JP2010139498A - Indicator electrode used for electrochemical measurement - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an indicator electrode which is made of a conductive material such as a metal, and used in an electrochemical measurement device for liquid and gas, and enables accurate and stable measurement of the electric potential of liquid and gas of any type. <P>SOLUTION: Conventional indicator electrodes having a surface polishing means which performs circumferential polishing by coaxial rotation and polishing in complicatedly crossing in up, down, right and left directions cause large movement error in the electric potential and current generated in the interface of indicator electrode and solution or air. Especially, in a solution, a diffusion potential is generated due to fine polishing streaks complicatedly crossing upon electric conduction at a negative and positive electron level in electron movement. In order to avoid the phenomenon that the reproduction value is different in measurement of the same solution or liquid, the surface of the indicator electrode is subjected to linear micro polishing in the flowing direction of the electric potential and current and linear micro polishing in a state which causes helical movement in a spiral way. This enables precise potential measurement on biological liquids (salivary) of human and the like with low buffering capacity as well as solutions with high buffering capacity, and improves reproducibility of absolute value measurement. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to an indicator electrode of an oxidation-reduction potential measuring device and an indicator electrode used for electrochemical measurement of these liquids and gases.

であり、酸化還元電位Ｅは次のネルンストの式で示される。
Ｅ＝Ｅｏ＋ｎＦ−ＲＴ １ｎ［Ｒｅｄ］［Ｏｘ］
ここに、Ｅｏ：標準酸化還元電位（［Ｏｘ］＝［Ｒｅｄ］のときのＥで、系に固有の値）
Ｒ：ガス定数 Ｔ：絶対温度 Ｆ：ファラデー定数

In an electrochemical measuring device that measures the potential and current generated at the interface between the indicator electrode and the liquid and the indicator electrode and the gas, as an indicator electrode of a conductive substance such as a metal provided in the liquid and gas electrochemical measuring device, There is a potential measuring device using an ion selective electrode, for example, a redox potential measuring device. The oxidation-reduction potential measuring device is equipped with an indicator electrode and a reference electrode of a conductive substance such as metal, and the solution is brought into contact with the indicator electrode, and the concentration of the electrolyte in the solution and the ion concentration ratio of the oxidant / reductant are measured. To do. That is, when an electrode such as gold or platinum that is not immersed in a solution is immersed in a solution containing an oxidant and a reductant, the electrode reaches equilibrium with a potential with respect to the solution. This potential is called a redox potential. If the oxidant is Ox and the reductant is Red, the redox reaction is

The oxidation-reduction potential E is expressed by the following Nernst equation.
E = Eo + nF-RT 1n [Red] [Ox]
Here, Eo: standard oxidation-reduction potential (E when [Ox] = [Red], a value specific to the system)
R: Gas constant T: Absolute temperature F: Faraday constant

In the indicator electrode used in the conventional electrochemical measuring apparatus for measuring potential and current, an error may occur in the reproduced value of the same solution. For example, if the concentration of the redox substance in a solution such as a biological fluid is low, or if the properties of the solution are too pure, an error in potential measurement occurs in the reproduced value of the redox potential E.
JP-A-11-118756 JP-A-2006-98390

The problem to be solved by the present invention is to overcome such drawbacks and to provide a metal included in a liquid and gas electrochemical measurement device that enables accurate and stable potential measurement regardless of the type of liquid and gas. An indicator electrode of a conductive material such as is provided.

The present invention takes the following means to solve the above problems. That is, an indicator electrode of a conductive substance such as a metal provided in a liquid and gas electrochemical measuring device, and the means for polishing the surface of this metal is a surface polishing potential and linear in the direction of current flow. Micropolished.

With conventional indicator electrodes for circumferential polishing by coaxial rotation and polishing that intersects vertically, horizontally, and complicatedly, the movement error is increased in the potential and current generated at the interface between the indicator and the solution or gas. In order to prevent diffusion potentials in the negative and positive conductions in electron transfer and the phenomenon of different reproducible values in the same solution or liquid measurement, conducting wires or rounds that are conductive materials such as metals that polish the surface This is a means for linearly micro-polishing all surface polishing in the direction in which the electric potential and current flow regardless of the shape such as a rod, a round tip, a flat plate, a sphere, and a cylindrical inner surface.

In the indicator electrode of conductive material such as metal provided in the liquid and gas electrochemical measuring device, the surface polishing means is the surface polishing potential, the spiral movement in the direction of current flow spirally By micro-polishing linearly in the resulting state, friction due to the contact surface with the polishing cloth to be polished is reduced, and the influence of extremely weak magnetism due to frictional heat is prevented (or less likely). The reproduction accuracy can be improved.

In the present invention, the means for applying a polishing treatment to the surface is an indicator electrode that is micro-polished linearly in the direction in which the surface polishing is performed in the direction in which the electric current and electric current flow, so that the movement of the electric potential and electric current is linear and smooth. The linear micropolishing in the form of the spiral shape reduces the friction due to the contact surface with the polishing cloth to be polished, and prevents (or the risk of) the generation of extremely weak magnetism due to frictional heat. This prevents the generation of a diffusion potential due to an electron transfer error in solution measurement, and the indicator electrode of the present invention used for measuring the potential and current generated at the interface with the solution further increases the reproducibility of the measurement. It was.

In addition, today, the polishing process is mainly a coaxial rotation or a polishing that intersects in a complicated manner vertically and horizontally, and means for polishing the surface is a means for micropolishing the surface polishing linearly in the direction in which the electric potential and current flow. However, after polishing of the conventional indicator electrode, it looks like it is mirror-polished by visual observation and about 30 times magnification, but a fine polishing line cannot be confirmed. When observing at a higher magnification at the level of a stereomicroscope, countless fine polishing lines that are coaxially rotated or complicatedly intersected vertically and horizontally can be seen. It has been found that this polishing line at the micro level causes a movement error in the potential and current generated at the interface between the indicator electrode and the solution or gas, thereby inhibiting stable potential measurement.

The indicator electrode of the present invention has a conductive wire, a round bar, a tip-end round bar, a flat plate, a sphere, a cylindrical inner surface, etc. (not shown) which is a conductive material such as a metal whose surface is polished. is there. However, the means for performing the polishing treatment on the surface of the indicator electrode is an electrode in which all surface polishing is linearly micro-polished in the traveling direction of potential and current regardless of the shape.

Here, the polishing of the indicator electrode disclosed in the prior art (Japanese Patent Publication-JP-A-11-118756 and JP-A-2006-98390) will be described. Although the public relations show that the surface of the indicator electrode is polished, it may cause a film such as an oxide film on the indicator electrode surface when the number of contact with the solution increases, such as repeated potential measurements. It is only polishing for removing such a film and returning the surface of the indicator electrode to its original state. There is no awareness of the adjustment of the surface roughness characteristic of the indicator electrode and precise polishing. The other is a surface polishing process adjusted at a micro level as disclosed, and the surface roughness characteristics are Ra (μm) 0.50 or less, Ry (μm) 1.70 or less, Rz (μm) 1 according to JIS BO601-1994. It is shown that the indicator electrode is set to 00 or less, but this is set by micro-level polishing in advance with a certain standard of surface roughness to remove irregularities and fine scratches on the indicator electrode surface and generate local batteries In order to solve these problems, the generation of an oxide film is suppressed, and washing is easily performed with purified water (pure water) before repeated potential measurement.

The indicator electrode according to the present invention is a method in which surface polishing is linearly micro-polished in the direction in which electric potential and current flow, and the electron conduction of ion concentration, which is a plus or minus electrolyte, becomes linear and smooth. Obviously, the improvement in measurement accuracy was confirmed. Electric potential measurement that suggests the state of human health requires more precise reproduction accuracy. The indicator electrode of the present invention was confirmed to be stable in the electronic conduction of biological fluid (saliva) (described later) by patient saliva clinical practice in a plurality of clinics. Therefore, the technical significance of the two prior art polishings is clearly different.

