JPH0249152A - Diffusion limit film holding tool - Google Patents

Abstract

PURPOSE:To curtail the trouble for installing and rejecting a diffusion limit film and to reduce the space for storage, etc., by forming plural openings for allowing a solution to be measured to pass through in the longitudinal direction on a long-sized sheet, and also, providing each opening so as to be covered with the diffusion limit film. CONSTITUTION:In the center part of a long-sized sheet 1 of prescribed width, openings 11 for allowing a solution to be measured to pass through are formed at every prescribed interval, and also, a diffusion limit film 12 having many minute holes and consisting of a polycarbonate film, etc., is stuck to the lower face of the long-sized sheet 1 so as to cover each opening 11. Position detecting holes 13 are formed in a prescribed position relation against all the openings except the terminal opening 11, and also, a position detecting long-sized hole 14 is formed in a prescribed position relation against the terminal opening 11. In an adjacent position of the opening 11, numerals 1-30 for displaying the remaining quantity of the diffusion limit film 12 are printed.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a diffusion-limiting membrane holder, and more specifically, to a diffusion-limiting membrane used to expand the measurable range of the concentration of a substance to be measured. The present invention relates to a novel diffusion-limiting membrane holder that is brought into close contact with the surface of a concentration measuring electrode and simplifies the operation of discarding it after measurement.

<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 attaching a diffusion-limiting membrane to the surface side of the immobilized enzyme membrane on which the physiologically active substance is immobilized, and by limiting the permeation rate of the target substance for DI. There is.

Specifically, a diffusion-limiting membrane is attached to a cap that is screwed onto the base of a rod-shaped enzyme electrode, and screwing in the cap automatically brings the diffusion-limiting membrane into close contact with the immobilized enzyme membrane. There is.

By employing such a configuration, the diffusion limiting membrane can limit the permeation rate of the ilJ target substance, making it possible to measure up to a considerably high concentration. In addition, the diffusion-limiting membrane is made removable in order to eliminate the influence of interfering substances contained in the solution to be measured (for example, an increase in the diffusion-limiting effect due to adhesion of interfering substances) and to perform a good measurement. Therefore, a screw-in mechanism using a cap is adopted.

<Problems to be Solved by the Invention> When the diffusion-limiting membrane holder with the above structure is adopted, the diffusion-limiting membrane can be replaced relatively easily, but the attachment of the enzyme electrode base is difficult due to the structure. In some cases, attachment and detachment becomes extremely difficult, and depending on the force applied during screwing, it may become impossible to achieve uniform adhesion to the immobilized enzyme membrane.

In addition, the enzyme electrode base becomes smaller in diameter, and as a result, the cap becomes smaller, making manual operation very difficult, making the above problems even more pronounced.

Furthermore, since the diffusion-limiting membrane is attached to the cap, there is a problem in that the space required for storage and transportation increases.

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. It is conceivable to measure the concentration of the test solution while the substance is in pressure contact with the immobilized enzyme membrane, but the thin plate material is usually not strained, and the solution containing the target substance to be measured (hereinafter referred to as the target solution) can be dripped. There is a problem in that it becomes difficult to work and to attach the measuring device to the main body. 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 thin sheets that have been attached, more sheets than necessary will be discarded, which is uneconomical. There is a problem in that a series of operations for measuring the concentration of a target substance 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 solution to be measured onto the thin plate material, collect blood if the solution to be measured is blood, and then spot the blood on the thin plate material), ■ Insert the thin plate material into the measuring device, ■ Insert the thin plate material into the inserted thin plate material. 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.

■ After that, release the diffusion-limiting membrane from the electrode surface, ■ Remove the thin plate from the measuring device, ■ Close the cover of the measuring device, ■ Discard the removed thin plate, and ■ Turn on the power switch of the measuring device. Open.

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.

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,
It is an object of the present invention to provide a diffusion-limiting membrane holder that can significantly reduce the frequency of attachment and disposal of diffusion-limiting membranes, and can also significantly simplify concentration measurement work.

