CN112748167B - Needle-shaped all-solid-state sensor for dopamine detection and preparation method thereof - Google Patents
Needle-shaped all-solid-state sensor for dopamine detection and preparation method thereof Download PDFInfo
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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
- G01N27/333—Ion-selective electrodes or membranes
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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
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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
- G01N27/283—Means for supporting or introducing electrochemical probes
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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
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- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
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Abstract
The invention relates to the field of neurotransmitter detection, and provides a needle-shaped all-solid-state sensor for dopamine detection and a preparation method thereof, aiming at solving the technical problems of complex operation, long time consumption, low precision, strict use conditions and the like in the conventional dopamine detection. Meanwhile, the invention also solves the problems that the traditional equipment is large and the in-vivo detection is difficult to realize, and provides possibility for in-vivo detection through the miniaturization of the electrode.
Description
Technical Field
The invention relates to the field of neurotransmitter detection, in particular to a needle-shaped all-solid-state sensor for dopamine detection and a preparation method thereof.
Background
Dopamine is a monoamine neurotransmitter and plays a role in signal transduction in the nervous system. Dopamine plays an important role in the process of perceiving pleasure, and is related to motor control, reward mechanisms, excitement, learning and memory and the like. Abnormal mental states also occur in humans when there is a dysfunction in the dopaminergic nervous system of the human brain. Schizophrenia may occur when dopaminergic neurons are overactive; when the secretion of dopamine is insufficient, diseases such as Parkinson's disease and the like can be generated; when dopaminergic neurons in the substantia nigra of the midbrain are damaged or lost, a person can have symptoms of tremor, stiffness, speech blurring and the like. Therefore, the method for monitoring the dopamine content in the human cerebrospinal fluid has important significance for monitoring patients and developing modern medical treatment.
There are many methods for dopamine detection currently available. The traditional methods include methods such as liquid chromatography, fluorescence, colorimetry, spectroscopy and capillary electrophoresis, which have the advantages of high precision and sensitivity, but generally require pretreatment steps such as derivatization of a sample, measurement instruments are expensive and complex to operate, and operators are generally required to be trained. Compared with the methods, the electrochemical method has the advantages of high sensitivity, low detection limit, good repeatability, low analysis cost, capability of measuring without pretreating a sample and the like. Electrochemical methods generally include amperometry, electrical impedance, and potentiometry, with amperometry being the most common method of electrochemical measurement. However, in order to explore the characteristics of the current in the amperometry, an extra high applied potential is usually required, which may cause some damage to the nervous system; other substances in the sample can also generate oxidation-reduction reaction under high potential, thereby causing interference to experimental results; in the amperometric detection, dopamine is catalyzed by amine oxidase, and the service life of the electrode is shortened due to the complex enzyme fixation and difficult storage. In the potentiometry based on the ion selective electrode, detection can be carried out without applying extra potential, and the influence on neuron cells is avoided; and the participation of enzyme is not needed, the preservation of the electrode is facilitated, and the service life of the electrode is prolonged.
However, the conventional ion selective electrode contains an internal filling electrolyte, so that problems of internal filling electrolyte leakage, sample pollution and the like are easily caused, the storage of the electrode is not facilitated, the detection lower limit is reduced, and the size of the electrode is larger.
Disclosure of Invention
In order to solve the technical problems of complex operation, long time consumption, low precision, strict use conditions and the like of the existing dopamine detection, the invention provides a needle-shaped all-solid-state sensor for dopamine detection and a preparation method thereof. Meanwhile, the invention also solves the problems that the traditional equipment is large and the in-vivo detection is difficult to realize, and provides possibility for in-vivo detection through the miniaturization of the electrode.
The invention is realized by the following technical scheme: the utility model provides a full solid-state sensor of acicular for dopamine detects, includes reference electrode, selective electrode include first gold wire, the one end of first gold wire is for selecting the output, other end from inside to outside cladding solid state electrolyte layer, dopamine sensitive membrane, macromolecule filter layer and soluble sclerosis layer in proper order, reference electrode include the second gold wire, one end is the reference output, the other end from inside to outside cladding solid state electrolyte layer, reference membrane, macromolecule filter layer and soluble sclerosis layer in proper order.
The solid electrolyte of the solid electrolyte layer replaces the filled electrolyte, so that the ion-electron conversion process is realized, and the dopamine ion concentration can be converted into electrons for measurement. The all-solid-state ion selective electrode has the advantages of easiness in storage, easiness in miniaturization and the like, and can be prepared into any shape and size.
Preferably, the needle-shaped all-solid-state sensor further comprises an electrode support and 2 outgoing lines, wherein 2 conductive silver pastes are arranged in the electrode support, the same side of the selected output end and the reference output end is inserted into the electrode support and is respectively connected with one end of each outgoing line through the conductive silver paste, and the other end of each outgoing line is arranged outside the electrode support. The electrode support is used for fixing the reference electrode and the selective electrode, and the 2 leading-out wires are respectively a leading-out wire of the reference electrode and a leading-out wire of the selective electrode, so that electric signal transmission and detection are facilitated.
More preferably, the electrode support is provided with 2 parallel through holes, conductive silver paste is respectively arranged in the 2 through holes, the selection output end and the 1 st outgoing line of the selective electrode penetrate into two ends of the first through hole and are connected through the conductive silver paste, one end of the outgoing line outside the electrode support is the outgoing line of the selective electrode, the reference output end and the 2 nd outgoing line of the reference electrode penetrate into two ends of the second through hole respectively and are connected through the conductive silver paste, and one end of the outgoing line outside the electrode support is the outgoing line of the reference electrode.
According to the invention, the sensitivity and selectivity of the all-solid-state dopamine sensor are improved by using a specific selective electrode and adding trimethyl-beta-cyclodextrin into the dopamine sensitive membrane, and the sensor can be prepared into any shape and size by miniaturization, is convenient to store, carry and measure, and is beneficial to realizing the in-vivo detection of the dopamine concentration. The preparation method of the needle-shaped all-solid-state sensor for detecting dopamine comprises the following steps:
s01, pre-treating 2 gold wires;
the gold wire pretreatment process comprises: respectively coating insulating layers on the middle parts of two gold wires, exposing two ends of each gold wire, respectively polishing one end of each gold wire on chamois leather by adopting alumina suspension, cleaning the polished gold wires by using deionized water, then sequentially putting the gold wires into 45-55.0% vol alcohol solution and 6.0-10.0% wt sulfuric acid solution for ultrasonic cleaning, finally cleaning the gold wires by using the deionized water, blow-drying the exposed parts of the gold wires by using nitrogen, and then putting the gold wires into a drying box for drying, preferably drying for 12-24 h.
