CN111610241A - Fe for nondestructive micro-measurement3+Selective microelectrode and preparation method and application thereof - Google Patents

Fe for nondestructive micro-measurement3+Selective microelectrode and preparation method and application thereof Download PDF

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CN111610241A
CN111610241A CN202010441402.0A CN202010441402A CN111610241A CN 111610241 A CN111610241 A CN 111610241A CN 202010441402 A CN202010441402 A CN 202010441402A CN 111610241 A CN111610241 A CN 111610241A
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microelectrode
tube
glass
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glass microelectrode
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CN111610241B (en
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于顺洋
曲红拥
张英红
张云超
李连祯
韩海涛
潘大为
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Yantai Institute of Coastal Zone Research of CAS
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    • 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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    • G01N27/333—Ion-selective electrodes or membranes
    • 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
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Abstract

The invention discloses Fe capable of being used for nondestructive micrometering3+A selective microelectrode and a preparation method and application thereof relate to the field of microelectrodes. The glass microelectrode tube comprises a glass microelectrode tube, wherein the front part of the glass microelectrode tube comprises a hot-drawn sharp end, a filling solution is filled in the glass microelectrode tube, a liquid ion exchanger is filled in the sharp end, an Ag/AgCl wire is arranged to extend into the glass microelectrode tube from the rear end of the glass microelectrode tube and to be immersed in the filling solution, and the Ag/AgCl wire is sealed and fixed through epoxy resin. Can realize Fe to the micro-area3+The real-time, dynamic and nondestructive detection of the information such as concentration, flow velocity and movement direction thereof is Fe on the surface of biological and non-biological materials3+The micro-process and mechanism research of (2) provides a new method.

Description

Fe for nondestructive micro-measurement3+Selective microElectrode and preparation method and application thereof
Technical Field
The invention relates to the field of microelectrodes, in particular to Fe for nondestructive micrometering3+A selective microelectrode and a preparation method and application thereof.
Background
Deep knowledge of Fe3+The microscopic process of (A) helps reveal Fe3+The micro motion process and mechanism of the device have important practical significance. Subject to the technical means and conditions of detection, Fe3+Mainly by chemical analysis methods, such as atomic absorption, atomic emission and their derivation, to determine Fe3+Static concentration changes are indirectly detected, described and discussed. The indirect detection has limitations which are mainly reflected in that the space-time resolution is low and Fe cannot be reflected3+Real-time data of (a).
A non-destructive micro-measuring technique based on microelectrode measurement is characterized by that under the control of computer, the ion/molecule selective electrode is used to measure ion/molecule concentration (mu m grade) and flow rate (10) of measured sample in and out in non-destructive mode without contacting measured material-12mole·S-1·cm-2) And the three-dimensional movement direction information thereof, thereby overcoming the problem that the test result can not be reasonably explained and even the research false image is caused due to the destructiveness to the sample. Meanwhile, the unique time (0.5 s) and space (2-5 μm) resolution has irreplaceable advantages in both time and space dimensions.
The types of the microelectrode of the nondestructive micrometering system are a glass electrode, a metal electrode, a carbon wire electrode and the like, and ions and molecules which can be measured have H+、Ca2+、K+、Na+、Mg2+、Cl-、NH4 +、NO3 -And O2、H2O2、CO2And NO, etc., the tested sample can be living materials such as single cells, multiple cells, tissue organs, etc., and can also be non-living materials such as metal materials, particle materials, membrane materials, etc. With the increasing number of ion/molecule selective electrode species andthe gradual improvement of electronic circuit systems and computer hardware and software, and the nondestructive micrometering technology is gradually and widely applied to the fields of life science, basic medicine, pharmacy, metal corrosion research and the like.
However, it is not possible to monitor Fe at present, limited to the technical conditions3+The flow of ions. There is therefore a need for an Fe3+ selective microelectrode which can be used for non-invasive microtest.
Disclosure of Invention
The invention aims to provide Fe capable of being used for nondestructive micro measurement3+Selective microelectrode and preparation method and application thereof, and Fe in micro region can be realized3+The real-time, dynamic and nondestructive detection of the information such as concentration, flow velocity and movement direction thereof is Fe on the surface of biological and non-biological materials3+The micro-process and mechanism research of the method provides the effect of a new method.