Means for Solving the Problems> In order to achieve the above object, the diffusion-limiting membrane holder of the present invention has a long sheet formed with a plurality of openings for passage of a solution to be measured in the longitudinal direction. At the same time, a diffusion limiting film is provided to cover each opening.

In addition, in the diffusion-limiting membrane holder of another invention, a plurality of openings for passing a measurement target solution and openings for penetrating a measurement electrode are formed alternately in the longitudinal direction of a long sheet, and each of the measurement target solutions A diffusion limiting membrane is provided to cover the passage opening.

However, it is preferable that a position detecting section is provided corresponding to each of the opening for passing the target solution and the opening for penetrating the measurement electrode. In this case, it is more preferable that a position detection section that serves both for detecting the tip and detecting the end is provided corresponding to each of the openings at the tip and the end.

With the diffusion-limiting membrane holder configured as above, the long sheet can be attached to the concentration measuring device, and the diffusion-limiting membrane can be tightly attached by placing one of the openings directly facing the concentration measuring electrode. By dropping the solution to be measured into the opening or near the opening, the concentration can be measured while the diffusion of the substance to be measured toward the concentration measurement electrode is restricted. Then, when performing the next concentration measurement, it is sufficient to move the long sheet a predetermined distance so that the next opening directly faces the concentration measurement electrode, and the concentration measurement can be performed in the same manner as described above.

After measuring the concentration using all the diffusion-limiting membranes as described above, remove the long sheet from the concentration measuring device, discard it, attach a new long sheet, and measure the concentration again. You can get it.

In addition, in the case of the diffusion-limiting membrane holder of another invention, by attaching the long sheet to the concentration measuring device and directly facing the concentration measuring electrode with the opening for penetrating one of the measuring electrodes, By penetrating the measurement electrode through the opening and bringing it into contact with the storage solution container, the measurement electrode can be stored with its characteristics stabilized. When measuring the concentration, the measurement electrode is removed from the opening, and then the long sheet is sent a predetermined distance so that the opening for passing the solution to be measured is directly opposed to the concentration measurement electrode, so that the diffusion-limiting membrane is brought into close contact with the electrode. By dropping the solution to be measured into the opening or in the vicinity of the opening, the concentration can be measured while the diffusion of the substance to be measured toward the concentration a1 constant electrode is restricted. Thereafter, by sequentially feeding the long sheet by a predetermined distance, the measurement electrodes can be stored and the concentration can be measured in the same manner as described above.

After measuring the concentration using all the diffusion-limiting membranes as described above, remove the long sheet from the concentration measuring device, discard it, install a new long sheet, and start measuring the concentration again. It can be put into a working condition.

If a position detection unit is provided corresponding to each opening, the feeding of the long sheet can be stopped in a state where the opening for passing the solution to be measured directly faces the measurement electrode, and the long sheet feeding can be automated.

In addition, if a position detection unit that also serves as end detection is provided in correspondence with the end opening, it is possible to detect that concentration measurement has been performed using all the diffusion limiting films.
The concentration measurement operation can be carried out only when there is an opening to which an unused diffusion limiting film is attached.

<Example> Hereinafter, embodiments will be described in detail with reference to the accompanying drawings showing examples.

FIG. 1 is a partially cutaway perspective view showing an embodiment of the diffusion-limiting membrane holder of the present invention, in which openings are provided at predetermined intervals in the center of a long sheet (1) of a predetermined width for passage of a solution to be measured. (II)
A diffusion limiting film (12) made of a polycarbonate film or the like having a large number of micropores is attached to the lower surface of the elongated sheet (1) so as to cover each opening (11). A position detection hole (13) is formed in a predetermined positional relationship with respect to all the openings except for the terminal opening (11), and a position detection hole (13) is formed in a predetermined positional relationship with respect to the terminal opening (11). A long hole (14) for position detection is formed. Note that the long sheet (1) may be made of any material as long as it has resistance to the test solution. In addition, the above-mentioned diffusion-limiting membrane port)
is a membrane whose main function is to separate interfering substances such as blood cells, such as a polycarbonate membrane with many micropores, and a diffusion-limiting membrane that restricts the permeation of the substance to be measured is attached to the concentration measuring electrode (3I), which will be described later. In this case, clogging of the diffusion limiting membrane attached to the concentration measuring electrode (31) 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 (12), and no diffusion-limiting membrane is attached to the concentration measuring electrode (31); In order to eliminate the decrease in measurement accuracy caused by clogging, a diffusion-limiting membrane (12) whose main function is to separate interfering substances is attached to the long sheet (1) to prevent the permeation of the substance to be measured. Preferably, a diffusion limiting membrane is attached to the concentration measuring electrode (31). Further, it is preferable that numbers for displaying the remaining amount of the diffusion limiting film (12) are printed near the opening (11).

