CN112924506A - Preparation method of simple electrochemical micro sensor, product and application thereof - Google Patents
Preparation method of simple electrochemical micro sensor, product and application thereof Download PDFInfo
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- 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
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- 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
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Abstract
The invention discloses a preparation method of a simple electrochemical micro sensor, a product and an application thereof, 1) preparing a CMFE/OxGO electrode: firstly, preparing a bare carbon fiber wire microelectrode, then depositing GO on the surface of the carbon fiber wire microelectrode by an electrodeposition method, and then carrying out electrooxidation treatment on the electrode to form a built-in correction signal, thus obtaining a CMFE/OxGO electrode; 2) preparation of CFME/OxGO/Ti3C2TxAg electrode: mixing Ti3C2TxModifying the CMFE/OxGO electrode obtained in the step 1), and then placing the modified electrode in a silver nitrate solution for reduction self-assembly to obtain CFME/OxGO/Ti3C2TxThe Ag electrode is the simple electrochemical micro sensor. The invention adopts Ti3C2TxReducing Ag NPs with uniform nanometer size, self-assembling the Ag NPs on the surface of a carbon fiber wire microelectrode as a recognition unit, specifically recognizing and detecting Cl‑Providing a built-in correction signal to improve Cl using electro-oxidized graphene oxide as an internal reference cell‑Accuracy of detection, Cl was prepared‑An electrochemical micro-sensor.
Description
Technical Field
The invention belongs to the technical fields of analytical chemistry, life science, medicine and the like, and particularly relates to a preparation method of a simple electrochemical micro sensor, a product and application thereof.
Background
Chloride ion (Cl)-) Is one of the important anions for maintaining the normal function of the brain, extracellular Cl-Dysregulation of levels is closely associated with certain psychiatric and neurological disorders. PD is the second most common neurodegenerative disease in the world, pathologically characterized by massive death of dopaminergic neurons, but the specific pathogenesis is not completely clear. It has been reported that the process of dopaminergic neuronal death is associated with a hypochlorite-dependent transformation-mediated oxidative stress process, Cl-The channel plays a non-negligible role in the process. From the quantitative analysis perspective, for Cl in vivo brain-The correlation between the concentration and the PD is elucidated, which is helpful for better exploring Cl-Involved dopaminergic neuronal death events. Thus, development of a simple, reliable Cl-Method for realizing PD model in vivo in brain Cl by analysis method-In situ detection of-The related dopaminergic neuron death process breaks through related PD pathogenesis and has important significance.
At present, common detection of Cl-The analytical method of (1) includes liquid chromatography, fluorescence spectrometry, colorimetry and the like. However, these methods are not suitable for in situ detection of living organisms. Electrochemical sensing technology is considered to be one of the most promising analytical techniques due to its advantages of low preparation cost and high spatial-temporal resolution detection. For this reason, the evolution from early ion-selective electrodes to the recently developed all-solid-state electrodes, Cl-Electrochemical sensors exhibit the advantages of high sensitivity and high selectivity detection. Wherein, for the construction of all-solid-state electrode, Ag andCl-formation of electroactive AgCl at specific potentials to develop potentiometric Cl-Electrochemical sensors are a more common detection principle. According to this principle, assembling a rough Ag nano surface of uniform size down to the nano-scale on the working electrode can effectively increase Cl-Performance of the assay. However, the reported electrochemical sensor involves multiple steps such as modification of conductive materials, synthesis of Ag nanomaterials, and assembly thereof, the preparation process is complex, the reproducibility of the sensor is greatly reduced, and a potential drift signal formed by a single Ag is susceptible to environmental influences, and a false signal is easily generated. Thus, there is currently little available Cl-The electrochemical sensor is suitable for in vivo analysis. The high-performance electrochemical micro-sensor with the self-in-band correction signal is prepared through a simple process, so that the high-performance electrochemical micro-sensor has the advantages of simplicity in preparation, good reproducibility, high detection performance and small size of a microelectrode, and can be used for realizing Cl in the brain of a living body-Is necessary.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method which has the advantages of simplicity, high sensitivity, high selectivity, good reproducibility, internal reference signal and capability of realizing Cl in the brain of a living body-A method for preparing a simple electrochemical micro sensor for horizontal in-situ detection, a product and application thereof.
The preparation method of the simple electrochemical micro sensor comprises the following steps:
1) preparing a CMFE/OxGO electrode: firstly, preparing a bare carbon fiber wire microelectrode, then depositing GO on the surface of the carbon fiber wire microelectrode by an electrodeposition method, and then carrying out electrooxidation treatment on the electrode to form a built-in correction signal, thus obtaining a CMFE/OxGO electrode;
2) preparation of CFME/OxGO/Ti3C2TxAg electrode: mixing Ti3C2TxModifying the CMFE/OxGO electrode obtained in the step 1), and then placing the modified electrode in a silver nitrate solution for reduction self-assembly to obtain CFME/OxGO/Ti3C2TxThe Ag electrode is the simple electrochemical micro sensor.
The bare carbon fiber wire microelectrode in the step 1) comprises the following steps:
1-1 preparation of bare electrode: cutting the carbon fiber wire, adhering one end of the carbon fiber wire to one end of the copper wire by using conductive silver adhesive, and drying in an oven to obtain a bare electrode;
1-2, manufacturing a carbon fiber wire microelectrode: drawing a tip of the glass capillary on a drawing instrument, and carefully penetrating the carbon fiber wire of the bare electrode in the step 1-1 through the tip of the capillary to expose the carbon fiber wire for several millimeters; then, injecting epoxy resin into the glass capillary tube by using a micro-injector, and drying to fix the exposed copper wire and the carbon fiber wire in the capillary tube; and then cutting the exposed carbon fiber yarns to a proper length by using a blade, and sequentially placing the exposed carbon fiber yarns in acetone, nitric acid, sodium hydroxide and distilled water for ultrasonic cleaning to obtain the bare carbon fiber yarn microelectrode.
