CN108469459B - Polyacid-based composite membrane electrode material for sensing L-tyrosine - Google Patents

Polyacid-based composite membrane electrode material for sensing L-tyrosine Download PDF

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CN108469459B
CN108469459B CN201810232100.5A CN201810232100A CN108469459B CN 108469459 B CN108469459 B CN 108469459B CN 201810232100 A CN201810232100 A CN 201810232100A CN 108469459 B CN108469459 B CN 108469459B
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马慧媛
张璐璐
焦佳
谭立超
庞海军
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Harbin University of Science and Technology
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Abstract

A polyacid-based composite membrane electrode material for sensing L-tyrosine, in particular to a polyacid (P) based on Dawson type2Mo16V2) Mixing withThe hybrid BMIMBr-CNTs composite material is used for an electrochemical working electrode for sensing L-tyrosine. The invention belongs to the field of electrochemical sensors, and aims to solve the problems of complex preparation process, narrow linear range, low stability and the like of the conventional electrochemical sensor for detecting L-tyrosine. The product is a carbon nano tube composite film PEI/[ P ] functionalized by an ITO electrode and a Dawson type heteropoly acid doped ionic liquid wrapped outside the ITO electrode2Mo16V2/BMIMBr‑CNTs]8The composite film has a multilayer structure, the number of the layers of the film is 8, and an electrochemical sensor constructed by taking the composite material as a working electrode can sense the L-tyrosine, and the linear range of the L-tyrosine is 1.80 × 10‑7M~1.24×10‑4M (M: mol/L), detection limit is 1.0 × 10‑7And M. The electrode has high stability and good selectivity, and can be used for true sample detection.

Description

Polyacid-based composite membrane electrode material for sensing L-tyrosine
Technical Field
The invention belongs to the technical field of electrochemical sensors, and particularly relates to a polyacid-based composite membrane electrode material for sensing L-tyrosine.
Background
L-tyrosine is also called 2-amino-3-p-hydroxyphenylalanine, is aromatic polar α -amino acid containing phenolic hydroxyl and is one of important raw materials for synthesizing protein molecules, in the central nervous system, the L-tyrosine is an important precursor substance for synthesizing dopamine, thyroid hormone and neurotransmitter, in daily life, the L-tyrosine is an important nutritional supplement and food additive.
The polyoxometallate is prepared from an early transition metal element, usually d0Electron configuration is linked to the oxygen atom to form a polyanionic oxygen cluster. The structural form of the basic unit is mainly { MO6Octahedron and { MO }4Two tetrahedrons. Polyoxometalates (POMs) have good redox reversibility, can undergo a rapid, multistep multi-electron transfer process, while maintaining the structure of the Polyoxometalates (POMs) unchanged, and are excellent electroactive materials which can be used for modified electrodes. The polyoxometallate has a variety of varieties, in recent years, a plurality of POMs (polyoxymethylene) based compounds with novel structures are designed and synthesized continuously, and the construction research of the polyacid-based electrochemical sensor has a large space.
Ionic liquids are one of the salts, which are composed mainly of organic cations and inorganic or organic anions, and are usually in a liquid state at or near room temperature. The ionic liquid belongs to environment-friendly chemical substances, has no pollution to the environment, and is suitable for being widely applied to various fields of social production. The ionic liquid has very outstanding performance in the aspects of thermal stability and chemical stability, and has more advantages in the aspect of keeping the activity of biomass molecules than common organic solvents.
Carbon Nanotubes (CNTs) are a new class of carbon materials with nanostructures synthesized by a top-down methodology. Due to the unique mechanical, electrochemical, electrical and field emission properties of the carbon nano tube, the carbon nano tube has great potential application value in the preparation of nano electronic components, catalytic materials, conductive and energy storage materials. In the field of nano material modified electrodes, researchers are dedicated to developing a series of novel functional composite materials based on nano carbon materials and other active substances by utilizing the high specific surface area and excellent conductivity of the carbon materials. In recent years, CNTs have found extremely wide application in the field of biosensors.
Disclosure of Invention
The invention belongs to the technical field of electrochemical sensors, and aims to solve the problems of complex preparation process, narrow linear range, low stability and the like of the conventional electrochemical sensor for detecting L-tyrosine.