FIG. 2 is a partially cutaway perspective view showing the state in which the long sheet (1) is stored in a cartridge. A winding part (22) that winds up into a roll, a bridge part (2) that integrally connects the supply part (21) and the winding part (22).
3). The central part of the bridge part (23) is curved into a protruding shape with a radius of curvature slightly larger than the radius of curvature of the upper surface of the concentration measuring electrode (31), and an opening (24) is formed in the central part of the curved part. is formed. Further, a supply shaft (21a) and a winding shaft (2) provided in the supplying section (21) and winding section (22), respectively,
2a) is made to protrude outside the cartridge ('2J), and the rotational force is selectively transmitted by a motor (38) to be described later.The winding part (22) has a long A cleaning member (25) (see FIG. 3) is provided for wiping off the solution to be measured that has been spotted on the length sheet (1).

FIG. 3 is a longitudinal sectional view showing the configuration of the concentration measuring device, and FIG. 4 is a perspective plan view showing that a space for accommodating the cartridge 0 is formed at a predetermined position of the housing (33), and a long A preservation liquid storage tank (34) is arranged at a predetermined position away from the travel path of the seat (1). Then, the concentration measuring electrode (31) is attached to the opening (2) of the cartridge (2).
4) and a position directly facing the storage solution storage tank (34), and also for raising and lowering the electrode at each movement limit position.
4) (see Figure 5) are arranged. The concentration measuring electrode (31) may include, for example, a hydrogen peroxide selectively permeable membrane made of acetylcellulose and glucose oxidase fixed on polyacrylonitrile so as to cover a working electrode made of Pt and a counter electrode made of Ag. This is a structure in which a COD fixing membrane made of 100% and a diffusion limiting membrane made of cellophane are attached in this order. Furthermore, the hole (13) of the long sheet (1)
), a pair of sensors (35) (8B) are arranged at predetermined positions that can directly face the elongated hole (14). The pair of sensors (85) and (18) are reflective photocouplers arranged at intervals that can be operated simultaneously only by the elongated hole (14) and cannot be operated simultaneously by the hole (13).

In addition, (37) is a motor for operating the concentration measuring electrode (31), (38) is a motor for feeding the long sheet (1), and the electric signal taken out by the concentration measuring electrode (31). A processing unit (not shown) and each motor (37
) (3g).

As shown in FIG. 5A-C, the electrode drive mechanism (4) includes a screw shaft (41) that is rotated forward and backward by a motor (37).
, a base (42) for supporting the concentration measuring electrode screwed onto the screw shaft (4I), and a groove (44) for guiding the protrusion (43) provided in one direction on the base (42). , and a regulating portion (45) that regulates movement of the protrusion. The groove (44) has a horizontal part (44a) extending in the horizontal direction and a horizontal part (44a) extending in the horizontal direction.
) vertical portions (44b) extending upward at both ends of (
44c). Therefore, the horizontal part (4
4a) and the vertical part (44b).
1) Simply by switching the rotation direction, the protrusion (43) moves along the horizontal part (44a) and the vertical part (44b).
It is possible to obtain a state that moves along the . Further, in the regulating portion (45), the protrusion (43) is located at the horizontal portion (44a).
This is for selecting a state of moving along the axis (45a) and a state of moving along the vertical part (44c).
It has a swinging member (45c) which is rotatable by a predetermined angle with the shaft (45d) as a fulcrum and is biased to rotate in the opposite direction by a spring (45b) when the dead point is exceeded. a stopper arm (45f) that is rotatable by a predetermined angle using the spring (45b) as a fulcrum and selectively biased to rotate to either side by a spring (45e) adjusted between the point of action of the spring (45b); have. A part of the swinging member (45c) is made to protrude to the horizontal part (44a) or the vertical part (44c) depending on the direction of the rotation biasing force by the spring (45b), and The amount is set such that the dead point can be exceeded by being forcibly pushed in by the protrusion (43). Further, the tip of the stopper arm (45f') protrudes from the end of the horizontal part (44a) or the end of the vertical part (44c) in accordance with the direction of the rotation biasing force by the spring (45e). . Therefore, the protrusion (43) moves the horizontal part (44a) and pushes the swinging member (45c), so that the stopper arm (45)
f') is in a state where it can prevent the backward movement of the protrusion (43),
The protrusion (43) moves on the vertical portion (44c) to rotate the swinging member (
45c), the protrusion (43) can be prevented from moving back after it has been lowered. Note that in order to achieve the same effect, a solenoid plunger or the like may be used instead of the above configuration.

