JPH02257050A - Concentration measuring device - Google Patents

Abstract

PURPOSE:To simplify the method of measuring concentrations by providing several apertures for transmission of solutions to be measured on a thin film sheet and a supporting tool of diffusion limiting films to cover the apertures with diffusion determining films and electrodes for measuring concentrations, and by making the supporting tool and concentration measuring electrodes possible to move in parallel planes to each other. CONSTITUTION:The aperture 15 for transmission of sample solutions is provided on a long size sheet 1 with desired intervals and the diffusion determining film 16 is provided to cover the aperture to constitute the supporting tool of diffusion determining films. This tool is mounted on a specified position in a casing 2 of the measuring device in a manner that the tool can move in a specified direction. When a sample solution is dropped on the aperture 15, the measuring electrode 22 is moved to make the determining film 16 contact to measure the concentration of the sample solution. On moving the supporting tool, the electrode 22 is made apart from the electrode driving mechanic 3. Thereby, it is unnecessary to change the limiting film 16 during measuring the same time as that of the films 16. Since the film 16 is apart from the electrode 22 on dropping sample solutions, infection of disease is prevented even when a body liquid is to be measured.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a concentration measuring device, and more specifically,
Relates to a novel concentration measuring device in which a substance to be measured is diffused through a diffusion-limiting membrane and the position of a concentration measuring electrode is changed to correspond to a state in which the concentration is measured based on the diffused substance to be measured and a state in which the concentration is not measured. .

<Conventional technology> Focusing on the characteristic of being able to selectively detect extremely complex organic compounds, proteins, etc. with extremely high sensitivity, bioactive substances are immobilized on the surface of an electrode. Research and development is being carried out to measure the above-mentioned organic compounds, proteins, etc. using enzyme electrodes.

When measuring a target substance using the enzyme electrode, the target substance is usually oxidized, reduced, etc. in the presence of the physiologically active substance to reduce the amount of produced substances or disappeared substances. Since the concentration of the substance to be measured is determined by measurement, the upper limit of the measurable concentration is limited by the amount of a substance that causes oxidation, reduction, etc., such as oxygen, to exist.

Focusing on this point, attempts have been made to increase the measurement limit concentration by installing a diffusion-limiting membrane on the surface side of the immobilized enzyme membrane on which the physiologically active substance is immobilized to limit the permeation rate of the substance to be measured. being done.

Specifically, a diffusion-limiting membrane is placed on a cap that is screwed onto the base of a rod-shaped enzyme electrode, and the diffusion-limiting membrane is automatically brought into close contact with the immobilized enzyme membrane by screwing the cap. configuration has been adopted.

By adopting such a configuration, the diffusion-limiting membrane can limit the permeation rate of the substance to be measured, making it possible to measure up to a considerably high concentration. In addition, the above-mentioned diffusion-limiting membrane is not affected by interfering substances contained in the solution to be measured (
In order to perform good measurements while eliminating problems such as increased diffusion-restricting effects caused by adhesion of interfering substances, etc., it is necessary to make the cap removable, and a screw-in mechanism using a cap is used.

<Problems to be Solved by the Invention> When the diffusion-limiting membrane holder having the above structure is adopted, the diffusion-limiting membrane can be replaced relatively easily, but the lTI depletion that accompanies use is a problem. In order to eliminate this problem, the diffusion-limiting membrane must be replaced more frequently, which poses the problem of significantly increasing the concentration measurement work as a whole. In some cases, there is a problem in that there is a risk of disease infection due to pathogenic bacteria remaining on the surface of the constant electrode due to its concentration.

Furthermore, if the enzyme electrode base becomes small in diameter and the cap becomes small as a result, manual operation becomes extremely difficult and the problem of complicating concentration measurement becomes even more pronounced.

Taking these problems into consideration, we have adopted a diffusion-limiting membrane holder that has an opening formed at a predetermined position in a thin plate material and a diffusion-limiting membrane pasted to cover one side of the opening. A solution containing the substance to be measured (hereinafter referred to as the test solution) is dropped into the holder in advance, and the concentration of the test solution can be measured with the diffusion-limiting membrane pressed against the immobilized enzyme membrane. However, thin plate materials are usually not strained, making it difficult to drip the test solution and attaching them to the measuring device body, as well as requiring replacement of the diffusion-limiting membrane holder quite frequently. Therefore, there is a problem that the concentration measurement work becomes complicated as a whole. Furthermore, since the above-mentioned diffusion-limiting membrane may become clogged with use, it should be discarded after each concentration measurement a predetermined number of times, or preferably after each concentration measurement, and a new diffusion-limiting membrane pasted. Since it is necessary to use the thin plate material that has been attached, the required amount of thin plate material is discarded, which is uneconomical, and it is necessary to dispose of the thin plate material and take out new thin plate material. However, there is a problem in that the series of operations for measuring the concentration of the substance to be measured becomes extremely complicated.

To explain in more detail the complicated operation, ■ Turn on the power switch of the measurement device, ■ Open the cover of the measurement device, ■ Unpack and take out the thin plate material to which the diffusion restriction membrane is attached, and ■ (Drop the test solution onto the thin plate, collect blood if it is the test solution or blood, and then spot the blood on the thin plate); ■ Insert the thin plate into the measuring device; ■ Insert the thin plate into the inserted thin plate. The attached diffusion-limiting film is brought into close contact with the surface of the electrode for concentration measurement, and in this state, the concentration of the substance to be measured is measured.