The invention relates to a polyacid-based composite membrane electrode material for sensing L-tyrosine, which is characterized in that the polyacid-based composite membrane electrode material for sensing L-tyrosine is composed of an ITO electrode and a composite membrane of a phosphomolybdovanadophosphoric acid doped ionic liquid functionalized carbon nano tube loaded outside the ITO electrode, the ITO electrode layer is sequentially provided with a polyethyleneimine layer (PEI) and a phosphomolybdovanadophosphoric acid doped ionic liquid functionalized carbon nano tube layer outwards, wherein the phosphomolybdovanadophosphoric acid doped ionic liquid functionalized carbon nano tube layer is in a multi-layer cycle, the cycle number is 8, and the label is PEI/[ P ] P2Mo16V2/BMIMBr-CNTs]8；
The number of the modified electrode layers is 8;
the phosphomolybdovanadophosphoric acid is polyoxometallate P of Dawson type2Mo16V2；
The ionic liquid BMIMBr is 1-butyl-3-methylimidazolium bromide;
the pipe diameter of the carbon nano-tube is 15-30 nm.
The invention has the beneficial effects that:
compared with the traditional L-tyrosine sensor, the L-tyrosine electrochemical sensing electrode based on the ionic liquid functionalized carbon nano tube doped with the phosphomolybdovanadophosphoric acid, which is constructed by the invention, solves the problems of complex preparation process, narrow linear range, low stability and the like in the L-tyrosine detection in the existing medicine and food, and the linear range of the L-tyrosine electrochemical sensor prepared on the basis of the electrochemical sensing electrode based on the ionic liquid functionalized carbon nano tube doped with the phosphomolybdovanadophoric acid, which is disclosed by the invention, is 1.80 × 10-7M ~ 1.24 × 10-4M (M: mol/L), detection limit is 1.0 × 10-7M, the prepared working electrode has wider linear range and better stability. In addition, the working electrode prepared by the invention also has the advantages of simple preparation method, easy operation and low cost.
Drawings
FIG. 1 shows PE on the ITO electrode obtained in the first experimentI/(P2Mo16V2/BMIMBr-CNTs)8Scanning electron microscope images of the surface appearance of the composite film;
FIG. 2 is a cyclic voltammogram for the catalytic oxidation of L-tyrosine in validation experiment (II);
FIG. 3 is a graph of current versus time for the electrochemical sensor to detect L-tyrosine in the validation experiment (III);
FIG. 4 is a graph showing the linear relationship between the steady-state current of the electrochemical sensor and the concentration of L-tyrosine in the system in the verification test (III);
FIG. 5 shows ITO/(P) in the verification test (IV)2Mo16V2/BMIMBr-CNTs)8A cyclic voltammogram of the working electrode over one hundred cycles;
FIG. 6 shows ITO/(P) in the verification test (IV)2Mo16V2/BMIMBr-CNTs)8Working electrode catalyzed oxidation of L-tyrosine within 30 days current change histogram.
Detailed Description
The first embodiment is as follows: the embodiment is a polyacid-based composite membrane electrode material for sensing L-tyrosine, which is composed of an ITO electrode and a phosphomolybdovanadophosphoric acid doped ionic liquid functionalized carbon nanotube composite membrane loaded outside the ITO electrode, wherein the ITO electrode layer is outwards provided with a polyethyleneimine layer (PEI) and a phosphomolybdovanadophosphoric acid doped ionic liquid functionalized carbon nanotube layer in sequence, the phosphomolybdovanadophosphoric acid doped ionic liquid functionalized carbon nanotube layer is in a multi-layer cycle, the cycle number is 8, and the label is PEI/[ P ] P2Mo16V2/BMIMBr-CNTs]8。
The second embodiment is as follows: a preparation method of a polyacid-based composite membrane electrode material for sensing L-tyrosine comprises the following steps:
one, P2Mo16V2Preparation of the solution:
① weighing P with analytical balance2Mo16V217-19 mg of heteropoly acid, and stirring the Dawson type polyoxometallate P under the condition of magnetic stirring at the stirring speed of 40-60 r/min2Mo16V2Dissolving in 6mL of deionized water, and stirring for 10min to obtain a solution A;
② transferring the solution A into a penicillin bottle B with the volume of 10mL for placement;
p in solution A in step one ①2Mo16V2The mass ratio of the heteropoly acid to the deionized water is 17-19: 6;
the volume ratio of the solution A to the penicillin bottle B in the step one ② is 3: 5;
secondly, preparing a BMIMBr-CNTs solution:
