KR101217734B1 - Manufacturing method of amperometric ion-selective microelectrode, amperometric ion-selective microelectrode made by the same, and electrochemical measuring method of ion concentration using the same - Google Patents
Manufacturing method of amperometric ion-selective microelectrode, amperometric ion-selective microelectrode made by the same, and electrochemical measuring method of ion concentration using the same Download PDFInfo
- Publication number
- KR101217734B1 KR101217734B1 KR1020100071884A KR20100071884A KR101217734B1 KR 101217734 B1 KR101217734 B1 KR 101217734B1 KR 1020100071884 A KR1020100071884 A KR 1020100071884A KR 20100071884 A KR20100071884 A KR 20100071884A KR 101217734 B1 KR101217734 B1 KR 101217734B1
- Authority
- KR
- South Korea
- Prior art keywords
- ion
- group
- selective electrode
- ion selective
- current
- Prior art date
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Biological Materials (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The present invention relates to a method for producing an amperometric based micro-ion selective electrode, a method for producing an ampereometric based micro-ion selective electrode, and a method for electrochemically quantifying ion concentration using the same.
The ion-selective electrode of the present invention is economical and convenient by forming a hole using a scanning needle in the manufacturing process, and reduces the resistance voltage drop as the thickness of the film is reduced, making it easy to measure current, and current in a steady state. Since ion concentration can be detected simply by measurement, it can be applied to various sensors using an ion selective electrode.
Description
The present invention relates to a method for producing an amperometric based micro-ion selective electrode, a method for producing an ampereometric based micro-ion selective electrode, and a method for electrochemically quantifying ion concentration using the same.
The conventional ion sensor detects specific ions in an assay sample and analyzes the concentration of the specific ions by using an ion-selective electrode (ISE) that generates a potential difference between the reference electrode and the reference electrode according to the concentration of the specific ions. I was referring to a sensor that can.
A schematic diagram of such a conventional ion sensor is shown in FIG. As shown in FIG. 1, in the ion sensor, an inner reference filling solution 30 including the
The ion selective electrode used in such an ion sensor includes an ion-selective membrane. The ion selective membrane is a membrane that generates a voltage at the boundary of the membrane by directly contacting the analyte and sensing the specific ions. The ion selective membrane is the most important part of the ion selective electrode and is based on conventional potentiometric measurements. Selective electrode is the basis.
The ion selective membrane is composed of a polymer used as a support, an ionophore that gives selectivity to specific ions, and a plasticizer, which is a nonvolatile organic solvent. And glass film type. Among them, the polymer type is freely used for fine molding and has an advantage of easy mass production, so it is widely used for ion or gas sensors.
Such potentiometric ion selective electrodes used in clinical and environmental analyzers are of liquid contact, solid form and electric field effect transistor type. The solid ion-selective electrode does not require an inner reference filling solution between the ion-selective membrane and the inner reference metal electrode that the liquid contact ion-selective electrode should have, thereby miniaturization and mass production. On the other hand, there is a problem that it is not suitable for the electrode using the current measurement method because the high resistance to interrupt the flow of current.
In order to solve this problem, liquid contact type ion selective membranes have been generally used.
In the case of the liquid-contacting ion selective membrane, that is, when two unmixed liquids generally cause contact with ions, separation of the two phases occurs because of the free energy of solvation, which causes a difference in Galvani potential between the interfaces. There is no movement from one side to the other. The polarized interface provides the free energy required to move ions from one phase to the other and, in this reversible process, ionic materials, such as redox inactive compounds, are current-dependently detected. It is also possible to create a sensing platform. In order to investigate the ion transfer reaction characteristics at the interface, Tetramethylammonium (TMA + ) ion, etc., is added to the aqueous solution, and a voltage is applied to the ion. The ion is an aqueous solution at a voltage corresponding to Gibbs transfer energy of the ion. When the phase shifts to the organic phase and the opposite voltage is applied, the phase shifts from the organic phase to the aqueous phase. At this time, the measured current value varies depending on the number (or concentration) of ions moved at a specific voltage to which the ions move, and in particular, since the amount of current and the concentration of ions maintain a direct proportional relationship, they can be used as useful ion sensors. However, the liquid contact type ion-selective membrane also has a disadvantage in that a resistance voltage drop occurs due to the large area between the liquid interfaces.
