CN111307891A - Electrode system for electrochemical detection and application thereof - Google Patents

Electrode system for electrochemical detection and application thereof Download PDF

Info

Publication number
CN111307891A
CN111307891A CN202010152963.9A CN202010152963A CN111307891A CN 111307891 A CN111307891 A CN 111307891A CN 202010152963 A CN202010152963 A CN 202010152963A CN 111307891 A CN111307891 A CN 111307891A
Authority
CN
China
Prior art keywords
chitosan
electrode
porous carbon
carbon foam
glutamic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010152963.9A
Other languages
Chinese (zh)
Other versions
CN111307891B (en
Inventor
王梅
马一飞
秦洁玲
黎子健
陈旭远
肖连团
贾锁堂
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanxi University
Original Assignee
Shanxi University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanxi University filed Critical Shanxi University
Priority to CN202010152963.9A priority Critical patent/CN111307891B/en
Publication of CN111307891A publication Critical patent/CN111307891A/en
Application granted granted Critical
Publication of CN111307891B publication Critical patent/CN111307891B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • 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
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
  • Investigating Or Analysing Biological Materials (AREA)

Abstract

The invention provides a preparation method of a chitosan-derived porous carbon foam electrode, which comprises the following steps: 1) uniformly mixing chitosan powder with an acetic acid aqueous solution to obtain a chitosan acetic acid solution, and freezing and drying the chitosan acetic acid solution at a low temperature to obtain chitosan foam; 2) calcining the chitosan foam in an inert atmosphere to obtain chitosan-derived porous carbon foam; 3) and slicing the chitosan-derived porous carbon foam to obtain a chitosan-derived porous carbon foam sheet, and fixing the chitosan-derived porous carbon foam sheet on a metal current collector through a conductive medium to obtain the chitosan-derived porous carbon foam electrode. The invention also provides application of the compound in detecting glutamic acid. The invention has the advantages of low cost, high sensitivity, wide detection range, low detection lower limit, good anti-interference performance, good stability and the like.