Preferably, the insulating layer is a prussian blue insulating layer.
Preferably, the gold wire is 0.25-0.5mm in diameter and 99.99-99.999% in purity;
preferably, the alumina suspension is prepared from 69-100mg/mL of alumina powder with the diameter of 0.05-1.5 μm in sequence. More preferably, an 80mg/mL suspension of alumina powders having a diameter of 1.5 μm, 0.5 μm and 0.05 μm is prepared, the suspension having a diameter of 1.5 μm is dropped on a chamois, the gold wire is wrapped with the chamois, the gold wire is drawn out and polished, and then polished with suspensions having a diameter of 0.5 μm and 0.05 μm in this order.
Preferably, the power of ultrasonic cleaning is 160-200 w, and the time is 8-15 min.
S02, coating the solid electrolyte layer: stirring the conductive polymer aqueous solution, the surfactant and the organic solvent to prepare a solid electrolyte mixed solution, respectively immersing one end of each of the two treated gold wires into the solid electrolyte mixed solution for 3-5s, taking out and airing, repeating the steps for a plurality of times to form a solid electrolyte layer, and drying the solid electrolyte layer in a drying oven until a uniform black solid film is generated on the surface.
In the solid electrolyte mixed solution, the usage amount of the surfactant is 0.5-1 per mill of the total mass of the conducting polymer aqueous solution, and the usage amount of the organic solvent is 1.5-3% of the total mass of the conducting polymer aqueous solution.
Preferably, the conductive polymer aqueous solution is poly 3, 4-ethylenedioxythiophene monomer/polystyrene sulfonic acid aqueous solution (PEDOT/PSS) with the mass concentration of 1.3-1.5%, is more stable relative to solid electrolytes such as polythiophene and polypyrrole, and is not easily interfered by light, oxygen, carbon dioxide and the like. More preferably, the poly 3, 4-ethylenedioxythiophene monomer and the polystyrene sulfonic acid aqueous solution (PEDOT/PSS) comprise 0.5 wt% of the poly 3, 4-ethylenedioxythiophene monomer and 0.8 wt% of the polystyrene sulfonic acid.
The surfactant is a cetyl trimethyl ammonium bromide solution with the concentration of 0.1-1M, compared with other surfactants such as triton and the like, the solid electrolyte aqueous solution has better viscosity and diffusion coefficient, and is not easy to crack in the spot coating process.
The organic solvent is selected from one or more of dimethyl sulfoxide, ethylene glycol, methanol and sorbitol, and can enhance the molecular bonding force of the solid electrolyte and change the molecular conformation, thereby being beneficial to improving the conductivity and the mechanical reliability of the solid electrolyte.
S03, coating a dopamine sensitive film: dissolving a high molecular polymer, an ion carrier, an ion exchanger and a plasticizer in tetrahydrofuran to prepare a dopamine sensitive membrane solution, repeatedly immersing a first gold wire in S02 into the dopamine sensitive membrane solution at the end coated with the solid electrolyte layer to form a dopamine sensitive membrane, drying in a drying box, and drying until the surface of the dopamine sensitive membrane generates a uniform and transparent solid membrane.
The dopamine sensitive membrane liquid comprises the following solutes in parts by weight:
the ratio of the dosage of the solvent tetrahydrofuran in the dopamine sensitive membrane liquid to the volume mass of the high molecular polymer is 10-12 mu L: 1mg, so that the phenomenon that the membrane is difficult to form due to too much solvent or the plasticizer is easy to leak due to too little solvent is avoided.
Preferably, the ionophore is selected from trimethyl-beta-cyclodextrin, so that the selectivity to dopamine is good, and dopamine can be identified under the condition that the pH value is 7-8;
preferably, the ion exchanger is selected from one of cation exchangers, more preferably from one of potassium tetrakis [3, 5-bis (trifluoromethylphenyl) borate ], potassium tetrakis (4-chlorophenyl) borate, sodium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate and sodium tetraphenylborate, has a certain selectivity and increases the stability of the detection result by repelling anions and specifically permeating cations.
Preferably, the plasticizer is nitrobenzene octyl ether.
Preferably, the high molecular polymer is one or more of polyvinyl chloride, polycarboxylate chloroethylene and polyurethane, and is used as a skeleton of the dopamine sensitive membrane, and carboxyl in the high molecular polymer can be specifically combined with dopamine to increase the selectivity of the sensitive membrane to dopamine.
S04, coating reference membrane: dissolving a high molecular polymer, an ion exchanger and a plasticizer in tetrahydrofuran to prepare a reference membrane solution, repeatedly immersing the end of the second gold wire coated with the solid electrolyte layer in the S02 in the reference membrane solution to form a reference membrane, putting the reference membrane into a drying box for drying, and drying until the surface of the reference membrane generates a uniform and transparent solid membrane.
The reference membrane solution comprises the following solutes in parts by weight:
33-33.2 parts of high-molecular polymer,
0.5-1 part of ion exchanger,
and 66-66.3 of a plasticizer.
The volume-mass ratio of the dosage of the solvent tetrahydrofuran in the reference membrane solution to the high molecular polymer is 10-12 muL: 1mg, so that the phenomenon that the membrane is difficult to form due to too much solvent or the plasticizer is easy to leak due to too little solvent is avoided.
Preferably, the ion exchanger is selected from one of cation exchangers. More preferably, the reagent is one selected from the group consisting of potassium tetrakis [3, 5-bis (trifluoromethylphenyl) borate ], potassium tetrakis (4-chlorophenyl) borate, sodium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate, and sodium tetraphenylborate, which has a certain selectivity and an increased stability of a detection result by specifically transmitting cations by repelling anions.
Preferably, the plasticizer is nitrobenzene octyl ether.
Preferably, the high molecular polymer is one or more of polyvinyl chloride, polycarboxylate vinyl chloride and polyurethane, and is used as a skeleton of the reference membrane.
