JP3236110B2 - Ion measuring tool - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a measuring instrument for determining the concentration of ions in a solution.

[0002]

2. Description of the Related Art In the field of clinical examination, it is known that measurement of the ion concentration in serum or urine can provide useful information on the condition of a patient. Various methods such as a flame photometric method, an ion-selective electrode method, and a colorimetric method have been used for measuring such an ion concentration.

[0003] Among them, the colorimetric method is a method of measuring the concentration of an ion as an absorbance or a fluorescence intensity at a specific wavelength by using various coloring reagents. Since the colorimetric method has a feature that the structure of the measuring device is simplified, disposable measuring tools have also been developed.

[0004] As a colorimetric ion concentration measuring instrument, an organic liquid phase containing an ionophore and a dye exhibiting a detectable response by interacting with the complex formation between the ion and the ionophore is supported on a porous carrier, and the absorbance or fluorescence is measured. A measuring instrument for measuring the ion concentration in a liquid as the intensity is already known.
For example, Japanese Patent Application Laid-Open No. 60-194360 discloses various ionophores and organic liquids containing a pH-sensitive dye called a reporter substance.
An ion concentration measuring device in which a phase is supported on a porous carrier is described. By contacting these measuring instruments with a sample aqueous solution containing specific ions, depending on the ion concentration,
Changes in absorption or fluorescence spectra of pH-sensitive dyes.

However, since these measuring instruments have high water repellency on the surface, it takes a long time for the sample aqueous solution to penetrate, and the time required for the measurement is long, or the measurement is performed without the response of the measuring instrument reaching the end point. Therefore, there is a problem that accurate measurement cannot be performed.

A solution to this problem is disclosed in Japanese Patent Application Laid-Open No. 60-19436.
No. 0 proposes this. That is, a substance called a wet substance, which reduces the surface tension of the sample aqueous solution, is replaced with an organic liquid.
It has been proposed to impregnate the phase and then support it on a porous carrier. It is described that agarose and a nonionic surfactant are preferably used as the wetting substance.

[0007] However, it is described in the same publication as a problem that these substances may interfere with the coloring system for the ion concentration of the ionophore, the dye and the organic phase . In addition, even when these wet substances are used, there is a problem that the color development response is slow when the amount of the ionophore, the dye, and the organic liquid phase supported on the porous carrier is large. Furthermore, when manufacturing these measuring instruments, it is necessary to add a step of impregnating the porous carrier with the wet substance and a step of drying the porous carrier. Was.

Further, it has been disclosed in Japanese Patent Application Laid-Open No. Sho 61 (1994) to use a hydrophobic polymer in which a hydrophilic polymer is finely dispersed as a membrane for analysis.
-84558, an attempt was made to facilitate the penetration of the aqueous sample solution into the hydrophobic polymer by using a hydrophilic polymer. However, in the membrane described therein, it takes about one minute to complete the reaction for analysis. In some cases, the measurement of the ion concentration needs to be performed in a time as short as possible, and it is desirable that the reaction for analysis is completed within 30 seconds. Therefore, further improvement is required.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to develop an ion concentration measuring instrument which can be easily manufactured and can measure an ion concentration in a short measuring time.

[0010]

This onset bright person SUMMARY OF THE INVENTION have been conducted extensive studies to solve the above technical problems, as a result, complexation or the ionophores and ionophore and ion having complexing ability of the ion By dispersing and containing hydrophilic polymer microparticles in an organic liquid phase containing a dye that shows a detectable response by interacting with complex dissociation, it has been found that the measurement time of ion concentration can be dramatically reduced,
The present invention has been completed.