① mixing 0.2g of CNTs and 0.3-0.5 g of BMIMBr directly in a mortar, and grinding for 30min to obtain uniform paste A;
② adding 3-5 mL (5 wt.%) of PDDA solution into the paste A, and grinding for 30min to obtain a solution B;
③ transferring the prepared solution B into a 10mL penicillin bottle, performing ultrasonic treatment for 4 hours, and setting the ultrasonic power to be 40-80 Hz to obtain a uniformly dispersed BMIMBr-CNTs solution with positive charges;
in the second ①, the mass ratio of the mass of the carbon nanotubes in the paste A to the mass of the BMIMBr is 1: 1.5-2.5;
in the second step ②, the ratio of the mass of the paste A in the solution B to the volume of the PDDA is 0.5-0.7 g: 3-5 mL;
in the second step ③, the volume ratio of the BMIMBr-CNTs solution to the penicillin bottle is 3-5: 10;
thirdly, the preparation method of the electrochemical electrode for sensing L-tyrosine based on the ionic liquid BMIMBr functionalized carbon nano tube doped with phosphomolybdovanadate comprises the following steps:
① soaking the ITO electrode in the polyethyleneimine water solution for 10-12 h, taking out, washing with deionized water, and washing with N2Drying by flow;
② immersing the electrodes ① in P2Mo16V2Soaking the solution and the BMIMBr-CNTs solution for 10-15 min respectively, taking out, washing with deionized water, and then using N2Drying by flow;
③ repeating the operation of ② for 2-10 times to obtain the phosphomolybdovanadophosphoric acid doped with the heteropoly acidElectrochemical electrode compounded by hybrid ionic liquid functionalized carbon nano tube and marked as PEI/[ P ]2Mo16V2/BMIMBr-CNTs]nA modified ITO electrode;
the concentration of the polyethyleneimine aqueous solution in the step III ① is 8-10 mM;
p in step three ②2Mo16V2The concentration of the solution is 3mg/mL, and the concentration of the BMIMBr-CNTs solution is 0.1 g/mL;
the number n of the modifying layers in the step three ③ is 2-10;
third embodiment the difference between the first embodiment and the second embodiment is that the step ①
Polyoxometallate P of Dawson type2Mo16V2In an amount of 18 mg. Other steps and parameters are the same as those in one of the first to second embodiments.
Fourth embodiment, the difference between this embodiment and the first to third embodiments is that the stirring speed of the magnetic stirrer in the first step ① is 50r/min, and the solution A is obtained after 10min of stirring.
Fifth embodiment, the difference between this embodiment and the first to fourth embodiments is that the amount of BMIMBr ionic liquid used in step two ① is 0.4g, the ionic liquid and the carbon nanotubes are milled for 30min to obtain a uniform paste a.
Sixth embodiment this embodiment differs from embodiments one to five in that the amount of PDDA (5 wt.%) solution used in step two ② is 4mL, and grinding is performed for 30min to obtain solution b.
Seventh embodiment mode, the difference between this embodiment mode and the first to sixth embodiment modes is that the ultrasonic power in the second step ③ is set to 80Hz, and ultrasonic treatment is carried out for 4 hours to obtain a uniformly dispersed BMIMBr-CNTs solution with positive charges.
Eighth embodiment different from the first to seventh embodiments, in the third embodiment, the ITO electrode described in the third step ① is immersed in the polyethyleneimine aqueous solution, taken out after being immersed for 12 hours, washed clean with deionized water after being taken out, and then washed with N2And (5) drying by flow. Other steps and parameters are the same as those in one of the first to seventh embodiments.
Ninth embodiment, the present embodiment is different from the first to eighth embodiments in that the ITO electrode is dipped in the polyethyleneimine aqueous solution in the third step ①, and other steps and parameters are the same as those of the first to eighth embodiments.
Tenth embodiment mode the difference between this embodiment mode and the first to ninth embodiment modes is that the ITO electrodes are respectively soaked in P in the step three ②2Mo16V2Soaking the solution and BMIMBr-CNTs solution for 15min, taking out, washing with deionized water, and adding N2And (5) drying by flow. Other steps and parameters are the same as those in one of the first to ninth embodiments.
Eleventh embodiment mode, which is different from the first to tenth embodiment modes, in that the ITO electrode is dipped in P in the step three ②2Mo16V2In solution, P2Mo16V2The concentration of the solution was 3 mg/mL. Other steps and parameters are the same as those in one of the first to tenth embodiments.
