinpaThe linear relation between the content of the baicalein and the content of c is in a range of 0.1-70 mu mol/L, the method can be used for quantitatively determining the content of the baicalein in the medicine, and has the advantages of high detection sensitivity, high response speed, strong response signals and the like.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-walled carbon nanotube modified glassy carbon electrode, which comprises the steps of polishing the surface of the glassy carbon electrode, cleaning, uniformly dropwise adding a Shewanella MR-1/multi-walled carbon nanotube composite material solution on the surface, drying to obtain a Shewanella MR-1/multi-walled carbon nanotube modified electrode, placing the Shewanella MR-1/multi-walled carbon nanotube modified electrode as a working electrode in a chloroauric acid aqueous solution, using a silver/silver chloride electrode as a reference electrode, depositing nanogold by a constant potential method by a timing current method to obtain the nanogold/Shewanella MR-1/multi-walled carbon nanotube modified electrode, using the nanogold/Shewanella MR-1/multi-walled carbon nanotube modified electrode as the working electrode, and performing cyclic voltammetry scanning in an L-phenylalanine solution, taking out, cleaning and drying to obtain the poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-walled carbon nanotube modified electrode.
As a further improvement of the invention, the method specifically comprises the following steps:
s1. preparation of bare electrode
Firstly, placing a glassy carbon electrode in Al2O3Polishing the powder chamois leather until the surface is mirror-finished, then washing with distilled water, sequentially putting into distilled water, absolute ethyl alcohol and distilled water, performing ultrasonic treatment for 2-5min, taking out, washing with distilled water, and naturally drying to obtain a bare electrode;
s2, preparation of Shewanella MR-1/multi-walled carbon nanotube composite material solution
Transferring the multi-wall carbon nano-tubes, uniformly dispersing in sterile water, adding Shewanella MR-1, and uniformly dispersing at 27-30 ℃ to obtain Shewanella MR-1/multi-wall carbon nano-tube composite material solution;
s3, preparation of Shewanella MR-1/multi-walled carbon nanotube modified electrode
Uniformly dropwise adding the Shewanella MR-1/multi-walled carbon nanotube composite material solution on the surface of the bare electrode prepared in S1, and drying to obtain a Shewanella MR-1/multi-walled carbon nanotube modified electrode;
s4, preparation of nanogold/Shewanella MR-1/multi-walled carbon nanotube modified electrode
Placing the Shewanella MR-1/multi-walled carbon nanotube modified electrode prepared in the step S3 in a 1g/L chloroauric acid solution, taking a silver/silver chloride electrode as a reference electrode, depositing nano-gold at constant potential by adopting a chronoamperometry, taking out the nano-gold at the voltage of-2V for 150 seconds in 120-channel, and drying the nano-gold/Shewanella MR-1/multi-walled carbon nanotube modified electrode by using nitrogen;
s5, preparation of poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-walled carbon nanotube modified electrode
And (3) placing the nano-gold/Shewanella MR-1/multi-walled carbon nanotube modified electrode prepared by S4 as a working electrode in an L-phenylalanine solution, performing cyclic voltammetry scanning, taking out, leaching with distilled water, and drying to obtain the poly-L-phenylalanine/nano-gold/Shewanella MR-1/multi-walled carbon nanotube modified electrode.
As a further improvement of the invention, the Al2O3The particle size of the powder is between 0.02 and 0.1 mu m.
As a further improvement of the invention, the concentration of the multi-walled carbon nanotube in the Shewanella MR-1/multi-walled carbon nanotube composite material solution is 0.5-1.5 mg/mL, and the preparation method comprises the following steps: weighing multi-wall carbon nano tube, diluting with sterile water solution to specified volume, adding Shewanella MR-1 in an amount of 1-2% of the total mass of the system, and performing ultrasonic treatment at 27-30 deg.C to mix thoroughly.
As a further improvement of the invention, the concentration of the L-phenylalanine in the L-phenylalanine solution is 0.5-2 x 10-3mol/L, the preparation method comprises the following steps: weighing L-phenylalanine, dissolving with a PBS (phosphate buffer solution) with the pH value of 3-6, and then diluting with the PBS buffer solution with the same pH value to a specified volume.
As a further improvement of the invention, the sweep voltage of the cyclic voltammetry sweep is-0.8-3.0V, and the sweep rate is 100-140 mV/s.
The invention further protects the poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-wall carbon nanotube modified glassy carbon electrode prepared by the preparation method.