Further, the configuration for moving the long sheet (1) by the motor (38) is as shown in FIG.

That is, a driving gear (Ha) is attached to the rotating shaft of the motor (38), and a gear (ssb) that meshes with the driving gear (38a) is rotatably supported on the rotating shaft by a support plate (38c). ing. The transmission mechanism (38d) (38e) meshes with the gear (38b) at different positions and transmits rotational force in different directions to the supply shaft (21a) and the take-up shaft (22a), respectively. are doing.

The concentration of the target substance in the test solution can be measured in the following manner with the elongated sheet (1) having the above configuration housed in the cartridge (2) and further incorporated into the concentration measuring device (3). However, FIG. 7 is a timing chart showing the operation of each part.

When no work necessary for concentration measurement is performed, both sensors (15) (3B) are directly facing the part of the long sheet (1) where no hole (13) is formed. , an ON signal is output from both sensors (35) and (36), and the leading end of the long sheet (1) is detected. In this state, the control unit causes the motor (38) to rotate normally to feed the long sheet (1). That is, the motor (3
8) is rotated in the normal direction, the gear (38b) rotates following the rotation of the drive gear (38a), and the transmission mechanism (88e)
The rotational force in the winding direction is transmitted to the winding shaft (22a) through the winding shaft (22a). First, an OFF signal is output from one sensor (35), an ON signal is output from the other sensor (3B), and then, by feeding the long sheet (1) a predetermined distance, one sensor (35) is output. ) outputs an ON signal, and the other sensor (3B) outputs an OFF signal, so on the condition that the latter combination of signals is output, the long sheet (1) can be fed by the motor (38). stop. At this point, the opening (11) of the long sheet (1) directly faces the concentration measuring electrode (31) at one movement limit position.

Note that at this point, the concentration measurement electrode (31) has been raised at the other movement limit position and is positioned at the opening of the storage solution storage tank (34), so the concentration measurement operation cannot be performed. Instead, the user waits for the next measurement switch operation.

Next, when the first measurement switch operation is performed, the concentration measurement electrode (31) is lowered by the motor (37) and an electrode drive mechanism (not shown), moved to one of the movement limit positions, and then raised. The diffusion limiting film (12) covering the opening (11) is brought into contact with the concentration measuring electrode (31). In this state, if the test solution is dropped through the opening (24) of the cartridge (2), the opening (11)
The substance to be measured that is guided to the concentration ia1 constant electrode 1) through the diffusion limiting membrane (12) undergoes a predetermined reaction,
Since an electric signal corresponding to the amount of the reaction product substance or the reaction disappearing substance is generated, the concentration of the substance to be measured can be obtained by performing predetermined processing in a processing section (not shown).

After the concentration measurement operation is completed, the motor (37)
The concentration measuring electrode (31) is moved to the storage solution storage tank (
34), and then the long sheet (1) is sent a predetermined distance by the motor (38).

Thereafter, the series of concentration measurement operations described above can be performed every time the measurement switch is operated.