In the step 1-1, the carbon fiber filaments are cut to a length of 0.5-1.5 cm and have a diameter of 5-10 μm.
In the step 1-2, the proper length is 0.5mm, the concentration of nitric acid is 2-4M, the concentration of sodium hydroxide is 0.5-1.5M, and the ultrasonic cleaning time is 4-6 min each time.
In the step 1), the electrodeposition method comprises the following specific steps: placing the bare carbon fiber wire microelectrode in a graphene oxide suspension, applying constant potential to electrodeposit graphite oxide, and washing after deposition to obtain the bare carbon fiber wire microelectrode deposited with graphene oxide; wherein: the concentration of the graphene oxide suspension is 0.5-1.5 mg/mL, and the constant voltage is 1.5-1.7V; the deposition time is 500-700 s.
In the step 1), the specific steps of the electrooxidation treatment are as follows: placing the bare carbon fiber wire microelectrode deposited with the graphene oxide in a NaCl solution, and performing constant potential oxidation treatment to obtain a CMFE/OxGO electrode; wherein: the concentration of the NaCl solution is 130-150 mM; the oxidation voltage is 1.8-2.0V, and the oxidation time is 150-250 s.
In said step 2), Ti3C2TxThe modification method comprises the following steps: the CMFE/OxGO electrode is put into Ti3C2TxSoaking the suspension, drying, and soaking+ drying cycle modification process of Ti3C2TxDecorating on the electrode; wherein: the soaking time is 1-3 min each time, and the cycle times are 4-6 times.
In the step 2), the specific steps of reduction self-assembly are as follows: will be decorated with Ti3C2TxThe CMFE/OxGO electrode is placed in silver nitrate solution for soaking, and Ti is utilized3C2TxReducing property of (2), Ag+Ions are reduced into Ag simple substance without adding extra reducing agent to obtain CFME/OxGO/Ti3C2Txan/Ag electrode;
wherein: the soaking time is 30-90 min.
The simple electrochemical microsensor is prepared according to the method.
The simple electrochemical micro sensor is used for detecting Cl-The use of (1).
The simple electrochemical micro sensor of the invention detects Cl-The method comprises the following steps:
s1, mixing CFME/OxGO/Ti3C2Txthe/Ag electrode is placed in a blank phosphoric acid buffer solution, and is scanned by adopting a DPV method, wherein the scanning requirement is-0.75V-0.4V; an oxidation peak was obtained at-500 mV and 112mV, respectively, and the electrode was placed in a chamber containing 100mM Cl-The oxidation peak at-500 mV keeps the peak potential unchanged, and the oxidation peak at 112mV moves to-52 mV;
s2, mixing CFME/OxGO/Ti3C2Txthe/Ag electrode was placed in sequence with a series of Cl concentrations-(0 to 700mM, specifically 0, 1, 5, 10, 20, 40, 60, 80, 100, 150, 200, 250, 300, 400, 500, 600, 700mM) in phosphate buffer solution at 112mVp(Ag/AgCl) Peak potential with Cl-Increasing concentration gradually moving in a negative direction, E at-500 mVp(OxGO) peak potential remains unchanged; by calculating the potential difference Delta E of two oxidation peaksp(OxGO/AgCl) with Cl-The logarithm of the concentration is in direct proportion, so that a standard curve of the concentration and the potential difference can be obtained;
s2, mixing CFME/OxGO/Ti3C2Txthe/Ag electrode is placed in Cl with unknown concentration-The solution or cerebral microdialysis solution or cerebral cortex or striatum or hippocampus, and the Delta E can be obtained by scanning with DPV methodp(OxGO/AgCl), and then the concentration of the chloride ions can be obtained through a standard curve.
The invention has the beneficial effects that: 1) the invention adopts Ti3C2TxReducing Ag NPs with uniform nanometer size, self-assembling the Ag NPs on the surface of a carbon fiber wire microelectrode as a recognition unit, specifically recognizing and detecting Cl-Providing a built-in correction signal to improve Cl using electro-oxidized graphene oxide as an internal reference cell-Accuracy of detection, Cl was prepared-An electrochemical micro-sensor. The preparation process is simple and efficient, the reproducibility is high, and the in vitro electrochemical behavior result shows that the sensor is used for Cl-The detection has good sensitivity, selectivity, stability and reproducibility. 2) The invention utilizes the sensor to measure the Cl of the rat hippocampus-The in-situ detection result proves that the sensor is used for Cl in the living body-The real-time change of the concentration is sensitive, and the method is comparable to the measurement result of the traditional Volvard method, and is a reliable platform for in vivo analysis. The electrochemical microsensor is further applied to the Cl of three subregions (cerebral cortex, striatum and hippocampus) in the brains of normal and Parkinson model mice-The in situ detection and the statistical analysis show that the Cl in the cerebral cortex of the Parkinson mice-Elevated levels and decreased hippocampus, indicating Cl-Has close relation with the occurrence and the development of the Parkinson disease. 3) The invention not only provides a simple in-situ self-assembly strategy for constructing the potential Cl-The electrochemical micro-sensor expands the design and development of high-performance electrochemical micro-sensors for other anions and is Cl in the living brain-Provides a reliable analysis platform and is helpful to promote the research of brain diseases related to various anions.
Drawings
FIG. 1 CFME/OxGO/Ti of the present invention3C2TxA flow chart of preparation and detection of the/Ag electrode;
FIG. 2 micro-topography of various electrodes prepared in example 1, wherein (A-B) bare CFME electrodes, (C-D) CFME/GO electrodes, (E-F) CFME/OxGO/Ti3C2TxElectrode, (G-L) CFME/OxGO/Ti3C2TxAg electrode, reduction time of Ag NPs: (G-H)30 minutes, (I-J)60 minutes, and (K-L)90 minutes.