Description

Electrode system for electrochemical detection and application thereof
Technical Field
The invention belongs to the technical field of biological detection, particularly relates to a chitosan-derived porous carbon foam electrode system, and particularly relates to a glutamic acid detection method which is simple to manufacture, non-enzymatic, wide in detection concentration range, high in sensitivity and strong in anti-interference capacity.
Background
Glutamic acid is a very important substance in the human body. Plays an important role in nerve transmission in vertebrates. Numerous studies have shown that changes in the concentration of glutamate in humans can be associated with a number of neurological disorders, such as stroke, autism, certain forms of intellectual impairment, huntington's disease, etc. In addition, glutamic acid is widely used as a food additive, but if it is excessively ingested, adverse reactions of the head and the stomach and intestine are caused. Therefore, the detection of the glutamic acid plays an important role in the fields of biomedicine, food safety and the like.
Among many glutamic acid detection methods, electrochemical detection has higher accuracy and sensitivity, but the current glutamic acid electrochemical detection method has the following problems: 1) the enzyme-based electrochemical sensor has the problems of complex preparation process, high cost, low sensitivity, poor enzyme stability and the like, so that the detection range of the sensor is narrow and the use conditions are limited; 2) non-enzyme electrodes such as Pt/Ni nanowire arrays can only achieve 102μA/mM·cm2Sensitivity and 10-6The linear detection range in the mol/L range is far from the actual detection requirement, and the manufacturing cost of the non-enzyme electrode in the prior art is high.
Disclosure of Invention
The invention aims to solve the technical problem of providing a chitosan-derived porous carbon foam electrode system and application thereof in glutamic acid concentration detection aiming at the defects in the prior art, wherein the electrode system has the advantages of wide test range, high sensitivity and low production cost when being applied to glutamic acid detection.
In a first aspect, the invention provides an electrode system for electrochemical detection, which is characterized by comprising a working electrode, a counter electrode and a reference electrode, wherein the working electrode is composed of a chitosan-derived porous carbon foam electrode;
the chitosan-derived porous carbon foam electrode is composed of a chitosan-derived porous carbon foam slice and a gold sheet current collector; the reference electrode is a silver/silver chloride electrode, and the counter electrode is an electrode formed by a platinum wire or a platinum sheet.
In one embodiment according to the invention, the chitosan-derivatized porous carbon foam electrode is prepared by a method comprising the steps of:
1) uniformly mixing chitosan powder with an acetic acid aqueous solution to obtain a chitosan acetic acid solution, and freezing and drying the chitosan acetic acid solution at a low temperature to obtain chitosan foam;
2) calcining the chitosan foam in an inert atmosphere to obtain chitosan-derived porous carbon foam;
3) and slicing the chitosan-derived porous carbon foam to obtain a chitosan-derived porous carbon foam sheet, and fixing the chitosan-derived porous carbon foam sheet on a metal current collector through a conductive medium to obtain the chitosan-derived porous carbon foam electrode.
In one embodiment of the invention, the concentration of the acetic acid aqueous solution in the step 1) is 0.05 to 1.0mol/L, preferably 0.3 to 0.5 mol/L; the concentration of chitosan in the chitosan acetic acid solution is 5-45 mg/mL, preferably 10-20 mg/mL.
In one embodiment according to the invention, the chitosan acetic acid solution in step 1) is frozen at-5 to-30 ℃ for 5 to 48 hours and then freeze-dried at-40 to-80 ℃.
In one embodiment according to the present invention, the inert atmosphere in step 2) is composed of one or more of vacuum, helium, neon, argon, krypton, xenon, radon, and nitrogen;
the calcination condition is that calcination is carried out at a temperature rise speed of 5-10 ℃/min to 800-.
In one embodiment according to the invention, the chitosan-derived porous carbon foam sheet has a thickness of 0.5 to 10mm, preferably 1 mm.
The invention further provides a method for detecting glutamic acid by using the electrode, which comprises the following steps:
a) constructing the electrode system;
b) and (3) drawing a glutamic acid concentration-current response standard curve:
adding water-soluble cationic metal salt powder into Phosphate Buffered Saline (PBS) with the pH value of 7.4 to obtain reaction detection electrolyte; detecting electrolyte through reactions with different glutamic acid concentrations, observing electrochemical behaviors of metal cation-glutamic acid complexes on a porous carbon foam electrode by adopting a Cyclic Voltammetry (CV), testing the glutamic acid with different concentrations by adopting a Chronoamperometry (CA), and drawing a glutamic acid concentration-current response curve;