Except for the ion carrier, the high molecular polymer, the ion exchanger and the plasticizer in the reference membrane are the same as those in the dopamine sensitive membrane, so that errors caused by other potential changes to detection results are avoided. Preferably, the reference membrane and the dopamine sensitive membrane are used in the same amount by ion exchange.
S05, coating a macromolecular filter layer: respectively dissolving a high molecular polymer and a macroporous polymer in a polar solvent, stirring and dissolving, then mixing the two solutions, stirring for 2-4 hours to prepare a high molecular polymer-macroporous polymer mixed solution, then respectively soaking a first gold wire coated dopamine sensitive membrane end of S03 and a second gold wire coated reference membrane end of S04 in the high molecular polymer-macroporous polymer mixed solution, repeatedly soaking to form a macromolecular filtering membrane, and drying for 2-3 days at the constant temperature of 40-50 ℃;
the mass ratio of the macroporous polymer to the high molecular polymer in the mixed solution is 2-3: 1. Preferably, the high molecular weight polymer is first prepared in polar solvent to concentration of 1.0-1.2g/dL and the macroporous polymer to concentration of 0.5-1g/dL separately and then mixed.
Preferably, the polar solvent is one or more of tetrahydrofuran, methyl ketene and dimethylformamide, has good solubility on a plurality of organic matters, and can be used for dissolving a plurality of polymers;
preferably, the high molecular polymer is one or more of polyvinyl chloride, polycarboxylate vinyl chloride and polyurethane, and the same substances as the polymers used in the sensitive membrane and the reference membrane are adopted, so that the affinity between the membranes is increased, and the outer membrane is not easy to fall off;
preferably, the macroporous polymer is one or more of polyvinyl acetate and polyvinyl alcohol, is easily and uniformly mixed with a high molecular polymer solution, selectively permeates small molecular substances such as dopamine and the like by forming pores in a polymer film, prevents interference on detection caused by permeation of large molecular substances and the like, and increases stability of detection potential.
S06, coating a soluble hardening layer: respectively immersing the ends of the S05 two gold wire coated macromolecular filter membranes into a molten biodegradable material, taking out the filter membranes, putting the filter membranes into a drying oven until the biodegradable material becomes hard, and respectively manufacturing a selective electrode and a reference electrode;
preferably, the biodegradable material is selected from one or more of polyethylene glycol and polylactic acid, a hard protective layer is formed outside the sensor to avoid damage to a solid electrolyte layer, a sensitive membrane and a macromolecular filter membrane in the body detection implantation process, and the biodegradable material can be dissolved in a body by itself due to the biodegradable property, has good biocompatibility and cannot influence the permeation of dopamine in the detection process.
The biodegradable material is heated to 50-80 ℃ to reach a molten state.
S07, arranging 2 non-crossed through holes in the electrode support, fixing conductive silver paste in the through holes respectively, connecting the selection output end of the selective electrode and the reference output end of the reference electrode with one end of the outgoing line through the conductive silver paste in the through holes respectively, arranging the other ends of the 2 outgoing lines outside the electrode support, and finally packaging and fixing the through holes through AB glue to obtain the needle-shaped all-solid-state sensor for detecting dopamine.
Preferably, the electrode support is made by 3D printing, and the 3D printing material of the electrode support is selected from one or more of polylactic acid, acrylonitrile-butadiene-styrene copolymer, polyethylene glycol terephthalate-1, 4-cyclohexane dimethanol ester, nylon, high impact polystyrene and polyvinyl alcohol, and has strong toughness. Through holes matched with the size and shape of the electrodes can be formed, and displacement and deformation in the electrode detection process are reduced.
In the actual measurement process, the detection ends of the working electrode and the reference electrode of the needle-shaped all-solid-state dopamine sensor for detecting dopamine are immersed into a dopamine solution to be detected, one end of the lead-out wire is connected with a circuit of an electrochemical workstation, and the potential difference generated by the change of the dopamine concentration is detected.
The solution to be tested makes good contact with the dopamine sensitive membrane and the reference membrane and reacts. The dopamine sensitive membrane has good lipophilicity, the ionophore in the dopamine sensitive membrane can generate strong binding force with dopamine, and the electrode potential of the sensitive membrane is changed through selective permeation of the dopamine.
Compared with the prior art, the invention has the beneficial effects that:
(1) the solid electrolyte layer used by the sensor has ion-electron conversion characteristics, can convert an ion signal detected by the sensitive film into a potential signal for conduction, and utilizes an external circuit for measurement;
(2) the sensitive membrane selectively penetrates through dopamine to detect the change of the concentration of the dopamine, so that the interference of external substances on a detection result is reduced;
(3) the macromolecule filter layer can increase the detection stability of the electrode by permeating micromolecule substances and blocking interference substances such as macromolecules and the like;
(4) the dissolvable hardened layer is made of biodegradable materials, so that damage to the electrode in the body detection implantation process is reduced, the electrode is dissolved in the body by itself due to biocompatibility, and the detection result is not influenced;
(5) the sensor provided by the invention integrates the dopamine selective electrode and the reference electrode into a whole, is convenient to store and use, and is beneficial to realizing the in-vivo detection of the concentration of dopamine.
Drawings
FIG. 1 is a cross-sectional view of a needle-like all-solid-state sensor for dopamine detection according to the present invention;
FIG. 2 is a front view of a needle-shaped all-solid-state sensor for dopamine detection according to the present invention;
FIG. 3 is a side view of a needle-like all-solid-state sensor for dopamine detection according to the present invention;
FIG. 4 is a calibration curve of the potential response of the present invention in dopamine solutions of different concentrations;
FIG. 5 is a graph of the potential response at different temperatures according to the present invention;
FIG. 6 is a graph of the sensitivity characteristics of the present invention over 25 days;
FIG. 7 is a graph showing the potential response characteristics of the present invention in human serum.
In the figure, 1 a: soluble hardened layer of selective electrode, 1 b: soluble hardened layer of reference electrode, 2 a: macromolecule filtration membrane of selective electrode, 2 b: macromolecular filtration membrane for reference electrode, 3 a: dopamine-sensitive membrane of selective electrode, 3 b: reference membrane of reference electrode, 4 a: solid electrolyte layer of selective electrode, 4 b: solid electrolyte layer of reference electrode, 5: AB glue, 6 a: gold wire of selective electrode, 6 b: gold wire of the reference electrode; 7 a: conductive silver paste for selective electrode, 7 b: conductive silver paste for reference electrode, 8: electrode holder, 9 a: lead-out line of selective electrode, 9 b: a lead-out wire for a reference electrode, wherein: a: selective electrode, b: a reference electrode.