■ Then, release the diffusion-limiting membrane from the electrode surface, ■ pull out the thin plate material from the measuring device, ■ close the cover of the measuring device, [phase] discard the extracted thin plate material, and ■ turn on the power source of the measuring device. Open the switch.

This requires a series of operations, and since there are some parts that are difficult to operate, the concentration measurement work as a whole becomes extremely complicated.

Furthermore, since the above does not mention at all the calibration work based on standard solutions with known concentrations, the necessary work becomes even more complicated as the calibration work is actually required. Become.

Furthermore, if the test solution is applied after attaching the thin plate material to the concentration measuring electrode, there is a problem in that the risk of infection by diseases caused by pathogenic bacteria or the like increases.

Although only the case where the concentration of the substance to be measured is measured using an enzyme electrode has been described above, the same problem occurs when the concentration of the substance to be measured is measured using an electrode other than the enzyme electrode.

<Object of the invention> This invention was made in view of the above problems,
Provided is a concentration measuring device that can significantly reduce the frequency of attachment and disposal of a diffusion limiting membrane, significantly simplify the concentration measurement work, and further allow a concentration measuring electrode to be brought into close contact with the diffusion limiting membrane only during concentration measurement. It is intended to.

Means for Solving the Problems> In order to achieve the above object, the concentration measuring device of the present invention has a thin sheet with openings for permeation of the test solution formed at predetermined intervals, and A predetermined position of a casing that accommodates a diffusion-limiting membrane holder, which is provided with a diffusion-limiting membrane so as to cover it and is movable in a predetermined direction, is set as a concentration measurement position, and a concentration-measuring electrode is provided on the casing. Furthermore, an electrode drive mechanism is provided for reciprocating the concentration measuring electrode in a plane substantially parallel to the movement plane of the diffusion limiting membrane holder and for raising and lowering the concentration measuring electrode at the re-movement limit position.

However, the electrode driving mechanism may be one that reciprocates the concentration measuring electrode in a direction that is not parallel to the moving direction of the thin sheet within a plane that is substantially parallel to the moving plane of the diffusion limiting membrane holder, or The concentration measuring electrode may be reciprocated in a direction parallel to the moving direction of the thin plate sheet in a plane substantially parallel to the moving plane of the diffusion limiting membrane holder.

Further, it is preferable that a storage solution storage member is further provided to directly face the concentration measuring electrode that has been moved to a position that does not directly face the measurement position.

In the concentration measuring device with the above configuration, openings for permeation of the test solution are formed in the thin sheet at predetermined intervals, and a diffusion limiting film is provided to cover each opening. The limiting membrane holder is housed in a predetermined position in the casing of the concentration measuring device so as to be movable in a predetermined direction, and the test solution is poured into the opening, and then the concentration measuring electrode is moved so that it comes into close contact with the diffusion limiting membrane. By doing so, the concentration of the substance to be measured contained in the test solution can be measured.

Therefore, not only is it unnecessary to attach and detach the diffusion limiting membranes while performing measurements equal to the number of diffusion limiting membranes installed in the diffusion limiting membrane holder, but also the diffusion limiting membranes are not required at the time of applying the test solution. Since the electrode and the concentration measuring electrode are separated from each other, the risk of disease infection can be eliminated even when measuring body fluids.

Furthermore, when moving the diffusion limiting membrane holder, keep the concentration measuring electrodes apart to prevent characteristic deterioration due to rubbing on both the concentration measuring electrode and the diffusion limiting membrane holder. be able to.

When the electrode drive mechanism is one that reciprocates the concentration measuring electrode in a direction that is not parallel to the moving direction of the thin sheet within a plane that is substantially parallel to the moving plane of the diffusion limiting membrane holder, the concentration measuring electrode It can be raised until it comes into close contact with the diffusion limiting membrane when directly facing the thin sheet, and can be raised any distance when not directly facing the thin sheet, creating an opening in the thin sheet for the concentration measurement electrode to pass through. There is no need to do this, and it is sufficient to form only the openings for the passage of the test solution, so the number of openings for the passage of the test solution per unit length can be increased. In this case, if the concentration measuring electrode is configured to reciprocate in a direction substantially perpendicular to the direction of movement of the thin sheet in a plane substantially parallel to the plane of movement of the diffusion-limiting membrane holder, the concentration in the plane The moving distance of the measurement electrode can be reduced.

Furthermore, if the electrode drive mechanism is one that reciprocates the concentration measuring electrode in a direction parallel to the moving direction of the thin sheet in a plane that is substantially parallel to the moving surface of the diffusion limiting membrane holder, the concentration measuring electrode is Side constant voltage] 1 Is it necessary to form an opening for the electrode to pass through? The width of the concentration measuring device as a whole can be made almost equal to the width of the thin sheet, and the reciprocating distance of the concentration measuring electrode can be can be freely set in accordance with the distance between the opening through which the concentration measuring electrode passes and the opening through which the test solution passes.

Furthermore, if a storage solution storage member is further provided that directly faces the concentration measurement electrode that has been moved to a position that does not directly face the measurement position, the concentration measurement electrode can be stored in the storage solution while the concentration measurement operation is not being performed. Since it can be brought into contact with the member, the concentration measurement electrode can be kept wet and active without being affected by the length of time until the next concentration measurement operation, and in turn, the concentration measurement electrode can be maintained in a wet state and kept active. Accurate concentration measurements can be made.

<Example> Hereinafter, a detailed explanation will be given with reference to the accompanying drawings showing examples.

FIG. 1 is a partially cutaway perspective view showing an embodiment of the concentration measuring device of the present invention, and FIG. 2 is a vertical sectional view showing the casing (2
) A space is formed at a predetermined position for accommodating the elongated sheet (1) housed in the cartridge (11).