Twelfth embodiment the difference between this embodiment and the first to eleventh embodiments is that the electrodes are respectively soaked in P in the step three ③2Mo16V2The electrochemical electrode compounded by the carbon nano tube functionalized by the ionic liquid doped with the phosphomolybdovanadophosphoric acid is obtained by 8 times through the solution and the BMIMBr-CNTs solution and is marked as PEI/[ P ]2Mo16V2/BMIMBr-CNTs]8A modified ITO electrode. Other steps and parameters are the same as those in one of the first to eleventh embodiments.
The following tests were conducted to confirm the effects of the present invention
Test one, a preparation method of a polyacid-based composite membrane electrode material for sensing L-tyrosine is carried out according to the following steps:
P2Mo16V2preparation of the solution:
one, P2Mo16V2Preparation of the solution:
① use analytical balance to weigh 18mg of P2Mo16V2Heteropolyacid, the polyoxometallate P of Dawson type is stirred under the condition of magnetic stirring with the stirring speed of 50r/min2Mo16V2Dissolving in 6mL of deionized water, and stirring for 10min to obtain a solution A;
② transferring the solution A into a 10mL penicillin bottle B for placement;
secondly, preparing a BMIMBr-CNTs solution:
① CNTs 0.2g and BMIMBr 0.4g were mixed directly in a mortar and ground for 30min to give a uniform paste A;
② then 4mL (5 wt.%) of PDDA solution was added to a and triturated for 30min to give solution B;
③, transferring the prepared nano composite material B into a penicillin bottle with the volume of 10mL, and performing ultrasonic treatment for 4 hours with the ultrasonic power set to 80Hz to obtain a uniformly dispersed BMIMBr-CNTs solution with positive charges;
thirdly, the preparation method of the electrochemical electrode for sensing the L-tyrosine based on the ionic liquid functionalized carbon nano tube doped with the phosphomolybdovanadate comprises the following steps:
① soaking the ITO electrode in 10mM polyethyleneimine water solution for 12h, taking out, washing with deionized water, and washing with N2Drying by flow;
② immersing the electrodes ① in P2Mo16V2Soaking in BMIMBr-CNTs solution for 15min, taking out, washing with deionized water, and adding N2Drying by flow;
③ repeating the operation of ② for 8 times to obtain the electrochemical electrode compounded by the carbon nano tube functionalized by the ionic liquid doped with the phosphomolybdovanadophosphoric acid, which is marked as PEI/[ P ]2Mo16V2/BMIMBr-CNTs]8A modified ITO electrode;
for the PEI/[ P ] obtained in test one2Mo16V2/BMIMBr-CNTs]8The ITO electrode modified by the composite film is characterized in that:
(one) testing a resulting PEI/[ P ] with a Scanning Electron Microscope (SEM) of the S-4300 type2Mo16V2/BMIMBr-CNTs]8The appearance of the composite membrane is characterized to obtain PEI/[ P ] shown in figure 12Mo16V2/BMIMBr-CNTs]8Scanning electron microscope image of the surface appearance of the composite film.
As can be seen from FIG. 1, PEI/[ P ]2Mo16V2/BMIMBr-CNTs]8The composite membrane is uniformly modified on the surface of the ITO electrode, and in addition, the carbon nano tubes which are criss-cross are covered on the surface of the electrode in a fluffy three-dimensional net structure basically, so that the surface of the electrode has a larger specific surface area, more catalytic active sites are obtained, and the electronic conduction capability of the electrode is improved.
(II) verification of PEI/[ P ] obtained in the first experiment of the present application2Mo16V2/BMIMBr-CNTs]8Catalytic performance of ITO electrode modified by composite film
Preparation of electrochemical sensor
PEI/[ P ] obtained by the test one of the present application2Mo16V2/BMIMBr-CNTs]8The ITO electrode modified by the composite membrane is used as a working electrode, the Ag/AgCl electrode is used as a reference electrode, the platinum wire electrode is used as a counter electrode, and a three-electrode system is formed, namely the electrochemical sensor.