When the last diffusion-limiting membrane (12) is sent to the predetermined position as described above, both sensors (35) and (3B) output an OFF signal, so subsequent operation of the measurement switch will not be accepted. At the same time, a display (not shown) indicates that the termination has been detected. Therefore, the long sheet (1) is taken out and discarded together with the cartridge (2) from the concentration measuring device C3), and a new long sheet (
By accommodating 1), the concentration measurement operation can be performed multiple times again.

In this embodiment, a long hole (
14) is used, but it is possible to make all the holes (13) the same by counting the number of times the measurement operation is performed, and also to make the openings (11) Since the distance is predetermined, it is also possible to omit the positioning hole (13) and position the opening (11) by controlling the amount of operation of the motor (38). It is also possible to form elongated holes for tip detection.

In addition, in conjunction with the lid opening operation for concentration measurement, the long sheet (1) is rewound by the distance between the openings (11), and in this state, the concentration measurement operation is performed in the same manner as above, and finally the long sheet (1) is preferably sent by a distance twice the distance between the openings (11), so that the test solution that has been spotted can be wiped off immediately after the concentration measurement operation is completed.

FIG. 8A is a timing chart when measuring the concentration of the calibration standard solution and determining the concentration of the test solution in this order.

However, in this case, in order to prevent mistakes by not changing the dropping position of the test solution, the cartridge ( The bridge part (23) of 2) is made longer so that the two openings (11) can be located in the bridge part (23) at the same time, and other openings are formed in addition to the opening (24). (not shown).

As shown in the timing chart above, since the concentration of the standard solution is measured first, the motor (38)
By rotating forward for a predetermined period of time, the long sheet (1) is fed by a distance of two openings (11), and in this state, the concentration measuring electrode (31) is brought into contact with the diffusion limiting membrane (■2). The concentration is measured based on a standard solution with a known concentration. Next, the long sheet (1) is returned by a distance of one opening (11) by rotating the motor (38) in the reverse direction for 1/2 of the normal rotation time, and in this state, the concentration measuring electrode (
31) is brought into contact with the diffusion limiting membrane (12) to measure the concentration of a test liquid whose concentration is unknown. Finally, the long sheet (
1) to bring the new diffusion limiting membrane (12) into contact with the concentration measuring electrode (31).

In order to improve the positioning accuracy when rewinding the long sheet (1), as shown in FIG. 8B, an ON signal is output from the sensor (3B), and an OFF signal is output from the sensor (35). The motor (38
) is reversed to rewind the long sheet (1), and then the motor (3
8) in the normal direction to feed the long sheet (1), it is possible to reliably eliminate the decrease in positioning accuracy caused by the size of the position detection hole (13), etc.

Therefore, after that, only the concentration measurement of the test solution shown in FIG. 7 can be performed, or the concentration measurement of the standard solution and the concentration measurement of the test solution can be performed in this order as shown in FIG. 8A.

In addition, a standard solution spotting position is provided on the downstream side of the test solution spotting position, and the long sheet (1) is moved so that the calibration operation based on the standard solution is performed first, and then the calibration operation based on the test solution is performed. A long sheet (1) for concentration measurement operation.
It is preferable to move the long sheet (1) by twice the distance between the openings (11), and to wipe off the standard solution and test solution immediately after the operation is completed. Can be done.

In addition, in this embodiment, the supply section (21) and the winding section (2
2) are set as shown in the figure, but the supply section (21)
Of course, the positional relationship between the winding section (22) and the winding section (22) may be reversed.

<Embodiment 2> FIG. 9 is a partially cutaway perspective view showing another embodiment of the diffusion-limiting membrane holder of the present invention, which differs from the diffusion-limiting membrane holder shown in FIG. ), and a large-diameter opening (15) for inserting the concentration measuring electrode (31) is formed at a predetermined distance from each opening (■1). , the hole (I6) for position detection is formed in a predetermined positional relationship with respect to the large-diameter opening (15), and the hole (I3) and the hole (lB) are mutually connected to each other in the long sheet (1). A hole (17) for position detection is formed on the opposite side of the hole (16) corresponding to the large diameter opening (15) formed between the opening (11) at the end. )
is formed, the large-diameter opening (15) at the tip is oval, and the large-diameter opening (11) preceding the opening (11)
5) is the distance from the opening (11) to the next large diameter opening (15).
) is the only point that is set larger than the distance from

FIG. 10 is a partially cutaway perspective view showing a state in which the long sheet is housed in a cartridge, and the difference from the cartridge (2) shown in FIG. 2 is that the bridge portion (23) is formed in an elongated shape. The winding part (2
The only difference is that an opening (2B) for penetrating the concentration measuring electrode (31) is formed on the 2) side.

