CN109142474B - Carbon nano material modified electrode capable of detecting Cu + and pH simultaneously and preparation method thereof - Google Patents
Carbon nano material modified electrode capable of detecting Cu + and pH simultaneously and preparation method thereof Download PDFInfo
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- CN109142474B CN109142474B CN201710502964.XA CN201710502964A CN109142474B CN 109142474 B CN109142474 B CN 109142474B CN 201710502964 A CN201710502964 A CN 201710502964A CN 109142474 B CN109142474 B CN 109142474B
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- 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
- G01N27/302—Electrodes, e.g. test electrodes; Half-cells pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes
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- C—CHEMISTRY; METALLURGY
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- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- 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
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- 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The invention discloses a carbon nano material modified electrode and a preparation method thereof, which uses carbon nano material and Cu+Recognition ligand, reference molecule and pH response molecule as raw materials, and preparing carbon nano material and Cu in solvent at 10-25 deg.C+And modifying the recognition ligand, the reference molecule and the pH response molecule on the carbon nano material to prepare the carbon nano material modified electrode. The invention also discloses the carbon nano material modified electrode for simultaneously detecting Cu in vivo and in vitro+And application in pH. The invention also discloses the simultaneous detection of Cu by the carbon nano material modified electrode+And the application in pH, the carbon nano-material modified electrode has the advantages of high selectivity and high sensitivity; for measuring metal ions (Cu) in vivo+) And pH, and can realize the simultaneous, in-situ and real-time online electrochemical detection. The carbon nano material modified electrode of the invention is used for further clarifying Cu+And the role of pH in physiology and pathology are of great significance.
Description
Technical Field
The invention belongs to the technical field of analysis, and relates to a novel carbon nano material modified electrode capable of simultaneously detecting cuprous ions and pH in vivo and/or in vitro.
Background
Copper metal ion (Cu)+And Cu2+) Are indispensable trace elements for human health, and play an important role in controlling biological metabolism, growth and the development process of an immune system. If the content of copper ions in the organism is too high, toxic effects can be caused to the organism system, and even neurological diseases can be caused, such as: alzheimer's disease, huntington's disease, etc., and oxidative stress process caused by excessive copper is considered as an important factor causing alzheimer's disease. The copper ion in organism has two states, oxidizing Cu2+And reducing Cu+. Most in vivo antioxidants such as ascorbic acid and glutathione can reduce Cu2+To Cu+. And a trace amount of Cu+Can initiate the reduction of molecular oxygen to superoxide anion and hydrogen peroxide. Therefore, abnormal Cu+The concentration may mean the excess production of active oxygen. At the same time, excessive reactive oxygen species can cause a decrease in pH, while slight fluctuations in pH can cause abnormalities in biochemical, ionic conduction, and neuroelectrical signaling behavior. More importantly, acidification of the brain environment exacerbates the occurrence of oxidative stress. Therefore, simultaneous detection of Cu was developed+Novel methods of and pH for the understanding of Cu in essence+And the role of pH in brain disease are of great importance.
The traditional metal ion analysis and detection methods mainly comprise Atomic Absorption Spectrometry (AAS), inductively coupled plasma mass spectrometry (ICP-MS), Ion Chromatography (IC), fluorescence analysis and the like. However, these methods are expensive and complex in operation, and cannot be used for on-site real-time and rapid detection. Therefore, a simple, rapid, highly selective method for realizing Cu in vivo has been sought+The method has important research significance and application value. The electrochemical method has the advantages of in-situ, real-time and rapid detection due to high sensitivity and high selectivity, and is concerned.
And Cu2+Except that Cu+The electrochemical analysis of (2) is more difficult, on one hand, due to unstable properties of the electrochemical probe itself, and on the other hand, because no effective electrochemical probe can perform selective recognition on the electrochemical probe. In addition to that, Cu+And simultaneous detection of pHIt is required that the electrochemical behaviors of both do not interfere with each other. In the prior art, no effective electrochemical method is available so far, and the simultaneous and accurate Cu-Cu treatment can be realized+And pH.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention adopts thioether compounds as basic structural units of organic ligands to synthesize a series of Cu-Cu complexes+Recognition ligand with high selectivity, the Cu+The recognition ligand, the reference molecule and the pH response molecule can be effectively combined on the carbon nano material with excellent performance to prepare the high-selectivity and high-sensitivity carbon nano material which can be used for simultaneously detecting Cu+And a pH ratio-type carbon nanomaterial-modified electrode. The invention combines the carbon fiber microelectrode technology and can simultaneously realize Cu in a biological living body+And electrochemical analysis of pH.