That is, the present invention relates to a hardly water-soluble nonvolatile organic solvent.
(Hereinafter referred to as an organic solvent) comprising an ionophore capable of forming a complex with an ion, a dye exhibiting a detectable response by interacting with the complex formation between the ionophore and the ion, and hydrophilic polymer fine particles. The organic liquid phase is an ion measuring instrument impregnated and supported on a porous carrier. Further, another invention is a complex of an ionophore and an ion capable of forming a complex with an ion in a poorly water-soluble nonvolatile organic solvent, and a dye exhibiting a detectable response by interacting with the complex dissociation of the ionophore and the ion. And an organic liquid phase containing hydrophilic polymer fine particles is an ion measuring instrument supported on a porous carrier.

[0012] The ionophore used in the present invention is a compound having a property of forming a complex with a specific ion and having no charge per se. The complex formed can be dissociated by a reverse reaction.

As the cation ionophore, there can be used several known cyclic peptide compounds, cyclic or acyclic polyether derivatives, potand derivatives, calixarene derivatives and the like. As the anion ionophore, an organic tin compound or the like can be used.

As specific examples of ionophores which can be suitably used, lithium ionophore is 6,6-
Dibenzyl-1,4,8,11-tetraoxacyclotetradecane, 2,9-dibutyl-1,10-phenanthroline and the like; sodium ionophore is 5,11,17,23-tetra-t-butyl
-25,26,27,28-tetrakis (ethoxycarbonyl) -methoxy-calix [4] arene, bis [(12-crown-
4) Methyl] methyldodecyl malonate and the like; potassium ionophores include valinomycin and bis [(benzo-
15-crown-5) -4'-hydroxymethyl] pimelate and the like; a calcium ionophore is diethyl-N, N'-
[(4R, 5R) -4,5-dimethyl-1,8-dioxo-3,6-dioxaoctamethylene] bis (12-methylaminododecanoate)
Examples of the magnesium ionophore include N, N'-diheptyl-N, N'-dimethylaspartamide; and examples of the chlorine ionophore include trioctyltin chloride and triphenyltin chloride.

Of course, there are other compounds which are known to form or dissociate with ions.
They can also be used. For literature on ionophores, see “Cati,” edited by Yoshihisa Inoue, George W. Gokel.
on Binding by Macrocycles ”(MARCEL DEKKER INCORPO
RATION 1990), edited by Hiroyuki Takeda, "Application of Functional Macrocycles to Analytical Chemistry" (IPC Inc., 1990), Analytical Chemistry (ANALYTICAL CHEMI)
STRY), Vol. 60, pp. 2013-2016 (1988).

The dye used in the present invention and exhibiting a detectable response by interacting with the complex formation or dissociation of the ionophore and the ion (hereinafter referred to as a reporter dye) is a dye that traps a hydrogen ion or forms a hydrogen ion. A dye whose absorption spectrum or fluorescence spectrum changes upon dissociation. The reporter dye may interact with each other and change the absorption spectrum or the fluorescence spectrum not only when the complex is formed but also when the formed complex is dissociated.

For example, when the ion is a cation, when the cation in the sample aqueous solution is taken into the organic liquid phase and the ionophore and the cation form a complex, the organic liquid phase is maintained to maintain the electrical neutrality in the organic liquid phase. Hydrogen ions are dissociated from the reporter dye present inside and released into the aqueous solution. The interaction in the present invention refers to a response reaction of hydrogen ions that occurs with such ion movement. At this time, the absorption spectrum or the fluorescence spectrum of the reporter dye changes, and the response can be measured as a detectable response.

If there are no hydrogen ions released from the organic liquid phase into the aqueous sample solution, cations cannot enter the organic liquid phase . This is because electrical neutrality cannot be maintained as described above.

Since the above reaction is a reversible reaction, when a complex of an ionophore and a cation and a reporter dye having dissociated a hydrogen ion are previously present in an organic liquid phase by utilizing a reverse reaction, the solution is brought into contact with an aqueous sample solution. The cations in the organic liquid phase dissociate due to equilibrium and move into the sample aqueous solution, and consequently, hydrogen ions are conversely incorporated into the organic liquid phase and captured by the reporter dye, changing the absorption spectrum or fluorescence spectrum. However, this can be detected and measured.