Secondly, the electrochemical sensor prepared in the step one is used for electrocatalytic oxidation of L-tyrosine
And (4) conclusion: a cyclic voltammogram of the electrochemical sensor shown in fig. 2 catalyzing L-tyrosine in 0.1M PBS (pH = 6.8) buffer solution and a response current as shown in fig. 2 as a function of the concentration of L-tyrosine added were obtained. Wherein 1 is cyclic voltammetry curve added with L-tyrosine with concentration of 0 μ M, 2 is cyclic voltammetry curve added with L-tyrosine with concentration of 10 μ M, and 3 is cyclic voltammetry curve added with L-tyrosine with concentration of 20 μ MAn ampere curve, 4 is a cyclic voltammetry curve with an L-tyrosine concentration of 30 μ M, 5 is a cyclic voltammetry curve with an L-tyrosine concentration of 40 μ M, and 6 is a cyclic voltammetry curve with an L-tyrosine concentration of 50 μ M, as can be seen from FIG. 2, when the L-tyrosine is subjected to electrocatalytic oxidation after 0-50 μ M of L-tyrosine is added, ITO/(P) is obtained2Mo16V2/BMIMBr-CNTs)8The catalytic peak potential for the oxidation reaction of the L-tyrosine is positioned at 0.78V, and the catalytic oxidation peak current shows good linear relation along with the change of the concentration of the added L-tyrosine, which indicates that ITO/(P)2Mo16V2/BMIMBr-CNTs)8Has good catalytic action on the oxidation reaction of the L-tyrosine, and can sense the L-tyrosine.
(III) verification of PEI/[ P ] obtained in the first experiment of the application2Mo16V2/BMIMBr-CNTs]8Sensing performance of ITO electrode modified by composite film
Preparing an electrochemical sensor: PEI/[ P ] obtained by the test one of the present application2Mo16V2/BMIMBr-CNTs]8The modified ITO electrode is used as a working electrode, the Ag/AgCl electrode is used as a reference electrode, the platinum wire electrode is used as a counter electrode, and a three-electrode system is formed, namely the electrochemical sensor.
The detection range and the detection limit of the electrochemical sensor are researched by adopting an electrochemical method for measuring current-time change, and the specific operation method comprises the following steps: 0.78V is set as a test potential, 40mL of 0.1M PBS (pH = 6.8) phosphoric acid solution is used as a buffer system, L-tyrosine is dripped into the system once every 30s, a current increase signal is recorded after a substance to be tested is added every time, a response signal is stable within 2s, an ampere response diagram of a stable step is obtained after 1200s continuous test, the accumulated concentration of the substance to be tested in the system is marked out, and a graph 3 is obtained, and the response signal is stable within 2 s. When L-tyrosine is added, the current is stepped, and the amplitude of the step is increased along with the increase of the concentration of the added L-tyrosine. By plotting the response current against the concentration of L-tyrosine added, a line of the steady-state current of the electrochemical sensor and the concentration of L-tyrosine in the system as shown in FIG. 4 was obtainedThe figure shows that the relation is 1.80 × 10-7~ 1.24 × 10-4Response current in M rangeIAnd L-tyrosine concentrationCHas good linear relation, linear regression equationI(μA) = 3.67+1.28C(μM)，R 2= 0.998. by this linear relationship, when the signal-to-noise ratio is 3, the detection limit is 1.0 × 10-7M。
(IV) verifying the PEI/[ P ] obtained in the first test of the application2Mo16V2/BMIMBr-CNTs]8Stability of ITO electrode modified by composite film
Preparing an electrochemical sensor: PEI/[ P ] obtained by the test one of the present application2Mo16V2/BMIMBr-CNTs]8The modified ITO electrode is used as a working electrode, the Ag/AgCl electrode is used as a reference electrode, the platinum wire electrode is used as a counter electrode, and a three-electrode system is formed, namely the electrochemical sensor.
In a buffer solution of 0.1M PBS (pH = 6.8) under a potential range of-0.6-1.0V at a concentration of 100mV · s-1Scanning speed of (2) to modify the electrode ITO/(P)2Mo16V2/BMIMBr-CNTs)8The results of the cyclic sweep of 100 cycles are shown in FIG. 5, and no significant change in both the shape of the voltammogram and the response current was observed, indicating that PEI/(P) was loaded on the electrode surface after successive cyclic voltammograms were performed2Mo16V2/BMIMBr-CNTs)8The nano composite film does not fall off from the glassy carbon electrode, and the operation stability is good.
