JPS6044860A - Electrode apparatus and automatic chemical analysis apparatus provided with electrode apparatus - Google Patents

Abstract

PURPOSE:To obtain an easily manufacturable and compact electrode apparatus, by allowing cathode and anode attached on an insulator to contact with an electrode film of wall surface of a cell immersed in constant-temperature water equivalent to an internal liquid. CONSTITUTION:An electrode apparatus 10 is so constructed that a cathode, for example, platinum electrode 12 is installed internally in an insulator, for example, glass cylinder 11 and at the same time, an anode, for example, silver/silverchloride electrode is installed externally. This electrode apparatus welded with lazer, etc. in an aperture provided sideways on the peripherial surface of a glass cell 17 held on a holder 16 free to be immersed in an internal liquid, for example, KCl solution 15 contained in the conventional electrode apparatus as constant-temperature water inside a constant-temperature tank 14. In this apperture, an electrode film 18 is spanned and the apparatus 10 is set free to contact with the film 18. By this construction, an operation of containing hermetically the internal liquid as is the case with the conventional apparatus is eliminated and common use of internal liquid and constant-temperature water becomes possible for easier handling of the internal liquid and consequently, the electrode apparatus can be manufactured with advanced easiness with miniaturized configuration.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an electrode device capable of electrochemically detecting a specific substance in a test liquid, and an automatic chemical analysis device having the electrode device.

[Technical background of the invention and its problems]

Conventionally, an electrode device shown in FIG. 1 has been used in a general analysis device.

The electrode device 1 shown in FIG.
For example, an acetyl cellulose solution is provided, and the housing 2 is filled with an internal solution 5, such as an MCI solution, and a cathode 6, such as a platinum electrode, is installed in the internal solution 5, and an anode 7, such as a silver/silver chloride electrode, is disposed inside the internal solution 5. The insulator 8 is made of, for example, a glass cylinder. The electrode device 1 includes:
By immersing this in a test liquid, applying a constant voltage, and simultaneously detecting the oxidation or reduction current generated in the test liquid, it is possible to quantify various components in the test liquid.

For example, when measuring the glucose concentration in a test solution,
As shown in the first equation, glucose is oxidized by glucose oxidase (COD) and reacts with oxygen and water in the test solution to produce gluconic acid and hydrogen peroxide. At this time, a constant voltage is applied to the test solution. When added, an oxidation current is generated due to the reaction of hydrogen peroxide, and since the amount of hydrogen peroxide and the oxidation current are in a proportional relationship, the glucose concentration can be determined by measuring the oxidation current with the electrode device 1. Can be quantified.

In addition to quantifying the glucose concentration, the electrode device 1 can also quantify dissolved oxygen in the test liquid in the first reaction. In quantifying dissolved oxygen, the electrode device 1 measures the reduction current in the liquid.

However, the electrode device 1 must fill the internal liquid 5 without producing bubbles in the cylinder 2, and requires a high level of manufacturing technology. Further, due to the structure in which the internal liquid 5 is enclosed, the electrode device 1 cannot be made as small as possible, and there is a limit to miniaturization. Further, the electrode device 1
In an automatic chemical analyzer incorporating this, a large amount of test liquid is required, and the electrode section must be cleaned after each measurement, so continuous measurement requires a large amount of time.

[Purpose of the invention]

The present invention has been made based on the above-mentioned circumstances, and provides an automatic chemical analyzer that has a small-sized electrode device that is easy to manufacture and that uses the electrode device to shorten continuous measurements and reduce the amount of sample liquid. The purpose is to provide

[Summary of the invention]

The outline of the present invention for achieving the above object includes an insulator, a negative electrode disposed inside the insulator, and an anode disposed on the outer surface of the insulator. It is characterized in that it is arranged so as to be able to contact an electrode membrane that is integrally stretched over an opening provided in the wall of the cell to be immersed, and the sample and reagent are mixed in the cell and the process proceeds. In an automatic chemical analyzer that quantifies components in a sample by detecting current changes caused by oxidation or reduction reactions, an insulator, a cathode placed inside the insulator, and an anode placed on the outside of the insulator are used. The cell is equipped with a measuring section that has an electrode device that is removably arranged on an electrode membrane that is integrally stretched over an opening provided in the wall of the cell that is immersed in constant temperature water that is a solution equivalent to the internal solution. It is characterized by this.

[Embodiments of the invention]

An embodiment of the first invention will be described with reference to the drawings. .

As shown in FIG. 2, the electrode device 10 has a cathode such as a platinum electrode 12 inside an insulator such as a glass tube 11 and an anode such as a silver/silver chloride electrode 13 on the outside. The holder 16 can be immersed in an internal solution, such as a Kcl solution 15, which has been sealed in the electrode device.
The electrode film 18 is welded with a laser or the like to an opening provided on the peripheral side of a glass cell 170 held in the glass cell 170, and is arranged so as to be able to come into contact with the integrated electrode film 18 under a predetermined pressure.

The electrode device 10 itself configured as described above has the glass tube 11, the platinum electrode 12, and the silver/silver chloride electrode 16 as its main components, so it can be made smaller, and the internal liquid can be reduced without creating bubbles inside the device. Since it does not require filling, it can be manufactured easily without requiring advanced technology. Since the internal liquid sealed in the conventional electrode device is also used as constant temperature water in the above embodiment, the difficult work of sealing the internal liquid into the electrode device is eliminated, and the handling of the internal liquid is simplified. It can make your work easier.

Further, since the electrode device 10 according to the embodiment does not need to be inserted into the cell 17, the internal volume of the cell 17 can be reduced. Therefore, with respect to the electrode device 10, the amount of necessary test liquid 19 can be reduced.

Next, another embodiment of this first invention is shown in FIG.