FIG. 3 an X-ray photoelectron spectrum of a different modified micro-electrode in example 1. Wherein, (A) is X-photoelectron spectrum total spectrogram, (B), (C) and (D) are typical X-photoelectron spectrum analysis of Ti 2p, F1 s and Ag 3D, and the electrodes are (a) naked CFME electrode, (B) CFME/GO electrode, (C) CFME/OxGO electrode, (D) CFME/OxGO/Ti3C2TxElectrode, (e) CFME/OxGO/Ti3C2Txan/Ag electrode.
FIG. 4 CFME/OxGO/Ti prepared in example 13C2TxX-ray energy spectrometry and energy dispersive X-ray spectrometry of the electrodes (60 minutes); (A to E) X-ray energy spectrum analysis, and (F) energy dispersive X-ray spectrum analysis.
FIG. 5 CFME/OxGO/Ti in example 23C2TxThe electrode is soaked in 0.5mg/mLAgNO3DPV profile tested in blank PBS after 5, 30, 60, 90, 120 minutes in aqueous solution.
FIG. 6 different electrodes of example 2 were immersed in 0.5mg/mL AgNO3After 60 minutes in aqueous solution, in a blank and containing 100mM Cl-A differential pulse voltammogram measured in a phosphoric acid buffer solution of (a); wherein (A) is blank phosphoric acid buffer solution, and (B) is 100mM Cl-The electrodes are respectively (a) a naked CFME electrode, (b) a CFME/GO electrode, (c) a CFME/OxGO electrode, (d) a CFME/OxGO/Ti electrode3C2TxAnd an electrode.
FIG. 7 examples 2 of differently modified microelectrodes in blanks and containing 100mM Cl-The obtained differential pulse voltammogram was scanned in the phosphoric acid buffer solution. Wherein (A) is blank phosphoric acid buffer solution, and (B) is 100mM Cl-The electrodes are respectively (a) a naked CFME electrode, (b) a CFME/GO electrode, (c) a CFME/OxGO electrode, (d) a CFME/OxGO/Ti electrode3C2TxElectrode, (e) CFME/OxGO/Ti3C2Txan/Ag electrode.
FIG. 8 is an X-ray photoelectron spectrum of a different modified microelectrode in example 2. (A) CFME/GO electrode, (B) CFME/OxGO electrode, (C) CFME/OxGO/Ti3C2TxAnd an electrode.
FIG. 9 CFME/OxGO/Ti in example 23C2TxAg electrode pair Cl-The study of selectivity and interference of detection shows that the interference substances are various amino acids (tyrosine, glycine, histidine, serine, isoleucine, arginine, threonine, lysine, cysteine, tryptophan, glutamic acid, valine).
FIG. 10 CFME/OxGO/Ti in example 23C2TxAg electrode pair Cl-The selectivity and interference of the detection are studied by the various cations (Na)+，K+，Mg2+，Cr3+，Cd2+，Fe2+，Fe3+，Co2+，Cu2+，Zn2+，Ca2+，Ni2+)。
FIG. 11 CFME/OxGO/Ti in example 23C2TxAg electrode pair Cl-The selectivity and interference of the detection are studied by the various anions (NO)2 -，Ac-，F-，CO3 2-，OH-，SO4 2-，NO3 -，S2 -，HCO3 -，ClO4 -)。
FIG. 12 CFME/OxGO/Ti in example 23C2TxAg electrode pair Cl-A study of the selectivity and interference of the assay, the interfering substances being typical of the biologically active substances (lactic acid, glucose, dopamine, ascorbic acid, uric acid, 3, 4-dihydroxyphenylacetic acid, hydrogen peroxide,. OH, ClO-，ONOO-，O2 ·-，O2，1O2)。
FIG. 13 CFME/OxGO/Ti in example 23C2Txthe/Ag electrode was in the blank and contained 1mM I-，1mM Br-And 1mM Cl-A graph of differential pulse voltammetry responses measured in a phosphate buffered solution of (a); wherein I-a blank phosphate buffer solution, II-contains 1mM I-，1mM Br-And 1mM Cl-Phosphoric acid buffer solution.
FIG. 14 CFME/OxGO/Ti in example 23C2TxCl in series concentrations for Ag electrode-Differential pulse voltammograms obtained by scanning in solution, a to q are 0, 1, 5, 10, 20, 40, 60, 80, 100, 150, 200, 250, 300, 400, 500, 600, 700mM, respectively.
FIG. 15 six CFME/OxGO/Ti in example 23C2TxAg electrode in blank and containing 100mM Cl-Scanning in a phosphoric acid buffer solution to obtain a differential pulse voltammogram; wherein (A) is blank phosphoric acid buffer solution, and (B) is 100mM Cl-Phosphoric acid buffer solution.
FIG. 16 example 2 shows the five electrochemical microsensors at a series of concentrations of Cl-The potential difference (delta E) of two oxidation peaks measured by scanning in the solutionp(OxGO/AgCl)) with Cl-Log of concentration correlation linear relationship.
FIG. 17 CFME/OxGO/Ti in example 23C2TxAg electrode in 100mM Cl-The cyclic voltammogram obtained by continuously scanning for 150 cycles in the phosphoric acid buffer solution.
FIG. 18 CFME/OxGO/Ti in example 23C2TxCl at series concentrations before and after storage of Ag electrode at 4 ℃ for 20 days-The difference between the two oxidation peak potentials (Delta E) measured in the solutionp(OxGO/AgCl)) with Cl-Log of concentration correlation linear relationship.
FIG. 19 CFME/OxGO/Ti in example 33C2TxUse of/Ag electrode (60 min) for murine intracerebral Cl-Schematic of in situ detection.
FIG. 20 six CFME/OxGO/Ti in example 33C2TxAg electrode (60 min) to Hippocampus Cl in rat brain-Differential pulse voltammogram obtained by horizontal in-situ detectionAnd (B) a difference in oxidation peak potentials (. DELTA.E) at two sitesp(OxGO/AgCl)) response.
FIG. 21 CFME/OxGO/Ti in example 33C2TxThe structure picture of the parallel assembly of the/Ag electrode and the capillary.