Openings (20a) (20b) for spotting are formed at predetermined positions upstream of the running path of the long sheet (1), and concentration measuring electrodes (22) are formed at predetermined positions downstream of the running path of the long sheet (1).
) is formed at a measurement position (2], a) that enables close contact with the diffusion-limiting film (16). In addition, long sheets (1
) at a position horizontally a predetermined distance away from the driving path.
A storage liquid storage tank (21) is arranged above the travel path.

An electrode drive mechanism (3) is disposed for reciprocating the concentration measuring electrode (22) to a position in close contact with the long sheet (1) and a position in close contact with the storage solution storage tank (21). A sheet drive mechanism (4) for reciprocating the long sheet (1) is arranged.

Furthermore, a hole (13) for positioning the long sheet (1),
A pair of sensors (24) and (25) are arranged at predetermined positions directly facing the end detection hole (14). The above-mentioned pair of sensors (24) (25) has a hole (14) for terminal detection.
) is arranged so that it can be operated simultaneously only when there is a reflection type photosensor, and cannot be operated simultaneously in other cases. In addition, (26) is a motor for raising and lowering the concentration measuring electrode (22) via the electrode drive mechanism (3), and (27) is a motor for raising and lowering the concentration measuring electrode (22) via the sheet drive mechanism (4). The motor (2 [i ) (27).

FIG. 3 is a perspective view of the diffusion-limiting membrane holder, in which openings (15) for permeation of the test solution are formed at predetermined intervals in the center of a long sheet (1) of a predetermined width, and each Opening (1
A diffusion-limiting film (16) is attached to the lower surface of the long sheet (1) so as to cover the film (5). Then, the opening at the end (15
) A hole for position detection (13) is formed in a predetermined positional relationship with respect to all the openings (15) except for the opening (15) at the end. A hole (14) is formed. In addition, the above long sheet (
1) may be any material as long as it is resistant to the test solution. The diffusion-limiting membrane (16) is a membrane whose main function is to separate substances that interfere with blood cell caps, such as a polycarbonate membrane having many micropores, and allows the substance to be measured to pass through the membrane to the concentration measuring electrode (22), which will be described later. When a diffusion-limiting membrane is attached to restrict the concentration measurement electrode (22), clogging of the diffusion-limiting membrane attached to the concentration measuring electrode (22) can be prevented. However, it is also possible to adopt a configuration in which a membrane capable of restricting the permeation of the substance to be measured is used as the diffusion-limiting membrane (16), and no diffusion-limiting membrane is attached to the concentration measuring electrode (22); In order to eliminate the decrease in measurement accuracy caused by clogging, it is necessary to use a diffusion-limiting membrane (1) whose main function is to separate interfering substances.
It is preferable to attach G) to the long sheet (1) and attach a diffusion-limiting membrane to the concentration measuring electrode (22) to limit permeation of the substance to be measured. Furthermore, it is preferable that numbers for displaying the remaining amount of the diffusion limiting film (16) are printed near the opening (15).

FIG. 4 is a partially cutaway perspective view showing a state in which the long sheet (1) is stored in a cartridge, and shows a supply section (17) in which the long sheet (1) is wound in advance, and a supply section (17) in which the long sheet (1) is wound in advance. A winding part (18) that winds up into a roll, a bridge part (1) that integrally connects the supply part (17) and the winding part (18).
9). The supply shaft (17a) provided in the supply section (17) and the take-up shaft (1, 8a) provided in the take-up section (18) are made to protrude outside the cartridge (11), and the above-mentioned Rotational force is selectively transmitted by the motor (27). In addition, (+8b) is the winding part (1
8), and is placed at a predetermined position where it can wipe off the test solution remaining on the long sheet (1).

The electrode drive mechanism (3) for reciprocating the concentration measuring electrode (22) by the motor (2B) is positioned at a predetermined position on the casing (2) at any time as shown in FIGS. 5A-H. a screw shaft (31) which is rotated forward and backward by a motor (26) and is provided in one direction with the base (30); and a short shaft (31) fitted into the screw shaft (31). 2
a coil spring (31a) with a diameter of approximately 100 lbs., a base (32) for supporting the concentration measuring electrode screwed onto the screw shaft (31), and a protrusion (33) provided integrally with the base (32). ) and a regulating portion (35) for regulating the movement of the protrusion. The groove (34) is composed of a horizontal portion (a4a) extending in the horizontal direction and vertical portions (34b) (34c) extending upward at both ends of the horizontal portion (34a).

Therefore, between the horizontal part (34a) and the vertical part (a4b), simply switching the direction of rotation of the screw shaft (31) allows the protrusion (33) to move along the horizontal part (34a) and move vertically. (34b). Further, the regulating portion (35) has a protrusion (3
3) is for selecting a state in which it moves along the horizontal part (34a) and a state in which it moves along the vertical part (34c), and is rotatable by a predetermined angle about the axis U5a) as a fulcrum. It also has a swinging member (35e) that is biased to rotate in the opposite direction by a spring (35b) when the dead point is exceeded, and is rotatable by a predetermined angle about the shaft (35d) as a fulcrum. together with the spring (3
spring (35e) adjusted between the point of application by 5b)
It has a stopper arm (35f) that can be selectively rotated to either side. A part of the swinging member (35c) is arranged in the horizontal part (34a) or in the vertical part (3
4c), and the amount of protrusion is
It is set so that the dead point can be crossed by being forcibly pushed in by the protrusion (33). Further, the distal end of the stopper arm (35f) protrudes from the end of the horizontal portion (34a) or the end of the vertical portion (34c) in accordance with the direction of the rotation urging force by the spring (35e).