drawing a standard curve by taking logC as an x axis and I as a y axis to obtain a linear relation formula I which is alogC + b; c is glutamic acid concentration, I is current value, a is linear slope, and b is intercept;
the water-soluble cationic metal salt is selected from one or more of water-soluble Fe, Cu, Co, Zn, Mn and Ti metal inorganic salts;
c) and (3) detecting the concentration of glutamic acid:
adding water-soluble cationic metal salt powder into a solution to be tested, performing a CA test by using the water-soluble cationic metal salt powder as an electrolyte to obtain a current value, and calculating according to a linear relation formula I-alogC + b to obtain the concentration C of the glutamic acid.
In one embodiment according to the invention, the reaction in step b) detects a concentration of metal salt ions in the electrolyte of 0.01 to 100 mmol/L.
The technical scheme of the invention has the following beneficial effects:
1) the non-enzymatic glutamic acid detection method based on cation complexation has the advantages of simplicity, easiness in implementation, low cost, high sensitivity, wide detection range, low detection lower limit, good anti-interference performance, good stability and the like.
2) The chitosan derived carbon foam electrode used by the invention has large electroactive surface area and rapid electron transmission, and the inherent nitrogen doping property of the chitosan derived carbon foam electrode can improve the hydrophilicity of the carbon foam electrode and the affinity of the electrode and a glutamic acid complex, so that the non-enzymatic glutamic acid detection method based on cation complexation can obtain high electrochemical sensitivity and wide application rangeAnd (4) detecting the range. At present, the glutamic acid detection method has the highest sensitivity and the widest detection concentration range. By taking chitosan derived carbon foam as an electrode and divalent copper ions as complex cations as an example, the sensitivity of the glutamic acid sensor can reach 1.9 multiplied by 104μA/mM·cm2The detection concentration range can reach 10-9mol/L-10-3Ultra-wide detection range of mol/L.
3) In the implementation process of the invention, 3, 4-dihydroxyphenylacetic acid, ascorbic acid, uric acid, glucose and dopamine hydrochloride are also adopted as interference reagents by the applicant, and the non-enzymatic glutamic acid detection method based on cation complexation provided by the invention is proved to have good anti-interference capability and selectivity.
Drawings
FIG. 1 is an SEM image and photograph of a chitosan foam prepared from a 10mg/mL chitosan acetic acid solution.
FIG. 2 is an SEM image and photograph of a chitosan-derived carbon foam prepared from a 10mg/mL chitosan acetic acid solution.
FIG. 3 is a cyclic voltammogram of a PBS solution containing 100. mu. mol/L glutamic acid, 4mmol/L copper chloride at different scan rates (curves a-m correspond to scan rates of 20, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600mV/s, respectively).
FIG. 4 is a cyclic voltammogram of various concentrations of glutamic acid in 4mmol/L copper chloride in PBS (curves a-j correspond to glutamic acid concentrations of 0, 0.001, 0.01, 0.05, 0.1, 1, 10, 100, 1000, 1500, 2000. mu. mol/L, respectively).
FIG. 5 is a graph showing the current response of various concentrations of glutamic acid (0.001, 0.01, 1, 5, 50, 200, 1000. mu. mol/L) in 4mmol/L copper chloride in PBS by Chronoamperometry (CA).
FIG. 6 is a glutamic acid concentration-current response curve under 4mmol/L copper chloride.
FIG. 7 shows that 200. mu. mol/L glutamic acid and 50. mu. mol/L3, 4-dihydroxyphenylacetic acid, ascorbic acid, uric acid, glucose and dopamine hydrochloride are sequentially added into 4mmol/CuCl2 of PBS solution to test the anti-interference performance of glutamic acid detection, and the detection result is analyzed by chronoamperometry.
Detailed Description
The following examples are merely illustrative of the present application and are not intended to limit the scope of the present application.
Specific embodiments of the present application will be described in more detail below. These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. The description which follows is a preferred embodiment of the present application, but is made for the purpose of illustrating the general principles of the application and not for the purpose of limiting the scope of the application. The protection scope of the present application shall be subject to the definitions of the appended claims.
Instruments and materials used in the examples:
l-glutamic acid monosodium salt monohydrate (glutamic acid, purity not less than 98%), copper chloride (CuCl)2Purity 97%), Ascorbic Acid (AA), Uric Acid (UA), dopamine hydrochloride (DA), glucose, 3, 4-dihydroxybenzoic acid (DOPAC), chitosan (medium molecular weight), acetic acid, CuCl2，FeCl3。
Unless otherwise specified, the reagents used in the present invention are commercially available.
The electrochemical measurement uses a traditional three-electrode system, and a chitosan-derived carbon foam electrode is used as a working electrode, a platinum sheet electrode is used as a counter electrode, and an Ag/AgCl (saturated KCl solution) electrode is used as a reference electrode. Wherein, the chitosan derivative carbon foam electrode can be prepared according to the method provided by the invention.