Detailed Description
The present invention will be described in further detail below with reference to examples and the accompanying drawings, in which the starting materials are commercially available or prepared by conventional methods.
In the examples, the aqueous solution of poly (3, 4-ethylenedioxythiophene) monomer/polystyrene sulfonic acid (PEDOT/PSS) was obtained from Sigma, wherein poly (3, 4-ethylenedioxythiophene) was 0.5 wt% and polystyrene sulfonic acid was 0.8 wt%.
Examples
As shown in fig. 1, fig. 2 and fig. 3, a needle-shaped all-solid-state sensor for detecting dopamine comprises a reference electrode b and a selective electrode a of dopamine, wherein the selective electrode of dopamine comprises a first gold wire 6a, one end of the first gold wire 6a is a selective output end, and the other end of the first gold wire is coated with a solid electrolyte layer 4a, a dopamine sensitive membrane 3a, a macromolecule filter layer 2a and a soluble hardened layer 1a from inside to outside in sequence, the reference electrode comprises a second gold wire 6b, one end of the reference electrode is a reference output end, and the other end of the reference electrode is coated with a solid electrolyte layer 4b, a reference membrane 3b, a macromolecule filter layer 2b and a soluble hardened layer 1b from inside to outside in sequence.
Preferably, the needle-shaped all-solid-state sensor further comprises an electrode support 8, a lead wire 9a of the selective electrode, and a lead wire 9b of the reference electrode. 2 non-crossed through holes are formed in the electrode support 8, stepped holes with gradually reduced diameters are formed in the opening, the stepped holes are matched with insertion of selective electrodes or reference electrodes, and displacement and deformation in the electrode detection process are reduced. Be equipped with 2 electrically conductive silver pastes in the electrode support 8, the electrically conductive silver paste 7a of selective electrode, the electrically conductive silver paste 7b of reference electrode, select output and reference output homonymy to cross to insert electrode support 8 respectively through electrically conductive silver paste 7a, 7b and selective electrode's lead-out wire 9a, the lead-out wire 9b one end of reference electrode is connected, 2 lead-out wires 9a, 9 b's the other end is established outside electrode support 8, encapsulate and fix the through-hole through AB glue 5 at last, obtain the full needle-like solid state sensor who is used for dopamine to detect.
Preparation example 1
S01, coating two gold wires with the diameter of 0.5mm and the purity of 99.999% with a Prussian blue insulating layer, and reserving exposed parts at two ends for film coating and detection ends; polishing two gold wire detection ends on chamois leather by using 80mg/mL alumina suspension prepared from alumina powder with the diameters of 1.5 microns, 0.5 microns and 0.05 microns respectively, cleaning the polished gold wire detection ends by using deionized water, respectively ultrasonically cleaning the gold wire detection ends for 10min by adding 50.0% vol alcohol solution and 8.0% wt sulfuric acid solution, wherein the ultrasonic cleaning power is 200w, and then washing the gold wire detection ends by using the deionized water; finally, drying the exposed part of the gold wire without water drops by using nitrogen, and drying the gold wire in a drying box for 20 hours;
s02, coating the solid electrolyte layer: adding 1 per thousand hexadecyl trimethyl ammonium bromide aqueous solution with the concentration of 0.1M and the mass percentage of 1 per thousand into poly 3, 4-ethylene dioxythiophene monomer/polystyrene sulfonic acid aqueous solution with the mass concentration of 1.3wt percent and the total mass of the poly 3, 4-ethylene dioxythiophene monomer/polystyrene sulfonic acid aqueous solution, uniformly stirring the mixture by using 3 percent of dimethyl sulfoxide to prepare a solid electrolyte mixed solution, respectively immersing one end of two gold wires treated by S01 into the solid electrolyte mixed solution for 4S, taking out and drying the mixture, repeating the steps for 20 times to form a solid electrolyte layer, and drying the solid electrolyte layer in a drying box until a uniform black solid electrolyte layer is generated on the surface;
s03, coating a dopamine sensitive film: dissolving 32.8mg of polycarboxylate vinyl chloride as a high-molecular polymer, 1mg of trimethyl-beta-cyclodextrin as an ion carrier, 0.5mg of potassium tetrakis [3, 5-bis (trifluoromethylphenyl) borate as an ion exchanger and 65.5mg of nitrobenzene octyl ether as a plasticizer in 330 mu L of tetrahydrofuran, and oscillating to obtain a uniform, transparent and viscous dopamine sensitive membrane solution. And repeatedly immersing the first gold wire in the step S02 in the dopamine sensitive membrane solution for 6 times at the end coated with the solid electrolyte layer to form a dopamine sensitive membrane, wrapping the dopamine sensitive membrane on the outer layer of the solid electrolyte and lower than the solid electrolyte, drying in a drying box, and drying until the surface of the dopamine sensitive membrane is uniform and transparent.
S04, coating reference membrane: high molecular polymer 33.2mg polycarboxylate chloroethylene, ion exchanger 0.5mg potassium tetrakis (4-chlorophenyl) borate are mixed uniformly, plasticizer 66.3mg nitrobeneoyl ether is dissolved in 340 muL tetrahydrofuran, and the mixture is shaken to obtain uniform, transparent and viscous reference membrane liquid. And repeatedly immersing the end of the second gold wire coated with the solid electrolyte layer in the S02 solution for 6 times to form a reference membrane, wrapping the reference membrane on the outer layer of the solid electrolyte and lower than the solid electrolyte, putting the reference membrane into a drying box for drying, and drying until the surface of the reference membrane is uniform and transparent.