Therefore, when the protrusion (33) moves on the horizontal part (34a) and pushes the swinging member (35c), the stopper arm (35f) becomes able to prevent the protrusion (33) from moving back. By moving the vertical portion (34c) and pushing the swinging member (35c), the protrusion (33) is in a state where it can prevent the protrusion (33) from moving back after being lowered.

Note that in order to achieve the same effect, a solenoid plunger or the like may be used instead of the above configuration.

FIGS. 5(B) to 5(H) are diagrams showing the operation of the electrode drive mechanism (3) in detail, in which the protrusion (33) descends along the vertical part (34c) and then moves to the horizontal part (34a). This shows the case of horizontal movement along.

In the same figure (B), the measurement electrode (22) is connected to the storage solution storage tank (2).
1) and has started to descend away from the protrusion (
33) is not in contact with the swinging member (35c), the swinging member (35c) is rotated around the shaft (35a) by the spring (3).
5b) in the counterclockwise direction.

Then, if the protrusion (33) further descends, the swinging member (
35c) and rotate the swinging part +4' (35c) clockwise against the spring (F15b) (see Figure (C)).
)reference). However, at the beginning of the movement of the swinging member (35c), the rotation bias direction by the spring (35b) does not change.

However, if the protrusion (33) descends further, the swinging member (
As the rotation angle of 35c) increases and exceeds the dead point, the direction of rotation biasing by the spring (35b) changes instantaneously, and the swinging member (35c) moves in the opposite direction, as shown in Figure (D). (clockwise direction) limit position (stopper pin (35)
g) until it comes into contact with the Following this movement, the stopper arm (35f) also springs (35e).
) rotates clockwise, and the stopper arm (35
The tip of f) enters the vertical part (34c) (see (E) in the same figure).
)reference). The protrusion (33) further descends and the spring (35e
), rotate the stopper arm (351') counterclockwise against the vertical part (351') (see (F) in the same figure)
4e) to the bottom (see figure (G)). At this point, the coil spring (31a) is held in pressure contact with the base (32), so the base (32) can be reliably rotated following the rotation of the screw shaft (31). . After that, the protrusion (33) horizontally moves away from the stopper arm (35f') as shown by the chain double-dashed line in the same figure (H), so the stopper arm (35f) is rotated clockwise by the spring (35e). direction to the limit position (the position where it contacts the stopper pin (35h)) (
(See H). In this state, the stopper arm (35
f) prevents the protrusion (33) from rising;
Thereafter, the protrusion (33) can be moved horizontally along the horizontal section (a4a), and further raised along the vertical section (34b), thereby connecting the measurement electrode (22) to the diffusion limiting film (16). can be brought into contact. In addition, the horizontal part (34
When the protrusion (33) moves along a), the protrusion (33) moves along the
33) engages with the regulating part (35) again and the regulating part (35)
is operated in the opposite direction, and the regulation control (35) is restored to the state shown in FIG. Moreover, when the measurement electrode (22) moves in the opposite direction, the regulating part (35) operates in the opposite direction, and the horizontal part (34) moves in the opposite direction.
The transition of the protrusion (33) from a) to the vertical portion (34c) can be achieved smoothly.

The sheet drive mechanism (4) for reciprocating the long sheet (1) by the motor (27) has a driving gear (41) attached to the rotating shaft of the motor (27), as schematically shown in FIG. At the same time, a switching gear (42) that meshes with the drive gear (41) is supported by a support plate (43) that is rotatable about the rotation axis. Then, support plate (43
), which meshes with the gear (42) at the bidirectional rotational position of the sheet and transmits rotational force in the feeding direction to the long sheet (1).
It has a transmission mechanism (44a) and a second transmission mechanism (44b) that transmits rotational force in the rewinding direction. Therefore, the gear (42) rotates in the rotational direction of the drive gear (41) and meshes with the corresponding transmission mechanism, and simply by selecting the rotational direction of the motor (27), the long sheet (1) can be rotated. You can easily control forwarding and rewinding.

The operation of the concentration measuring device having the above configuration is as follows.

When only performing concentration measurement operations based on the test solution,
By reversing the motor (27) in conjunction with the operation of opening the lid (not shown), the long sheet (1) is rewound by the distance between the openings (15), and in this state, it is passed through the downstream spotting opening (20a). After the test solution is spotted in the test solution permeation opening (15), the long sheet (1) is sent a predetermined distance by rotating the motor (27) in the normal direction. In this state, the sensor (24) is connected to the positioning hole (13).
) and outputs an OFF signal, and the sensor (25) outputs an ON signal. Next, by rotating the motor (26) in the normal direction, the concentration measuring electrode (22)
The diffusion restriction membrane (16) is lowered to separate it from the storage solution storage tank (21), horizontally rotated, and then raised.
Measure the concentration by placing it in close contact with the After that, the motor (2
6) is reversed to bring the concentration measuring electrode (22) into contact with the storage solution storage tank (21), and then the motor (2
7) in the normal direction to feed the long sheet (1) by twice the distance between the openings (15) in preparation for the next concentration measurement operation.

Thereafter, by repeating the above series of operations, concentration measurement operations can be performed multiple times without attaching or discarding the diffusion limiting membrane (see the timing chart shown in FIG. 7).