FIG. 22 CFME/OxGO/Ti in example 33C2TxThe Ag electrode was injected with artificial cerebrospinal fluid (pH 7.4, 140mM Cl in it) near the hippocampal sensor in the rat brain-) Front and rear in-situ detection of Cl-The obtained differential pulse voltammogram; wherein I is before injection and II is after injection.
FIG. 23 CFME/OxGO/Ti in example 33C2TxAg electrodes in situ determine differential pulse voltammetry response graphs of normal and Parkinson mouse cerebral cortical areas; wherein I is a normal mouse, and II is a Parkinson mouse.
FIG. 24 CFME/OxGO/Ti in example 33C2TxThe Ag electrode is used for measuring differential pulse voltammetry response graphs of striatum areas in normal and Parkinson mouse brains in situ; wherein I is a normal mouse, and II is a Parkinson mouse.
FIG. 25 CFME/OxGO/Ti in example 33C2TxAg electrodes in situ to determine the differential pulse voltammetry response graphs of the hippocampal region in the normal and Parkinson mouse brains; wherein I is a normal mouse, and II is a Parkinson mouse.
FIG. 26 CFME/OxGO/Ti in example 33C2Txthe/Ag electrode was used to determine the chloride concentration of three subregions (cerebral cortex, striatum and hippocampus) in 8 normal and Parkinson mice, respectively.
Detailed Description
EXAMPLE 1 preparation of a simple electrochemical microsensor
The preparation flow chart of the simple electrochemical microsensor is shown in fig. 1, and specifically comprises the following steps:
1. preparing bare carbon fiber wire microelectrode (CMFE): cutting carbon fiber wires (with the diameter of 5-10 mu m) into 1cm in length, adhering one end of each carbon fiber wire to one end of a copper wire by using conductive silver adhesive, and drying in an oven; drawing the capillary tip on a drawing instrument (P100) by using a glass capillary, and carefully passing the carbon fiber filaments of the bare electrode through the capillary tip (which can be operated under a microscope), wherein the carbon fiber filaments are exposed by 4-7 mm; then, injecting epoxy resin into the tip of the capillary tube by using a micro-injector and drying to realize the fixation, sealing and insulation of the exposed copper wire and the carbon fiber wire in the capillary tube; and finally, cutting the exposed carbon fiber filaments to 0.5mm by using a blade under a microscope, and sequentially placing the carbon fiber filaments in acetone, nitric acid (3M), sodium hydroxide (1M) and distilled water for ultrasonic treatment for 5 minutes to obtain the bare CFME electrode.
2. Depositing graphene oxide: and (2) placing the bare carbon fiber wire microelectrode of the electrode prepared in the step (1) in a graphene oxide suspension (1mg/mL), applying constant potential to electrodeposit graphene oxide, keeping the voltage at 1.6V for 600s, and cleaning with distilled water.
3. Preparation of CMFE/OxGO electrode: and (3) placing the electrode deposited with the graphene oxide in the step (2) in 140mM sodium chloride solution for constant potential oxidation treatment, keeping the voltage at 1.9V for 200s, and washing with distilled water to obtain the CMFE/OxGO electrode.
4. Modified Ti3C2Tx: placing the CMFE/OxGO electrode in the step 3) in Ti3C2TxSoaking the suspension (4mg/mL) for 2min, drying for 2min, repeating five cycles, and washing with distilled water to obtain CFME/OxGO/Ti3C2TxAnd an electrode.
5. Preparation of CFME/OxGO/Ti3C2TxAg electrode: a plurality of CFME/OxGO/Ti modified in the step (4)3C2TxSoaking the electrode in silver nitrate solution (0.5mg/mL) for 30min, 60min and 90min, respectively, and cleaning with distilled water to obtain 3 kinds of CFME/OxGO/Ti3C2TxThe Ag electrode is the simple electrochemical micro sensor.
For the bare CFME electrode, CFME/GO electrode, CFME/OxGO/Ti prepared in this example3C2TxElectrode, 3 kinds of CFME/OxGO/Ti3C2TxSEM test of Ag/electrode results are shown in FIG. 2, from which it is evident that CFME electrode surface light is observed in FIG. 2The electrode is smooth and clean, the surface of the CFME/GO electrode has specific folds of graphene, CFME/OxGO/Ti3C2TxElectrode surface loaded presentation Ti3C2TxRigid sheet, without graphene-specific folds, CFME/OxGO/Ti3C2TxThe Ag electrode has obvious silver nano particles loaded on the surface, the silver nano particles with the reduction time of 30 minutes are just formed, the number of the silver nano particles is small, the silver nano particles with the reduction time of 60 minutes are uniform and dense in size, and the silver nano particles with the reduction time of 90 minutes are agglomerated.
For the bare CFME electrode, CFME/GO electrode, CFME/OxGO/Ti prepared in this example3C2TxElectrode, CFME/OxGO/Ti3C2TxThe result of X-ray photoelectron spectroscopy performed on the Ag electrode (60 minutes) is shown in FIG. 3, and it can be seen from FIG. 3 that: CFME/OxGO/Ti3C2TxThe presence of Ti and F components in the modified electrode confirmed Ti3C2TxSuccessful modification of (2), CFME/OxGO/Ti3C2TxThe preparation of silver nanoparticles is confirmed by the existence of Ag component of the/Ag modified electrode; from the valence state of the Ti element, the original high valence state (+4 valence) of the Ti element is reduced to low valence state (+2 valence) after the reduction of silver, which indicates that the valence state of the Ti element is changed into the low valence state (+2 valence state)3C2TxAfter the silver ion solution is soaked, an oxidation-reduction reaction occurs, and silver ions are reduced into a silver simple substance in the process.
CFME/OxGO/Ti prepared by the implementation3C2Txthe/Ag electrode (60 min) was subjected to X-ray photoelectron spectroscopy and X-ray spectroscopy under a scanning electron microscope, as shown in FIG. 4, from which it can be seen that: ag. F, Ti element is uniformly loaded on the carbon fiber filament, and the content of the reduced silver nano-particles is as high as 40.77%.