To achieve the above effects, the present application discloses a Fe for nondestructive micro-measurement3+The selective microelectrode comprises a glass microelectrode tube, wherein the front part of the glass microelectrode tube comprises a hot-drawn sharp end, a filling solution is filled in the glass microelectrode tube, a liquid ion exchanger is filled in the sharp end, an Ag/AgCl wire is arranged to extend into the glass microelectrode tube from the rear end of the glass microelectrode tube and to be immersed in the filling solution, and the Ag/AgCl wire is sealed and fixed through epoxy resin.
Further, the diameter of the pointed end of the glass microelectrode tube is 4-5 mu m.
Further the filling solution is prepared from 1.0mM FeCl3And 1.0mM Na2EDTA composition, pH adjusted to 7.0.
The liquid ion exchanger consists of 10-25 wt% of glyoxal bis-o-aminophenol, 10-20 wt% of sodium tetraphenylborate, 3-5 wt% of tetradodecyl ammonium tetrakis (4-chlorophenyl) borate, 40-60 wt% of 2-nitrophenyloctyl ether and 10-25 wt% of polyvinyl chloride.
The invention also discloses Fe for nondestructive micro-measurement3+The preparation method of the selective microelectrode comprises the following steps:
(a) preparing a glass microelectrode tube, namely drawing one end of a borosilicate glass capillary tube into a pointed end with the diameter of 4-5 mu m to prepare the glass microelectrode tube;
(b) performing hydrophobic treatment, namely silanizing the inner wall of the glass microelectrode tube to ensure that the surface of the glass microelectrode tube has hydrophobic property;
(c) filling a filling solution, and filling a tank at the rear end of the glass microelectrode tube with the filling solution;
(d) pouring liquid ion exchanger, pouring liquid ion exchanger at the pointed end of the glass microelectrode tube;
(e) fixing Ag/AgCl wire, inserting a lead made of the Ag/AgCl wire into the glass microelectrode tube, and sealing and fixing the tail of the glass microelectrode tube by using epoxy resin to obtain Fe3+A selective microelectrode.
When the filling solution is filled in the step (c), the filling length is 1/3-1/2 of the length of the glass microelectrode tube; and (d) when the liquid ion exchanger is filled in the step (d), the filling length of the liquid ion exchanger is 120-150 mu m.
Further preparing the Ag/AgCl wire in the step (e) as follows:
firstly, taking a silver wire with proper length, and polishing the silver wire by using sand paper to remove an oxide layer on the surface of the silver wire;
and then connecting a noble metal wire or a carbon rod to the cathode of a power supply, connecting the polished silver wire to the anode of the power supply, and electroplating for 2s in a saturated potassium chloride solution under the direct current voltage of 1.5V to prepare the Ag/AgCl wire.
And (e) when the Ag/AgCl wire is fixed in the step (e), inserting the Ag/AgCl wire into the filling solution in the glass microelectrode tube from the rear end of the glass microelectrode tube, sealing a rear end pipe orifice of the glass microelectrode tube by using epoxy resin, and exposing the Ag/AgCl wire out of the rear end of the glass microelectrode tube to facilitate external connection of a lead.
Finally, the invention discloses the Fe for nondestructive micrometering3+Use of a selective microelectrode of said Fe3+Selective microelectrode applied to real-time, dynamic and nondestructive determination of Fe in microscopic region3+Concentration, flow rate and direction of movement.
Particularly, the Fe is adopted on a solid-liquid interface of a sample to be detected3+Selective microelectrode determination of Fe in microscopic region of surface3+Concentration, flow rate and direction of movement.
The beneficial effects of the invention include:
fe of the invention3+Selective microelectrode capable of carrying out Fe on microscopic region3+The real-time, dynamic and nondestructive detection of the information such as concentration, flow velocity and movement direction thereof is Fe on the surface of biological and non-biological materials3+The micro-process and mechanism research of (2) provides a new method. The diameter of the pointed end of the microelectrode tube is 4-5 mu m, so that the ion flow detection requirement of cells and tissues can be met; the filling length of the liquid ion exchanger at the tip is 120-150 mu m; the microelectrode is at 10-6M～10-2M Fe3+Has good linear relation in the concentration detection rangeR 2 =0.9996, Nernst slope 18.2 mV/dec; the response time t95% of the microelectrode is less than 15 s.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is Fe of the present invention3+A schematic diagram of a selective microelectrode structure;
FIG. 2 shows Fe provided in the examples of the present invention3+Plot of measured linear response range for selective microelectrodes.
Wherein, 1, glass microelectrode tube, 101, pointed end, 2, filling solution, 3, Ag/AgCl wire, 4, epoxy resin and 5, liquid ion exchanger.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Fe3+The selective microelectrode is shown in figure 1 and comprises a glass microelectrode tube 1, wherein the front part of the glass microelectrode tube comprises a hot-drawn sharp end 101, the glass microelectrode tube is filled with filling solution 2, the sharp end is filled with liquid ion exchanger 5, an Ag/AgCl wire 3 is arranged and extends into the filling solution from the rear end of the glass microelectrode tube, and the Ag/AgCl wire is sealed and fixed through epoxy resin 4.
The glass microelectrode tube 1 is a single-layer tube, and the filling liquid after the film is filled with 1.0mM FeCl3And 1.0mM Na2EDTA composition, pH adjusted to 7.
Fe3+The selective microelectrode has a tip of 4-5 mu m and a linear response range of 10-2～10-6M, slope 18.2mV/-log [ Fe ]3+]The lower limit of detection is 10-6M。
The first embodiment is as follows:
Fe3+a method of making a selective microelectrode comprising the steps of:
(a) drawing a microelectrode tube: according to a conventional drawing mode, a borosilicate glass capillary tube (with the outer diameter of 1.5 mm, the inner diameter of 1.05 mm and the length of 5 cm) is fixed at the middle position of a heating coil, heated to freely fall down, the tip end of the glass tube is upward and fixed on a clamp, and heated again to enable the tip end diameter to be within the range of 4 mu m. Before use, the microelectrode tube needs to be checked by a microscope for the shape, particularly whether the tube opening is flat or not. Microelectrode tubes with an irregular orifice and orifices that are not circular cannot be used.
(b) Silanization hydrophobic treatment: in the silanization process, firstly, pre-drying for more than 1 h at 150 ℃ to remove residual moisture and impurities in the microelectrode tube; then, the microelectrode was placed in a glass vessel with a lid, 2mL of 5% dimethyldichlorosilane (national chemical group chemical reagent Co., Ltd., Beijing) as a silane reagent was poured into the glass vessel, and n-hexane was used as a solvent, and the vessel was baked at 150 ℃ for 30 min to allow the vapor to enter and adhere to the tip of the microelectrode. The silanized microelectrodes should be stored in a dry, dust-free, light-tight container.
(c) Filling solution pouring: 1.0mM FeCl was injected using an l.0 mL syringe attached to a thin tube3And 1.0mM Na2EDTA, the filling liquid with the pH adjusted to 7 is slowly pushed into the silicon-alkylated microelectrode tube from the rear end of the tube to generate a 10.0 mm filling liquid column. Observing whether bubbles exist in the electrode under a microscope, and if the bubbles exist, keeping the tip of the electrode downwards for a period of time until the bubbles completely disappear from the microelectrode tube.
(d) Filling Fe3+Liquid ion exchanger (LIX): under a binocular microscope, firstly dipping a little Fe by using a glass capillary with a tip opening of 50-60 mu m3+LIX, the tip is full to obtain the Fe container3+And the glass capillary of the LIX is the LIX carrier. The pressure is given from the tail part by a syringe to make the LIX liquid surface bulge. And placing the LIX carrier and the tip of the microelectrode tube to be filled on the same horizontal plane under a microscope, carefully contacting the tip of the microelectrode tube to be filled with the convex liquid surface of the LIX, and gradually permeating the LIX into the tip of the microelectrode tube. And when the length of the LIX at the tip of the microelectrode tube reaches 120 mu m, filling is finished.
(e) Fixing Ag/AgCl wire as shown in figure 1, inserting Ag/AgCl wire 3 into the filling liquid until approaching the tip of the glass microelectrode tube 1, fixing Ag/AgCl wire 3 and sealing the glass microelectrode tube 1 at the orifice of the glass microelectrode tube 1 by epoxy resin 4, and exposing one end of the Ag/AgCl wire 3 out of the tail of the glass microelectrode tube 1 to obtain Fe3+A selective microelectrode.
The preparation steps of the Ag/AgCl wire 3 are as follows:
taking a silver wire with proper length, and polishing the silver wire by using sand paper to remove an oxide layer on the surface of the silver wire;
a noble metal wire or a carbon rod is connected to the cathode of a power supply, the polished silver wire is connected to the anode of the power supply, and the Ag/AgCl wire can be prepared by electroplating for 2s in a saturated potassium chloride solution under the direct current voltage of 1.5V.
The filling solution is prepared from 1.0mM FeCl3And 1.0mM Na2EDTA, pH adjusted to 7. Fe3+Liquid ion exchanger (LIX) was, by mass percent, 12% glyoxalated bis-o-aminophenol, 12% sodium tetraphenylborate, 5% tetradodecyl ammonium tetrakis (4-chlorophenyl) borate, 55% 2-nitrophenyloctyl ether and 16% polyvinyl chloride.
For the Fe obtained above3+Testing the detection range of the selective microelectrode:
the ion selective microelectrode has a linear relation between the potential and the logarithm of the ion concentration within a certain detection range, so that the measured ion concentration can be calculated according to the measured microelectrode potential. For detection of Fe3+Detection range of selective microelectrode, preparation of serial FeCl3Standard solution, background solution is a simplified nutrient solution (containing 0.1 mM Ca (NO)3)2, 0.1 mM Mg(NO3)2, 0.1 mM KNO3、1.0 mM NaNO30.3 mMMES) as test solution. The solution is an actual test solution used in the ion flow test of the plant root system, has the same components with the nutrient solution of crops, and can simulate the use environment of the ion selective microelectrode. The pH of the solution was 6.0, adjusted with NaOH and HCl, MES morpholine ethanesulfonic acid was used as pH buffer. Thereby obtaining different Fe3+The corresponding relation between the concentration logarithm and the microelectrode potential is used for evaluating the performance of the microelectrode. The performance test procedure of the ion selective microelectrode was performed on NMT system (YG-MS-001, Yangg USA).
The microelectrode pair Fe obtained by the above method3+Each concentration is 10-8、10-7、10-6、10-5、10-4、10-3、10-2And 10-1FeCl of M3The calibration liquid is subjected to potential measurement. The average value was taken by 3 repeated measurements using the same microelectrode to obtain different Fe3+The correspondence between the logarithm of the concentration and the potential of the microelectrodes is shown in figure 2. In FIG. 2, Fe3+Selective microelectrode in Fe3+At a concentration of 10-6～10-2The Nernst response slope in the M range is 18.2 mV/dec, the microelectrode potential and Fe3+Linear correlation coefficient R between concentration logarithms2=0.999, indicating that there is a good linear relationship within this range, so that the corresponding ion concentration can be accurately obtained by measuring the microelectrode potential. Thus the Fe3+The selective microelectrode can meet the requirement of measuring Fe in micro-regions of plant cells, tissues and organs3+Concentration and dynamic change requirements.
3+ selection microelectrode nernst response test:
micro electrode potentialEWith a calibration liquid Fe3+Concentration ofCThe relationship between can be defined by the Nernst equationE=k±slgC(formula 1). In the formulaEVoltage between microelectrode and reference electrode, mV;Cfor calibrating Fe in solution3+Concentration, M;snernst slope, mV/dec;knernst intercept, mV.
Wherein the slope of the nernstsThe theoretical value is calculated by the formulas=2.303RT/nF(formula 2) wherein, in the formula,R8.314J/(K.mol) as gas constant;Tabsolute temperature, K;Fas Faraday constant, 9.6487 × 104C/mol；nFor the valency of the ion to be detected, for Fe3+And n = 3. At 25 deg.C, Fe3+Can slopesThe theoretical value is 19.7 mV/dec.
An Ag/AgCl lead in the microelectrode is connected with a microelectrode preamplifier of an NMT system (YG-MS-001, Yangge company, USA), and a reference electrode is connected with a ground terminal of the microelectrode amplifier and a data acquisition system. The calibration liquid is Fe3+FeCl at concentrations of 1, 0.1 and 0.01 mM, respectively3And (3) respectively immersing the microelectrode and the reference electrode into the three calibration solutions, and reading and recording the ground potential of the microelectrode, namely the potential difference change of the microelectrode and the reference electrode, by NMT acquisition software. The Nernst slope of the electrode can be obtained by substituting the electrode potentials in different calibration solutions into the formula (1). This study used Fe at room temperature, 25 deg.C3+The test solutions with concentrations of 1, 0.1 and 0.01 mM are used as calibration solutions, the measured microelectrode potentials are 455.86, 438.12 and 419.51 mV respectively, and the measured microelectrode potentials are substituted intoThe Nernst slope obtained in the formula (1) is 18.20 mV/dec, and compared with the theoretical value of 19.6 mV/dec, the conversion rate reaches 92.8 percent, and the working requirement that the conversion rate of the ion selective microelectrode is more than or equal to 90 percent is met. Nernst slope andsthe closer the theoretical values are, the better the performance is.
Example two:
Fe3+a method of making a selective microelectrode comprising the steps of:
(a) drawing a microelectrode tube: according to a conventional drawing mode, a borosilicate glass capillary tube (with the outer diameter of 1.5 mm, the inner diameter of 1.05 mm and the length of 5 cm) is fixed at the middle position of a heating coil, heated to freely fall down, the tip end of the glass tube is upward and fixed on a clamp, and heated again to enable the tip end diameter to be within the range of 5 mu m. Before use, the microelectrode tube needs to be checked by a microscope for the shape, particularly whether the tube opening is flat or not. Microelectrode tubes with an irregular orifice and orifices that are not circular cannot be used.
(b) Silanization hydrophobic treatment: in the silanization process, firstly, pre-drying for more than 1 h at 150 ℃ to remove residual moisture and impurities in the microelectrode tube; then, the microelectrode was placed in a glass vessel with a lid, 2mL of 5% dimethyldichlorosilane (national chemical group chemical reagent Co., Ltd., Beijing) as a silane reagent was poured into the glass vessel, and n-hexane was used as a solvent, and the vessel was baked at 150 ℃ for 30 min to allow the vapor to enter and adhere to the tip of the microelectrode. The silanized microelectrodes should be stored in a dry, dust-free, light-tight container.
(c) Filling solution pouring: 1.0mM FeCl was injected using an l.0 mL syringe attached to a thin tube3And 1.0mM Na2EDTA, the filling liquid with the pH adjusted to 7 is slowly pushed into the silicon-alkylated microelectrode tube from the rear end of the tube to generate a 25.0 mm filling liquid column. Observing whether bubbles exist in the electrode under a microscope, and if the bubbles exist, keeping the tip of the electrode downwards for a period of time until the bubbles completely disappear from the microelectrode tube.
(d) Filling Fe3+Liquid ion exchanger (LIX): under a binocular microscope, firstly, glass wool with a tip opening of 50-60 mu m is usedDipping a little Fe in the thin tube3+LIX, the tip is full to obtain the Fe container3+And the glass capillary of the LIX is the LIX carrier. The pressure is given from the tail part by a syringe to make the LIX liquid surface bulge. And placing the LIX carrier and the tip of the microelectrode tube to be filled on the same horizontal plane under a microscope, carefully contacting the tip of the microelectrode tube to be filled with the convex liquid surface of the LIX, and gradually permeating the LIX into the tip of the microelectrode tube. And when the length of the LIX at the tip of the microelectrode tube reaches 160 mu m, filling is finished.
(e) Fixing Ag/AgCl wire as shown in figure 1, inserting Ag/AgCl wire 3 into the filling liquid until approaching the tip of the glass microelectrode tube 1, fixing Ag/AgCl wire 3 and sealing the glass microelectrode tube 1 at the orifice of the glass microelectrode tube 1 by epoxy resin 4, and exposing one end of the Ag/AgCl wire 3 out of the tail of the glass microelectrode tube 1 to obtain Fe3+A selective microelectrode.
The filling liquid is FeCl with the concentration of 1.0mM3And 1.0mM Na2EDTA, pH adjusted to 7. Fe3+Liquid ion exchanger (LIX) 22% (w/w) glyoxal bis-o-aminophenol, 18% (w/w) sodium tetraphenylborate, 2% (w/w) tetradodecyl ammonium tetrakis (4-chlorophenyl) borate, 46% 2-nitrophenyloctyl ether and 12% polyvinyl chloride in mass%.
At room temperature 25 ℃ using Fe3+The test solutions with the concentrations of 1, 0.1 and 0.01 mM are respectively used as calibration solutions, the measured potentials of the microelectrodes are 439.22 mV, 420.75 mV and 400.97 mV, the Nernst slope obtained by substituting the formula (1) is 18.60mV/dec, compared with the theoretical value of 19.6 mV/dec, the conversion rate reaches 94.9 percent, and the working requirement that the conversion rate of the ion selective microelectrode is more than or equal to 90 percent is met. Nernst slope andsthe closer the theoretical values are, the better the performance is.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims (10)

1. Fe for nondestructive micro-measurement3+Selective microelectrode, including glass microelectrode tube (1), its characterized in that: the front part of the glass microelectrode tube comprises a hot-drawn sharp end (101), the glass microelectrode tube is filled with filling solution (2), the sharp end is filled with liquid ion exchanger (5), and an Ag/AgCl wire (3) is also arranged, extends into the filling solution from the rear end of the glass microelectrode tube and is immersed in the filling solution, and the Ag/AgCl wire is sealed and fixed through epoxy resin (4).
2. Fe for nondestructive microassay according to claim 13+A selective microelectrode characterized by: the diameter of the pointed end of the glass microelectrode tube is 4-5 mu m.
3. Fe for nondestructive microassay according to claim 13+A selective microelectrode characterized by: the filling solution is prepared from 1.0mM FeCl3And 1.0mM Na2EDTA composition, pH adjusted to 7.0.
4. Fe for nondestructive microassay according to claim 13+A selective microelectrode characterized by: the liquid ion exchanger comprises, by mass, 10-25% of glyoxaline bis-o-aminophenol, 10-20% of sodium tetraphenylborate, 3-5% of tetradodecyl ammonium tetrakis (4-chlorophenyl) borate, 40-60% of 2-nitrophenyloctyl ether and 10-25% of polyvinyl chloride.
5. Fe for nondestructive micro-measurement according to any one of claims 1 to 43+The preparation method of the selective microelectrode is characterized by comprising the following steps:
(a) preparing a glass microelectrode tube, namely drawing one end of a borosilicate glass capillary tube into a pointed end with the diameter of 4-5 mu m to prepare the glass microelectrode tube;
(b) performing hydrophobic treatment, namely silanizing the inner wall of the glass microelectrode tube to ensure that the surface of the glass microelectrode tube has hydrophobic property;
(c) filling a filling solution, and filling a tank at the rear end of the glass microelectrode tube with the filling solution;
(d) pouring liquid ion exchanger, pouring liquid ion exchanger at the pointed end of the glass microelectrode tube;
(e) fixing Ag/AgCl wire, inserting a lead made of the Ag/AgCl wire into the glass microelectrode tube, and sealing and fixing the tail of the glass microelectrode tube by using epoxy resin to obtain Fe3+A selective microelectrode.
6. Fe for non-invasive microassays according to claim 53+The preparation method of the selective microelectrode is characterized by comprising the following steps: when the filling solution is filled in the step (c), the filling length is 1/3-1/2 of the length of the glass microelectrode tube; and (d) when the liquid ion exchanger is filled in the step (d), the filling length of the liquid ion exchanger is 120-150 mu m.
7. Fe for non-invasive microassays according to claim 53+The preparation method of the selective microelectrode is characterized by comprising the following steps: the Ag/AgCl wire of the step (e) is prepared by the following steps:
firstly, taking a silver wire with proper length, and polishing the silver wire by using sand paper to remove an oxide layer on the surface of the silver wire;
and then connecting a noble metal wire or a carbon rod to the cathode of a power supply, connecting the polished silver wire to the anode of the power supply, and electroplating for 2s in a saturated potassium chloride solution under the direct current voltage of 1.5V to prepare the Ag/AgCl wire.
8. Fe for non-invasive microassays according to claim 53+The preparation method of the selective microelectrode is characterized by comprising the following steps: and (e) when the Ag/AgCl wire is fixed in the step (e), inserting the Ag/AgCl wire into the filling solution in the glass microelectrode tube from the rear end of the glass microelectrode tube, sealing the rear end opening of the glass microelectrode tube by using epoxy resin, and exposing the Ag/AgCl wire out of the rear end of the glass microelectrode tube to facilitate external connection of a lead.
9. Fe for nondestructive micro-measurement according to any one of claims 1 to 43+Use of a selective microelectrode characterized in that: said Fe3+Selective microelectrode applied to real-time, dynamic and nondestructive determination of Fe in microscopic region3+Concentration, flow rate and direction of movement.
10. Fe for non-invasive microassays according to claim 93+Use of a selective microelectrode characterized in that: applying the Fe on a solid-liquid interface of a sample to be measured3+Selective microelectrode determination of Fe in microscopic region of surface3+Concentration, flow rate and direction of movement.
CN202010441402.0A 2020-05-22 2020-05-22 Fe for nondestructive micro-measurement3+Selective microelectrode and preparation method and application thereof Active CN111610241B (en)

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