The invention provides a preparation method of a carbon nano material modified electrode, which comprises the following steps: in a solvent, under the condition of 10-25 ℃, mixing a carbon nano material and Cu+Mixing recognition ligand, reference molecule and pH response molecule in a certain proportion, and adding Cu+And modifying the recognition ligand, the reference molecule and the pH response molecule on the carbon nano material to prepare the carbon nano material modified electrode.
In the invention, the carbon nano material is selected from one or more of graphene, single-walled carbon nanotubes and multi-walled carbon nanotubes, and the diameter of the carbon fiber is less than 10 μm.
In the present invention, the Cu+The recognition ligand is shown as a formula (I), and the Cu+The recognition ligand may be selected from one or more of the formulae (I):
wherein R may be selected from the following groups:
in the present invention, the reference molecule is selected from 2, 2-diaza-bis (3-ethyl-benzothiazole-6-sulphonic acid) diammonium salt (ABTS), ferrocene; preferably, ABTS.
In the invention, the pH response molecule is selected from 1, 2-naphthoquinone, 1, 3-naphthoquinone, 1, 4-naphthoquinone, 1, 2-anthraquinone, 1, 2-phenanthrenequinone, 1, 3-phenanthrenequinone, 2, 4-phenanthrenequinone, naphtho blue, naphtho red or azure blue and the like; preferably 1, 2-naphthoquinone, 1, 4-naphthoquinone, 1, 2-anthraquinone.
In the present invention, the Cu+The mole ratio of the recognition ligand, the reference molecule and the pH response molecule is 1:1-10: 1-50; preferably 1:10: 2.
In the invention, the solvent is selected from water, dichloromethane, methanol, ethyl acetate, N-dimethylformamide and dimethyl sulfoxide; preferably, it is methanol.
In the present invention, preferably, the temperature of the modification is room temperature.
In the invention, the modification time is 12-24 hours; preferably, the time is 24 hours.
In the invention, preferably, before modification, the carbon nanomaterial needs to be activated, and the carbon nanomaterial is sequentially soaked in acetone, 3M nitric acid, 10M potassium hydroxide and ultrapure water for 3 minutes respectively by ultrasonic treatment to be cleaned and activated. The mixture was heated to 600 ℃ in a tube furnace under nitrogen protection for 5 hours and then cooled to room temperature for about 2 hours before use.
The invention also provides the in vitro Cu determination of the carbon nano material modified electrode+pH or simultaneous determination of Cu+And application in pH.
The invention also provides a method for measuring Cu in a biological living body by using the carbon nano material modified electrode+pH or simultaneous determination of Cu+And pH, wherein the organism comprises a mouse, a rat, or the like.
The invention also provides Cu+The preparation method of the recognition ligand adopts the thioether compound as the basic structural unit of the organic ligand to synthesize a series of Cu-Cu complexes+A recognition ligand with high selectivity comprising the steps of: in an organic solvent, adding R-COOH, thioether, carbodiimide and N-hydroxysuccinimideAmidation of the ester to give the Cu+The ligand is identified.
Wherein the temperature of the amidation reaction is 20-50 ℃; preferably, it is 20-40 ℃.
Wherein the amidation reaction time is 12 to 36 hours; preferably, it is 36 hours.
Wherein the organic solvent is selected from ethanol, methanol, N-dimethylformamide, dimethyl sulfoxide and dichloromethane; preferably, it is ethanol.
Wherein the molar ratio of R-COOH, thioether, carbodiimide and N-hydroxysuccinimide ester is 1-2: 1-2: 1.5-3.0: 1.5-3.0; preferably, 1: 1: 1.5: 1.5.
in one embodiment of the present invention, Cu is implemented+A process for the preparation of the recognition ligand comprising the steps of stirring R-COOH (10-15mmol) and thioether (10-15mmol) in ethanol under nitrogen protection at 30-50 ℃ for 36 hours under carbodiimide (10-15mmol) and N-hydroxysuccinimide ester (10-15mmol), cooling the reaction solution to room temperature, extraction with 100m L ethyl acetate, column separation on an organic phase, (petroleum ether: ethyl acetate 1: 5-1:10) to give the amidated product as a colorless oil (50-80% yield).
The invention also provides the carbon nano material modified electrode prepared by the method, the carbon nano material is heated to 600 ℃ in a tube furnace under the protection of nitrogen before use and is maintained for 5 hours, and then the temperature is reduced to room temperature for about 2 hours before use.
The invention has the beneficial effects that the invention uses carbon nano material and Cu+Preparing a new carbon nano material modified electrode by identifying ligand, reference molecule and pH response molecule, and preparing each probe molecule (Cu)+Recognition ligand, reference molecule, pH responsive molecule) can be effectively bound to the carbon nanomaterial. The carbon nano material modified electrode can detect Cu simultaneously+And pH, electrochemical signals are clearly distinguishable from Cu+And a reference molecule of a pH response signal, the preparation method has the advantages of simplicity, low cost, greenness and reliability, and the prepared carbon nano material modified electrode has the advantages of high selectivity and high sensitivity. Book (I)The carbon nano material modified electrode is used for measuring metal ions (Cu) in a living organism+) And when the pH value is regulated, the on-line electrochemical detection can be realized simultaneously, in situ and in real time. The invention further clarifies Cu by preparing the carbon nano material modified electrode with high selectivity and high sensitivity+And the role of pH in physiology and pathology are of great significance; the method improves the reliability for analyzing the action of metal ions in the physiological and pathological activities and provides an efficient and feasible analysis method for analyzing the pathogenic mechanism of related diseases.
Drawings
Fig. 1 is a linear sweep voltammogram of an electrode modified by carbon nanomaterial distribution prepared in example 1 of the present invention in artificial cerebrospinal fluid: a is bare carbon nano material, b is electrode modified by pH response molecule 1.2-anthraquinone molecule, c is electrode modified by reference molecule ABTS, d is pH response molecule 1, 2-anthraquinone and Cu+An electrode co-modified with recognition ligand NS4 and reference molecule ABTS.
FIG. 2 is a linear sweep voltammogram of the carbon nanomaterial-modified electrode prepared in example 1 of the present invention in artificial cerebrospinal fluid, a is in a solution containing 5 μ M Cu+And linear sweep voltammograms in artificial cerebrospinal fluid, b is the linear sweep voltammogram following addition of 20 μ M EDTA.
FIG. 3 shows the carbon nanomaterial modified electrode prepared in example 1 of the present invention with different Cu+Linear scan curve in concentration.
Fig. 4 is a linear scanning curve of the carbon nanomaterial-modified electrode prepared in example 1 of the present invention in artificial cerebrospinal fluid of different pH.
Fig. 5 is a linear scanning curve of the carbon nanomaterial-modified electrode prepared in example 1 of the present invention in the live mouse brain.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and the accompanying drawings. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1
Performing linear voltammetric scanning on the carbon nanomaterial modified electrode prepared in example 1 by using a CHI660 electrochemical workstation at a scanning speed of: 0.05V/s, as shown in FIG. 1; wherein, a is a linear scanning oxidation curve of a bare carbon nano material (bare carbon fiber electrode) in artificial cerebrospinal fluid, b is a linear scanning oxidation curve of an electrode modified by a pH response molecule 1.2-anthraquinone molecule in artificial cerebrospinal fluid, c is a linear scanning oxidation curve of an electrode modified by a reference molecule ABTS in artificial cerebrospinal fluid, and d is a pH response molecule 1, 2-anthraquinone, Cu+Recognition of the ligand (in formula I, R is
) C and reference molecule ABTS co-modified electrode linear scan oxidation curve in artificial cerebrospinal fluid. Wherein the bare carbon nanomaterial has only charging background current (fig. 1 a). The linear scanning oxidation curve (figure 1b) of the electrode modified by the pH response molecule 1.2-anthraquinone molecule can see that the electrode has an obvious oxidation peak near-0.45V, which indicates that the 1.2-anthraquinone molecule has good electrochemical activity. An oxidation peak around 0.55V can be seen on the linear scan oxidation graph (fig. 1c) of the ABTS modified electrode, indicating that the reference ABTS molecule is electrochemically active. Two oxidation peaks at-0.45V and 0.55V can be seen on a linear scanning oxidation curve (figure 1d) of the 1, 2-anthraquinone, NS4 and ABTS three-molecule co-modified electrode, which shows that the 1, 2-anthraquinone molecule and ABTS can be simultaneously modified on the carbon nano material and have good electrochemical activity. As can be seen from FIG. 1, the electrochemical signals of the pH responsive molecule and the reference molecule are well separated, and signal interference between the two can be avoided.
Example 2
Performing linear voltammetric scanning on the carbon nanomaterial modified electrode prepared in example 1 by using a CHI660 electrochemical workstation at a scanning speed of: 0.05V/s, the experimental results are shown in FIG. 2, curve a is 5 μ M Cu added into artificial cerebrospinal fluid+The linear scanning curve of the carbon nano material modified electrode shows that an oxidation peak appears near 0.3V, and the oxidation peak signals are well separated from the oxidation peak signals of a pH response molecule and a reference molecule. Curve b is carbon after addition of 20 μ M basic EDTA on a basisThe linear scanning voltammetry curve of the nano material modified electrode can be clearly seen, after EDTA is added into the artificial cerebrospinal fluid, Cu is at 0.3V+The oxidation peak of (A) disappears, and proves that the complexing force of EDTA is stronger than that of selective Cu+Recognition of a ligand (in the formula (I), the R group is
) May be prepared from Cu+Re-release from the electrode surface, thus causing the oxidation peak at 0.3V to disappear. Meanwhile, after the artificial cerebrospinal fluid is added with an alkaline EDTA solution, the pH value rises, so that the potential of the pH probe is shifted negatively. These results prove that the carbon nanomaterial-modified electrode prepared in example 1 can effectively and selectively recognize Cu at the same time+And pH.
Example 3
Performing monovalent copper ion Cu on the carbon nanomaterial modified electrode prepared in example 1 by using CHI660 electrochemical workstation+Then performing linear voltammetric scanning in sequence, and scanning at a scanning speed: 0.05V/s, and the experimental result is shown in figure 3, wherein the carbon nano material modified electrode is aligned with Cu+Has good response. Cu captured on electrode surface by identified ligand+There is an oxidation peak at 0.3V, and the peak current density of the oxidation peak gradually increases with the increase in the copper ion concentration, and exhibits good linearity in the range of 0.5 μ M to 11.0 μ M. And in the process of measurement, signals of the pH probe molecule and the reference molecule are stable, and interference on detection of copper ions is avoided.
Example 4
The pH performance of the carbon nanomaterial-modified electrode prepared in example 1 was examined using the CHI660 electrochemical workstation. After changing the pH, linear voltammetric scans were performed sequentially, sweep rate: 0.05V/s, and the experimental results are shown in FIG. 4, in this example, the linear scanning oxidation curves of the carbon nanomaterial-modified electrode prepared in example 1 at different pH concentrations are recorded. The pH values of the solutions were 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, respectively. As shown in FIG. 4, the carbon nanomaterial modified electrode shows good response to pH, and the oxidation peak of the pH probe gradually shifts positively along with the reduction of pH, and meanwhile, the reference peak potential is kept unchanged. The carbon nano material modified electrode has very good response to pH within the range of 6.0-8.0, and can meet the requirement of pH change detection in organisms.
Example 5 measurement of pH and cuprous ion concentration in pathological model mouse
Real-time detection of live mice:
the APPswe/PS1dE9 transgenic AD mice and normal mice used in the experiments were purchased from the animal model center in the south of Shanghai.
a. Preparation work before in vivo experiments
Anesthetizing a mouse: first, 0.1g/ml of nougat was prepared, and then the rats were weighed and anesthetized by injecting 30mg/100g of the rats with an anesthetic. Thereafter, about 0.3ml was injected every 3 hours.
Sterilizing surgical instruments: preparing 75% ethanol, and soaking surgical instruments in the ethanol for sterilization.
b. Craniotomy for living body
First, a mouse was fixed to a stereotaxic apparatus, a constant temperature heating pad was placed, the temperature of a living body was controlled to be 37 ℃, then, a wound having a length of about 1cm was vertically drawn at the central position of the brain by a scalpel, the wound was fixed by a hemostatic clip, cleaned, and the skull was exposed, and finally, the position of the hippocampus (AP ═ 5.0mm, L ═ 5.0mm, and V ═ 2.5mm), the striatum (AP ═ 0mm, L ═ 2.5mm, and V ═ 7.0mm) and the cortex (AP ═ 0.2mm, L ═ 5.6mm, and V ═ 3.0mm) was determined from the brain spectrum, and after marking by a marker pen, the cranium was opened by a cranial drill having a hole diameter of about 5mm for placing a working electrode.
The experimental result is shown in figure 5, and the carbon nano material modified electrode can be used for treating Cu in the brain of a living rat+Has good response and is very sensitive to pH detection. Curve a represents the linear scan oxidation curve in normal rat brain and curve b represents the linear scan oxidation curve in AD rat brain. Cu trapped by recognized ligands+There was an oxidation peak at 0.3V and an oxidation peak at-0.45V at pH. Simultaneous determination of pH probe and reference molecule signalsStable and does not interfere with the detection of copper ions. Comparing curves a and b, it can be seen that the pH does not vary significantly in normal and pathological mouse models, whereas Cu does+In pathological model mice, the concentration of the compound in the brain of the mice is 2.2 times that in the brain of normal mice.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected.
Claims (15)
1. A preparation method of a carbon nano material modified electrode comprises the following steps: in a solvent, under the condition of 10-25 ℃, mixing a carbon nano material and Cu+Mixing recognition ligand, reference molecule and pH response molecule, and adding Cu+And modifying the recognition ligand, the reference molecule and the pH response molecule on the carbon nano material to prepare the carbon nano material modified electrode.
2. The method of claim 1, wherein the carbon nanomaterial is selected from one or more of graphene, single-walled carbon nanotubes, and multi-walled carbon nanotubes, and the carbon nanomaterial carbon fibers have a diameter of less than 10 μm.
3. The method of claim 1, wherein the Cu is present in a composition comprising Cu and Cu+The recognition ligand is shown as a formula (I), and the Cu+The recognition ligand is selected from one or more of the formulae (I):
wherein R is selected from the following groups:
4. the method of claim 1, wherein the reference molecule is 2, 2-diaza-bis (3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt or ferrocene.
5. The method of claim 1, wherein the pH-responsive molecule is selected from the group consisting of 1, 2-naphthoquinone, 1, 3-naphthoquinone, 1, 4-naphthoquinone, 1, 2-anthraquinone, 1, 2-phenanthrenequinone, 1, 3-phenanthrenequinone, 2, 4-phenanthrenequinone, neyer blue, neyer red, and azure blue.
6. The method of claim 1, wherein the Cu is present in a composition comprising Cu and Cu+The mol ratio of the recognition ligand, the reference molecule and the pH response molecule is 1:1-10: 1-50.
7. The method of claim 1, wherein the solvent is selected from the group consisting of water, dichloromethane, methanol, ethyl acetate, and N, N-dimethylformamide, dimethylsulfoxide.
8. The method of claim 1, wherein the modification time is 12 to 24 hours.
9. A carbon nanomaterial-modified electrode prepared by the method of any one of claims 1 to 8.
10. The carbon nanomaterial-modified electrode of claim 9 for simultaneous in vitro determination of Cu+And application in pH.
11. The carbon nanomaterial-modified electrode of claim 9 for measuring Cu in a living organism+And the use of pH.
12. Cu+A method for preparing a recognition ligand, said method comprising: in an organic solvent, performing amidation reaction on R-COOH, thioether, carbodiimide and N-hydroxysuccinimide ester to obtain the Cu+The ligand is identified.
13. The process of claim 12, wherein the temperature of the amidation reaction is 20 to 50 ℃; the time for the amidation reaction is 12 to 36 hours.
14. The method of claim 12, wherein the organic solvent is selected from the group consisting of ethanol, methanol, N-dimethylformamide, dimethylsulfoxide, and methylene chloride.
15. The method of claim 12, wherein the molar ratio of R-COOH, thioether, carbodiimide, and N-hydroxysuccinimide ester is from 1 to 2: 1-2: 1.5-3.0: 1.5-3.0.
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