Example 2 preparation Process and Property Studies
1. Effect of silver reducing self-assembly time on Performance
On the basis of example 1, the preparation soaking time in step 5 is changed to 5 and 120 minutes of CFME/OxGO/Ti3C2TxAg electrode, then the different reduction times (5, 30, 60, 90, 120 min) CFME/OxGO/Ti prepared in example 1 and example 23C2Txthe/Ag electrode was placed in a blank phosphoric acid buffer solution for differential pulse voltammetry scanning as shown in FIG. 3. Scanning parameters are as follows: the potential step was 4mV, the pulse width was 0.05s, the pulse period was 0.3s, and the pulse amplitude was 50 mV.
As is evident from FIG. 3, the reduction time of 60 minutes resulted in CFME/OxGO/Ti3C2TxThe Ag electrode presents a sharp and narrow silver oxidation peak which is obviously superior to silver oxidation peaks obtained by other reduction times, so that the reduction time is CFME/OxGO/Ti prepared in 60 minutes3C2Txthe/Ag electrode is most preferred. (FIG. 5 is to be noted)
2. Bare CFME electrode, CFME/GO electrode, CFME/OxGO/Ti electrode prepared in example 13C2TxThe electrode is respectively at 0.5mg/mL AgNO3Electrochemical performance test is carried out after soaking in aqueous solution for 60 minutes
Preparation of bare CFME electrode, CFME/GO electrode, CFME/OxGO/Ti electrode from example 13C2TxElectrode at 0.5mg/mL AgNO3After 60 minutes of immersion in aqueous solution, the mixture was then placed in a blank and contained 100mM Cl-A differential pulse voltammetric scan was performed in a phosphate buffer solution as shown in fig. 6. As can be seen from fig. 6: the CFME/OxGO electrode gave an oxidation peak at-500 mV in the blank and containing 100mM Cl-The differential pulse voltammetry curve is scanned in the phosphoric acid buffer solution, and the oxidation peak potential is unchanged. And CFME/OxGO/Ti3C2TxThe electrode has reduction performance, can reduce silver ions into silver simple substance, presents a sharp and narrow silver oxidation peak positioned at 112mV, and after scanning in a solution containing chloride ions, the potential of the silver oxidation peak is shifted negatively to-52 mV. The naked CFME electrode, the CFME/GO electrode and the CFME/OxGO electrode do not have the reduction function, and the silver oxidation peak is obtained by applying negative potential to reduce a small amount of Ag simple substance and then oxidizing.
3. Electrochemical Performance testing of various electrodes prepared in example 1
Preparation of bare CFME electrode, CFME/GO electrode, CFME/OxGO/Ti electrode from example 13C2TxElectrode, CFME/OxGO/Ti3C2TxAg electrode (60 min), placed in blank and containing 100mM Cl-The phosphoric acid buffer solution of (2) was subjected to differential pulse voltammetry scanning as shown in FIG. 7.
As can be seen from FIG. 7, the graphene oxide with-500 mV oxidation peak appears after electro-oxidation treatment, and the graphene oxide with 112mV oxidation peak is CFME/OxGO/Ti3C2TxElectrode reduced silver, control in blank and 100mM Cl-The oxidation at-500 mV is not related to chloride ions, while the oxidation peak at 112mV is shifted negatively in potential after the addition of chloride ions. This indicates that the prepared electrochemical micro-sensor has a built-in reference signal and is in the presence of Cl-Has good potential response.
4. Investigation of chemical reactions during the preparation of electrodes
CFME/GO, CFME/OxGO, and CFME/OxGO/Ti electrodes prepared in example 13C2TxThe electrodes were characterized on an X-ray photoelectron spectrometer and the data analyzed as shown in figure 8 and table 1. Obviously, after the graphene oxide is subjected to electrooxidation treatment, C-C (sp)3) And C ═ O content was remarkably increased, and Ti was modified3C2TxThereafter, the Ti-C bond was increased, and the content of other chemical bonds showed a slight decrease in physical proportionality, indicating that the oxidation peak at-500 mV was due to the oxidation of C ═ O bonds, corresponding to the quinone group in OxGO.
TABLE 1
5. Investigation of electrode Selectivity
CFME/OxGO/Ti prepared in example 13C2Txthe/Ag electrode (60 min) was placed in a bath containing the single amino acids (tyrosine, glycine, histidine, serine, isoleucine, arginine)Threonine, lysine, cysteine, tryptophan, glutamic acid, valine) or each amino acid with Cl-The results of differential pulse voltammetric scanning (concentration of each amino acid was 10. mu.M) in the coexisting phosphate buffer solution are summarized in FIG. 9, and the ordinate shows the difference in oxidation peak potentials (. DELTA.E) at two sites in the presence of each interfering amino acidp(OxGO/AgCl)) response to raw response ratio, which indicates that the sensor can be used against various amino acids in physiological concentrations, with the presence of Cl-Specificity of the analysis.
CFME/OxGO/Ti prepared in example 13C2Txthe/Ag electrode (60 min) was placed in a bath containing each single cation (Na)+，K+，Mg2+，Cr3+，Cd2+，Fe2+，Fe3+，Co2+，Cu2+，Zn2+，Ca2+，Ni2+) Or each cation with Cl-The concentrations of the cations in the coexisting phosphate buffer solution were subjected to differential pulse voltammetry scanning: na (Na)+100mM，K+5mM,Mg2+And Ca2+1mM, the remainder 10. mu.M), and the results are summarized in FIG. 10, wherein the ordinate represents the difference between the oxidation peak potentials (. DELTA.E) at two positions in the presence of each cationp(OxGO/AgCl)) response to raw response ratio, indicating that the sensor is active against physiological concentrations of cations, with Cl-Specificity of the analysis.