The invention further protects the application of the poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-wall carbon nanotube modified glassy carbon electrode in the determination of baicalein.
As a further improvement of the method, in a scanning voltage range of-0.45-0.6V and a scanning speed of 80-120 mV/s, the electrochemical behavior of the baicalein solution on modification electricity is determined by adopting cyclic voltammetry, and quantitative analysis of the baicalein solution with different concentrations is carried out by using a differential pulse voltammetry at room temperature.
As a further improvement of the invention, the baicalein solution is prepared from a phosphate buffer solution with 0.1mol/L, pH ═ 6.3.
The invention has the following beneficial effects: the invention discloses a poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-walled carbon nanotube repairThe modified glassy carbon electrode has a good catalytic effect on baicalein, and has the characteristics of high sensitivity, high detection speed and the like. The electrode is combined with cyclic voltammetry scanning and differential pulse voltammetry to carry out electrochemical behavior research of baicalein and realize quantitative detection of baicalein, I of baicaleinpaThe linear relation between the content of the baicalein and the content of c is in a range of 0.1-70 mu mol/L, the method can be used for quantitatively determining the content of the baicalein in the medicine, and has the advantages of high detection sensitivity, high response speed, strong response signals and the like.
Shewanella MR-1 is a typical dissimilatory metal-reducing bacterium, has remarkable electrochemical activity, and can reduce iron oxide, Au (III), Pd (II), U (VI) and the like through cytochrome c on the surface of a cell membrane and a secreted redox mediator. In the invention, the diffusion process of transferring the Au (III) bulk solution to the surface of the electrode is influenced by the adsorption of the thalli, and the Au is adsorbed to the surface of the electrode by the thalli, thereby accelerating the deposition and obtaining the uniform Shewanella MR-1/nano-gold/multi-wall carbon nanotube layer, and the electrode after the nano-gold is deposited, and the metal nano-particles have higher stability and good electrocatalytic performance, can obviously enhance the electron transfer efficiency of the modified electrode, and improve and enhance the electrochemical performance.
As a nano material, the multi-wall carbon nano tube (MWCNT) has very high specific surface area, electrical conductivity and good mechanical property, and is an excellent electrochemical material. Due to the unique electrochemical properties, the method has been widely applied to the preparation and application of chemically modified electrodes. Amino acids are the most basic substances of organisms and contain an amino group (-NH)2) And a carboxyl (-COOH) group. Amino acid is modified on the surface of the electrode by a chemical or electrochemical method, and the modified electrode has the advantages of high detection sensitivity, high response speed, strong response signal and the like when being used for measuring ions, molecules and chemical organic pollutants.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a CV diagram of potassium ferricyanide at various modified electrodes;
FIG. 2 is a CV diagram of potassium ferricyanide at various modified electrodes;
FIG. 3 is a diagram of potential windows for different modified electrodes;
FIG. 4 is a chronocoulombic diagram of P-LP/Au/MR-1/MWCNT/GCE and GCE;
FIG. 5 is a chronocoulombic linear plot of P-LP/Au/MR-1/MWCNT/GCE and GCE;
FIG. 6 is CV diagram of baicalein on different modified electrodes;
FIG. 7 is a CV diagram of baicalein solution at different pH determined by P-LP/Au/MR-1/MWCNT/GCE;
FIG. 8 is a graph of peak current versus pH linearity;
FIG. 9 is a plot of peak current versus pH;
FIG. 10 is a graph of CV measured on baicalein solution by P-LP/Au/MR-1/MWCNT/GCE at different scanning speeds;
FIG. 11 is IpaAnd IpcA linear regression equation graph with sweep rate;
FIG. 12 is a DPV graph of baicalein at various concentrations measured by P-LP/Au/MR-1/MWCNT/GCE;
FIG. 13 shows baicalein solutions of different concentrations and IpaA linear relationship graph between the two.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Electrochemical workstation (shanghai chenhua instrument limited), ultrasonic cleaner (KQ2200E type ultrasonic cleaner), electronic balance (shanghai yuping scientific instrument limited), three-electrode system: the poly-L-phenylalanine/multi-walled carbon nanotube modified electrode is a working electrode, the platinum wire is an auxiliary electrode, and the Saturated Calomel Electrode (SCE) is a reference electrode.
Baicalein (chinese institute for pharmaceutical and biological products); l-phenylalanine solution (Aladdin reagent, Inc., AR); potassium ferrocyanide (AR, telemedicine chemical agents ltd, tianjin); potassium ferricyanide (AR, permanent chemical reagent development center, Tianjin); sodium dihydrogen phosphate (phase geology research institute, AR); disodium hydrogen phosphate (Tianjin Bodi chemical Co., Ltd., AR); potassium chloride (Tianjin Bodi chemical Co., Ltd., AR).
The preparation method of the solution comprises the following steps:
PBS buffer solution is prepared from 0.1mol/L Na2HPO4·12H2O solution and 0.1mol/L NaH2PO4·12H2And mixing the O solution, and preparing PBS with different pH values for subsequent experiments.
The concentration is 1X 10-3And (3) weighing a certain mass of L-phenylalanine solution, dissolving the L-phenylalanine solution by using a small amount of PBS (phosphate buffered saline) buffer solution with the pH value of 5, and then diluting the L-phenylalanine solution to a specified volume by using the PBS buffer solution with the pH value of 5.
Weighing a certain mass of chloroauric acid with the concentration of 1g/L, and diluting the chloroauric acid with deionized water to a specified volume.
The concentration is 1X 10-3Weighing a certain mass of baicalein in a mol/L baicalein solution, and diluting the baicalein with absolute ethyl alcohol to a specified volume.
The concentration is 1X 10-4Diluting the prepared baicalein solution with pH 6 PBS buffer solution at 1 × 10-3mol/L baicalein to the specified volume.
Weighing a certain amount of multi-walled carbon nanotube solution with the mass concentration of 1mg/mL, diluting the multi-walled carbon nanotube solution to a specified volume by using a DMF solution, and performing ultrasonic treatment in an ultrasonic cleaner for 24 hours to fully and uniformly mix the solution.
Example 1
S1. preparation of bare electrode (GCE)
Firstly, a glassy carbon electrode is put with 0.05 mu m Al2O3Polishing the powder on chamois leather until the surface is mirror-finished, and then washing the mirror-finished chamois leather with distilled water. Sequentially putting into distilled water, anhydrous alcohol and distilled water, performing ultrasonic treatment for 3min, taking out, washing with distilled water, and naturally drying to obtain the bare electrode (GCE).
S2, preparation of Shewanella MR-1/multi-walled carbon nanotube composite material solution
Weighing 1mg of multi-walled carbon nanotube, diluting with 1mL of sterile aqueous solution, adding 0.03mg of Shewanella MR-1, and performing ultrasonic treatment at 30 ℃ to fully and uniformly mix the mixture;
s3, preparation of Shewanella MR-1/multi-wall carbon nanotube modified electrode (MR-1/MWCNT/GCE)
Transferring 5.0 mu L of Shewanella MR-1/multi-wall carbon nanotube composite material solution, uniformly dropwise adding on the surface of the bare electrode prepared in S1, and drying to obtain a Shewanella MR-1/multi-wall carbon nanotube modified electrode (MR-1/MWCNT/GCE);
s4, preparation of nano gold/Shewanella MR-1/multi-wall carbon nanotube modified electrode (Au/MR-1/MWCNT/GCE)
Placing the Shewanella MR-1/multi-walled carbon nanotube modified electrode (MR-1/MWCNT/GCE) prepared in the step S3 in a 1g/L chloroauric acid solution, taking a silver/silver chloride electrode as a reference electrode, depositing nano-gold at constant potential by a time-current method, taking out the nano-gold at a voltage of-2V for 130S, and drying the nano-gold/Shewanella MR-1/multi-walled carbon nanotube modified electrode (Au/MR-1/MWCNT/GCE) by nitrogen;
s5, preparation of poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-wall carbon nanotube modified electrode (P-LP/Au/MR-1/MWCNT/GCE)
Placing a nanogold/Shewanella MR-1/multi-walled carbon nanotube modified electrode (Au/MR-1/MWCNT/GCE) prepared by S4 as a working electrode at 1 × 10-3And (3) carrying out Cyclic Voltammetry (CV) scanning on a mol/L (PBS buffer solution pH is 5) LP solution under the conditions that the scanning voltage is-0.8-3.0V and the scanning speed is 120mV/s, taking out, leaching and airing by using distilled water, and thus obtaining the poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-walled carbon nanotube modified electrode (P-LP/Au/MR-1/MWCNT/GCE).
COMPARATIVE EXAMPLE 1 bare electrode (GCE)
Firstly, a glassy carbon electrode is placed in0.05μm Al2O3Polishing the powder on chamois leather until the surface is mirror-finished, and then washing the mirror-finished chamois leather with distilled water. Sequentially putting into distilled water, anhydrous alcohol and distilled water, performing ultrasonic treatment for 3min, taking out, washing with distilled water, and naturally drying to obtain the bare electrode (GCE).
COMPARATIVE EXAMPLE 2 Poly-L-phenylalanine modified electrode (P-LP/GCE)
S1. preparation of bare electrode (GCE)
Firstly, a glassy carbon electrode is put with 0.05 mu m Al2O3Polishing the powder on chamois leather until the surface is mirror-finished, and then washing the mirror-finished chamois leather with distilled water. Sequentially putting into distilled water, anhydrous alcohol and distilled water, performing ultrasonic treatment for 3min, taking out, washing with distilled water, and naturally drying to obtain the bare electrode (GCE).
S2, preparation of poly-L-phenylalanine modified electrode (P-LP/GCE)
GCE prepared in S1 was used as a working electrode, and 1X 10 cells were placed-3And (3) in a mol/L (PBS buffer solution pH is 5) LP solution, carrying out Cyclic Voltammetry (CV) scanning under the conditions of scanning voltage of-0.8-3.0V and scanning speed of 120mV/s for 8 circles, taking out, leaching and airing by using distilled water, and thus obtaining the poly-L-phenylalanine modified electrode (P-LP/GCE).
COMPARATIVE EXAMPLE 3 Multi-walled carbon nanotube modified electrode (Au/MR-1/MWCNT/GCE)
S1. preparation of bare electrode (GCE)
Firstly, a glassy carbon electrode is put with 0.05 mu m Al2O3Polishing the powder on chamois leather until the surface is mirror-finished, and then washing the mirror-finished chamois leather with distilled water. Sequentially putting into distilled water, anhydrous alcohol and distilled water, performing ultrasonic treatment for 3min, taking out, washing with distilled water, and naturally drying to obtain the bare electrode (GCE).
S2, preparation of Shewanella MR-1/multi-walled carbon nanotube composite material solution
Weighing 1mg of multi-walled carbon nanotube, diluting with 1mL of sterile aqueous solution, adding 0.03mg of Shewanella MR-1, and performing ultrasonic treatment at 30 ℃ to fully and uniformly mix the mixture;
s3, preparation of Shewanella MR-1/multi-wall carbon nanotube modified electrode (MR-1/MWCNT/GCE)
Transferring 5.0 mu L of Shewanella MR-1/multi-wall carbon nanotube composite material solution, uniformly dropwise adding on the surface of the bare electrode prepared in S1, and drying to obtain a Shewanella MR-1/multi-wall carbon nanotube modified electrode (MR-1/MWCNT/GCE);
s4, preparation of nano gold/Shewanella MR-1/multi-wall carbon nanotube modified electrode (Au/MR-1/MWCNT/GCE)
And (4) placing the Shewanella MR-1/multi-walled carbon nanotube modified electrode (MR-1/MWCNT/GCE) prepared in the step (S3) in a 1g/L chloroauric acid solution, taking the silver/silver chloride electrode as a reference electrode, depositing nano-gold at constant potential by a time-current method, taking out the electrode and drying the electrode by nitrogen to obtain the nano-gold/Shewanella MR-1/multi-walled carbon nanotube modified electrode (Au/MR-1/MWCNT/GCE).
Example 2
In a scanning voltage range of-0.45-0.6V and a scanning speed of 80-120 mV/s, the electrochemical behavior of the baicalein solution on modification electricity is determined by adopting cyclic voltammetry, and the quantitative analysis of the baicalein solution with different concentrations is carried out by using a differential pulse voltammetry at room temperature. The baicalein solution was prepared from 0.1mol/L, pH ═ 6.3 phosphate buffer solution.
Test example 1 electrochemical Performance test
1. Electrochemical behavior of potassium ferricyanide on different modified electrodes
The electrodes prepared in example 1 and comparative examples 1 to 3 were used as working electrodes in a scanning voltage range of-0.45 to 0.6V and a scanning speed of 100mV/s, and the electrode pairs contained 1X 10-3mol/L of Fe (CN)6 3-/Fe(CN)6 4-And 0.1mol/L of KNO3The mixed solution was subjected to CV scanning. CV diagrams of potassium ferricyanide on different modified electrodes are obtained, as shown in FIG. 1, and parameters are shown in Table 1. As can be seen from FIG. 1 and Table 1, the peak current of potassium ferricyanide on GCE is small and the peak shape is flat and wide, the peak current on Au/MR-1/MWCNT/GCE and on P-LP/GCE is increased, the symmetry of oxidation peak and reduction peak on P-LP/Au/MR-1/MWCNT/GCE is increased, and the peak current is increased. And the delta E of the P-LP/Au/MR-1/MWCNT/GCE is 0.093V and less than the delta E of the GCE is 0.122V, which indicates that the reversibility of the P-LP/Au/MR-1/MWCNT/GCE is enhanced and the detection sensitivity is high.
TABLE 1 CV parameters of potassium ferricyanide on different modified electrodes
2. AC impedance electrochemical behavior of differently modified electrodes
At 1 × 10-3mol/L Fe(CN)6 3-/Fe(CN)6 4-And taking the mixed solution of KCI and KCI of 0.1mol/L as an impedance solution, and carrying out impedance experiments on different modified electrodes by adopting an alternating current impedance method (EIS) to obtain EIS graphs of the different modified electrodes, wherein the EIS graphs are shown in figure 2. As can be seen from FIG. 2, the Au/MR-1/MWCNT/GCE has a constant impedance when the arc diameter is the smallest and the impedance is the same line. The arc diameter of GCE is maximum at the beginning, and the arc diameter of P-LP/Au/MR-1/MWCNT/GCE is larger than that of Au/MR-1/MWCNT/GCE and smaller than that of P-LP/GCE. The data show that the electrode impedance can be reduced by P-LP/GCE and Au/MR-1/MWCNT/GCE, and the conductivity is improved relative to the GCE electrode when MWCNT dots are coated on the P-LP/GCE.
3. Potential window electrochemical behavior of differently modified electrodes
The results of the potential window of different modified electrodes in PBS buffer solution with pH 6 were investigated in the range of-2.5 to 2.5V using Linear Sweep Voltammetry (LSV), and are shown in fig. 3. The potential window range is shown by fig. 3: -1.6-1.3V, and the potential range of baicalein studied in this experiment is-0.45-0.6V, within this range.
4. Chronocoulometric electrochemical behavior of P-LP/Au/MR-1/MWCNT/GCE and GCE
At 1mmol/L Fe (CN)6 3-In solution, the chronocoulombic electrochemical behavior of GCE and P-LP/Au/MR-1/MWCNT/GCE was studied using the chronocoulometry method, and the results are shown in Table 2, FIG. 4 and FIG. 5.
TABLE 2 chronocoulombic parameters for P-LP/Au/MR-1/MWCNT/GCE and GCE
| t/s | t1/2/s | Q/u c (bare electrode) | Q/u c (composite electrode) |
| 0.09 | 0.3 | -0.908 | -0.907 |
| 0.36 | 0.6 | -3.63 | -3.63 |
| 0.81 | 0.9 | -8.17 | -8.17 |
| 1.44 | 1.2 | -14.4 | -14.5 |
| 2.25 | 1.5 | -20.5 | -22.6 |
| 3.24 | 1.8 | -26.0 | -28.9 |
| 4.41 | 2.1 | -31.2 | -34.3 |
| 5.76 | 2.4 | -36.1 | -39.1 |
| 7.29 | 2.7 | -40.9 | -43.7 |
According to the chronocoulometry equation:
Q＝2nFAcD0.5t0.5π0.5+Q dc+Q ds
n is the electron transfer number of the electrode reaction; a is the electrode reaction specific surface area of the working electrode; slope 2 nFACCD0.5π0.5。
Analysis of Q and t of GCE by experiment0.5The linear relationship between them is:
Q＝-17.3t0.5+5.87
the specific surface area A of the GCE electrode can be obtained to be 0.018cm by a chronocoulometry method formula2。
Q and t of P-LP/MWNT/GCE0.5The linear relationship between them is:
Q＝-19.1t0.5+6.93
the specific surface area A of the P-LP/Au/MR-1/MWCNT/GCE electrode is 0.020cm through a timing coulometry formula2。
The data show that the specific surface area of the P-LP/Au/MR-1/MWCNT/GCE is larger than that of the GCE electrode, so that the P-LP/Au/MR-1/MWCNT/GCE can be used as an electrochemical sensor to accelerate the transfer of electroactive substances, accelerate the electron exchange, enhance the electrochemical reaction capacity and enhance reaction signals.
Test example 2 determination of baicalein
1. Electrochemical behavior of baicalein on different modified electrodes
Under the conditions that the scanning voltage is-0.45-0.6V and the scanning speed is 100mV/s, the electrodes prepared in the example 1 and the comparative examples 1-3 are used as working electrodes, and the scanning voltage is 1 multiplied by 10 to 0.6V-4Performing cyclic voltammetry scanning on the baicalein solution with mol/L. CV diagrams of baicalein on different modified electrodes are obtained, as shown in FIG. 6, and parameters are shown in Table 3. From FIG. 6 and Table 3, it can be observed that baicalein has the least peak current on GCE, flat and wide peak shape, and increased peak current on Au/MR-1/MWCNT/GCE and P-LP/GCE. The baicalein has good symmetry on P-LP/Au/MR-1/MWCNT/GCE compared with GCE, and has large peak current. The I of BAI on P-LP/Au/MR-1/MWCNT/GCE can be obtained by analysispaAbout 6 times of GCE, IpcAbout 22 times of GCE, the best sensitivity of P-LP/Au/MR-1/MWCNT/GCE for baicalein can be obtained.
TABLE 3 CV parameters of baicalein on different modified electrodes
2. Effect of pH on P-LP/Au/MR-1/MWCNT/GCE electrochemical behavior of baicalein determination
The concentration is 1X 10-4CV diagram of mol/L baicalein solution at different pH is shown in FIG. 7, CV parameters are shown in Table 4, as shown in FIG. 7, the peak potential of baicalein moves towards negative potential direction with the increase of pH, as shown in FIG. 8, E of baicalein within the range of pH 5.7-8.0paLinear relation with pH, and linear regression equation is that E is 0.680-0.077pH, R2＝0.998，EpcThe pH is also in a linear relation, and the linear regression equation is that E is 0.672 to 0.092pH, R20.992. From FIG. 9 plot of peak current against pHIt is known that baicalein has the maximum peak current at pH 6.3, and the optimum pH of 6.3 was selected in this experiment.
TABLE 4 CV parameters of P-LP/Au/MR-1/MWCNT/GCE for baicalein solutions at different pH
| pH | Epc/V | Epa/V | ΔE/V | Ipc/μA | Ipa/μA |
| 5.7 | 0.149 | 0.247 | 0.098 | 12.49 | -19.45 |
| 5.9 | 0.133 | 0.247 | 0.114 | 15.27 | -21.54 |
| 6.3 | 0.092 | 0.193 | 0.101 | 17.47 | -29.48 |
| 6.7 | 0.051 | 0.167 | 0.116 | 17.08 | -25.43 |
| 7.1 | 0.009 | 0.135 | 0.126 | 17.71 | -24.92 |
| 7.5 | -0.023 | 0.107 | 0.13 | 18.52 | -26.85 |
| 8.0 | -0.055 | 0.068 | 0.123 | 13.37 | -14.92 |
3. Influence of sweep rate on peak current
The concentration is 1X 10-4CV diagram of mol/L baicalein solution (PBS buffer solution with pH 6.3) at different sweep rates is shown in FIG. 10, with CV parametersSee table 5. E of baicalein with increasing sweeping speedpaIncrease of IpaAlso increasing, EpcNegative shift, IpcAnd is increased. As can be seen from FIG. 11, the sweep rate is in the range of 20 to 180mV/s, the peak current and the sweep rate are in a linear relationship, and the linear regression line equation is: i ispc＝-2.46+0.111v，R2＝0.995；Ipa＝1.95-0.116v，R20.995. The electrochemical behavior of baicalein on the surface of P-LP/Au/MR-1/MWCNT/GCE is mainly influenced by the adsorption control of baicalein to the surface of the electrode, which is illustrated by the linear relation.