Then, the prepared ITO/(P)2Mo16V2/BMIMBr-CNTs)8The electrode was stored dry and protected from light at ordinary temperature, and the current response of the electrode to 0.05mM of L-tyrosine was measured every five days, and the change in current response after each measurement was recorded. As shown in fig. 6, after 5, 10, 15, 20, 25 and 30 days, the sensors maintained 99.0%, 96.1%, 94.5%, 92.3%, 88% and 86.7% of their initial current responses, which demonstrates that the prepared L-tyrosine sensors had relatively long storage stability (lifetime).
In conclusion, the polyacid-based composite membrane electrode material for sensing the L-tyrosine is successfully prepared, and the electrochemical sensor for sensing the L-tyrosine, which is constructed on the basis of the working electrode, has the advantages of simple preparation method, wide linear detection range and good electrode stability.

Claims (1)

1. A polyacid-based composite membrane electrode material for sensing L-tyrosine is characterized in that the material is composed of an ITO electrode, a polyethyleneimine layer and a composite membrane of an ionic liquid/carbon nanotube doped with phosphomolybdovanadophosphoric acid; the carbon nanotube layer functionalized by the ionic liquid doped with the phosphomolybdovanadophosphoric acid is taken as a multi-layer cycle, and the cycle unit is cycled for n times to obtain the polyacid-based composite membrane electrode for sensing the L-tyrosine, wherein n is an integer of 8 and is marked as PEI/[ P ]2Mo16V2/BMIMBr-CNTs]8；
The pipe diameter of the carbon nano tube is 15-30 nm;
the preparation method of the polyacid-based composite membrane electrode material for sensing L-tyrosine comprises the following steps:
one, P2Mo16V2Preparation of the solution:
① weighing P with analytical balance2Mo16V218mg of heteropoly acid, and stirring the resulting mixture under magnetic stirring at a stirring speed of 50r/min with a Dawson-type polyoxometallate P2Mo16V2Dissolving in 6mL of deionized water, and stirring for 10min to obtain a solution A;
② transferring the solution A into a penicillin bottle B with the volume of 10mL for placement;
p in solution A in step one ①2Mo16V2The mass ratio of the heteropoly acid to the deionized water is 3: 1;
the volume ratio of the solution A to the penicillin bottle B in the step one ② is 3: 5;
secondly, preparing a BMIMBr-CNTs solution:
① CNTs 0.2g and BMIMBr 0.4g were mixed directly in a mortar and ground for 30min to give a uniform paste A;
② adding 4mL of 5wt.% PDDA solution to paste A, and grinding for 30min to obtain solution B;
③ transferring the prepared solution B into a 10mL penicillin bottle, performing ultrasonic treatment for 4 hours, and setting the ultrasonic power at 80Hz to obtain a uniformly dispersed BMIMBr-CNTs solution with positive charges;
in the second step ①, the mass ratio of the carbon nanotubes in the paste A to the BMIMBr is 1: 2;
the ratio of the mass of the paste A in the solution B in the step two ② to the volume of the PDDA is 0.6 g: 4 mL;
thirdly, the preparation method of the electrochemical electrode for sensing L-tyrosine based on the ionic liquid BMIMBr functionalized carbon nano tube doped with phosphomolybdovanadate comprises the following steps:
① soaking the ITO electrode in the aqueous solution of polyethyleneimine for 12h, taking out, washing with deionized water, and washing with N2Drying by flow;
② immersing the electrodes ① in P2Mo16V2Soaking the solution and BMIMBr-CNTs solution for 15min, taking out, washing with deionized water, and adding N2Drying by flow;
③ repeating ② operations n times to obtain the electrochemical electrode compounded by the carbon nano tube functionalized by the ionic liquid doped with the phosphomolybdovanadophosphoric acid, which is marked as PEI/[ P ]2Mo16V2/BMIMBr-CNTs]nA modified ITO electrode;
the concentration of the polyethyleneimine aqueous solution in the step three ① is 10 mM;
p in step three ②2Mo16V2The concentration of the solution is 3mg/mL, and the concentration of the BMIMBr-CNTs solution is 0.1 g/mL;
the number n of the modified layers in the step three ③ is 8.
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CN106770552B (en) * 2016-12-16 2019-04-26 哈尔滨理工大学 A kind of heteropoly acid containing vanadium/carbon nanotube dopamine electrochemical sensing electrode based on bimetal nano particles doping
CN107607602B (en) * 2017-09-07 2019-12-24 哈尔滨理工大学 Electrochemical working electrode for sensing tyrosine

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