CFME/OxGO/Ti prepared in example 13C2Txthe/Ag electrode (60 min) was placed in a chamber containing each single anion (NO)2 -，Ac-，F-，CO3 2-，OH-，SO4 2-，NO3 -，S2 -，HCO3 -，ClO4 -) Each anion with Cl-Differential pulse voltammetric scanning was performed in a coexisting phosphoric acid buffer solution (concentration of each anion: CO:. RTM.3 2-And HCO3 -1mM, the remainder 10. mu.M), and the results are summarized in FIG. 11, in which the ordinate represents the difference between the oxidation peak potentials (. DELTA.E) at two positions in the presence of each anionp(OxGO/AgCl)) response to raw response ratio, thisIndicating that the sensor is active against physiological concentrations of anions, with a counter of Cl-Specificity of the analysis.
CFME/OxGO/Ti prepared in example 13C2Txthe/Ag electrode (60 min) was placed in a chamber containing the individual biologically active substances (lactic acid, glucose, dopamine, ascorbic acid, uric acid, 3, 4-dihydroxyphenylacetic acid, hydrogen peroxide,. OH, ClO)-，ONOO-，O2 ·-，O2，1O2) Each bioactive substance and Cl-Differential pulse voltammetric scanning was performed in the coexisting phosphate buffer solution (concentration of each active substance was 10. mu.M, ascorbic acid was 100. mu.M, uric acid was 10. mu.M, oxygen was 0.25mM, lactic acid was 1mM, glucose was 1mM, hydrogen peroxide was 1. mu.M), and the results are summarized in FIG. 12, in which the ordinate represents the difference in oxidation peak potentials (. DELTA.E) at two sites in the presence of each bioactive substancep(OxGO/AgCl)) response to raw response ratio, indicating that the sensor is active against physiological concentrations of bioactive substances, with a response to Cl-Specificity of the analysis.
CFME/OxGO/Ti prepared in example 13C2Txthe/Ag electrode (60 min) was left blank and contained 1mM I-，1mM Br-And 1mM Cl-Differential pulse voltammetric scanning was performed in phosphate buffered solution, the results are shown in fig. 13: the oxidation peak potential at 500mV remained unchanged, while the original silver oxidation peak at 112mV shifted negatively and presented three split peaks, 52mV, -44mV and-188 mV, assigned to AgCl, AgBr and AgI, respectively, indicating that the sensor has a charge of Cl against the halogen ions of the same family-Specificity of the analysis.
6. Establishment of a Standard Curve
CFME/OxGO/Ti prepared in example 13C2Txthe/Ag electrode (60 min) was placed in a series of concentrations (a-q corresponding to 0, 1, 5, 10, 20, 40, 60, 80, 100, 150, 200, 250, 300, 400, 500, 600, 700mM, respectively) of Cl-The results of differential pulse voltammetric scanning in the phosphoric acid buffer solution of (1) are shown in FIG. 14: peak potential at-500 mV vs Cl-The increase in concentration does not shift, but at 112mVSilver oxidation peak potential with Cl-The concentration rise shows a gradual negative shift, calculated by the difference of oxidation peak potentials (Delta E)p(OxGO/AgCl))，Cl-Logarithm of concentration and Δ Ep(OxGO/AgCl) shows good linear correlation, and the Cl is used as the quantitative calculation-Based on the concentration, the calculation formula is fitted as-0.05375X + 0.3964.
7. Study of stability
According to CFME/OxGO/Ti in example 13C2TxAg electrode (60 min.) multiple electrodes were prepared, followed by six CFME/OxGO/Ti3C2Txthe/Ag electrode was left blank and contained 100mM Cl-Differential pulsed voltammetric scanning in phosphate buffered solution is shown in FIG. 15. Six electrodes each exhibited a reference oxidation peak at-500 mV and an original silver oxidation peak at 112mV in a blank phosphate buffer solution containing 100mM Cl-The phosphoric acid buffer solution shows a reference oxidation peak at-500 mV and an AgCl oxidation peak at-52 mV, and the signals are stable. This indicates that the sensor has good manufacturing reproducibility.
Combining the five CFME/OxGO/Ti3C2Txthe/Ag electrode is placed in Cl with series concentration-The difference between two oxidation peak potentials (Delta E) measured after differential pulse voltammetry scanning in solutionp(OxGO/AgCl)) with Cl-The log correlation of concentrations is shown in FIG. 16. Cl of five microsensor series concentration-The detection signal is stable. This indicates that the sensor has good manufacturing reproducibility.
Mixing CFME/OxGO/Ti3C2Txthe/Ag electrode is placed in a blank phosphoric acid buffer solution to continuously carry out cyclic voltammetry scanning for 150 times, as shown in figure 17, the original silver oxidation peak at 112mV does not shift, and the signal is stable. This indicates that the sensor has good scan reproducibility.
The CFME/OxGO/Ti3C2TxThe Ag electrode was stored at 4 ℃ for 20 days and then charged with Cl of a series of concentrations-The difference between two oxidation peak potentials (Delta E) measured after differential pulse voltammetry scanning in solutionp(OxGO/AgCl)) with Cl-Correlation linear correlation of logarithm of concentrationAs shown in fig. 18. The microsensor is stored for 20 days and then is subjected to series concentration of Cl-The detection signal is stable. This indicates that the sensor has good storage stability.
Example 3 Cl in animal brains-Detection of concentration
CFME/OxGO/Ti adopted in the embodiment3C2Txthe/Ag electrodes were all CFME/OxGO/Ti prepared in example 13C2TxAg electrode (60 min immersion in silver nitrate).
In this embodiment, CFME/OxGO/Ti is used3C2TxAg electrode in-brain Cl of rat-Fig. 19 shows a schematic diagram of in situ detection, which comprises the following steps: referring to rat brain stereotaxic chart, the electrochemical micro-sensor is implanted into rat hippocampal region (anterior chimney point: anterior 5.0mm, left side of midline 5.0mm, subdural 2.5mm) by brain stereotaxic apparatus, and calomel reference electrode and counter electrode are placed in a position with self-made KNO3A plastic cannula of the salt bridge (tip size: 2mm) placed into the dura mater of the brain. And acquiring an in-situ signal through the electrochemical workstation, and outputting the signal by a computer terminal.