Therefore, by repeating the series of operations described above, concentration measurements can be performed multiple times without requiring work for attaching and disposing of the diffusion limiting membrane. In addition, when spotting the test solution, the concentration measuring electrode (22) is in contact with the storage solution storage tank (21), and the spotting opening (2
0a), it is possible to reliably eliminate the risk of infection by diseases caused by pathogenic bacteria and the like.

However, it is also possible to omit the operation of rewinding the long sheet (1) before spotting, and also to omit the operation of feeding the long sheet (1) after the concentration measurement.

When performing a calibration operation based on a calibration standard solution before performing a concentration measurement operation based on a test solution, the long sheet (1) is not unwound even when the lid is opened, and the spotting opening on the upstream side is A calibration standard solution of known concentration is spotted at the opening (15) for passing through the test solution through the spotting opening (20a), and the opening (15) for passing through the test solution through the spotting opening (20a).
After applying the test solution, the motor (27) is rotated in the normal direction to feed the long sheet (1) a predetermined distance. However, since the predetermined distance in this case is approximately twice the distance between the openings (15), the diffusion-limiting membrane (16) covering the openings (15) where the calibration standard solution is spotted is used for concentration measurement. Electrode (2
2) will be in a state where it can be in close contact with. Next, the motor (26)
By rotating in the normal direction, the concentration measuring electrode (22) is lowered and separated from the storage solution storage tank (21), horizontally rotated and then raised to bring it into close contact with the diffusion restriction membrane (16), and the calibration standard solution is removed. Measure the concentration and perform a calibration operation. After that, the concentration measuring electrode (22) is separated from the diffusion limiting membrane (16) by reversing the motor (26).
By reversing the motor (27), the long sheet (1) is rewound by the distance between the openings (15), and the motor (26)
) in the normal direction to connect the concentration measuring electrode (22) to the diffusion limiting film (1).
By bringing it into close contact with 6), it is possible to measure the concentration based on the test solution. And finally, the motor (26
) to bring the concentration measuring electrode (22) into contact with the storage solution storage tank (21), and then turn the motor (2
7) in the normal direction to open the long sheet (1) (
15) Prepare for the next concentration measurement operation by feeding twice the distance between the membranes (see the timing chart shown in Figure 8A).Then, by repeating the above series of operations, the diffusion limiting membrane is attached and discarded. The calibration operation and concentration measurement operation can be performed multiple times without performing the calibration operation and concentration measurement operation.

Therefore, by repeating the series of operations described above, the calibration operation and concentration measurement operation can be performed multiple times without requiring work for attaching and disposing of the diffusion limiting membrane. In addition, when applying the test solution, the concentration measuring electrode (22) is in contact with the storage solution storage tank (21) and does not directly face the opening (20a) for applying the test solution, so pathogenic bacteria etc. It is possible to reliably eliminate the risk of infection with the disease caused by the disease.

However, it is also possible to make the feed amount of the long sheet (1) after the density measurement equal to the interval between the openings (15).

In addition, the positioning accuracy when feeding the long sheet (1),
The positioning accuracy when rewinding the long sheet (1) generally involves a certain degree of error due to the size of the positioning hole (13), etc., but the timing chart in Figure 8B As shown in FIG. By feeding and positioning the sheet (1), it is possible to finally achieve positioning accuracy without error.

In addition, in this embodiment, the upstream dotting opening (20b
) If a light emitting element (not shown) is provided directly facing the test solution and the calibration standard, the light can be recognized through the diffusion limiting film (16) and the aperture (15). The effect of preventing mistakes in the placement of liquid can be further enhanced.

Figure 9 shows an electrode drive mechanism (3
'), FIG. 10 is a side view of the main part, and FIG. 11 is a cross-sectional view taken along the line XI-XI in FIG. (34c)
The point where the leaf spring (36a) (3
8b), the swinging arm (37), which is biased by the spring (38) in the direction away from the protrusion (33), is moved to the base (
32).

The leaf springs (38a) (38b) have upper edges that are horizontal (
It is attached to the curved plate part of the casing (2) so as to be located slightly above the bottom part of 34a), with the upper end of the tip penetrating the most into the vertical part, and the lower end of the curved plate part. along the outer surface. In addition, the above rocking arm (37
) and a regulating arm (37a) that regulates the swing range in one direction.
is formed.

FIGS. 12(A) to 12(F) are diagrams for explaining the operation of the electrode drive mechanism (3'); (
As shown in A), the protrusion (33) is located at the upper end of the vertical portion (34c), and the swing arm (37) is separated from the protrusion (33) to its limit position. In addition, in this state, the base (32) is connected to the coil spring (31a).
Since it is far away from the screw shaft (31), almost no force is applied to rotate the base (32), following the rotation of the screw shaft (31), and by rotating the screw shaft (31), the base (
32) can be raised and lowered. In this state, if the screw shaft (31) is rotated to lower the measuring electrode (22) together with the base (32), the swinging arm (37) will first come into contact with the upper edge of the leaf spring (3Gb) and lower. is blocked and the protrusion (33) continues to descend together with the base (32), so the protrusion (33) and the swing arm (37) approach each other as shown in FIG. , leave it as it is and move it to the horizontal part (3
4a). Also, in this state, the base (32) strongly compresses the coil spring (31a), so a sufficiently large friction acts between them, causing the base (32) to follow the screw shaft (31). become a state. Therefore, after that, by rotating the screw shaft (31), both the protrusion (33) and the swinging arm (37) can be moved along the horizontal part (34a), but the swinging arm ( 37) moves to the bottom of the horizontal portion (g4a) when it is disengaged from the leaf spring (36b). As a result, at the end of the movement along the horizontal portion (34a), the tip of the swing arm (37) engages with the inner surface of the leaf spring (36a), deforming the leaf spring (3[ia) outward (same as (See figures (C) and (D)). At this time, the leaf spring (3Ba
) is further away from the upper end, the suppressing force on the swinging arm (37) becomes weaker, so the swinging arm (37)
) and is located at the bottom of the vertical portion (34b) (see (E) in the same figure). After that, the swing arm (37
) remains apart from the protrusion (33) and the vertical part (34
b), the protrusion (33) and the swinging arm (37) do not face the horizontal part (34a) at the same time (see (F) in the same figure), and the measurement electrode (22) It can be raised to contact the diffusion limiting membrane (16). In this case, if the base (32) rises even a little, the pressure force between the base (32) and the coil spring (31a> will become weaker, the friction will become smaller, and the base (32) will be pulled up against the screw shaft. (31), the force for rotating the screw shaft (31) can be reduced, so the base (32) can be smoothly raised following the rotation of the screw shaft (31).

The same holds true when moving the Al11 constant electrode (22) in the opposite direction.

In addition, the length of the coil spring (31a) is such that the spring force does not act until the base (32) is sufficiently lowered, and the screw shaft (31)
It is preferable to make the spring force short so that it descends smoothly following the rotation of the base (32), and the spring force is set such that sufficient friction due to compression of the coil spring (31a) is generated when the base (32) is sufficiently lowered. The base (32) may be set so as to follow the rotation of the screw shaft (31) and rotate the base (32) smoothly. However, it is preferable to determine the spring force so that the force for rotating the screw shaft (31) does not become too large.

<Example 2> Fig. 13 is a partially cutaway perspective view showing another example of the concentration measuring device.The major difference from the above example is that the electrode drive mechanism (3) drives the concentration measuring electrode (22). The long seal l) is reciprocated in the moving direction, and the length has a large diameter opening (15a) for inserting a constant electrode with a concentration Δ1 between the openings (15) for passing the test solution. The only point is to attach the shaku sheet (1).

To explain these points in detail, the electrode drive frame structure (3) has the same structure as in the first embodiment, and is simply different in its arrangement. That is, both the movement limit positions in the horizontal direction are set directly below the traveling path of the long sheet (1), and the distance between both movement limit positions is set between the opening (15) for permeation of the test solution and the concentration measurement electrode. The distance is set equal to the distance from the large diameter opening (15a) for insertion. and,
A storage liquid storage tank (21) is placed at one of the movement limit positions, directly facing the elongated sheet (1) with the long sheet (1) sandwiched therebetween.

As shown in FIG. 14, the long sheet (1) has openings (15) and large-diameter openings (L5a) formed alternately, and a diffusion-limiting film covering only the openings (15). (16) is provided. A positioning hole (13) is formed in a predetermined positional relationship with respect to the opening (15), and a positioning hole (13a) is formed in a predetermined positional relationship with respect to the large diameter opening (15a). It is formed. Further, a sensor (24) is arranged to be operated by the hole (■3), and a sensor (24) is arranged so as to be operated by the hole (13a).
A sensor (25) is arranged so as to be operated by the sensor (25). The relative positional relationship between the holes (13) (1, 38) is set so that the sensors (24) and (25) do not output OFF signals at the same time, and the opening at the end (]5) The end detection hole (14) formed in a predetermined positional relationship with the sensor and the hole (13a) are set so that both sensors (24) and (25) output an OFF signal at the same time.

In addition, to explain the details, the upstream spotting opening (20b) is used as the measurement position.

The operation of the concentration measuring device having the above configuration is as follows.

When only measuring the concentration based on the test solution, the concentration measuring electrode (22) passes through the large-diameter opening (15a) and rises, and issues a measurement start instruction while in contact with the storage solution storage tank (21). Since the test solution is waiting, all you have to do is apply the test solution to the test solution permeation opening (I5) through the test solution opening (20b) and then instruct the start of measurement by operating the switch (not shown). .

When the start of measurement is instructed, the concentration measuring electrode (22) is lowered by rotating the motor (26) in the normal direction, and then moved horizontally and then raised to open the opening (15) where the test solution is spotted. The concentration of the test solution can be measured by bringing it into close contact with the diffusion-limiting membrane (16) that covers the sample.

Thereafter, the concentration measuring electrode (22) is lowered by reversing the motor (26), and in this state, the motor (27)
) is rotated in the normal direction to feed the long sheet (1).

Since the timing to stop feeding the long sheet (1) is set to the timing when the sensor (24) outputs an OFF signal and the sensor (25) outputs an ON signal, the opening (15) The long sheet (1) can be fed by the distance between the long sheets (1). And long sea 1-
(1), the concentration measuring electrode (22) is horizontally moved by further rotating the motor (26) in the reverse direction;
Then, by raising it, it passes through the large diameter opening (15a) and comes into contact with the storage solution storage tank (21), and the concentration measuring electrode (22) is prepared for the next concentration measurement while maintaining a good preservation state.

Therefore, by repeating the series of operations described above, concentration measurements can be performed multiple times without requiring work for attaching and disposing of the diffusion limiting membrane. In addition, when spotting the test solution, the concentration measuring electrode (22) is in contact with the storage solution storage tank (21), and the spotting opening (2
0b), it is possible to reliably eliminate the risk of infection by diseases caused by pathogenic bacteria and the like.

When performing a calibration operation based on a calibration standard solution with a known concentration before performing concentration measurement based on the test solution, the concentration measurement electrode (22) passes through the large diameter opening (L5a) and rises, and the storage Since it is in contact with the liquid storage tank (21) and is waiting for an instruction to start measurement, the test solution is applied to the test solution permeation opening (15) through the test solution opening (20b), and the other The start of operation may be instructed by applying a calibration standard solution to the opening (15) for permeating the test solution through the opening (20a) and then operating a switch (not shown).

When the start of operation is instructed, the concentration measuring electrode (22) is lowered by rotating the motor (26) in the normal direction, and in this state, the opening (
15) Rewinding the long sheet (1) by the distance between the sheets, and then moving the concentration measuring electrode (22) horizontally and then raising it to cover the opening (15) where the calibration standard solution was spotted, thereby restricting diffusion. It is possible to measure the concentration of a calibration standard solution whose concentration is known by bringing it into close contact with the membrane (16), and perform a calibration operation based on the concentration measurement result.

After performing the calibration operation, the concentration measuring electrode (22) is lowered by rotating the motor (26) in the reverse direction, and in this state, the opening (
15) The long sheet (1) is fed by the distance between the electrodes (15) and the concentration measuring electrode (
22) is raised to bring it into close contact with the diffusion limiting membrane (1B), and the concentration of the test solution is measured.

Finally, by rotating the motor (26) in the reverse direction, the concentration measuring electrode (22) is lowered, and in this state, by rotating the motor (27) in the normal direction, the distance between the openings (15) is increased by twice the distance between the openings (15). A series of calibration operations are carried out by feeding the length sheet (1), then moving the concentration measuring electrode (22) horizontally by further reversing the motor (26), and further raising it to contact the storage solution storage tank (21). and ends the concentration measurement operation.

Therefore, by repeating the above series of operations, the calibration operation and the concentration δIII constant operation can be performed multiple times without requiring any work for attaching or discarding the diffusion limiting membrane. In addition, when spotting the test solution, the concentration measuring electrode (22) is in contact with the storage solution storage tank (21) and does not directly face the spotting opening (20b), so pathogenic bacteria etc. It is possible to reliably eliminate the risk of infection with the disease caused by the disease.

However, regarding positioning when unwinding the long sheet (1), it is preferable to unwind the long sheet (1) an extra amount and then feed it a little further, as in the above embodiment, to achieve extremely accurate positioning.

<Example 3> Fig. 15 is a longitudinal sectional view showing still another embodiment of the concentration measuring device, and the difference from the embodiment shown in Fig. 13 is that the point is raised through the dotting opening (20b). Landing (30)
The dot and concentration measuring electrode (22) are placed on the spotting table (
30) Only the points raised so as to come into close contact with the diffusion limiting membrane (16) located above.

Therefore, in the case of this embodiment as well, it is possible to achieve the same effect as in the above embodiment, and also to achieve the same effect as in the above embodiment.
Even if b) and the storage solution storage tank (21) are close to each other,
The height difference between the upper surface of the storage solution storage tank (21) and the upper surface of the spotting table (30) can be significantly reduced, and the work of spotting the test solution can be significantly simplified.

<Example 4> Fig. 16 is a perspective view showing still another example of the concentration measuring device, and Fig. 17 is a longitudinal cross-sectional view. Disc-shaped sheet (1a
) is rotatably housed.

More specifically, a space is formed in a predetermined position of the casing (2a) for accommodating a disk-shaped sheet (1, a) housed in a thin large-sized cartridge (11a). An opening (20) for spotting is formed at a predetermined position on the travel path of the disc-shaped sheet (1a), and a storage solution storage tank (21) is provided at a position away from the disc-shaped sheet (1a). is located. Then, an electrode drive mechanism (see Fig. 5A - This is a mechanism similar to that shown in H, so detailed explanation will be omitted)
is located. In addition, (23) is a disk-shaped sheet t□(1
This is a rotation shaft for rotating the a), and is driven by a motor (not shown).

In addition, as shown in FIG. 18, the disc-shaped seam) (+, a) has an opening (1
5), and a diffusion limiting film (16) covering each opening (15). Furthermore, (28
) is a removable cover that covers the dosing opening (20).

Therefore, after spotting the solution to be measured into the test solution permeation opening (15) exposed through the spotting opening (20) with the cover (28) removed, the concentration measuring electrode (22) The concentration measurement operation can be performed by moving the membrane and bringing it into close contact with the diffusion limiting membrane (16). Thereafter, the concentration measuring electrode (22) is moved in the opposite direction and brought into close contact with the storage solution storage tank (21) in preparation for the next concentration measurement.

That is, also in the case of this embodiment, the number of times the diffusion restriction membrane (16) is attached or discarded can be significantly reduced, and the risk of disease infection can be significantly reduced.

In addition, in this embodiment, the opening (20) for dotting is formed at only one location, but similarly to the above embodiment, the opening for dotting is formed at two locations. It is also possible to provide a cover that selectively covers the opening for dotting.

<Example 5> FIG. 19 is a longitudinal cross-sectional view showing still another example of the concentration measuring device, and the difference from Example 4 is that the storage solution storage tank (21) The point located above is the storage solution storage tank (21) of the disc-shaped sheet (1a).
) is located directly opposite the large diameter opening (1
5a) and the electrode drive mechanism (3) are connected to the test solution permeation opening (15) and the storage solution storage tank (21), which are determined based on the rotational state of the disk-shaped sheet (1a).
) The only difference is that the concentration measuring electrode (22) is moved back and forth between the two.