TABLE 5 determination of CV parameters of BAI by P-LP/Au/MR-1/MWCNT/GCE at different sweep rates
| Sweep Rate/mV/s | Epc/V | Epa/V | ΔE/V | Ipc/μA | Ipa/ |
| 20 | 0.137 | 0.196 | 0.059 | 1.561 | -1.988 |
| 50 | 0.130 | 0.209 | 0.079 | 3.609 | -4.343 |
| 80 | 0.121 | 0.217 | 0.096 | 5.955 | -6.857 |
| 100 | 0.122 | 0.225 | 0.103 | 7.899 | -8.952 |
| 120 | 0.115 | 0.229 | 0.114 | 7.899 | -8.952 |
| 150 | 0.122 | 0.237 | 0.115 | 13.42 | -14.79 |
| 180 | 0.107 | 0.245 | 0.138 | 16.81 | -18.16 |
4. P-LP/Au/MR-1/MWCNT/GCE determination of linear range of baicalein
Taking P-LP/Au/MR-1/MWCNT/GCE as a working electrode, in baicalein solutions with different concentrations, which are prepared from phosphate buffer solutions with 0.1mol/L, pH ═ 6.3, Differential Pulse Voltammetry (DPV) scanning is carried out on the baicalein solutions with different concentrations to obtain a DPV graph, as shown in FIG. 11, the DPV parameters are shown in Table 6, and I can be obtained from FIG. 12 along with the increase of the concentration of the baicalein solutionpaAre increasing continuously. As can be seen from FIG. 13, when the concentration of baicalein is in the range of 0.1-70 μmol/L, IpaIs in linear relation with concentration, and the linear regression equation is Ipa＝-0.359c-1.77，R2＝0.999。
TABLE 6 DPV parameters for P-LP/Au/MR-1/MWCNT/GCE measurements of baicalein solutions at different concentrations
| C/μmol/L | Epa/V | Ipa/μA |
| 0.1 | 0.120 | -1.518 |
| 0.3 | 0.116 | -1.733 |
| 0.7 | 0.120 | -2.003 |
| 1 | 0.120 | -2.171 |
| 3 | 0.124 | -2.801 |
| 7 | 0.128 | -4.347 |
| 10 | 0.132 | -5.580 |
| 30 | 0.128 | -12.93 |
| 70 | 0.124 | -26.71 |
Compared with the prior art, the poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-wall carbon nanotube modified glassy carbon electrode prepared by the invention has good catalysis effect on baicalein, and has the characteristics of high sensitivity, high detection speed and the like. The electrode is combined with cyclic voltammetry scanning and differential pulse voltammetry to carry out electrochemical behavior research of baicalein and realize quantitative detection of baicalein, I of baicaleinpaThe content of the baicalein in the medicine is in a linear relation with the c within the range of 0.1-70 mu mol/L, and the method can be used for quantitatively determining the content of the baicalein in the medicineThe method has the advantages of high detection sensitivity, high response speed, strong response signal and the like.
Shewanella MR-1 is a typical dissimilatory metal-reducing bacterium, has remarkable electrochemical activity, and can reduce iron oxide, Au (III), Pd (II), U (VI) and the like through cytochrome c on the surface of a cell membrane and a secreted redox mediator. In the invention, the diffusion process of transferring the Au (III) bulk solution to the surface of the electrode is influenced by the adsorption of the thalli, and the Au is adsorbed to the surface of the electrode by the thalli, thereby accelerating the deposition and obtaining the uniform Shewanella MR-1/nano-gold/multi-wall carbon nanotube layer, and the electrode after the nano-gold is deposited, and the metal nano-particles have higher stability and good electrocatalytic performance, can obviously enhance the electron transfer efficiency of the modified electrode, and improve and enhance the electrochemical performance.
As a nano material, the multi-wall carbon nano tube (MWCNT) has very high specific surface area, electrical conductivity and good mechanical property, and is an excellent electrochemical material. Due to the unique electrochemical properties, the method has been widely applied to the preparation and application of chemically modified electrodes. Amino acids are the most basic substances of organisms and contain an amino group (-NH)2) And a carboxyl (-COOH) group. Amino acid is modified on the surface of the electrode by a chemical or electrochemical method, and the modified electrode has the advantages of high detection sensitivity, high response speed, strong response signal and the like when being used for measuring ions, molecules and chemical organic pollutants.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-walled carbon nanotube modified glassy carbon electrode is characterized in that the surface of the glassy carbon electrode is polished and cleaned, Shewanella MR-1/multi-walled carbon nanotube composite material solution is uniformly dripped on the surface, and the Shewanella MR-1/multi-walled carbon nanotube modified electrode is obtained after drying, the Shewanella MR-1/multi-walled carbon nanotube modified electrode is taken as a working electrode, the working electrode is placed in chloroauric acid aqueous solution, a silver/silver chloride electrode is taken as a reference electrode, nanogold is deposited by adopting a timing current method to realize constant potential deposition, the nanogold/Shewanella MR-1/multi-walled carbon nanotube modified electrode is obtained, the nanogold/Shewanella MR-1/multi-walled carbon nanotube modified electrode is taken as the working electrode, and performing cyclic voltammetry scanning in an L-phenylalanine solution, taking out, cleaning and drying to obtain the poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-walled carbon nanotube modified electrode.