1. And (3) reproducibility characterization: six CFME/OxGO/Ti preparations from example 13C2TxAg electrodes (60 min) were implanted sequentially in the hippocampal region of the same rat and subjected to differential pulse voltammetric scanning in situ e.g. recording Cl-The in situ signal is shown in FIG. 20: comparing the difference between the two oxidation peak potentials (Δ E)p(OxGO/AgCl)), no potential difference drift, the electrochemical microsensor is applied to living Cl-The detection has excellent reproducibility.
2. And (3) sensitivity detection: mixing CFME/OxGO/Ti3C2Txthe/Ag electrode (60 min) was assembled with a capillary (inner diameter: 75 μm, outer diameter: 150 μm), the tips were kept flush, and the hippocampus was co-implanted in parallel (see FIG. 21 for a specific operation), followed by microinjection of artificial cerebrospinal fluid (pH 7.4, 140 Cl-containing) using a programmable syringe pump equipped with an airtight syringe at a flow rate of 0.6 μ L/min-mM)10min, record Cl-The in situ detected signal, results are shown in fig. 22: AgClThe oxidation peak potential of the injection is obviously shifted negatively, and the difference between the oxidation peak potentials (delta E) at the front and the back of the injectionp(OxGO/AgCl)) and calculating Cl-The concentration of (3) increased to 118.7 mM. The electrochemical micro-sensor is used for measuring Cl in vivo-The change in concentration has good sensitivity.
3. And (3) evaluating the accuracy: taking microdialysis liquid from the hippocampal region in the brain of three rats, and determining Cl in the microdialysis liquid by adopting the traditional Voerhard method-And with CFME/OxGO/Ti of the invention3C2TxThe results of the in-situ detection of the Ag electrode are shown in Table 2, and the results are highly similar, which shows that the electrochemical micro-sensor of the invention can realize Cl in vivo-And (4) accurately detecting the concentration.
TABLE 2
Example 4 Parkinson and mouse intracerebral Cl-Investigation of concentration relationship
CFME/OxGO/Ti adopted in the embodiment3C2Txthe/Ag electrodes were all CFME/OxGO/Ti prepared in example 13C2TxAg electrode (60 min immersion in silver nitrate).
And (3) testing: prepared CFME/OxGO/Ti3C2TxApplication of/Ag electrode (60 min.) to Cl in three subregions (cerebral cortex, striatum and hippocampus) of normal and Parkinson-model mice-The in-situ detection and the statistical analysis are carried out, and the method specifically comprises the following steps:
1. refer to FIG. 19 for mouse intracerebral Cl-In-situ detection, an electrochemical micro-sensor is implanted into cerebral cortex regions (anterior chimney point: posterior 2.0mm, left side of midline 0.25mm, 1.2mm under dura mater), striatum regions (anterior chimney point: anterior 0.5mm, left side of midline 1.5mm, 3.0mm under dura mater), hippocampus regions (anterior chimney point: posterior 1.5mm, left side of midline 1.5mm, 1.8mm under dura mater) of mice in normal and Parkinson models respectively through a brain stereotaximeter, and a calomel reference electrode and a counter electrode are placed in a position with self-made KNO3A plastic cannula of the salt bridge (tip size: 2mm) placed into the dura mater of the brain. And acquiring an in-situ signal through the electrochemical workstation, and outputting the signal by a computer terminal. According to the difference between two oxidation peak potentials (Delta E)p(OxGO/AgCl)), calculating Cl in each subregion in the normal and Parkinson model mice brains-The concentration of (c).
2. Respective in situ determination of Cl in brain sub-regions of 8 normal and Parkinson model mice-Is calculated and statistically analyzed.
3. And (4) analyzing results:
mixing the CFME/OxGO/Ti3C2TxImplanting Ag electrode into cerebral cortex of normal mouse and Parkinson mouse, performing in-situ differential pulse voltammetry scanning as shown in FIG. 23, and respectively testing eight normal mice and eight Parkinson mice repeatedly according to the measured difference between two oxidation peak potentials (delta E)p(OxGO/AgCl)) to obtain the Cl of the cerebral cortex of the normal mouse-The concentration was 62.0. + -. 5.0mM, while the concentration of Cl in the cerebral cortex of Parkinson's mice-The concentration was 103.7. + -. 8.4mM, showing an upward trend.
Mixing the CFME/OxGO/Ti3C2TxImplanting Ag electrode into striatal region of normal mouse and Parkinson mouse, performing in-situ differential pulse voltammetry scanning as shown in FIG. 24, and respectively testing eight normal mice and eight Parkinson mice repeatedly according to the measured difference between two oxidation peak potentials (Δ E)p(OxGO/AgCl)) to obtain the Cl of the cerebral cortex of the normal mouse-The concentration was 66.5. + -. 6.1mM, while the concentration of Cl in the cerebral cortex of Parkinson's mice-The concentration was 76.3. + -. 7.3mM with no statistical variation.
Mixing the CFME/OxGO/Ti3C2Txthe/Ag electrodes were implanted in the hippocampal regions of normal and Parkinson mice and subjected to in situ differential pulse voltammetric scanning as shown in FIG. 25. Eight normal mice and eight Parkinson mice were tested repeatedly, respectively, based on the measured difference in potential between two oxidation peaks (Δ E)p(OxGO/AgCl)) to obtain the Cl of the cerebral cortex of the normal mouse-The concentration was 90.6. + -. 8.6mM, whereas the Cl in the cerebral cortex of Parkinson's mice-The concentration was 64.6. + -. 9.3mM, showing a downward trend.
Cl in three brain areas (cerebral cortex, striatum and hippocampus) of normal and eight Parkinson mice-Concentration statistics, as shown in fig. 26; this indicates Cl-Has close relation with Parkinson's disease.