S05, coating a macromolecular filter layer: respectively preparing 1.2g/dL polycarboxylate vinyl chloride solution and 0.5g/dL polyvinyl acetate solution by taking tetrahydrofuran as a solvent, mixing the two polymer solutions according to the mass ratio of solute of 3:1 to obtain viscous liquid, stirring for 3 hours to prepare a high polymer-macroporous polymer mixed solution, respectively soaking a first gold wire coated with dopamine sensitive membrane end of S03 and a second gold wire coated with reference membrane end of S04 in the high polymer-macroporous polymer mixed solution for 6 times repeatedly to form a macromolecular filter membrane, wrapping the macromolecular filter membrane on the outer layer of the sensitive membrane or the reference membrane and lower than the sensitive membrane or the reference membrane, and drying for 2 days at the constant temperature of 45 ℃;
s06, coating a soluble hardening layer: heating a biodegradable material polyethylene glycol to 60 ℃ to reach a molten state, respectively soaking the ends of the S05 two gold wire coated macromolecular filter membranes into the molten biodegradable material to enable the ends to be wrapped on the outer layer of the macromolecular filter membrane and lower than the macromolecular filter membrane, taking out the materials and putting the materials into a drying oven until the biodegradable material becomes hard, and respectively preparing a selective electrode and a reference electrode;
s07, 3D printing is carried out by adopting a polylactic acid material to manufacture an electrode support, 2 non-crossed through holes are arranged in the electrode support, a stepped hole with the diameter gradually reduced is arranged at the opening, and the stepped hole is matched with the insertion of a selective electrode or a reference electrode, so that the displacement and deformation in the electrode detection process are reduced. And conductive silver paste is respectively fixed in the through holes, the selection output end of the selective electrode and the reference output end of the reference electrode are respectively connected with one end of the outgoing line through the conductive silver paste in the through holes, the other ends of the 2 outgoing lines are arranged outside the electrode support, and finally, the through holes are packaged and fixed through AB glue to obtain the needle-shaped all-solid-state sensor 1 for detecting dopamine.
Preparation example 2
S01, coating two gold wires with the diameter of 0.4mm and the purity of 99.99% with a Prussian blue insulating layer, and reserving exposed parts at two ends for film coating and detection ends; polishing two gold wire detection ends on chamois leather by using 100mg/mL alumina suspension prepared from alumina powder with the diameters of 1.2 microns, 0.8 microns and 0.07 microns respectively, cleaning the polished gold wire detection ends by using deionized water, respectively ultrasonically cleaning the gold wire detection ends for 10min by using 45.0% vol alcohol solution and 10.0% wt sulfuric acid solution respectively, wherein the power of ultrasonic cleaning is 180w, then washing the gold wire detection ends by using the deionized water, finally drying the exposed part of the gold wire by using nitrogen gas without water drops, and drying the gold wire detection ends in a drying box for 15 h;
s02, coating the solid electrolyte layer: adding 0.8 per thousand of hexadecyl trimethyl ammonium bromide aqueous solution with the concentration of 0.5M into poly 3, 4-ethylene dioxythiophene monomer/polystyrene sulfonic acid aqueous solution with the mass concentration of 1.4 wt% of the total mass of the poly 3, 4-ethylene dioxythiophene monomer/polystyrene sulfonic acid aqueous solution, uniformly stirring the mixture with 2% of ethylene glycol to prepare solid electrolyte mixed solution, respectively soaking one end of two gold wires treated by S01 into the solid electrolyte mixed solution for 5 seconds, taking out and airing the mixture, repeating the steps for 22 times to form a solid electrolyte layer, and placing the solid electrolyte layer into a drying box to dry until a uniform black solid electrolyte layer is formed on the surface;
s03, coating a dopamine sensitive film: dissolving 32.6mg of high-molecular polymer polyvinyl chloride, 1.5mg of ionophore trimethyl-beta-cyclodextrin, 0.6mg of ion exchanger sodium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate and 65.3mg of plasticizer nitrobenzene octyl ether in 390 mu L of tetrahydrofuran, and oscillating to obtain uniform, transparent and viscous dopamine sensitive membrane liquid. And repeatedly immersing the first gold wire in the step S02 into the dopamine sensitive membrane solution for 5 times at the end coated with the solid electrolyte layer to form a dopamine sensitive membrane, wrapping the dopamine sensitive membrane on the outer layer of the solid electrolyte and lower than the solid electrolyte, drying in a drying box, and drying until the surface of the dopamine sensitive membrane is uniform and transparent.
S04, coating reference membrane: 33.1mg of high molecular polymer polyvinyl chloride, 0.6mg of sodium tetrakis [3, 5-bis (trifluoromethyl) phenyl ] borate as an ion exchanger are uniformly mixed, 66.3mg of nitroben-zene ether as a plasticizer is dissolved in 390 mu L of tetrahydrofuran, and the mixture is shaken to obtain uniform, transparent and viscous reference membrane liquid. And repeatedly immersing the end of the second gold wire coated with the solid electrolyte layer in the S02 for 5 times into the reference membrane solution to form a reference membrane, wrapping the reference membrane on the outer layer of the solid electrolyte and lower than the solid electrolyte, putting the reference membrane into a drying box for drying, and drying until the surface of the reference membrane is uniform and transparent.
S05, coating a macromolecular filter layer: preparing a polyvinyl chloride solution with the concentration of 1.1g/dL and a polyvinyl alcohol solution with the concentration of 0.8g/dL by taking dimethylformamide as a solvent, mixing the two polymer solutions according to the solute mass ratio of 2: 1 to obtain a viscous liquid, stirring for 4 hours to prepare a high polymer-macroporous polymer mixed solution, then respectively soaking a first gold wire coating dopamine sensitive membrane end S03 and a second gold wire coating reference membrane end S04 into the high polymer-macroporous polymer mixed solution, repeatedly soaking for 5 times to form a macromolecular filter membrane, wrapping the macromolecular filter membrane on the outer layer of the sensitive membrane or the reference membrane and making the macromolecular filter membrane lower than the sensitive membrane or the reference membrane, and placing the macromolecular filter membrane at the constant temperature of 40 ℃ for drying for 3 days.
S06, coating a soluble hardening layer: heating a biodegradable material polylactic acid to 80 ℃ to reach a molten state, respectively soaking the ends of two gold wire coating macromolecular filtering membranes of S05 into the molten biodegradable material to enable the ends to be wrapped on the outer layer of the macromolecular filtering membrane and lower than the macromolecular filtering membrane, taking out the materials and putting the materials into a drying oven until the biodegradable material is hardened, and respectively preparing a selective electrode and a reference electrode;
s07, performing 3D printing by using an acrylonitrile-butadiene-styrene copolymer material to manufacture an electrode support, wherein 2 non-crossed through holes are formed in the electrode support, stepped holes with gradually reduced diameters are formed in the openings, and the stepped holes are matched with insertion of selective electrodes or reference electrodes to reduce displacement and deformation in the electrode detection process. And conductive silver paste is respectively fixed in the through holes, the selection output end of the selective electrode and the reference output end of the reference electrode are respectively connected with one end of the outgoing line through the conductive silver paste in the through holes, the other ends of the 2 outgoing lines are arranged outside the electrode support, and finally, the through holes are packaged and fixed through AB glue to obtain the needle-shaped all-solid-state sensor 2 for detecting dopamine.
Preparation example 3
S01, coating two gold wires with the diameter of 0.3mm and the purity of 99.99% with a Prussian blue insulating layer, and reserving exposed parts at two ends for film coating and detection ends; polishing two gold wire detection ends on chamois leather by using 70mg/mL alumina suspension prepared from alumina powder with the diameters of 1.5 microns, 0.3 microns and 0.08 microns respectively, cleaning the polished gold wire detection ends by using deionized water, respectively ultrasonically cleaning the gold wire detection ends for 15min by using 55.0% vol alcohol solution and 6.0% wt sulfuric acid solution respectively, wherein the power of ultrasonic cleaning is 160w, then washing the gold wire detection ends by using the deionized water, finally drying the exposed part of the gold wire by using nitrogen gas without water drops, and drying the gold wire detection ends in a drying box for 20 h;
s02, coating the solid electrolyte layer: adding 0.5 per mill of 0.8M hexadecyl trimethyl ammonium bromide aqueous solution in percentage by mass and 1.5 percent of methanol into the conductive polymer aqueous solution with the mass concentration of 1.5 percent of poly 3, 4-ethylene dioxythiophene monomer/polystyrene sulfonic acid aqueous solution, based on the total mass of the conductive polymer aqueous solution, uniformly stirring to prepare a solid electrolyte mixed solution, respectively immersing one end of each of two gold wires processed by S01 into the solid electrolyte mixed solution for 3 seconds, taking out and drying in the air, repeating for 18 times to form a solid electrolyte layer, and drying in a drying oven until the surface of the solid electrolyte layer generates a uniform black solid electrolyte layer;
s03, coating a dopamine sensitive film: 32.7mg of high molecular polymer polyurethane, 1.3mg of trimethyl-beta-cyclodextrin serving as an ion carrier, 0.7mg of potassium tetrakis (4-chlorophenyl) borate serving as an ion exchanger and 65.3mg of nitrobenzene octyl ether serving as a plasticizer are dissolved in 350 mu L of tetrahydrofuran, and the mixture is shaken to obtain uniform, transparent and viscous dopamine sensitive membrane liquid. And repeatedly immersing the first gold wire in the step S02 in the dopamine sensitive membrane solution for 7 times at the end coated with the solid electrolyte layer to form a dopamine sensitive membrane, wrapping the dopamine sensitive membrane on the outer layer of the solid electrolyte and lower than the solid electrolyte, drying in a drying box, and drying until the surface of the dopamine sensitive membrane is uniform and transparent.
S04, coating reference membrane: 33.1mg of high molecular polymer polyurethane and 0.7mg of ion exchanger potassium tetrakis (4-chlorophenyl) borate are uniformly mixed, 66.2mg of nitrobenzene octyl ether plasticizer is dissolved in 350 mu L of tetrahydrofuran, and the mixture is shaken to obtain uniform, transparent and viscous reference membrane liquid. And repeatedly immersing the end of the second gold wire coated with the solid electrolyte layer in the S02 for 7 times into the reference membrane solution to form a reference membrane, wrapping the reference membrane on the outer layer of the solid electrolyte and lower than the solid electrolyte, putting the reference membrane into a drying box for drying, and drying until the surface of the reference membrane is uniform and transparent.
S05, coating a macromolecular filter layer: preparing a polyurethane solution with the concentration of 1.0g/dL and a cellulose acetate solution with the concentration of 1g/dL respectively by taking methyl ketene as a solvent, mixing the two polymer solutions according to the mass ratio of solute of 2.5: 1 to obtain a viscous liquid, stirring for 3 hours to prepare a high polymer-macroporous polymer mixed solution, then respectively immersing a first gold wire coating dopamine sensitive membrane end of S03 and a second gold wire coating reference membrane end of S04 in the high polymer-macroporous polymer mixed solution, repeatedly infiltrating for 7 times to form a macromolecular filter membrane, wrapping the macromolecular filter membrane on the outer layer of the sensitive membrane or the reference membrane and lower than the sensitive membrane or the reference membrane, and drying for 3 days at the constant temperature of 50 ℃.
S06, coating a soluble hardening layer: heating a biodegradable material polyethylene glycol to 70 ℃ to reach a molten state, respectively soaking the ends of the S05 two gold wire coated macromolecular filter membranes into the molten biodegradable material to enable the ends to be wrapped on the outer layer of the macromolecular filter membrane and lower than the macromolecular filter membrane, taking out the materials and putting the materials into a drying oven until the biodegradable material becomes hard, and respectively preparing a selective electrode and a reference electrode;
s07, 3D printing is carried out on the polyethylene glycol terephthalate-1, 4-cyclohexane dimethanol ester material to manufacture an electrode support, 2 non-crossed through holes are formed in the electrode support, stepped holes with gradually-reduced diameters are formed in the openings, the stepped holes are matched with insertion of selective electrodes or reference electrodes, and displacement and deformation in the electrode detection process are reduced. And conductive silver paste is respectively fixed in the through holes, the selection output end of the selective electrode and the reference output end of the reference electrode are respectively connected with one end of the outgoing line through the conductive silver paste in the through holes, the other ends of the 2 outgoing lines are arranged outside the electrode bracket, and finally, the through holes are packaged and fixed through AB glue to obtain the needle-shaped all-solid-state sensor 3 for detecting dopamine.
Use example
When the needle-shaped all-solid-state sensor for detecting dopamine, which is prepared in the embodiment, is used, the reference electrode and the dopamine selective electrode are respectively immersed in deionized water to be activated for 1 hour. And after the activation is finished, immersing the reference electrode and the dopamine selective electrode into a dopamine solution to be detected, respectively connecting the reference electrode and the dopamine selective electrode with leading-out wires of the reference electrode by using an electrochemical workstation, detecting the potential difference between the selective electrode and the reference electrode, and recording the time for 60 s. The potential difference value and the logarithm of the concentration of the dopamine in the detected liquid show linear correlation, and the concentration of the dopamine in the solution can be calculated according to the response electromotive force detected by an instrument.
Test example
1. Calibration curve of needle-shaped all-solid-state sensor for dopamine detection prepared by using method
Fig. 4 is a potential response calibration curve obtained by measuring different dopamine solutions (pH 7.4 in solution and 0.01M acetic acid-lithium acetate solution as a background solution) by using the needle-shaped all-solid-state sensor for dopamine detection prepared by the embodiment of the present invention, and the linear relationship is EMF (mv) ═ 48.423LogC (mol/L) +331.14, wherein EMF represents response electromotive force, C represents dopamine concentration in solution, and the correlation coefficient R2 ═ 0.9983.
2. Coefficient of selectivity
K +, Na +, Ca2+, GC, AA, EP are common interfering substances in the human body. Is divided intoThe sensor prepared in the embodiment 1 of the invention is used for measuring the dopamine concentration at 10 by taking KCl, NaCl, CaCl2, GC, AA and EP as background solutions -710-1The potential response at M is shown in table 1:
TABLE 1 selectivity coefficient of dopamine electrode for interfering substances
The selectivity coefficient was calculated according to the fixed ion interference method specified by IUPAC. The dopamine sensor prepared by the invention has certain selectivity on common interferents in human bodies.
3. Potential response of the invention at different temperatures
With reference to the human body temperature range, 33-43 ℃ was selected as the measurement range, and the sensor 10 prepared in example 1 of the present invention was used to measure-5M～10-1The response characteristics of the M dopamine solution in the temperature range of 33-43 deg.C, as shown in FIG. 5, can be seen that the working characteristics of the sensor of the present invention are not substantially affected by temperature in this temperature range.
4. Repeatability and consistency
Standard dopamine buffers were prepared at concentrations of 0.1mM, 1mM and 10mM, respectively, and the standard solutions were measured using the sensors prepared in examples 1-3, as shown in FIG. 2:
table 2:
the average value (Means) of the measured concentration and the standard deviation (S.D.) of the electrode are calculated, and the error of the measured result of the sensor prepared by the invention is seen to be in a reasonable range, which indicates that the sensor prepared by the invention has good repeatability and consistency.
5. Service life of the electrode
Preparing fresh dopamine solution with concentration range of 10-710-1M, response characteristics of the sensor prepared in example 1 were measured every 5 daysAnd (4) carrying out one-time measurement. The sensitivity characteristics of the electrode in 25 days are shown in fig. 6, and the sensitivity does not obviously deviate, which indicates that the sensor prepared by the invention can normally work for at least 25 days.
6. Response of the invention in serum
Collecting fresh blood of human body, removing blood cells in the blood through anticoagulation and centrifugation, and preventing blood serum from coagulating. And adding a high-concentration dopamine standard solution into the serum to obtain dopamine solutions with different concentrations, and recording corresponding potential responses. As shown in FIG. 7, the sensor prepared in example 2 of the present invention was used in 10 the background solution of blood-4～10-2The response can be generated in the M dopamine solution, which shows that the sensor prepared by the invention can be used for detecting the concentration of dopamine in a human body.
Claims (10)
1. An acicular all-solid-state sensor for dopamine detection, characterized in that: the selective electrode comprises a first gold wire, one end of the first gold wire is a selective output end, the other end of the first gold wire is sequentially coated with a solid electrolyte layer, a dopamine sensitive membrane, a macromolecular filter layer and a soluble hardened layer from inside to outside, the reference electrode comprises a second gold wire, one end of the reference electrode is a reference output end, and the other end of the reference electrode is sequentially coated with the solid electrolyte layer, the reference membrane, the macromolecular filter layer and the soluble hardened layer from inside to outside;
the preparation method of the needle-shaped all-solid-state sensor for detecting dopamine comprises the following steps:
s01, pre-treating 2 gold wires;
s02, coating the solid electrolyte layer: stirring a conductive polymer aqueous solution, a surfactant and an organic solvent to prepare a solid electrolyte mixed solution, respectively immersing one end of each of the two treated gold wires into the solid electrolyte mixed solution for 3-5s, taking out and drying, repeating the steps for a plurality of times to form a solid electrolyte layer, and drying in a drying oven;
s03, coating a dopamine sensitive film: dissolving a high molecular polymer, an ion carrier, an ion exchanger and a plasticizer in tetrahydrofuran to prepare a dopamine sensitive membrane liquid, repeatedly immersing a first gold wire in S02 into the dopamine sensitive membrane liquid at the end coated with a solid electrolyte layer to form a dopamine sensitive membrane, and drying the dopamine sensitive membrane in a drying box, wherein the dopamine sensitive membrane comprises an ion carrier trimethyl-beta-cyclodextrin;
s04, coating reference membrane: dissolving a high molecular polymer, an ion exchanger and a plasticizer in tetrahydrofuran to prepare a reference membrane solution, repeatedly immersing the end of a second gold wire coated with a solid electrolyte layer in S02 in the reference membrane solution to form a reference membrane, and drying in a drying oven;
s05, coating a macromolecular filter layer: respectively dissolving a high molecular polymer and a macroporous polymer in a polar solvent, stirring and dissolving, then mixing the two solutions, stirring for 2-4 hours to prepare a high molecular polymer-macroporous polymer mixed solution, then respectively soaking a first gold wire coated dopamine sensitive membrane end of S03 and a second gold wire coated reference membrane end of S04 in the high molecular polymer-macroporous polymer mixed solution, repeatedly soaking to form a macromolecular filtering membrane, and drying at the constant temperature of 40-50 ℃ for 2-3 days, wherein the macroporous polymer is one or more of cellulose acetate and polyvinyl alcohol;
s06, coating a soluble hardening layer: respectively immersing the ends of the S05 two gold wire coated macromolecular filter membranes into a molten biodegradable material, taking out the filter membranes, putting the filter membranes into a drying oven until the biodegradable material becomes hard, and respectively manufacturing a selective electrode and a reference electrode;
s07, arranging 2 non-crossed through holes in the electrode support, fixing conductive silver paste in the through holes respectively, connecting the selection output end of the selective electrode and the reference output end of the reference electrode with one end of the outgoing line through the conductive silver paste in the through holes respectively, arranging the other ends of the 2 outgoing lines outside the electrode support, and finally packaging and fixing the through holes through AB glue to obtain the needle-shaped all-solid-state sensor for detecting dopamine.