Therefore, in the case of this embodiment, the three density measuring devices can have a planar size approximately equal to that of the large cartridge (ILa), and moreover, it is possible to achieve the same effect as in the above embodiment.

Note that the opening (15) and the large diameter opening (15a) are arranged one to one.
However, as shown in FIG. 15)
If it is formed into an almost oval shape to correspond to the opening (15
) can be suppressed to a large number of 1].

<Example 6> FIG. 21 is a longitudinal sectional view showing still another example of the concentration measuring device, and the difference from Example 5 is that the opening for spotting (1
5) and large-diameter openings (15a) for the insertion of the concentration measuring electrode are formed alternately on the same circumference, and the electrode drive mechanism (3).
) The only difference is that the direction of reciprocating movement of the concentration measuring electrode (22) due to the change in direction is changed.

Therefore, in the case of this embodiment, the disk-shaped sheet 1-(1
, a), the number of apertures (15) that can be formed is considerably reduced, but the number of apertures (15) that can be formed in The concentration of the test solution can be measured. In a state where concentration measurement is not performed, the concentration measurement electrode (22)
can be brought into contact with the storage solution storage tank (21), and a good electrode preservation state can be achieved.

<Effects of the Invention> As described above, the first invention not only eliminates the need to attach and detach the diffusion limiting membranes while performing measurements equal to the number of diffusion limiting membranes provided in the diffusion limiting membrane holder; Since the diffusion-limiting membrane and the concentration measuring electrode are separated from each other when the test solution is applied, the risk of disease infection can be eliminated even when measuring body fluids. When moving the limiting membrane holder, by keeping the concentration measuring electrodes apart, it is possible to prevent characteristic deterioration of both the concentration measuring electrode and the diffusion limiting membrane holder due to rubbing. It has a unique effect.

In the second invention, there is no need to form an opening in the thin sheet for the concentration measurement electrode to pass through, and it is only necessary to form an opening for the passage of the test solution. This provides a unique effect in that the number of transmission apertures can be increased.

The third aspect of the invention is that the width of the concentration measuring device as a whole can be made almost equal to the width of the thin sheet, and moreover, the reciprocating distance of the concentration measuring electrode can be made equal to the opening for the concentration measuring electrode to penetrate and the width of the sample to be measured. This has the unique effect of being able to be freely set in accordance with the distance from the solution permeation opening.

The fourth invention is capable of keeping the concentration measuring electrode in a wet state and maintaining its activity without being affected by the length of time until the next concentration measuring operation is performed, and as a result, accurate concentration measurement can be carried out. It has the unique effect of being able to

[Brief explanation of drawings]

Fig. 1 is a partially cutaway perspective view showing an embodiment of the concentration measuring device of the present invention, Fig. 2 is a vertical sectional view, Fig. 3 is a perspective view of a diffusion limiting membrane holder, and Fig. 4 is a diffusion limiting membrane holder. A partially cutaway perspective view showing the holder housed in the cartridge; FIG. 5 is a diagram showing the electrode drive mechanism; FIG. 6 is a schematic diagram showing the sheet drive mechanism; f? Figure J7 is a timing chart showing the operation of each part when performing only the concentration measurement operation, Figure 8 is a timing chart showing the operation of each part when performing the calibration operation and concentration measurement operation sequentially, and Figure 9 is the same as that of Figure 5. FIG. 10 is a side view of the main parts; FIG. 11 is a sectional view taken along the line XI-XI in FIG. 9; FIG. 12 explains the operation of the electrode drive mechanism. 13 is a partially cutaway perspective view showing another embodiment of the concentration measuring device, FIG. 14 is a perspective view of a diffusion limiting membrane holder, and FIG. 15 is a perspective view showing still another embodiment of the concentration measuring device. FIG. 16 is a perspective view showing still another embodiment of the concentration measuring device, FIG. 17 is a vertical sectional view, FIG. 18 is a perspective view of the diffusion limiting membrane holder, and FIG. 19 is a perspective view of the concentration measuring device. FIG. 20 is a perspective view showing another example of the diffusion-limiting membrane holder; FIG. 21 is a longitudinal cross-sectional view showing still another example of the concentration measuring device.

Claims (1)

[Claims] 1. A plurality of openings (15) for permeation of the solution to be measured are formed in the thin sheet (1) (1a), and a diffusion limiting membrane (16) is formed to cover each opening (15). ) is provided with a concentration measurement position (2
1a) and the casing (2
) (2a) is provided with a concentration measuring electrode (22),
Further, an electrode drive mechanism (3) is provided which reciprocates the concentration measurement electrode (22) in a plane substantially parallel to the movement plane of the diffusion-limiting membrane holder and raises and lowers the concentration measurement electrode (22) at both movement limit positions. A concentration measuring device comprising: 2. The electrode drive mechanism (3) reciprocates the concentration measuring electrode (22) in a direction that is not parallel to the moving direction of the thin sheet (1) (1a) in a plane that is almost parallel to the moving plane of the diffusion limiting membrane holder. The concentration measuring device according to claim 1, wherein the concentration measuring device is configured to move. 3. The electrode drive mechanism (3) reciprocates the concentration measuring electrode (22) in a direction parallel to the moving direction of the thin sheet (1) (1a) in a plane substantially parallel to the moving plane of the diffusion limiting membrane holder. The concentration measuring device according to claim 1, wherein the concentration measuring device is configured to move. 4. The preservation solution storage member (2) facing directly the concentration measuring electrode (22) that has been moved to a position that does not directly face the measurement position (21a).
1) The concentration measuring device according to any one of claims 1 to 3 above, further comprising: 1).