Fig. 11 is a vertical sectional view showing the configuration of the concentration measuring device;
The figure is a schematic plan view of the main part, and the difference from the concentration measuring device shown in FIGS. 3 and 4 is that the concentration measuring electrode (31) is provided so that it can only be moved up and down, and that The storage solution storage tank (34) is arranged above, the predetermined position of the long sheet running path (hereinafter referred to as a spotting table) is configured to be able to move up and down, and the motor (37) (38
) and that the housing (33) is elongated.

The elevating mechanism (5) for elevating the concentration measuring electrode (31) and the spotting table (30) has a mechanism for feeding the long sheet (1), as also shown in FIGS. 13A-D. It also has two systems of rotational force transmission mechanisms (51) and (61) with a one-way clutch interposed in order to perform the lifting and lowering operations and the feeding operations in synchronization with each other. Furthermore, the distance between the spotting table (30) and the concentration measuring electrode (31) is set large because the distance between the opening (11) and the preceding large-diameter opening (15) is set large. .

Rotational force transmission mechanism (51) for feeding the long sheet (1)
is a disc (52) that is rotated forward and backward by a motor (39).
) is provided with an engagement pin (53) at a predetermined position, and a cam (54) that engages with the engagement pin (53) and rotates as the disc (52) rotates by a predetermined angle.
is provided. The shaft of the cam (54) and the winding shaft (22a) are arranged concentrically, and the long sheet (1) is wound around both wheels so as to transmit rotational force only in the winding direction. A one-way clutch (55) made of a coil spring is provided.

The configuration of the rotational force transmission mechanism (61) for raising and lowering the concentration measuring electrode (31) and the spotting table (30) is as explained below. A cylindrical protruding shaft (63) is provided at the center of the disk (62) which is rotated forward and backward by the motor (39), and a cylindrical protruding portion (6) concentric with the protruding shaft (63) is provided.
4) is provided. A protruding shaft (65) having the same diameter as the protruding shaft (63) and a cylindrical protrusion (66) having the same diameter as the cylindrical protrusion (64) are integrally formed with each other, and )
and the cylindrical protrusion (B4), and are arranged to directly face the cylindrical protrusion (B4), and each of the outer peripheries of the double protrusion shafts (83) (65') and the cylindrical protrusion (84) (8B) is provided with a coil spring. One-way clutches (67) and (68) are provided.

The one-way clutches (67) and (88) transmit rotational force in different directions, and a regulating cylinder (69) is disposed around the outer periphery of the one-way clutch (68). This regulating cylinder (69) has a notch (69a) formed at a predetermined position that is connected to the one-way clutch (69).
), it rotates following the one-way clutch (68), and the flange (69b) formed in a predetermined range on the outer peripheral surface of the regulating cylinder (69) ) engages with a regulating protrusion (89c) provided at a predetermined position on the main body of the measuring device, thereby canceling rotational force transmission by the one-way clutch (68). Furthermore, a rotary cam (7
0) are connected. This rotary cam (70) has a small diameter cam portion (70b) and a gradually increasing radius cam portion (70c) in a range determined based on the formation range of the flange (89b),
The remaining range is defined as a large diameter cam portion (70d). A pantograph mechanism (71) that raises and lowers the concentration measuring electrode (31) using the rotating cam (70) and a spotting table (3)
0) is operated. The pantograph mechanism (71) is
A pair of bases (71a) separated by a predetermined distance are each marked with an X.
Two pairs of units (71b) rotatably connected in a letter shape (
71c) and two pairs of simplexes (71b)
The receiver supported by (71c) has a stand (71d), and also has an engaging protrusion (71e) that engages with the rotating cam (70) at a predetermined position on one unit (71b). are doing. Furthermore, the single unit (71b) is a stand (71
d), and the unit (7Lc) is rotatably and slidably engaged with the base (7La), and
A tension spring (
71f) is provided.

Note that the configuration of the pantograph mechanism (72) is the same as that of the pantograph mechanism (71) described above, so a description thereof will be omitted.

The long sheet (1) having the above configuration is housed in the cartridge (2), and further incorporated into the concentration measuring device (3),
The concentration of the target substance in the test solution can be measured as follows. However, FIG. 14 is a timing chart showing the operation of each part.

In a state where no work necessary for concentration measurement is performed, both sensors (35) (3B) are directly facing the part of the long sheet (1) where the holes (13) (16) are not formed. Therefore, ON signals are output from both sensors (35) (3B), and the leading edge of the long sheet (1) is detected.

However, in this state, the concentration measuring electrode (31) passes through the oval-shaped large diameter opening (15) into the storage solution storage tank (
34).

In this state, the control unit controls the motor (39
) to drive the concentration measuring electrode (31) and spotting table (30
) is lowered, and then the long sheet (1) is sent. That is, the motor (39) is rotated in the forward direction, the one-way clutch (68) is caused to transmit rotational force until the flange (69b) of the regulating cylinder (69) engages with the regulating protrusion (69c), and the rotating cam ( By rotating the spotting table (30)
and the concentration measuring electrode (31) are evacuated in this order. Then, when the retracting operation is completed, the engagement pin (53) and the cam (54) engage, so that the one-way clutch (55) then transmits the rotational force to the winding shaft (22a). , a long sheet (1) can be sent.

In addition, while the long sheet (1) is being fed, the regulating cylinder (B
9) is prevented from rotating, so the rotary cam (70) remains stopped.

Then, on condition that one sensor (35) outputs an ON signal and the other sensor (36) outputs an OFF signal, the motor (39) generates a long sheet (
1) Stop feeding. At this point, the opening (11) of the long sheet (1) directly faces the spotting table (30), and the large diameter opening (15) directly faces the concentration measuring electrode (31). Therefore, by reversing the motor (39) in this state, the rotational force is transmitted to the rotating cam (70) via the other one-way clutch (67), and the concentration measuring electrode (
31) and the spotting table (30) can be raised in this order. In this state, since the distance between the concentration measuring electrode (31) and the spotting table (30) is set large, a sufficient space should be secured near the spotting table (30) to perform the dropping operation of the test solution. It can be facilitated.

Furthermore, even if the distance between the concentration measuring electrode (31) and the spotting table (30) is increased, the large-diameter opening (■1) and the next large-diameter opening (1)
5) by reducing the distance from the long sheet (1
) can suppress the increase in the total length.

Next, after dropping the test solution into the opening (11) located on the spotting table (30), when the first measurement switch operation is performed, the motor (39) rotates forward and the spotting table (30) is rotated forward. 30)
and after lowering the concentration measuring electrode (31) in this order,
By feeding the elongated sheet (1) a predetermined distance, the diffusion limiting film (12) is brought to face the concentration n constant electrode (3I).

Next, the motor (
39) for a short period of time, only the concentration measuring electrode (31) is slightly raised, and the diffusion limiting membrane (12)
The concentration of the target substance contained in the test solution is measured. Thereafter, the motor (39) is rotated forward to lower only the concentration measuring electrode (31), and then the long sheet (
1) by a predetermined distance, the motor (39) is reversed to raise the concentration measuring electrode (31) and the spotting table (30) in this order.

Thereafter, by performing the series of operations described above, the concentration of the target substance contained in the test solution or the concentration of the target substance contained in the standard solution can be measured.