The other embodiment differs from the embodiment shown in FIG. The electrode film 21 is arranged so as to be able to come into contact with the electrode film 21 under a predetermined pressure.

This other embodiment provides the same effects as the above embodiment, but is suitable for cases where it is difficult to arrange the electrode device 10 near the outer periphery of the cell 20.

Next, an embodiment of the second invention will be described with reference to the drawings.

Automatic chemical analyzer 30 according to an embodiment of this second invention
As shown in FIGS. 4 and 5, a large number of cells 32 are attached to a holder 31 formed in an annular plate and configured to be rotatable in the direction of the arrow in the figure.
is immersed in constant temperature water 4-3 containing a solution corresponding to the internal solution in a conventional electrode device, such as a KCl solution. Then, the cell 62 is placed at an appropriate position in the holder 61.
A dispensing/dispensing unit 66 having a dispensing nozzle (not shown) capable of dispensing and dispensing a predetermined amount of reagent and sample, a measuring unit 64 (described later), and a measuring unit 64 that aspirates the measured liquid in the cell 62 and then , and a cleaning section 65 that cleans the inside of the cell 32 by injecting a cleaning liquid into the empty cell 62. As shown in FIG. 5, the measuring section 34 is horizontally coupled to the tip of a movable shaft 67 of the solenoid 36, and has a cathode, e.g., a platinum electrode 39, housed in an insulator, e.g., a glass tube 68, and an anode. For example, an electrode is formed by enclosing a silver/silver chloride electrode 40, welding the tip of the glass cylinder 38 to an opening provided on the circumferential side of the cell 620 using a laser or the like, and placing it in contact with the integrated electrode film 41. It has a device 42. It goes without saying that the driving of the holder 36, the operations of the dispensing/dispensing section 63, the measuring section 64, the cleaning section 65, etc., and their timings are controlled by a control device (not shown).

According to the automatic chemical analyzer having the above configuration, chemical analysis is performed as follows. That is, when the cell 32 attached to the holder 61 reaches a predetermined position within the dispensing and dispensing section 66 due to rotation of the holder 61, a predetermined amount of reagent and sample are dispensed into the cell 32 from a discharging nozzle (not shown). The cell 62 containing the reagent and sample is heated by the constant temperature water 46 from the dispensing/dispensing part 33 to the measuring part 64, and the sample and reagent in the cell 62 react with each other. Cell 62 is measurement section 3
When the glass cylinder 68 having both negative and negative electrodes is moved horizontally by the solenoid 66, its tip comes into contact with the electrode film 41 in the cell 62. Then, the electrode device 42 detects the oxidation current or reduction current in the test liquid in the cell 32, and a data processing section (not shown) performs calculations for quantifying various components in the sample.

After the measurement, the cell 32 is moved, and the cleaning section 65 cleans the inner wall of the cell 62.

As described above, the automatic chemical analyzer having the electrode device according to the first invention does not require the cleaning operation of the electrode device 42 itself, and the electrode membrane 41 can be cleaned only by cleaning the inside of the cell 32. By simplifying the analysis operation, continuous measurements can be shortened, and the required amount of the test liquid, especially the sample, can be reduced.

Although one embodiment of each of this invention has been described above, this invention is not limited to the above embodiments, and can be implemented with appropriate modifications within the scope of the gist of this invention. Needless to say.

〔Effect of the invention〕

According to the invention described in detail above, the electrode device mainly includes an insulator and both negative and negative electrodes, so that it can be miniaturized and easily manufactured. Moreover,
Since the internal liquid used in the conventional electrode device is also used as constant temperature water for heating the cell, the difficult work of sealing the internal liquid can be omitted in the electrode device according to the invention. Further, since the electrode device according to the present invention is not directly immersed in the test liquid in the cell, it is possible to reduce the required amount of the test liquid.

In addition, the automatic chemical analyzer using the electrode device can omit the cleaning process of the electrode device itself from the process of continuous measurement, so the time required for continuous measurement can be shortened and the measurement operation can be simplified. . In addition, cells with electrode membranes are cleaned in the cleaning section after each measurement, and the electrode device itself tends to come into direct contact with the sample liquid, so it is difficult to prevent contamination from the electrode device and perform accurate quantitation. can.

[Brief explanation of the drawing]

FIG. 1 is a schematic sectional view showing a conventional electrode device, FIG. 2 is a schematic explanatory view showing an embodiment of the first invention, and FIG. 6 is a schematic explanatory diagram showing another embodiment of the first invention. 4 are explanatory diagrams showing an embodiment of the second invention, and FIG. 5 is an end view taken along the line v--v in FIG. 4. 10.42... Electrode device, 11.38... Glass cylinder, 12.39... Platinum electrode, 15.40... Silver/silver chloride electrode, 15.43... Constant temperature water, 17, 20. !
+2... Cell, 18.21.41... Electrode film, 60
...Automatic chemical analyzer, 34...Measurement section,

Claims (2)

[Claims] (1) An opening in the wall of a cell that is equipped with an insulator, a negative electrode placed inside the insulator, and an anode placed on the outside of the insulator, and is immersed in constant-temperature water, which is a solution equivalent to the internal solution. An electrode device characterized in that the electrode device is arranged so as to be able to come into contact with an electrode membrane that is integrally stretched across the section. (2) In an automatic chemical analyzer that quantifies components in the sample by mixing a sample and a reagent in a cell and detecting changes in current caused by the proceeding oxidation or reduction reaction, an insulator and
It is equipped with a cathode placed inside the insulator and an anode placed on the outside of the insulator, and is attached integrally to an opening in the wall of the cell that is immersed in constant temperature water, which is a solution equivalent to the internal liquid. 1. An automatic chemical analysis device comprising a measuring section having an electrode device that is arranged separably on an electrode membrane.