The electrolyte is PBS solution containing cation metal salt powder with certain concentration.
Example 1
1) Chitosan powder was added to an acetic acid aqueous solution having a concentration of 0.3mol/L to prepare a chitosan acetic acid solution having a concentration of 10 mg/mL. Pouring the solution into a cylindrical glass beaker, freezing at constant temperature of-20 deg.C for 24 hr, and drying at-80 deg.C in a freeze dryer to obtain cylindrical chitosan foam, wherein SEM image of chitosan foam prepared from chitosan acetic acid solution is shown in FIG. 1. Placing the chitosan foam in a tube furnace, calcining to 900 ℃ at the heating rate of 5 ℃/min under the argon environment, and then maintaining for 2 h. SEM images of chitosan-derivatized carbon foams prepared from the chitosan acetic acid solution are shown in fig. 2.
2) The chitosan-derived porous carbon foam is cut into circular sheets with the diameter of 1mm, the circular sheets are fixed on a gold sheet current collector by using a conductive carbon adhesive tape to serve as working electrodes, silver/silver chloride electrodes serve as reference electrodes, and platinum sheet electrodes serve as counter electrodes to form a three-electrode system.
3) 1.4mmol/L KH is prepared2PO4、4.3mmol/L Na2HPO4A mixed aqueous solution of 137mmol/L NaCl and 2.7mmol/L KCl, then adjusted to pH7.4 with HCl to give a PBS salt solution. Adding CuCl into PBS buffer solution2Powdering to give CuCl2PBS solution with the concentration of 4mmol/L is used as detection electrolyte.
4) And (3) observing the electrochemical behavior of the copper-glutamic acid complex on the chitosan-derived porous carbon foam electrode by adopting a Cyclic Voltammetry (CV) method and an alternating current impedance spectroscopy (EIS) method, testing the glutamic acid with different concentrations by adopting a Chronoamperometry (CA) method, and drawing a glutamic acid concentration-current response curve. And drawing a standard curve by taking logC (C is glutamic acid concentration) as an x axis and I (current value) as a y axis to obtain a linear relation formula I which is alogC + b. a is the slope of the straight line and b is the intercept.
5) And testing the anti-interference performance of the glutamic acid detection method by adopting a timing amperometry method. The electrolyte is CuCl2(4mmol/L) PBS solution, performing amperometric detection in the electrolyte, sequentially adding 200 mu mol/L glutamic acid and 50 mu mol/L3, 4-dihydroxyphenylacetic acid, ascorbic acid, uric acid, glucose and dopamine hydrochloride as interference reagents, and detecting the change of current signals. If no interference exists, the current has no obvious change.
6) And detecting the glutamic acid in the sample solution to be detected by adopting a standard addition method. Adding CuCl into the solution to be detected2The powder is prepared into 4mmol/L, and the solution is used as electrolyte to carry out CA test to obtainThe current value is calculated according to the formula of linear relationship I ═ alogC + b, and logC ═ I-b)/a to obtain the glutamic acid concentration C.
FIG. 3 shows cyclic voltammograms at different scan rates for PBS solutions containing 100. mu. mol/L glutamic acid, 4mmol/L copper chloride (curves a-m correspond to scan rates of 20, 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600mV/s, respectively). As the scan rate increases, the peak current increases accordingly. The scan rate is linear with peak current, indicating that the electrochemical redox process is a kinetic control process.
The invention also detects the cyclic voltammograms of glutamic acid with different concentrations in 4mmol/L copper chloride PBS solution, and as shown in FIG. 4, curves a-j respectively correspond to glutamic acid concentrations of 0, 0.001, 0.01, 0.05, 0.1, 1, 10, 100, 1000, 1500 and 2000. mu. mol/L. As shown in the figure, the peak current increases as the glutamic acid concentration increases.
The current responses of glutamic acid (0.001, 0.01, 1, 5, 50, 200, 1000. mu. mol/L) at different concentrations under Chronoamperometry (CA) were simultaneously detected in 4mmol/L copper chloride PBS solution, and the results are shown in FIG. 5. As shown in the figure, the corresponding value of the current is rapidly increased along with the increase of the concentration of the glutamic acid, and the curve is in a 'step shape'.
The glutamic acid concentration-current response curve under the condition of 4mmol/L copper chloride is shown in FIG. 6.
At 4mmol/CuCl 2200 mu mol/L glutamic acid and 50 mu mol/L3, 4-dihydroxyphenylacetic acid, ascorbic acid, uric acid, glucose and dopamine hydrochloride are sequentially added into the PBS solution to test the anti-interference performance of the glutamic acid detection, and the timing amperometric analysis detection result is shown in figure 7.
Example 2
1) Chitosan powder was added to an acetic acid aqueous solution having a concentration of 0.3mol/L to prepare a chitosan acetic acid solution having a concentration of 10 mg/mL. Pouring the solution into a cylindrical glass beaker, freezing for 24 hours at constant temperature of-20 ℃, and drying in a freeze dryer at-80 ℃ to obtain cylindrical chitosan foam. Placing the chitosan foam in a tube furnace, calcining to 900 ℃ at the heating rate of 5 ℃/min under the argon environment, and then maintaining for 2 h.