In order to further reduce the resistance voltage drop of the liquid contact type ion selective electrode, a method of forming a small hole in the ion selective membrane has been introduced (Lee, HJ et al, 1997, Amperometric ion sensors based on laser). -patterned composite polymer membranes, J. Electroanal. Chem. 440, 73-82). However, the prior art has a disadvantage that the expensive and complicated manufacturing process because it had to use an expensive laser on the special polymer film to form a hole.
The present invention can be manufactured in a simple manufacturing process using a low-cost material to solve the above problems, a method of manufacturing a micro-ion selective electrode using a liquid-liquid interface based on the current method with excellent accuracy, It is an object of the present invention to provide a current-based micro-ion selective electrode and a method for electrochemically quantifying the ion concentration using the same.
The present invention to solve the above object is
a) forming an elliptical hole in a transparent synthetic resin film having a thickness of 5 to 20 μm by using a needle to produce an ion selective membrane;
b) preparing an organic gel by mixing a polyvinylchloride (PVC) solution, an ionophore, an auxiliary electrolyte, and an organic solvent; And
c) dropping 5-15 μl of the organic gel prepared in step b) to one surface of the ion-selective membrane prepared in step a) and coagulating at room temperature for 4 to 8 hours. Provided is a method of manufacturing a method based micro-ion selective electrode.
In the present invention, the elliptical hole of step a) has a long radius of 80 to 140㎛, a short radius of 5 to 25㎛, the interval between the elliptical holes is characterized in that 90 to 130㎛.
In the present invention, the transparent synthetic resin film of step a) is at least one selected from the group consisting of polyvinyl chloride resin (polyvinylchloride, PVC), polyvinyllidene chloride (PVDC) and low density polyethylene (low density polyethylene) It features.
In the present invention, the secondary electrolyte of step b) is characterized in that any one of BTPPATPBCl, TBATPBCl and TPeATFPB.
In the present invention, the organic solvent of step b) is nitrophenyloctylether, adipate group, maleate group, oleate group, paraffin group ), A phosphate group, a phthalate group, a sebacate group, and a stearate group.
In the present invention, the ion sensing material of step b) is quaternary ammonium salt (valternomycin), ballinomycin (valinomycin), ballinomycin derivatives, monensin (monensin), nonactin (nonactin), non-lactin derivatives, Tertiary amine, metal porphyrin, metal phthalocyanine, trifluoroacetophenone, trifluoroacetophenone derivative, crown ether, dibenzo-18-crown -6 (dibenzo-18-crown-6), organophosphorus ion sensing material, organotin ion sensing material, at least one selected from the group consisting of ETH1778, ETH1062, ETH1001, ETH129, ETH149, ETH1644, ETH1117, ETH5214, ETH227 and ETH157 It is characterized by one.
The present invention also provides a current-based micro-ion selective electrode produced by the above manufacturing method.
In addition, the present invention provides a method for electrochemically quantifying ion concentration using the ammeter-based micro-ion selective electrode.
In the method of electrochemically quantifying an ion concentration using the ammeter-based micro-ion selective electrode of the present invention, the electrochemical quantification is characterized by measuring by dynamic electrochemical measurement.
In the method of electrochemically quantifying ion concentration using the ammeter-based micro-ion selective electrode of the present invention, the dynamic electrochemical measurement method is cyclic voltammetry, differential pulse voltammetry (differential) pulse voltammetry) or square wave voltammetry.
In the method of electrochemically quantifying ion concentration using the ammeter-based micro-ion selective electrode of the present invention, the dynamic electrochemical measurement method is characterized in that the current value increases as the ion concentration increases.
Hereinafter, a step-by-step look at the method of manufacturing the current-based micro-ion selective electrode in more detail.
First, in step a), an elliptic microhole is formed on a transparent synthetic resin film having a thickness of 5 to 20 μm using a scanning needle to prepare an ion selective membrane.
Since the tip of a common needle is obliquely cut, the hole made of the needle has an ellipse rather than a perfect circle, and the elliptical hole can be easily repeated using the needle.
The elliptical hole is 80 to 140㎛ long radius, 5-25㎛ short radius, it is preferable that the interval between elliptical holes is 90 to 130㎛. If the radius of the elliptical hole is larger than the above range or the spacing between the elliptical holes is less than 90 μm, the sum of the interface areas becomes wider, and the effect of reducing the resistance is reduced. This is because the transfer reaction does not occur sufficiently.
The transparent synthetic resin film is characterized in that at least one selected from the group consisting of polyvinyl chloride (polyvinyl chloride, PVC), polyvinyl chloride (polyvinyllidene chloride, PVDC) and low density polyethylene (low density polyethylene). The transparent synthetic resin film is generally preferably used for packaging wraps used at home. The household wrap is not only cheap and easy to obtain, but also is suitable as the transparent synthetic resin film of the present invention because of its thickness of 5 to 20 μm for the purpose of transparency, adhesiveness, and the like. The thin plastic film reduces the resistance, creating a good amperometric sensor. Generally, wrap film is mainly composed of synthetic resins such as polyvinyl chloride (PVC), polyvinyllidene chloride (PVDC), low density polyethylene, etc., but polyvinyl chloride resin Polyvinylchloride (PVC) is widely used because of its excellent price and performance. However, the present invention is not limited to the packaging wrap film, and may be used as long as the synthetic resin film satisfies the above conditions.
Next, b) a polyvinyl chloride (PVC) solution, an ionophore, an auxiliary electrolyte and an organic solvent are mixed to prepare an organic gel.
The auxiliary electrolyte is preferably any one of BTPPATPBCl, TBATPBCl, and TPeATFPB, but is not necessarily limited thereto. BTPPATPBCl, TBATPBCl and TPeATFPB are bis (triphenylphosphoranylidene) ammonium tetrakis (4-chlorophenyl) borate (bis (triphenylphosphoranylidene) ammonium tetrakis (4-chlorophenyl) borate, BTPPATPBCl), tetrabutylammonium tetraphenylborate 1,2-dichloroethane solution of tetrabutylammonium tetraphenylborate (TBATPBCl) and tetrapentylammonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate (tetrapentylammonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, TPeATFPB).
The organic solvent is nitrophenyl octyl ether, adipate group, maleate group, oleate group, paraffin group, phosphate group, phthalate ( at least one selected from the group consisting of a phthalate group, a sebacate group and a stearate group, preferably nitrophenyloctyl ether. In the present invention, the organic solvent acts as a plasticizer to allow the ion selective membrane to be cured with flexibility, thereby obtaining an ion selective membrane that is not easily broken. Preferably, the organic solvent is 50% by weight or less based on the total weight of the ion-selective membrane.
The ion sensing material (ionophore) is a substance causing covalent bonds, coordination bond reactions or ion exchange reactions with ions to be analyzed. Preferably, the ion sensing material is quaternary ammonium salt, valineomycin, valenomycin derivative, monensin, nonactin, nonactin derivative, tertiary amine , Metal porphyrin, metal phthalocyanine, trifluoroacetophenone, trifluoroacetophenone derivative, crown ether, dibenzo-18-crown-6 (dibenzo-18 crown-6), at least one selected from the group consisting of organophosphorus ion sensing material, organotin ion sensing material, ETH1778, ETH1062, ETH1001, ETH129, ETH149, ETH1644, ETH1117, ETH5214, ETH227 and ETH157, but is not limited thereto. It doesn't happen. The quaternary ammonium salt is tridodecylmethylammonium chloride (TDMAC), and the trifluoroacetophenone derivative is trifluoroacetyl-p-decylbenzene (TFADB).
The ion sensing material lowers the Gibbs free transfer energy required when the hydrophilic ions move at the interface, so that the reaction proceeds very quickly, not only making the ionic cross-signal at the interface visible, but also selectively transferring only certain ions. Play a role. For example, as an ion sensing material for selectively detecting hydrogen ions, dibenzo-18-crown-6 or ETH1778, as an ion sensing material for selectively detecting potassium ions, Ballinomycin or ballinomycin derivatives are used. By using a specific ion sensing material, 'ion selectivity' of an ion selective membrane is realized.
The polyvinyl chloride, which is a polymer serving as a support, is preferably 1 to 5% by weight of a semisolid solution, but is not necessarily limited thereto.