Claims (10)
1. A preparation method of a simple electrochemical micro sensor comprises the following steps:
1) preparing a CMFE/OxGO electrode: firstly, preparing a bare carbon fiber wire microelectrode, then depositing GO on the surface of the carbon fiber wire microelectrode by an electrodeposition method, and then carrying out electrooxidation treatment on the electrode to form a built-in correction signal, thus obtaining a CMFE/OxGO electrode;
2) preparation of CFME/OxGO/Ti3C2TxAg electrode: mixing Ti3C2TxModifying the CMFE/OxGO electrode obtained in the step 1), and then placing the modified electrode in a silver nitrate solution for reduction self-assembly to obtain CFME/OxGO/Ti3C2TxThe Ag electrode is the simple electrochemical micro sensor.
2. The method for preparing the simplified electrochemical micro-sensor according to claim 1, wherein the bare carbon fiber wire microelectrode in the step 1) comprises the following steps:
1-1 preparation of bare electrode: cutting the carbon fiber wire, adhering one end of the carbon fiber wire to one end of the copper wire by using conductive silver adhesive, and drying in an oven to obtain a bare electrode;
1-2, manufacturing a carbon fiber wire microelectrode: drawing a tip of the glass capillary on a drawing instrument, and carefully penetrating the carbon fiber wire of the bare electrode in the step 1-1 through the tip of the capillary to expose the carbon fiber wire for several millimeters; then, injecting epoxy resin into the glass capillary tube by using a micro-injector, and drying to fix the exposed copper wire and the carbon fiber wire in the capillary tube; and then cutting the exposed carbon fiber yarns to a proper length by using a blade, and sequentially placing the exposed carbon fiber yarns in acetone, nitric acid, sodium hydroxide and distilled water for ultrasonic cleaning to obtain the bare carbon fiber yarn microelectrode.
3. The method for preparing the simple electrochemical micro sensor according to claim 2, wherein in the step 1-1, the carbon fiber filaments are cut to have a diameter of 5-10 μm and a length of 0.5-1.5 cm; in the step 1-2, the proper length is 0.5mm, the concentration of nitric acid is 2-4M, the concentration of sodium hydroxide is 0.5-1.5M, and the ultrasonic cleaning time is 4-6 min each time.
4. The method for preparing the simplified electrochemical micro sensor according to claim 1, wherein in the step 1), the electrodeposition method comprises the following specific steps: placing the bare carbon fiber wire microelectrode in a graphene oxide suspension, applying constant potential to electrodeposit graphite oxide, and washing after deposition to obtain the bare carbon fiber wire microelectrode deposited with graphene oxide; wherein: the concentration of the graphene oxide suspension is 0.5-1.5 mg/mL, and the constant voltage is 1.5-1.7V; the deposition time is 500-700 s.
5. The method for preparing the simple electrochemical micro-sensor according to claim 1, wherein in the step 1), the specific steps of the electro-oxidation treatment are as follows: placing the bare carbon fiber wire microelectrode deposited with the graphene oxide in a NaCl solution, and performing constant potential oxidation treatment to obtain a CMFE/OxGO electrode; wherein the concentration of the NaCl solution is 130-150 mM; the oxidation voltage is 1.8-2.0V, and the oxidation time is 150-250 s.
6. The method for preparing a simplified electrochemical micro-sensor according to claim 1, wherein in step 2), Ti3C2TxThe modification method comprises the following steps: the CMFE/OxGO electrode is put into Ti3C2TxSoaking the suspension, drying, and modifying Ti by soaking and drying3C2TxDecorating on the electrode; wherein: the soaking time is 1-3 min each time, and the cycle times are 4-6 times.
7. The simple power supply of claim 1The preparation method of the chemical microsensor is characterized in that in the step 2), the specific steps of reduction self-assembly are as follows: will be decorated with Ti3C2TxThe CMFE/OxGO electrode is placed in silver nitrate solution for soaking, and reduction reaction can occur in the soaking process to obtain CFME/OxGO/Ti3C2Txan/Ag electrode; wherein: the soaking time is 30-90 min.
8. The simple electrochemical microsensor is prepared by the method for preparing the simple electrochemical microsensor according to any one of claims 1 to 7.
9. The simplified electrochemical microsensor according to claim 8 for the detection of Cl-The use of (1).
10. The simplified electrochemical microsensor for the detection of Cl as recited in claim 8-The method comprises the following steps:
s1, mixing CFME/OxGO/Ti3C2Txthe/Ag electrode is placed in a blank phosphoric acid buffer solution, and is scanned by adopting a DPV method, wherein the scanning requirement is-0.75V-0.4V; respectively obtaining an oxidation peak outside-500 mV and 112mV, and placing the electrode in a container containing 100M Cl-The oxidation peak at-500 mV keeps the peak potential unchanged, and the oxidation peak at 112mV moves to-52 mV;
s2, mixing CFME/OxGO/Ti3C2TxThe Ag electrode is sequentially placed in Cl with the concentration of 0-700 mM-In a phosphoric acid buffer solution of (1), specifically, E at a concentration of 0, 1, 5, 10, 20, 40, 60, 80, 100, 150, 200, 250, 300, 400, 500, 600, 700mM, 112mVp(Ag/AgCl) Peak potential with Cl-Increasing concentration gradually moving in a negative direction, E at-500 mVp(OxGO) peak potential remains unchanged; by calculating the potential difference Delta E of two oxidation peaksp(OxGO/AgCl) with Cl-The logarithm of the concentration is in direct proportion, so that a standard curve of the concentration and the potential difference can be obtained;
s3, mixing CFME/OxGO/Ti3C2Txthe/Ag electrode is placed in Cl with unknown concentration-The solution or cerebral microdialysis solution or cerebral cortex or striatum or hippocampus, and the Delta E can be obtained by scanning with DPV methodp(OxGO/AgCl), and then the concentration of the chloride ions can be obtained through a standard curve.
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