2. The needle-like all-solid-state sensor for dopamine detection according to claim 1, characterized in that: the needle-shaped all-solid-state sensor further comprises an electrode support and 2 outgoing lines, wherein 2 conductive silver pastes are arranged in the electrode support, the output end and the reference output end are selected to penetrate into the electrode support from the same side and are connected with one end of each outgoing line through the conductive silver pastes, and the other ends of the 2 outgoing lines are arranged outside the electrode support.
3. A method for preparing an acicular all-solid-state sensor for dopamine detection according to claim 1 or 2, characterized in that: the preparation method comprises the following steps:
s01, pre-treating 2 gold wires;
s02, coating the solid electrolyte layer: stirring a conductive polymer aqueous solution, a surfactant and an organic solvent to prepare a solid electrolyte mixed solution, respectively immersing one end of each of the two treated gold wires into the solid electrolyte mixed solution for 3-5s, taking out and drying, repeating the steps for a plurality of times to form a solid electrolyte layer, and drying in a drying oven;
s03, coating a dopamine sensitive film: dissolving a high molecular polymer, an ion carrier, an ion exchanger and a plasticizer in tetrahydrofuran to prepare a dopamine sensitive membrane solution, repeatedly immersing a first gold wire in S02 into the dopamine sensitive membrane solution at the end coated with the solid electrolyte layer to form a dopamine sensitive membrane, and drying in a drying oven;
s04, coating reference membrane: dissolving a high molecular polymer, an ion exchanger and a plasticizer in tetrahydrofuran to prepare a reference membrane solution, repeatedly immersing the end of a second gold wire coated with a solid electrolyte layer in S02 in the reference membrane solution to form a reference membrane, and drying in a drying oven;
s05, coating a macromolecular filter layer: respectively dissolving a high molecular polymer and a macroporous polymer in a polar solvent, stirring and dissolving, then mixing the two solutions, stirring for 2-4 hours to prepare a high molecular polymer-macroporous polymer mixed solution, then respectively soaking a first gold wire coated dopamine sensitive membrane end of S03 and a second gold wire coated reference membrane end of S04 in the high molecular polymer-macroporous polymer mixed solution, repeatedly soaking to form a macromolecular filtering membrane, and drying for 2-3 days at the constant temperature of 40-50 ℃;
s06, coating a soluble hardening layer: respectively immersing the ends of the S05 two gold wire coated macromolecular filter membranes into a molten biodegradable material, taking out the filter membranes, putting the filter membranes into a drying oven until the biodegradable material becomes hard, and respectively manufacturing a selective electrode and a reference electrode;
s07, arranging 2 non-crossed through holes in the electrode support, fixing conductive silver paste in the through holes respectively, connecting the selection output end of the selective electrode and the reference output end of the reference electrode with one end of the outgoing line through the conductive silver paste in the through holes respectively, arranging the other ends of the 2 outgoing lines outside the electrode support, and finally packaging and fixing the through holes through AB glue to obtain the needle-shaped all-solid-state sensor for detecting dopamine.
4. The method for preparing an acicular all-solid-state sensor for dopamine detection according to claim 3, characterized in that: in step S01, the gold wire preprocessing process includes: respectively coating the insulating layers on the middle parts of the two gold wires, exposing two ends of each gold wire, respectively polishing one end of each gold wire on chamois leather by adopting alumina suspension, cleaning the polished gold wires by using deionized water, then sequentially putting the gold wires into 45-55.0% vol alcohol solution and 6.0-10.0% wt sulfuric acid solution for ultrasonic cleaning, finally cleaning the gold wires by using the deionized water, drying the gold wires after drying the gold wires by using nitrogen.
5. The method for preparing an acicular all-solid-state sensor for dopamine detection according to claim 4, wherein: the alumina suspension is prepared from 0.05-1.5 μm alumina powder in sequence at a concentration of 69-100 mg/mL.
6. The method for preparing an acicular all-solid-state sensor for dopamine detection according to claim 3, characterized in that: in the step S02, in the solid electrolyte mixed solution, the usage amount of the surfactant is 0.5 to 1 per mill of the total mass of the conductive polymer aqueous solution, and the usage amount of the organic solvent is 1.5 to 3 percent of the total mass of the conductive polymer aqueous solution.
7. The method for preparing an acicular all-solid-state sensor for dopamine detection according to claim 6, characterized in that: the conductive polymer aqueous solution is a poly 3, 4-ethylenedioxythiophene monomer/polystyrene sulfonic acid aqueous solution with the mass concentration of 1.3-1.5%; the surfactant is cetyl trimethyl ammonium bromide solution with the concentration of 0.1-1M; the organic solvent is selected from one or more of dimethyl sulfoxide, ethylene glycol, methanol and sorbitol.
8. The method for preparing an acicular all-solid-state sensor for dopamine detection according to claim 3, characterized in that: step S03, the weight parts of solutes in the dopamine sensitive membrane liquid are:
1-1.5 of an ionophore;
0.5-0.75 ion exchanger;
65.2 to 65.7 portions of plasticizer,
32.6-33.8 parts of high molecular polymer;
the volume mass ratio of the dosage of solvent tetrahydrofuran in the dopamine sensitive membrane liquid to the high molecular polymer is 10-12 mu L: 1 mg.
9. The method for preparing an acicular all-solid-state sensor for dopamine detection according to claim 3, characterized in that: in step S04, the solute comprises, by weight:
33-33.2 parts of high-molecular polymer,
0.5-1 part of ion exchanger,
and 66-66.3 of a plasticizer.
The volume mass ratio of the dosage of solvent tetrahydrofuran in the reference membrane solution to the high molecular polymer is 10-12 μ L: 1 mg.
10. The method for preparing an acicular all-solid-state sensor for dopamine detection according to claim 3, characterized in that: in step S05, the concentration of the high molecular polymer in the polar solvent is 1.0-1.2g/dL, the concentration of the macroporous polymer is 0.5-1g/dL, and the mass ratio of the macroporous polymer to the high molecular polymer in the mixed solution is 2-3: 1.
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