When the polyvinyl chloride, the ion sensing material, and the auxiliary electrolyte are put together and dissolved in an organic solvent, an organic gel is prepared.
Then, in step c) 5-15 μl of the organic gel prepared in step b) is dropped on one surface of the transparent synthetic resin film in which the elliptical hole obtained in step a) is formed and solidified at room temperature for 4-8 hours. Prepare an ion selective membrane.
As the organic gel solidifies on one surface of the transparent synthetic resin, gelation occurs. The gelation process occurs simultaneously in the part of the organic gel that flows into the interior of the elliptical microhole. In the gelation process, particles are aggregated or entangled with each other to form a three-dimensional polymer material. The resulting three-dimensional network material is a support of the ion-selective membrane, the ion sensing material is trapped inside the support having the three-dimensional network structure. The ion sensing material trapped inside the support functions as a membrane active material.
Thereafter, the other surface to which the organic gel of the ion-selective membrane prepared as described above is not applied is immersed in an analytical solution to form an interface, thereby preparing a micro-ion-selective electrode based on the current method. The analytical solution is often water-soluble, but LiCl is preferred as the water-soluble electrolyte, but is not necessarily limited thereto. Before solidifying the
An inner reference filling solution 30 is in contact with the surface on which the organic gel is applied, with the microhole-type ion-selective membrane interposed therebetween. The internal reference solution is an organic electrolyte solution, preferably TBACl or BTPPACl.
Inner
The ammeter-based micro-ion selective electrode manufactured by the above-described method can be used as an electrode of an ion concentration sensor. The ion sensor of the present invention can be used as a medical device for measuring sodium, potassium, calcium or chloride ion concentration in blood or serum for clinical examination, and in particular can detect glucose (glucose).
As shown in FIG. 3, the glucose sensor has a reaction mechanism in which gluconic acid, which is produced by the decomposition of glucose by glucose oxidase in the presence of oxygen, dissociates and releases hydrogen cations to transfer them to the organic phase. I use it. At this time, since the amount of hydrogen cation from which gluconic acid is dissociated depends on the concentration of glucose, a blood glucose measurement sensor for measuring the concentration of glucose by measuring the amount of hydrogen cation is possible.
The present invention also provides a method for electrochemically quantifying ion concentration using the ion selective electrode.
Hereinafter, the method of electrochemically quantifying the ion concentration will be described in detail. The principle of the method of electrochemically quantifying the ion concentration according to the present invention is as follows. When the shape of the hole is elliptical as in the present invention, the current in the steady state is represented by the following equation.
Iss = 2π z i FDca / K (ε) (1)
Where n is the number of hole, zi is charge number of ionic species, F is Faraday constant, D is diffusion coefficient, c is concentration of ionic species, ε =
Substituting ε at steady state, Equation (1) above is represented by Equation (2) as follows.
From the above equation (2), since the current Iss in the steady state has a linear relationship with the ion concentration c, the ion concentration can be calculated by measuring the current Iss in the steady state.
The current-based micro-ion-selective electrode of the present invention is economical and convenient by forming a hole using a scanning needle in the manufacturing process, and reduces the resistance voltage drop as the thickness of the film decreases, thereby making it easy to measure current. In addition, since ion concentration can be detected simply by measuring current in a steady state, the present invention can be applied to various sensors using a current-based micro-ion selective electrode.
Figure 1 schematically shows a conventionally used voltage-based micro-ion selective electrode.
Figure 2 shows an SEM image of the elliptical microhole formed by one embodiment of the present invention.
3 illustrates a mechanism for sensing glucose using the present invention.
FIG. 4 shows cyclic voltammetry using an analytical solution in which the concentration of TMA + ions is changed as a sensor when ions move from an analytical solution to a reference solution according to an embodiment of the present invention.
FIG. 5 shows the relationship between steady state current and TMA + ion concentration in the cyclic current voltage curve of FIG. 4.
Figure 6 shows a cyclic voltammogram according to the scan speed at 0.1mM TMA + concentration.
FIG. 7 shows the relationship with the scan rate by measuring the current maximum value according to the scan rate from FIG. 6.