2) The chitosan-derived porous carbon foam is cut into circular sheets with the diameter of 1mm, the circular sheets are fixed on a gold sheet current collector by using a conductive carbon adhesive tape to serve as working electrodes, silver/silver chloride electrodes serve as reference electrodes, and platinum sheet electrodes serve as counter electrodes to form a three-electrode system.
3) 1.4mmol/L KH is prepared2PO4、4.3mmol/L Na2HPO4A mixed aqueous solution of 137mmol/L NaCl and 2.7mmol/L KCl, then adjusted to pH7.4 with HCl to give a PBS salt solution. Adding CuCl into PBS buffer solution2Powdering to give CuCl2PBS solution with the concentration of 6mmol/L is used as detection electrolyte.
4) And then, observing the electrochemical behavior of the copper-glutamic acid complex on the chitosan-derived porous carbon foam electrode by adopting a Cyclic Voltammetry (CV) method and an alternating current impedance spectroscopy (EIS) method, testing the glutamic acid with different concentrations by adopting a Chronoamperometry (CA) method, and drawing a glutamic acid concentration-current response curve. And drawing a standard curve by taking logC (C is glutamic acid concentration) as an x axis and I (current value) as a y axis to obtain a linear relation formula I which is alogC + b. a is the slope of the straight line and b is the intercept.
5) And testing the anti-interference performance of the glutamic acid detection method by adopting a timing amperometry method. The electrolyte is CuCl2(6mmol/L) PBS solution, timing amperometric detection is carried out in the electrolyte, 200 mu mol/L glutamic acid and 50 mu mol/L3, 4-dihydroxyphenylacetic acid, ascorbic acid, uric acid, glucose and dopamine hydrochloride are sequentially added to be used as interference reagents, and the change of current signals is detected. If no interference exists, the current has no obvious change.
6) And detecting the glutamic acid in the sample solution to be detected by adopting a standard addition method. Adding CuCl into the solution to be detected2The powder was prepared to 6mmol/L, and CA test was performed using this solution as an electrolyte to obtain a current value, and the glutamic acid concentration C was calculated according to the linear relationship formula I ═ alogC + b reverse-deducted, logC ═ I-b)/a.
Example 3
1) Chitosan powder was added to an acetic acid aqueous solution having a concentration of 0.5mol/L to prepare a chitosan acetic acid solution having a concentration of 10 mg/mL. Pouring the solution into a cylindrical glass beaker, freezing at constant temperature of-20 ℃ for 12 hours, and drying in a freeze dryer at-80 ℃ to obtain cylindrical chitosan foam. Placing the chitosan foam in a tube furnace, calcining to 900 ℃ at a heating rate of 10 ℃/min in an argon environment, and then maintaining for 3 h.
2) The chitosan-derived porous carbon foam is cut into circular sheets with the diameter of 1mm, the circular sheets are fixed on a gold sheet current collector by using a conductive carbon adhesive tape to serve as working electrodes, silver/silver chloride electrodes serve as reference electrodes, and platinum sheet electrodes serve as counter electrodes to form a three-electrode system.
3) 1.4mmol/L KH is prepared2PO4、4.3mmol/L Na2HPO4A mixed aqueous solution of 137mmol/L NaCl and 2.7mmol/L KCl, then adjusted to pH7.4 with HCl to give a PBS salt solution. Adding FeCl into PBS buffer solution3Powdering to obtain FeCl3PBS solution with the concentration of 3mmol/L is used as detection electrolyte.
4) And then observing the electrochemical behavior of the iron-glutamic acid complex on the chitosan-derived porous carbon foam electrode by adopting a Cyclic Voltammetry (CV) method and an alternating current impedance spectroscopy (EIS) method, testing the glutamic acid with different concentrations by adopting a Chronoamperometry (CA) method, and drawing a glutamic acid concentration-current response curve. And drawing a standard curve by taking logC (C is glutamic acid concentration) as an x axis and I (current value) as a y axis to obtain a linear relation formula I which is alogC + b. a is the slope of the straight line and b is the intercept.
5) And testing the anti-interference performance of the glutamic acid detection method by adopting a timing amperometry method. The electrolyte is FeCl3(3mmol/L) PBS solution, performing amperometric detection in the electrolyte, sequentially adding 200 mu mol/L glutamic acid and 50 mu mol/L3, 4-dihydroxyphenylacetic acid, ascorbic acid, uric acid, glucose and dopamine hydrochloride as interference reagents, and detecting the change of current signals. If no interference exists, the current has no obvious change.
6) And detecting the glutamic acid in the sample solution to be detected by adopting a standard addition method. Adding FeCl into the solution to be detected3The powder was prepared to 3mmol/L, and CA test was carried out using this solution as an electrolyte to obtain a current value, which was back-extrapolated according to the linear relationship of formula I ═ alogC + b, logC ═ I-bThe glutamic acid concentration C is calculated.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (9)