2. The preparation method of the poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-walled carbon nanotube modified glassy carbon electrode according to claim 1, which is characterized by comprising the following steps:
s1. preparation of bare electrode
Firstly, placing a glassy carbon electrode in Al2O3Polishing the powder chamois leather until the surface is mirror-finished, then washing with distilled water, sequentially putting into distilled water, absolute ethyl alcohol and distilled water, performing ultrasonic treatment for 2-5min, taking out, washing with distilled water, and naturally drying to obtain a bare electrode;
s2, preparation of Shewanella MR-1/multi-walled carbon nanotube composite material solution
Transferring the multi-wall carbon nano-tubes, uniformly dispersing in sterile water, adding Shewanella MR-1, and uniformly dispersing at 27-30 ℃ to obtain Shewanella MR-1/multi-wall carbon nano-tube composite material solution;
s3, preparation of Shewanella MR-1/multi-walled carbon nanotube modified electrode
Uniformly dropwise adding the Shewanella MR-1/multi-walled carbon nanotube composite material solution on the surface of the bare electrode prepared in S1, and drying to obtain a Shewanella MR-1/multi-walled carbon nanotube modified electrode;
s4, preparation of nanogold/Shewanella MR-1/multi-walled carbon nanotube modified electrode
Placing the Shewanella MR-1/multi-walled carbon nanotube modified electrode prepared in the step S3 in a 1g/L chloroauric acid solution, taking a silver/silver chloride electrode as a reference electrode, depositing nano-gold at constant potential by adopting a chronoamperometry, taking out the nano-gold at the voltage of-2V for 150 seconds in 120-channel, and drying the nano-gold/Shewanella MR-1/multi-walled carbon nanotube modified electrode by using nitrogen;
s5, preparation of poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-walled carbon nanotube modified electrode
And (3) placing the nano-gold/Shewanella MR-1/multi-walled carbon nanotube modified electrode prepared by S4 as a working electrode in an L-phenylalanine solution, performing cyclic voltammetry scanning, taking out, leaching with distilled water, and drying to obtain the poly-L-phenylalanine/nano-gold/Shewanella MR-1/multi-walled carbon nanotube modified electrode.
3. The method for preparing poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-walled carbon nanotube modified glassy carbon electrode according to claim 2, wherein the Al is2O3The particle size of the powder is between 0.02 and 0.1 mu m.
4. The preparation method according to claim 2, wherein the concentration of the multi-walled carbon nanotubes in the Shewanella MR-1/multi-walled carbon nanotube composite material solution is 0.5-1.5 mg/mL, and the preparation method comprises the following steps: weighing multi-wall carbon nano tube, diluting with sterile water solution to specified volume, adding Shewanella MR-1 in an amount of 1-2% of the total mass of the system, and performing ultrasonic treatment at 27-30 deg.C to mix thoroughly.
5. The method according to claim 2, wherein the concentration of L-phenylalanine in the L-phenylalanine solution is 0.5 to 2X 10-3mol/L, the preparation method comprises the following steps: weighing L-phenylalanine, dissolving with a PBS (phosphate buffer solution) with the pH value of 3-6, and then diluting with the PBS buffer solution with the same pH value to a specified volume.
6. The method according to claim 2, wherein the sweep voltage of the cyclic voltammetric sweep is-0.8 to 3.0V, and the sweep rate is 100 to 140 mV/s.
7. The poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-walled carbon nanotube modified glassy carbon electrode prepared by the preparation method of any one of claims 1 to 6.
8. The application of the poly-L-phenylalanine/nanogold/Shewanella MR-1/multi-walled carbon nanotube modified glassy carbon electrode in the determination of baicalein as claimed in claim 7.
9. The application of the baicalein compound as claimed in claim 8, wherein the electrochemical behavior of the baicalein compound solution on a modification electrode is determined by cyclic voltammetry scanning in a scanning voltage range of-0.45-0.6V and a scanning speed of 80-120 mV/s, and the quantitative analysis of the baicalein compound solution with different concentrations is carried out by differential pulse voltammetry at room temperature.
10. Use as claimed in claim 9, wherein the baicalein solution is formulated from 0.1mol/L, pH ═ 6.3 phosphate buffer solution.
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