8 is a cyclic voltammogram when the glucose concentration in the glucose sensor manufactured by one embodiment of the present invention is (i) 0mM, (ii) 6mM, and (iii) 18mM.
Figure 9 (a) shows the differential pulse voltammogram curve when the glucose concentration is 2mM, 6mM, 10mM, 14mM, 18mM in the glucose sensor manufactured by one embodiment of the present invention, Figure 9 (b) is Figure 9 It is a graph which shows the maximum current value of the differential pulse voltage current curve of (a) according to glucose concentration.
The present invention is described in more detail through the following implementation. However, the examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.
< Example 1>
<Example 1-1> Preparation of selective electrodes and TMA + ion sensor
An ammeter-based micro-hydrogen ion selective electrode according to the present invention was prepared as follows.
First, a PVC film (Lotte Lab) having a thickness of 12 μm was prepared, and holes were made with an injection needle to make elliptical holes having a long radius of 114 μm and a short radius of 20 μm. At this time, because the hole is manually drilled, the long and short radius may have a minute difference as described above. The oval hole-formed PVC film was attached to the inside of the glass tube using a silicone adhesive.
An organic gel was prepared by dissolving 10 mM TBATPBCl and PVC (3% wt / wt semisolid solution) as an auxiliary electrolyte in nitrophenyloctylether, an organic solvent.
10 μl of this organic gel was taken and manually dropped onto the PVC film in which elliptical microholes were formed and solidified at room temperature for 8 hours to form a gel. SEM images of the elliptical holes formed are shown in FIG. 2.
The prepared ion-selective electrode contained the analysis solution on the other surface of the PVC film not coated with the organic gel to form an aqueous solution / organic solution elliptical hole interface, and immersed it in an internal reference solution composed of 10 Mm TBACl. 10 Mm LiCl was used as an aqueous electrolyte in an aqueous solution, and Ag / AgCl was used as an internal reference electrode connected to an internal reference solution and an analysis solution. The internal reference electrode was connected to a potentiometer to make the ion sensor during current measurement.
<Example 1-2> fitness determination as ion movement sensor to the reference solution in the analysis solution
Whether the ion sensor made in Example 1-1 is suitable as a sensor was determined for the ions moving forward from the assay solution to the reference solution and the reverse from the reference solution to the assay solution, respectively.
Cyclic voltammetry was determined using an analytical solution with varying concentrations of TMA + ions as the sensor when ions were transferred from the analytical solution to the reference solution.
The cyclic voltammetry is a method of linearly changing a voltage with time and measuring a change in the amount of current of a working electrode according to a change in voltage. In this case, the cyclic means that the voltage is changed in time from the set initial voltage to the end voltage, and then the voltage is changed from the end voltage to the initial voltage again.
The cyclic voltammetry was performed with 20mV / s scan rate, while varying the concentration of TMA + ions in 10mM LiCl solution to (i) 0mM, (ii) 0.1mM, (iii) 0.2mM and (iv) 0.3mM, respectively. It measured in the range of 0 to 0.8V by using, as a result obtained a cyclic current voltage curve as shown in FIG.
The relationship between the steady state current and the TMA + ion concentration in the circulating current voltage curve of FIG. 4 is shown in FIG. 5, and as shown in FIG. A linear relationship was established, confirming that the sensor using the ion selective electrode of this example is suitable.
<Example 1-3> fitness determination as ion movement sensor in the reference solution to the analysis solution
It was determined by cyclic voltammetry with varying scan speeds as to whether the ions were reversed from the reference solution to the assay solution.
Cyclic voltammograms were obtained according to scan speeds at 0.1 mM TMA + concentration and are shown in FIG. 6. In addition, it is shown in Figure 6 by measuring the current maximum value according to the scan rate from the curve.
It can be seen from FIG. 7 that the reciprocal of the maximum current shows a linear relationship with the scan rate, and thus it is found that the ion is suitable as a sensor even when the ion moves from the reference solution to the analysis solution.
<Example 2> glucose sensor
<Example 2-1> Production of a glucose sensor
First, a PVC film having elliptical holes was prepared in the same manner as in Example 1-1, and the film was attached to the inside of the glass tube using a silicone adhesive. 10mM TBATPBCl, PVC (3% wt / wt semisolid solution) and 10mM of ETH1778 (octadecyl isonicotinate), a hydrogen ion sensing material, were dissolved together in an organic solvent, Nitrophenyloctylether, at 120 ° C for 30 minutes. Was prepared. 10 μl of this organic gel was taken and manually dropped onto the PVC film in which the oval hole was formed and solidified at room temperature for 6 hours to form a gel.
The prepared ion-selective electrode was immersed in the analysis solution on the other surface of the PVC film not coated with the organic gel to form an aqueous solution / organic solution elliptical hole interface, which was immersed in an internal reference solution consisting of 10 mM TBACl.
<Experimental Example 2-2> fitness determination as a glucose sensor
1. Judgment by cyclic voltammetry
Cyclic voltammetry was performed using the glucose sensor of Example 2-1. (i) 0 mM, (ii) 6 mM, and (iii) 18 mM glucose were used and the scan rate was set at 20 mM / s. As can be seen in Figure 8, as the concentration of glucose increases, the concentration of hydrogen ions decomposed in glucose increases, it can be seen that the steady state current also increases.
2. Judgment by differential pulse voltammetry
After reacting 2mM, 6mM, 10mM, 14mM, 18mM glucose with the precipitation potential at 0.6V for 20 seconds, the differential pulse is set at the potential increment 20mV, pulse potential 50mV, pulse duration 50ms, scan speed 20mV / s Differential pulse voltammetry was performed.
The results are shown in Fig. 9 (a). The maximum current value within the range of 2 to 18 mM corresponding to the most common concentration of glucose in human blood increases linearly as the glucose concentration increases, and thus it has a linear relationship. In FIG. 9 (b), it can be seen that the average maximum current value of the experiment conducted with three electrodes shows a linear relationship with the concentration of glucose. Accordingly, the sensor including the hydrogen ion selective electrode according to the present invention is provided. It was found that it is suitable as a glucose sensor.
3. Measurement of inhibitory ion effect
Inhibition of redox reactions in glucose sensors Ascorbic acid and uric acid, which are ionic species, were found to exhibit negligible inhibitory effects in the range of 0 to 0.3 mM. Therefore, regardless of the inhibitory ion species present in the blood, it was found that the sensor including the hydrogen ion selective electrode according to the present invention is suitable as a glucose sensor.
10 clear synthetic resin film
20 organic gels
30 Internal reference solution
40 Assay Solution
50, 50 'internal reference electrode
60 potentiometer
A ion selective membrane
70 store
71 caps
72 microfluidic channels
80 Ag / AgCl Print
Claims (11)
b) preparing an organic gel by mixing a polyvinylchloride (PVC) solution, an ionophore, an auxiliary electrolyte, and an organic solvent; And
c) dropping 5-15 μl of the organic gel prepared in step b) to one surface of the ion-selective membrane prepared in step a) and coagulating at room temperature for 4 to 8 hours. Method for producing a base micro-ion selective electrode.
The elliptical hole of step a) has a long radius of 80 to 140㎛, short radius of 5 to 25㎛, elliptic hole spacing is characterized in that the manufacturing method of the current-based micro-ion selective electrode.
The transparent synthetic resin film of step a) is a polyvinyl chloride (polyvinylchloride, PVC), polyvinyl chloride (polyvinyllidene chloride, PVDC) and a low density polyethylene (low density polyethylene) characterized in that at least one selected from the group consisting of Method for producing a base micro-ion selective electrode.
The auxiliary electrolyte of step b) is bis (triphenylphosphoranylidene) ammonium tetrakis (4-chlorophenyl) borate (BTPPATPBCl), 1,2-dichloroethane solution of tetrabutylammonium tetraphenylborate (TBATPBCl) and tetra Pentylammonium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate (TPeATFPB).
The organic solvent of step b) is nitrophenyloctylether, adipate group, maleate group, oleate group, paraffin group, phosphate ( phosphate group), phthalate group (phthalate group), sebacate group (sebacate group) and stearate (stearate group) is a method for producing a current-based micro-ion selective electrode, characterized in that at least one selected from the group consisting of (stearate group) .
The ion sensing material of step b) is quaternary ammonium salt (valternomycin), ballinomycin (valinomycin), ballinomycin derivatives, monensin (nonensin), nonactin, nonactin derivatives, tertiary amine ), Metal porphyrin, metal phthalocyanine, trifluoroacetophenone, trifluoroacetophenone derivative, crown ether, dibenzo-18-crown-6 (dibenzo- 18-crown-6), organophosphorus ion sensing material, organotin ion sensing material, ETH1778, ETH1062, ETH1001, ETH129, ETH149, ETH1644, ETH1117, ETH5214, ETH227 and ETH157, characterized in that at least one selected from the group consisting of Method for producing a current-based micro-ion selective electrode.
The electrochemical quantification method is a method for electrochemically quantifying the ion concentration using a current-based micro-ion selective electrode, characterized in that measured by dynamic electrochemical measurement.
The kinetic electrochemical measurement method is ammeter-based micro-current, characterized in that the cyclic voltammetry, differential pulse voltammetry, or square wave voltammetry voltammetry A method of electrochemically quantifying ion concentration using an ion selective electrode.
The kinetic electrochemical measurement method is a method of electrochemically quantifying the ion concentration using an ammeter-based micro-ion selective electrode, characterized in that the current value increases as the ion concentration increases.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100071884A KR101217734B1 (en) | 2010-07-26 | 2010-07-26 | Manufacturing method of amperometric ion-selective microelectrode, amperometric ion-selective microelectrode made by the same, and electrochemical measuring method of ion concentration using the same |
| PCT/KR2011/005492 WO2012015213A2 (en) | 2010-07-26 | 2011-07-26 | Method for manufacturing amperometry-based micro-ion selective electrode, amperometry-based micro-ion selective electrode manufactured thereby, and method for electrochemically determining ion-concentration using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100071884A KR101217734B1 (en) | 2010-07-26 | 2010-07-26 | Manufacturing method of amperometric ion-selective microelectrode, amperometric ion-selective microelectrode made by the same, and electrochemical measuring method of ion concentration using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20120010386A KR20120010386A (en) | 2012-02-03 |
| KR101217734B1 true KR101217734B1 (en) | 2013-01-03 |
Family
ID=45530588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020100071884A KR101217734B1 (en) | 2010-07-26 | 2010-07-26 | Manufacturing method of amperometric ion-selective microelectrode, amperometric ion-selective microelectrode made by the same, and electrochemical measuring method of ion concentration using the same |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR101217734B1 (en) |
| WO (1) | WO2012015213A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101392666B1 (en) | 2013-01-16 | 2014-05-14 | 광운대학교 산학협력단 | Composition for solid state ion-selective membrane electrodes and ion sensors manufactured from the same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101440031B1 (en) * | 2013-02-13 | 2014-09-17 | 한국수자원공사 | Portable stick type amperometric ion sensor using liquid/gel interface |
| US10335781B2 (en) | 2014-05-16 | 2019-07-02 | Konkuk University Industrial Cooperation Corp | Nanopipette provided with membrane containing saturated ion-sensitive material, method for preparing same, and ion measuring apparatus comprising same |
| CN113588753A (en) * | 2021-07-09 | 2021-11-02 | 中国科学院烟台海岸带研究所 | Ion selective electrode current detection method |
| CN114034687B (en) * | 2021-10-29 | 2023-12-29 | 中国科学院烟台海岸带研究所 | Method and device for high-precision detection of calcium ions |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR920003086B1 (en) * | 1987-07-09 | 1992-04-13 | 데루모 가부시끼가이샤 | On sensor |
| KR970010881A (en) * | 1995-08-26 | 1997-03-27 | 차근식 | A composition for forming an ion selective membrane provided on an electrode of a chloride ion sensor and a method for forming an ion selective membrane using the same |
| KR20020058937A (en) * | 2000-12-30 | 2002-07-12 | 이성희 | Compositions of ion selective membrane, manufacturing and total nitrogen analyzer |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8705907D0 (en) * | 1987-03-12 | 1987-04-15 | Genetics Int Inc | Ion selective electrodes |
| DE19621241C2 (en) * | 1996-05-25 | 2000-03-16 | Manfred Kessler | Membrane electrode for measuring the glucose concentration in liquids |
| US6197172B1 (en) * | 1998-09-28 | 2001-03-06 | David H. Dicks | Electrochemical sensor with gelled membrane and method of making |
| US7150975B2 (en) * | 2002-08-19 | 2006-12-19 | Animas Technologies, Llc | Hydrogel composition for measuring glucose flux |
-
2010
- 2010-07-26 KR KR1020100071884A patent/KR101217734B1/en not_active IP Right Cessation
-
2011
- 2011-07-26 WO PCT/KR2011/005492 patent/WO2012015213A2/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR920003086B1 (en) * | 1987-07-09 | 1992-04-13 | 데루모 가부시끼가이샤 | On sensor |
| KR970010881A (en) * | 1995-08-26 | 1997-03-27 | 차근식 | A composition for forming an ion selective membrane provided on an electrode of a chloride ion sensor and a method for forming an ion selective membrane using the same |
| KR20020058937A (en) * | 2000-12-30 | 2002-07-12 | 이성희 | Compositions of ion selective membrane, manufacturing and total nitrogen analyzer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101392666B1 (en) | 2013-01-16 | 2014-05-14 | 광운대학교 산학협력단 | Composition for solid state ion-selective membrane electrodes and ion sensors manufactured from the same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012015213A2 (en) | 2012-02-02 |
| WO2012015213A3 (en) | 2012-05-10 |
| KR20120010386A (en) | 2012-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| van de Velde et al. | Solid contact potassium selective electrodes for biomedical applications–a review | |
| Qin et al. | Improved detection limits and unbiased selectivity coefficients obtained by using ion-exchange resins in the inner reference solution of ion-selective polymeric membrane electrodes | |
| US6663756B2 (en) | Microchip-type oxygen gas sensor based on differential potentiometry | |
| Zhang et al. | Advantages and limitations of reference electrodes with an ionic liquid junction and three-dimensionally ordered macroporous carbon as solid contact | |
| EP3054290B1 (en) | Ion-selective electrode | |
| KR101217734B1 (en) | Manufacturing method of amperometric ion-selective microelectrode, amperometric ion-selective microelectrode made by the same, and electrochemical measuring method of ion concentration using the same | |
| Bartoszewicz et al. | Calibration free solid contact electrodes with two PVC based membranes | |
| GB1584788A (en) | Ion-selective electrode | |
| Anderson et al. | Solid-contact ion-selective and reference electrodes covalently attached to functionalized poly (ethylene terephthalate) | |
| Jadhav et al. | Voltammetric and amperometric transduction for solvent polymeric membrane ion sensors | |
| Han et al. | Anomalous potentiometric response of solid-contact ion-selective electrodes with thin-layer membranes | |
| Tatsumi et al. | An all-solid-state thin-layer laminated cell for calibration-free coulometric determination of K+ | |
| AU639005B2 (en) | Electrochemical cell, reference electrode and electrochemical method | |
| Gan et al. | A solid-contact reference electrode based on silver/silver organic insoluble salt for potentiometric ion sensing | |
| Pendley et al. | A chronoamperometric method to estimate changes in the membrane composition of ion-selective membranes | |
| Soda et al. | Emulsion Doping of Ionophores and Ion-Exchangers into Ion-Selective Electrode Membranes | |
| Chang et al. | Healthcare chip based on integrated electrochemical sensors used for clinical diagnostics of BUN | |
| Guagneli | Novel design of a flow-through potentiometric sensing device | |
| Oyama et al. | Ion-selective electrodes based on bilayer film coating | |
| Vanamo | Solid-state reference and ion-selective electrodes: towards portable potentiometric sensing | |
| Bakker | Potentiometric Sensors | |
| KR101440031B1 (en) | Portable stick type amperometric ion sensor using liquid/gel interface | |
| Marple et al. | Potentiometry: pH and Ion-Selective Electrodes | |
| Henn et al. | Voltammetric Ion‐Selective Electrodes (VISE) | |
| Asein | Flow-Through Cell for Ion-selective Electrodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20151223 Year of fee payment: 4 |
|
| FPAY | Annual fee payment |
Payment date: 20161216 Year of fee payment: 5 |
|
| LAPS | Lapse due to unpaid annual fee |