The indicator electrode of the present invention is used for electrochemical measurement of electric potential and electric current by not only measuring electric potential in a solution but also performing surface polishing for electric conduction in a linear micro-polishing in the direction in which electric potential and electric current flow. Since the response of the indicator electrode is smooth and it is difficult to receive the noise resistance to be charged, this is an indicator electrode polishing method and method for electrochemically using a metal used for electric conduction for various purposes as well as potential measurement.

Examples according to the present invention will be described below together with comparative examples. In the examples and comparative examples, the indicator electrode is in the form of a round bar (FIG. 1) with a rounded platinum tip. As a means for confirming the significance, a test device for measuring the oxidation state and reduction state in the body by human saliva having information equivalent to blood information well known in the medical society was used. The inspection equipment is a general medical equipment / special maintenance medical equipment that has already been released. The indicator electrode part of the redox confirmation meter “Ara Genki” measuring instrument using the oxidation-reduction potential (mV) as an index is replaced with the indicator electrode of the present invention, and this redox confirmation meter is used in internal medicine / pediatric clinics and clinics. Thus, the significance of the redox state was confirmed.

With reference to FIG. Reference numeral 1 denotes an indicator electrode of the present invention in which the surface of a platinum electrode, which is a metal, is polished linearly in the direction in which electric potential and current flow. Reference numeral 2 denotes an electrical lead, and 3 denotes indicator electrode polishing in which the indicator electrode surface 1 according to the polishing method of the present invention is micro-polished linearly in the direction in which electric potential and current flow between A and B. As a result, the response of the electronic conduction which is the electrolyte concentration of the biological fluid and the activity of the oxidant and the reductant becomes smooth, the influence of the charged noise is reduced, and the reproduction accuracy of the potential measurement of the biological fluid is improved. Referring to FIG. 2, 4 is a view of the indicator electrode according to the polishing method of the present invention as viewed from directly above. When polishing linearly in the direction of travel so as not to cause uneven polishing on the surface of the round bar 360 degrees. In this case, the polishing is stopped by stopping polishing at regular time intervals and rotating by 30 degrees in the clockwise direction coaxially. . By repeating this process 12 times, the polishing was performed in a straight line in the forward and backward directions without unevenness of 360 degrees. With reference to FIG. 6 shows a state in which a spiral movement is generated in a spiral shape in the direction of current flow. This reduces the friction caused by the contact surface with the polishing cloth to be polished, prevents the influence of extremely weak magnetism due to frictional heat, and improves the reproducibility in the same solution or liquid measurement. In FIG. 4, 7 indicates a spiral movement in the form of a spiral in the vertical direction. Reference numeral 8 denotes a vertical motion and a spiral motion in the form of a spiral in the direction of traffic.

In order to confirm the significance, the measurement was performed by impregnating saliva into a cotton swab sterilized one by one and bringing it into contact with the indicator electrode of the present invention. Directed micro-polishing of the platinum electrode, which is the indicator electrode, in the direction of the potential and current flow of the present invention after clinical practice of saliva at Yokohama-Okazawa Clinic, Yokohama-Sankeien Clinic, and Yokohama-Satsukidai Clinic The results of confirming the significance using the electrode and the conventional indicator electrode are shown in [Table 1], [Table 2], and [Table 3].

As means for confirming the significance of the polishing method of the indicator electrode of the present invention, saliva clinical practice at each clinic shown in [Table 1], [Table 2], and [Table 3] was carried out by 10 persons each. Conventional saliva measurement with an indicator electrode that has undergone surface polishing has a fluctuation range of a maximum of 11 mV when the same saliva is measured three times in succession, and the saliva measurement result with the indicator electrode of the present invention is a chronic disease. Or, even in patient measurements during treatment due to transient fever symptoms etc., the same saliva was measured three times in succession and was a reproducible value within a maximum of 2 mV. The redox potential is measured in thousandths of (mV). The reproducibility of the redox potential measurement of biological fluids as a means of knowing the health condition requires more stability. The significance of the micropolishing of the indicator electrode and the surface polishing method of the present invention linearly in the direction of traffic was confirmed.