When measuring cations,
Depending on the reporter dye used, it is necessary to add a compound having specific properties. That is, when using a pH-sensitive dye having no dissociable hydrogen ion (hydrogen ion trapping dye) as described above, a metal salt of a fat-soluble anion such as a potassium salt of tetrakis (p-chlorophenyl) borate; That is, it is necessary to add an equimolar amount of a compound having a dissociable cation to the reporter dye and dissolve it in an organic solvent. In this case, when the sample aqueous solution comes into contact with the measuring tool, the complex of the ionophore and the metal salt previously formed in the organic liquid phase is dissociated, and the cation moves into the sample aqueous solution. At this time reverse the hydrogen ions in order to maintain the electrical neutrality of the organic liquid phase in is taken into the organic liquid phase in the organic solution
Hydrogen ions taken into the phase trapped reporter dye, the absorption spectrum or fluorescence spectrum changes.

When the ion is an anion, the ionophore and the anion form a complex and the anion is taken into the organic liquid phase . At this time, hydrogen ions are combined to maintain electrical neutrality in the organic liquid phase . Is taken into the organic liquid phase . Hydrogen ions taken into the organic liquid phase are captured by the reporter dye, and the absorption spectrum or the fluorescence spectrum changes. In this case as well, similarly to the case of the cation, measurement can be performed by detecting a change in an absorption spectrum or a fluorescence spectrum due to dissociation of a complex using a reverse reaction.

The reporter dyes that interact with the complex formation or dissociation described above include a series of dyes called pH indicators or pH-sensitive dyes. Because reporter dyes used in the present invention to be contained solubilized in organic solvent, a water-soluble remarkably small reporter dye is preferably used. Because of its availability and the degree of color development response when used as an ion concentration measuring instrument,
A reporter dye having a pKa of 5 to 10 is preferably used.

Specific examples thereof include phenolphthalein derivatives such as phenolphthalein, tetrabromophenolphthalein and phenolsulfophthalein;
Indophenol derivatives such as 2,6-dichloroindophenol, 2,6-dibromo-3'-methylindophenol and indophenol blue; oxazine dye derivatives such as Neil Blue and Basic Blue 3; tris such as fuchsin and Victoria Pure Blue. There are phenylmethane dye derivatives and the like.

Examples of the reporter dye having a dissociable hydrogen ion include the above-mentioned phenolphthalein, tetrabromophenolphthalein, phenolsulfophthalein and other phenolphthalein derivatives, 2,6-dichloroindophenol, 6-dibromo-3'-methylindophenol, indophenol derivatives such as indophenol blue, etc., and the like. A dichloroindophenol derivative is shown below as an example.

[0025]

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Examples of the reporter dye having no dissociable hydrogen ion include the above-mentioned oxazine dye derivatives such as Neil Blue and Basic Blue 3, fuchsin, and the like.
And triphenylmethane dye derivatives such as Victoria Pure Blue.

Using this reporter dye, a complex dissociation of the ionophore and the cation, that is, a mechanism in which the complex formed in advance in the organic liquid phase reacts with the dissociation of the cation to take in hydrogen ions and develop a color. The following is an example of Neil Blue.

[0028]

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As a reporter dye used when preparing a measuring tool for measuring anions, a reporter dye having no dissociable hydrogen ion, that is, a hydrogen ion trapping dye must be used. .

For example, the above-mentioned Neil Blue,
Oxazine dye derivatives such as Basic Blue 3 and triphenylmethane dye derivatives such as fuchsin and Victoria Pure Blue.

The structural change of a dye that traps hydrogen ions by interacting with the complex formation between an ionophore and an anion is described below using Neil Blue as an example.

[0032]

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As the organic solvent used in the present invention, a high boiling point and hardly soluble in water ( this property is considered to be hardly water-soluble and non-volatile)
And a compound that does not have an ionizable functional group and is liquid at room temperature. Specifically, it is generally desirable that the boiling point be 100 degrees Celsius or more and the solubility in 1 liter of water is about 1 g or less in order to obtain a stable response.

Examples of compounds preferably used as the organic solvent include high boiling esters such as dibutyl adipate and dioctyl phthalate, and high boiling ethers such as o-nitrophenyloctyl ether and diphenyl ether.

In order to reduce the fluidity and improve the physical strength, polymers such as polyvinyl chloride and polymethyl methacrylate may be dissolved in the organic solvent within a range not to impair the effects of the present invention. it can.

The concentrations of the ionophore and the reporter dye in the organic liquid phase cannot be limited because the upper limit varies depending on the solubility of the compound used. The lower limit also varies depending on the absorbance or change in fluorescence required by the absorbance measurement device or the fluorescence measurement device. A preferred range is 0.1 to 200 mM. A more preferably used range is 5-120 mM. When the concentration is low, the absorbance response or the fluorescence response becomes small, and the measurement becomes difficult. If the concentration is too high, precipitation of the ionophore or reporter dye occurs, and the measurement is still difficult.

It is most desirable that the molar ratio between the ionophore and the reporter dye is 1: 1 in principle. But,
If the molar ratio is other than this, there is no problem in measurement. The molar ratio of ionophore to reporter dye preferably used in the present invention is from 1: 0.2 to 1: 5. Ionophore,
The method for incorporating the reporter dye into the organic solvent is not particularly limited, and a known method can be used. For example, an organic solvent, an ionophore, and a reporter dye can be placed in a container such as an Erlenmeyer flask, and dissolved and contained by shaking. When the solubility of the ionophore or reporter dye in the organic solvent is low, the organic solvent can be dissolved and contained by heating and stirring. It is necessary that the ionophore and the reporter dye are at least partially dissolved in an organic solvent. Particularly, when all of the ionophore and the reporter dye are dissolved in an organic solvent, accurate and highly sensitive measurement can be performed.

When a complex of an ionophore and an ion or a reporter dye is contained in an organic solvent, it may be carried out according to the above-mentioned method.

As the hydrophilic fine polymer particles used in the present invention, known fine particles can be used as long as they are insoluble in an organic solvent and do not have an ionic functional group capable of dissociating ions.

Specific examples of those which can be preferably used include ethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, and agarose.

The hydrophilic polymer fine particles must not be dissolved in the organic solvent and must be dispersed as fine particles. The shape of the fine particles is not particularly limited, such as a spherical shape or an irregular shape, and the size is usually about 1 to 50 μm. For prompt penetration of the sample aqueous solution, the fine particles are uniformly dispersed in an organic solvent in a discrete state. Is desirable.

When the amount of the hydrophilic polymer fine particles dispersed in the organic solvent is too small, the ability to penetrate the sample aqueous solution becomes insufficient, and when the amount is too large, the pores of the porous carrier are closed and the sample aqueous solution is blocked. Therefore, there is a preferable range depending on the combination of the materials used. Generally, if the amount of the hydrophilic polymer fine particles dispersed in the organic solvent is at least 3% of the weight of the organic liquid phase , the ability to promote the penetration of the aqueous sample solution can be obtained.
The maximum value varies depending on the type of the porous carrier to be used and the amount of the organic liquid phase to be impregnated. However, the maximum value can be favorably used as long as it is 150% or less with respect to the weight of the organic liquid phase .

The method for dispersing the hydrophilic polymer fine particles in the organic solvent is not particularly limited, and a known method can be used. For example, a method in which a hydrophilic polymer powder is simply put into an organic solvent and stirred in a container, or both are once dissolved in an organic solvent that dissolves both the organic solvent and the hydrophilic polymer fine particles, and the organic For example, there is a method in which the solvent is evaporated to cause phase separation to precipitate hydrophilic polymer fine particles in the organic solvent.

The organic liquid phase of the present invention, as described above, a complex of ionophore or ionophore and ion, and reporter dye are contained is dissolved in an organic solvent, is further hydrophilic polymer microparticles dispersed in said phase Almost uniformly contained. Then, this organic liquid phase is impregnated and supported on a porous carrier shown below.

The porous carrier used in the present invention has porosity and does not dissolve in an organic solvent. Specific examples that can be suitably used include glass filters, glass fiber filter papers, membrane filters, and paper.

The porous carrier used in the present invention needs to have an opening through which an aqueous sample solution can penetrate even after the organic liquid phase is supported. For this reason, the amount of the organic liquid phase to be impregnated depends on the porosity of the porous carrier and cannot be limited, but generally the organic liquid phase having a weight of 0.1 to 2 times the weight of the porous carrier is used. It is carried.

A known method can be used as a method for supporting an organic liquid phase containing an ionophore or a complex of an ionophore and an ion and a reporter dye and further dispersing and further containing hydrophilic polymer fine particles on a porous carrier. .

Typically, once dissolved in a solvent capable of dissolving both an ionophore or a complex of an ionophore and an ion, and an organic liquid phase containing a reporter dye and a hydrophilic polymer, the solution is added to a porous carrier. Impregnated,
Then, a method of removing the solvent (drying) is suitably used.

A sample aqueous solution to be measured by the ion measuring instrument of the present invention cannot be measured with good reproducibility unless the pH is kept at a constant value by a pH buffer or the like. This is an analytical
This is described in ANALYTICAL SCIENCE, pp. 715-720, 1990, and is attributed to the occurrence of ion exchange between the organic liquid phase and the aqueous sample solution. As a method for keeping the pH constant, for example, there is a method described below.

(1) A known amount of an aqueous solution
A method in which a pH buffer is added to adjust the pH to a predetermined value, and then brought into contact with the measuring instrument of the present invention.

(2) Prior to supporting the organic liquid phase on the porous carrier matrix, a known amount of a pH buffer is dispersed in advance, and the aqueous solution of the sample is impregnated with the porous buffer matrix to impregnate the pH buffer. A method in which the agent is dissolved so as to exhibit a predetermined pH.

When the measuring device of the present invention is brought into contact with an aqueous sample solution, the measuring device immediately changes its absorption spectrum or fluorescence spectrum. This change in spectrum can be quantified by measuring a reflected light absorption spectrum, a transmitted light absorption spectrum, a reflected fluorescence spectrum, and the like. The ion concentration in the unknown concentration sample aqueous solution can be known by measuring the sample concentration aqueous solution of the known concentration, measuring the correspondence between the concentration change and the spectrum change in advance, and then measuring the unknown concentration sample aqueous solution.

[0053]

[Function] The color development mechanism when an organic liquid phase containing an ionophore and a reporter dye is brought into contact with an aqueous sample solution containing ions is described in Analytical Science.
CAL SCIENCE), 1990, pp. 715-720. For example, when the ionophore selectively incorporates specific ions into the organic liquid phase , the reporter dye releases hydrogen ions into the aqueous sample solution to compensate for electrical neutrality, which causes the reporter dye to undergo a spectral change. It is.

The ion measuring instrument of the present invention contains an ionophore and a reporter dye, and is further characterized by an organic liquid phase in which fine particles of a hydrophilic polymer are dispersed. By using an organic liquid phase containing an ionophore and a reporter dye, the ion concentration can be converted into a change in the absorption or fluorescence spectrum of the reporter dye. Further, since the hydrophilic polymer microparticles in organic liquid phase is dispersed, the water repellency of organic liquid phase is reduced, allowing rapid penetration into the porous carrier inside the sample solution. In addition, since the organic liquid phase is partially separated by the hydrophilic polymer fine particles, the sample aqueous solution can penetrate the hydrophilic polymer fine particles and enter the inside of the organic liquid phase . For this reason, compared to the case where the hydrophilic polymer fine particles are not present or the case where the hydrophilic polymer fine particles are simply dispersed in the organic liquid phase without the porous carrier matrix, the organic liquid phase is the sample. The area in contact with the aqueous solution increases dramatically, and as a result, the speed of the color reaction increases.

[0055]

According to the present invention, since the color measuring response of the ion measuring device of the present invention is high, the color developing response of the measuring device is completed quickly, and the measurement result of the ion concentration can be quickly known. This has a great advantage in the case of highly urgent measurement, that is, in the measurement of blood ion concentration in the field of emergency medical care or the operating room. In addition, the number of serum or urine samples measured within a limited period of time in a general clinical test is increased, thereby improving work efficiency and facilitating diagnosis.

In view of the above, the industrial value of the present invention is extremely large.

[0057]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1 2.6 mg (2.3%) of valinomycin as potassium ionophore
μmol), Victoria Pure Blue 1.1m previously deprotonated in an aqueous alkali solution as a reporter dye
g (2.1 μmol), potassium tetrakis (chlorophenyl) borate 1.1 mg (2.1 μmol), o-nitrophenyloctyl ether 80 mg as organic solvent, polyvinyl chloride 8.
0mg, anhydrous polyvinylpyrrolidone as hydrophilic polymer
8.0 mg was dissolved in 1.6 ml of tetrahydrofuran as a solvent . 45 μl of this solution was impregnated into 1.5 cm square filter paper (Toyo Roshi Kaisha No. 7) and dried. The measuring instrument thus prepared was mounted on the reflection absorption spectrum measuring apparatus shown in FIG.
At that time, the change in reflection absorbance at a wavelength of 620 nm was measured.
The results are shown in FIG. It took 20 seconds immediately after the dropping to complete the response.

Comparative Example 1 2.6 mg (2.3%) of valinomycin as potassium ionophore
μmol), Victoria Pure Blue 1.1m previously deprotonated in an aqueous alkaline solution as a reporter dye
g (2.1 μmol), potassium tetrakis (chlorophenyl) borate 1.1 mg (2.1 μmol), o-nitrophenyloctyl ether 80 mg as organic solvent, polyvinyl chloride 1
6.0 mg was dissolved in 1.6 ml of tetrahydrofuran. This solution
45 μl was impregnated into 1.5 cm square filter paper (Toyo Roshi Kaisha No. 7) and dried. The measuring device thus manufactured was mounted on the reflection absorption spectrum measuring device shown in FIG.
50 mM sodium acetate 10 mM buffer (adjusted with sodium hydroxide to pH 5.5) as a sample aqueous solution
μl was added dropwise, and the change in reflection absorbance at a wavelength of 620 nm was measured. Even after 2 minutes from the dropping, the absorbance continued to change, and the response did not end.

Comparative Example 2 A 0.5% agarose aqueous solution was added to the measuring device prepared in Comparative Example 1.
impregnated with [mu] l, and dried for 30 minutes at 60 ° C. in a constant temperature bath.
The measuring instrument thus obtained was attached to the reflection absorption spectrum measuring apparatus shown in FIG. 1, and 50 μl of sodium acetate 10 mM buffer solution (adjusted to pH 5.5 with sodium hydroxide) having a potassium chloride concentration of 10 mM was added dropwise. At that time, the change in reflection absorbance at a wavelength of 620 nm was measured. The change in absorbance was terminated 60 seconds after the addition.

Comparative Example 3 2.6 mg (2.3 mg) of valinomycin as potassium ionophore
μmol), Victoria Pure Blue 1.1m previously deprotonated in an aqueous alkali solution as a reporter dye
g (2.1 μmol), potassium tetrakis (chlorophenyl) borate 1.1 mg (2.1 μmol), o-nitrophenyloctyl ether 80 mg as organic solvent, polyvinyl chloride 1
6.0 mg, 30 mg of polyethylene glycol (average molecular weight: 2000) as a hydrophilic polymer and 1.6 m of tetrahydrofuran
dissolved in l. This solution was cast on a polyester film (non-porous carrier) and dried at room temperature to obtain a film having an average film thickness of 20 μm in which hydrophilic polymer fine particles were dispersed. This is 1.5
It was cut into a cm square to obtain a measurement tool, which was attached to the reflection absorption spectrum measuring device shown in FIG. 50 μl of 10 mM sodium acetate buffer solution (adjusted to pH 5.5 with sodium hydroxide) having a potassium chloride concentration of 10 mM was added dropwise, and the change in reflection absorbance at a wavelength of 620 nm was measured. Even after 2 minutes from the dropping, the change in absorbance did not end.

From Example 1 and Comparative Examples 1 to 3,
Ionophore containing reporter dye and dispersing the hydrophilic polymer microparticles, the organic liquid phase is a porous carrier containing free
It was found that a quick response was obtained only when immersed and loaded.

Example 2 Bis [(12-crown-4) as sodium ionophore
Methyl] methyldodecylmalonate 1.5 mg (2.3 μmol),
2,6-dichloroindophenol 0.6m as reporter dye
g (2.1 μmol), 80 mg of o-nitrophenyloctyl ether as an organic solvent, and 8.0 mg of polyvinyl chloride were dissolved in 1.6 ml of tetrahydrofuran. To this solution, 8.0 mg of fine powder of various hydrophilic polymers shown in Table 1 was added. 45 μl of this solution was impregnated into a 1.5 cm square filter paper (Toyo Roshi Kaisha No. 7) and then dried. The measuring device thus prepared was mounted on the reflection absorption spectrum measuring device shown in FIG. 1, and a 10 mM N-2-hydroxyethylpiperazine-N′-2-ethanesulfonic acid buffer (pH 7.2) having a sodium chloride concentration of 100 mM was used.
(Adjusted with potassium hydroxide) was added dropwise, and the change in reflection absorbance at a wavelength of 660 nm was observed at that time, and the time required until the response was completed was measured. The results are shown in Table 1. The time required to complete the response when using each hydrophilic polymer fine particle was very short, within 30 seconds, indicating that the measuring instrument of the present invention was useful for rapid measurement.

[0064]

[Table 1]

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of a reflection absorption spectrum measuring device used in Examples and Comparative Examples of the present invention.

FIG. 2 is a diagram showing the relationship between the elapsed time from the dropping of the sample aqueous solution and the absorbance at a wavelength of 660 nm, measured in Example 1.

[Explanation of symbols]

 1 Xenon lamp 2 Lens 3 Light emitting fiber 4 Glass plate 5 Measuring tool 6 Light receiving fiber 7 Instantaneous multi-photometer 8 Data processor

Claims (3)

(57) [Claims] 1. An ionophore capable of forming a complex with an ion in a poorly water-soluble nonvolatile organic solvent, a dye and a hydrophilic polymer fine particle exhibiting a detectable response by interacting with the complex formation between the ionophore and the ion. An ion measuring device in which an organic liquid phase is impregnated and supported on a porous carrier. 2. A complex of an ionophore and an ion capable of forming a complex with an ion in a poorly water-soluble nonvolatile organic solvent, a dye exhibiting a detectable response by interacting with the complex dissociation of the ionophore and the ion, and An ion measuring instrument in which an organic liquid phase containing hydrophilic polymer fine particles is impregnated and supported on a porous carrier. 3. A complex of an ionophore capable of forming a complex with a cation and a metal salt of a fat-soluble anion in a poorly water-soluble nonvolatile organic solvent, and hydrogen which exhibits a detectable response upon mutual reaction with the dissociation of the complex. An organic liquid phase containing an ion-trapping dye and hydrophilic polymer fine particles is impregnated into a porous carrier.
A cation measuring tool carried and carried.