1. An electrode system for electrochemical detection, comprising a working electrode, a counter electrode and a reference electrode, wherein the working electrode, the counter electrode and the reference electrode are formed by chitosan-derived porous carbon foam electrodes;
the chitosan-derived porous carbon foam electrode is composed of a chitosan-derived porous carbon foam slice and a gold sheet current collector; the reference electrode is a silver/silver chloride electrode, and the counter electrode is an electrode formed by a platinum wire or a platinum sheet.
2. The electrode system of claim 1, wherein the chitosan-derivatized porous carbon foam electrode is prepared by a method comprising:
1) uniformly mixing chitosan powder with an acetic acid aqueous solution to obtain a chitosan acetic acid solution, and freezing and drying the chitosan acetic acid solution at a low temperature to obtain chitosan foam;
2) calcining the chitosan foam in an inert atmosphere to obtain chitosan-derived porous carbon foam;
3) and slicing the chitosan-derived porous carbon foam to obtain a chitosan-derived porous carbon foam sheet, and fixing the chitosan-derived porous carbon foam sheet on a metal current collector through a conductive medium to obtain the chitosan-derived porous carbon foam electrode.
3. The electrode system of claim 2, wherein the concentration of the aqueous acetic acid solution in step 1) is 0.05 to 1.0mol/L, preferably 0.3 to 0.5 mol/L; the concentration of chitosan in the chitosan acetic acid solution is 5-45 mg/mL, preferably 10-20 mg/mL.
4. The electrode system of claim 2 or 3, wherein the chitosan acetic acid solution in step 1) is frozen at-5 to-30 ℃ for 5 to 48 hours and then freeze-dried at-40 to-80 ℃.
5. The electrode system of any of claims 2-4, wherein the inert atmosphere in step 2) is comprised of one or more of vacuum, helium, neon, argon, krypton, xenon, radon, and nitrogen.
6. The electrode system as claimed in any one of claims 2 to 5, wherein the calcination condition in step 2) is to calcine at a temperature-raising speed of 5-10 ℃/min to 800-1000 ℃ and then maintain for 1-5 h.
7. The electrode system of any one of claims 2 to 6, wherein the chitosan-derived porous carbon foam sheet has a thickness of 0.5 to 10mm, preferably 1 mm.
8. A method for detecting glutamic acid, comprising:
a) constructing the electrode system of any one of claims 1-8;
b) and (3) drawing a glutamic acid concentration-current response standard curve:
adding water-soluble cationic metal salt powder into Phosphate Buffered Saline (PBS) with the pH value of 7.4 to obtain reaction detection electrolyte; detecting electrolyte through reactions with different glutamic acid concentrations, observing electrochemical behaviors of metal cation-glutamic acid complexes on a porous carbon foam electrode by adopting a Cyclic Voltammetry (CV), testing the glutamic acid with different concentrations by adopting a Chronoamperometry (CA), and drawing a glutamic acid concentration-current response curve;
drawing a standard curve by taking logC as an x axis and I as a y axis to obtain a linear relation formula I which is alogC + b; c is glutamic acid concentration, I is current value, a is linear slope, and b is intercept;
the water-soluble cationic metal salt is selected from one or more of water-soluble Fe, Cu, Co, Zn, Mn and Ti metal inorganic salts;
c) and (3) detecting the concentration of glutamic acid:
adding water-soluble cationic metal salt powder into a solution to be tested, performing a CA test by using the water-soluble cationic metal salt powder as an electrolyte to obtain a current value, and calculating according to a linear relation formula I-alogC + b to obtain the concentration C of the glutamic acid.
9. The method of claim 8, wherein the reaction in step b) detects a concentration of metal salt ions in the electrolyte of 0.01 to 100 mmol/L.
CN202010152963.9A 2020-03-06 2020-03-06 Electrode system for electrochemical detection and application thereof Active CN111307891B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010152963.9A CN111307891B (en) 2020-03-06 2020-03-06 Electrode system for electrochemical detection and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010152963.9A CN111307891B (en) 2020-03-06 2020-03-06 Electrode system for electrochemical detection and application thereof