In carrying out the method for polishing the indicator electrode of the present invention, each of the current polishing equipment manufacturers is a polishing apparatus that rotates by a concentric shaft, and there is no apparatus that polishes linearly in the direction of travel. In order to confirm the significance of the above, the vertical reciprocating motion for linearly polishing in the forward and backward directions and constant polishing each time when polishing linearly in the forward and backward directions so as not to cause polishing unevenness on the round bar surface 360 degrees. Polishing is stopped at time intervals, and polishing is performed by rotating it by 30 degrees in the clockwise direction on the same axis or with a free width at an arbitrary setting. The number of repetitions can be set arbitrarily, and a special polishing machine equipped with these functions, such as spiral up and down movements can be arbitrarily set, and can be polished linearly in the direction of travel with 360 degrees of uniformity. The indicator electrode of the present invention was completed.

As a result, the indicator electrode according to the present invention was further improved in measurement accuracy even for a solution having a low buffering capacity, and the potential measurement with a stable reproducible value was verified by salivary clinic in the clinic, and the significance could be confirmed. Therefore, it can greatly contribute to daily health management and can be widely used in industry.

FIG. 4 is an enlarged front view of an indicator electrode that is linearly micro-polished in a traveling direction. It is the figure which looked at the indicator electrode from right above. The figure which looked at the state which brings about a spiral movement in the shape of a spiral from right above. The figure which showed the motion of the spiral shape in the shape of a spiral in the up-and-down motion and the traffic direction.

DESCRIPTION OF SYMBOLS 1 Indicator electrode 2 of this invention Electrical conducting wire 3 The surface of the indicator electrode of this invention is micro-polished linearly in the direction of the electric current and the current flow between A and B. 4 5 seen from above A state in which the indicator electrode of the present invention is rotated in the clockwise direction 6 FIG.
7 shows spiral movement in the form of a spiral of the present invention.
8 Vertical movement and movement in the direction of the helix in the spiral shape of the present invention are shown.

Claims (4)

Means for polishing the surface of an indicator electrode used for measuring an electric potential and an electric current generated at an interface between a liquid and a gas, and an indicator electrode made of a conductive material such as a metal provided in an electrochemical measuring device for the liquid and gas An indicator electrode, characterized in that surface polishing is micro-polished linearly in the direction in which electric potential and current flow. An indicator electrode used for measuring electric potential and current generated at the interface between liquid and gas, and a metal for polishing the surface of an indicator electrode made of a conductive material such as a metal provided in an electrochemical measuring device for liquid and gas Conductive materials such as conductive wires, round bars, tip-end round bars, flat plates, spheres, cylindrical inner surfaces, etc. All surface polishing is linearly micro-polished in the direction in which the electric potential and current flow The indicator electrode according to claim 1. Polishing linearly in the direction of travel of indicator electrodes used for measuring potentials and currents generated at the interface between liquid and gas, and for conducting electrodes such as metals provided in liquid and gas electrochemical measuring devices In order to prevent uneven polishing on the surface of the round bar 360 degrees, polishing is stopped at regular time intervals and rotated coaxially by 30 degrees in the clockwise or counterclockwise direction or freely set with a free width. Polish it. The indicator electrode according to claim 1 or 2, wherein the number of repetitions can be arbitrarily set, and the indicator electrode surface is micro-polished linearly in the direction in which the potential and current flow. Means for polishing the surface of an indicator electrode used for measuring an electric potential and an electric current generated at an interface between a liquid and a gas, and an indicator electrode made of a conductive material such as a metal provided in an electrochemical measuring device for the liquid and gas 4. The indicator electrode according to claim 1, wherein the surface electrode is linearly micro-polished in a state in which spiral movement is generated in a spiral shape in a direction in which electric current and electric current flow.

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