As a result of feeding the long sheet (1), the sensor (35
) (3G), when the holes (18) and (17) are detected, since this is the last diffusion limiting membrane (12), the operation after performing the concentration measurement operation only once is blocked, and If necessary, it will be displayed that the concentration has been measured using the diffusion limiting membrane (Step 2) on the wall. Therefore, by removing the long sheet (1) together with the cartridge (3) from the concentration measuring device (3), discarding it, and storing a new long sheet (1), it is possible to perform the concentration measurement operation multiple times again. can.

In this embodiment, a hole (16
) (17) is used, and the holes (17) are formed by counting the number of times the measurement operation is performed.
7) can be omitted, and since the distance between the opening (11) and the large diameter opening (15) is predetermined, the positioning holes (13) and (16) can be omitted. The opening (1) is controlled by controlling the operating amount of the motor (39).
1) and the large diameter opening (15), it is also possible to form a hole for tip detection.

<Effects of the Invention> As described above, in the first invention, since a plurality of openings are formed in a long sheet and each opening is covered with a diffusion limiting film, by feeding the long sheet a predetermined distance at a time, The concentration of target substances contained in the test solution can be measured sequentially.
It has the unique effect of greatly reducing the time and effort required to install and dispose of the diffusion-limiting membrane, as well as reducing the space required for storage, transportation, etc.

In the second invention, a plurality of openings for passage of a test solution and openings for insertion of a concentration measuring electrode are formed in a long sheet, and each opening for passage of a test solution is covered with a diffusion limiting film. By feeding the long sheet by a predetermined distance, the concentration of the target substance contained in the test solution can be determined by +11J and the concentration measurement electrode can be brought into contact with the storage solution storage part alternately.As a result, the concentration measurement The unique feature of this method is that it can continue to maintain the activity of the electrode, and it can greatly reduce the effort of attaching and disposing of the diffusion-limiting membrane, as well as reducing the space required for storage, transportation, etc. Creates an effect.

The third invention has the unique effect that the feeding of the long sheet can be stopped in a state where the opening for passing the measurement target solution directly faces the measurement electrode, and the feeding of the long sheet can be automated. .

The fourth invention is capable of detecting that concentration measurement has been performed using all the diffusion limiting films, and performs the concentration n1 constant operation in a state where there is an opening to which an unused diffusion limiting film is attached. It has the unique effect of being able to be carried out only in

[Brief explanation of the drawing]

Fig. 1 is a partially cutaway perspective view showing an embodiment of the diffusion-limiting membrane holder of the present invention, Fig. 2 is a partially cutaway perspective view showing a state in which a long sheet is accommodated in a cartridge, and Fig. 3 is a concentration FIG. 4 is a perspective plan view showing the configuration of the measuring device, FIG. 5 is a diagram showing the electrode drive mechanism, FIG. 6 is a diagram showing the long sheet drive mechanism, and FIG. 7 is a diagram showing the operation of each part. 8 is a timing chart when measuring the concentration of a standard solution for calibration and measuring the concentration of a test solution in this order. FIG. 9 is another embodiment of the diffusion-limiting membrane holder of the present invention. FIG. 1O is a partially cutaway perspective view showing a state in which a long sheet is accommodated in a cartridge. FIG. 11 is a longitudinal cross-sectional view showing the configuration of the concentration measuring device.
The figure is a schematic plan view of the main parts, FIG. 13 is a diagram showing the elevating mechanism, and FIG. 14 is a timing chart showing the operation of each part. (14)...Long hole for position detection, (15)...Large diameter opening

Claims (1)

[Claims] 1. A plurality of openings (11) for passage of the solution to be measured are formed in the long sheet (1) in the longitudinal direction, and a diffusion limiting film is provided to cover each opening (11). (12) A diffusion-limiting membrane holder, characterized in that it is provided with (12). 2. The long sheet (1) has a plurality of openings (11) for passing the solution to be measured and openings (
15) are formed alternately, and a diffusion limiting membrane (12) is provided so as to cover each opening (11) for passage of a solution to be measured. 3. Position detection parts (
13) The diffusion-limiting membrane holder according to claim 1 or 2, which is provided with (14), (16), and (17). 4. The diffusion-limiting membrane holder according to claim 3, wherein position detecting portions (14) and (17) which also serve as end detection are provided in correspondence with the end openings (11) and (15).