Publications (2)

Publication Number Publication Date
CN111307891A true CN111307891A (en) 2020-06-19
CN111307891B CN111307891B (en) 2022-03-29

Family

ID=71145579

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010152963.9A Active CN111307891B (en) 2020-03-06 2020-03-06 Electrode system for electrochemical detection and application thereof

Country Status (1)

Country Link
CN (1) CN111307891B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105013490A (en) * 2015-07-03 2015-11-04 湘潭大学 Metal nanoparticle-foamy carbon catalyst, and preparation method and application thereof
CN110220959A (en) * 2019-06-19 2019-09-10 长沙理工大学 A kind of Pidolidone detection method and sensor based on polymerization film modified electrode

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105013490A (en) * 2015-07-03 2015-11-04 湘潭大学 Metal nanoparticle-foamy carbon catalyst, and preparation method and application thereof
CN110220959A (en) * 2019-06-19 2019-09-10 长沙理工大学 A kind of Pidolidone detection method and sensor based on polymerization film modified electrode

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
RAJESH MADHU ET AL: "Heteroatom-enriched and renewable banana-stem-derived porous carbon for the electrochemical determination of nitrite in various water samples", 《SCIENTIFIC REPORTS》 *
YANBO HOU ET AL: "Three-dimensional graphene oxide foams loaded with AuPd alloy: a sensitive electrochemical sensor for dopamine", 《MICROCHIMICA ACTA》 *
ZHENG LING ET AL: "Freeze-drying for sustainable synthesis of nitrogen doped porous carbon cryogel with enhanced supercapacitor and lithium ion storage performance", 《NANOTECHNOLOGY》 *

Also Published As

Publication number Publication date
CN111307891B (en) 2022-03-29

Similar Documents

Publication Publication Date Title
Baikeli et al. Electrochemical determination of chloramphenicol and metronidazole by using a glassy carbon electrode modified with iron, nitrogen co-doped nanoporous carbon derived from a metal-organic framework (type Fe/ZIF-8)
Gao et al. Rod-like hydroxyapatite and Nafion nanocomposite as an electrochemical matrix for simultaneous and sensitive detection of Hg2+, Cu2+, Pb2+ and Cd2+
Wang et al. Magnetic Fe 3 O 4@ MOFs decorated graphene nanocomposites as novel electrochemical sensor for ultrasensitive detection of dopamine
Devi et al. Construction and application of an amperometric uric acid biosensor based on covalent immobilization of uricase on iron oxide nanoparticles/chitosan-g-polyaniline composite film electrodeposited on Pt electrode
Ensafi et al. Characterization of MgFe2O4 nanoparticles as a novel electrochemical sensor: application for the voltammetric determination of ciprofloxacin
Deng et al. Electrochemical detection of l-cysteine using a boron-doped carbon nanotube-modified electrode
Garbellini et al. Voltammetric determination of ciprofloxacin in urine samples and its interaction with dsDNA on a cathodically pretreated boron-doped diamond electrode
KR102423250B1 (en) Enzyme-based glucose sensor using potentiometric detection and method for preparing the same
Zen et al. Amino acid analysis using disposable copper nanoparticle plated electrodes
Sen et al. A novel third-generation xanthine biosensor with enzyme modified glassy carbon electrode using electrodeposited MWCNT and nanogold polymer composite film
Wang et al. A novel biosensor for reduced l-glutathione based on cobalt phthalocyaninetetrasulfonate-intercalated layered double hydroxide modified glassy carbon electrodes
Zhu et al. Ordered mesoporous carbon paste electrodes for electrochemical sensing and biosensing
CN109270140B (en) Preparation method and application of electrochemical sensor made of high-dispersion graphene/Zn-based metal organic framework composite material
CN109364995B (en) Preparation method and application of high-dispersion graphene/Fe-based metal organic framework composite material electrochemical sensor
Liu et al. An electrochemical sensor based on an anti-fouling membrane for the determination of histamine in fish samples
Şenocak et al. Crosslinker polycarbazole supported magnetite MOF@ CNT hybrid material for synergetic and selective voltammetric determination of adenine and guanine
Guo et al. A novel label-free hypochlorite amperometric sensor based on target-induced oxidation of benzeneboronic acid pinacol ester
Niu et al. A direct electron transfer biosensor based on a horseradish peroxidase and gold nanotriangle modified electrode and electrocatalysis
Sun et al. A novel sensing platform based on a core–shell Fe@ Fe 3 C–C nanocomposite for ultrasensitive determination of vanillin
Zhu et al. Differential pulse stripping voltammetric determination of metronidazole with graphene-sodium dodecyl sulfate modified carbon paste electrode
Pari et al. Electrochemical Investigation of Uric Acid using MWCNTs-Decorated Novel Substituted Cobalt (II) Phthalocyanine Modified GCE
CN109916976B (en) Preparation method and application of zinc germanate nanorod-modified functionalized graphene composite material
Torrinha et al. Microfluidic platform with an embedded pencil graphite electrode biosensor for the detection of glucose and cadmium
CN111307891B (en) Electrode system for electrochemical detection and application thereof
CN109828010B (en) Preparation method and detection method of electrochemical sensor for detecting chloride ions

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant