JP2003327579A - Ionophore comprising azaannulene derivative, sensitive membrane and ion sensor using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an ionophore having high sensitivity to a transition metal ion and an ion sensor and an ion-exchange membrane containing the same. <P>SOLUTION: The ionophore for the transition metal ion comprises a [14] azaannulene derivative represented by formula (I) (R<SP>1</SP>to R<SP>4</SP>are the same or different and are each a hydrogen atom or an alkyl group; R<SP>5</SP>and R<SP>6</SP>are the same or different and are each a hydrogen atom, a halogen atom, a carbonyl group, an azo group or an alkyl group containing an electronegative substituent group; R<SP>2</SP>and R<SP>5</SP>, R<SP>4</SP>and R<SP>6</SP>or R<SP>5</SP>and R<SP>6</SP>may be connected by an alkylene chain which may contain a substituent group; R<SP>a</SP>to R<SP>d</SP>are the same or different and are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a carbonyl group; R<SP>a</SP>and R<SP>b</SP>and R<SP>c</SP>and R<SP>d</SP>may be connected by an alkylene group which may contain a substituent group). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ionophore capable of recognizing transition metal ions such as copper ions and anions such as halogen ions with high selectivity, an ion sensor using the same, and an ion selective electrode. .
More specifically, the invention of this application relates to an ionophore comprising a [14] azaannulene derivative or a cation thereof, an ion sensor using the same, and an ion selective electrode.

[0002]

2. Description of the Related Art Ion-selective electrodes use the membrane potential generated across a membrane sensitive to specific ions to selectively recognize target ions and measure their ion concentration and activity. It is a sensor. Conventionally, a membrane-type ion-selective electrode in which a polymer membrane such as polyvinyl chloride (Ionophore), which is an ion transport carrier, is carried on a polymer membrane is known, and is excellent for potassium ion, sodium ion, ammonium ion, etc. It is widely used in the medical field and environmental measurement because of its sensitivity and selectivity, rapid and easy analysis, and its applicability to automatic continuous analysis.

However, since many crown and azacrown compounds, which are promising as ionophores, are molecularly designed with emphasis on the kind of coordinating atom, the pore size, and the lipophilicity, the coordinating property so far. Regarding transition metal ions with similar ion sizes and similar ion sizes, the ionophore that can be distinguished with high accuracy is not known.

On the other hand, since many transition metal ions are toxic, their emission amount is limited from the viewpoint of environmental protection. Therefore, it is necessary to constantly monitor that the concentration of metal ions in the wastewater does not exceed the emission standard value in plating plants and the like. For example, copper content is 3 mg / L or less, lead and lead compound content is 0.1 mg / L or less, zinc content is 5 mg / L
The following is stipulated by the Environment Agency (Environment Agency Notification No. 64). However, at present, the development of ionophores for transition metal ions has been delayed, and there is no ion sensor that can measure these ions easily. Although some copper ion selective electrodes are commercially available, they are expensive (about 13
In addition, the measurement concentration range is 6.4 × 10 to 6350 (ppm) ("GENERAL CATALOGUE A-
7000 "p.554) and its sensitivity is low, so it is not something that can monitor the drainage standard value. Therefore, the actual condition is that the standard values for wastewater are implemented by chemical analysis.

Therefore, an object of the invention of this application is to solve the above problems and provide an ionophore having high sensitivity to transition metal ions, an ion sensor containing the ionophore, and an ion exchange membrane. There is.

[0006]

The invention of this application is intended to solve the above-mentioned problems. First, firstly, the following formula (I) is used.

[0007]

[Chemical 3]

(Wherein R ^{1 to} R ⁴ are the same or different and each is a hydrogen atom or an alkyl group, and R ⁵ and R ⁶ are the same or different and are a hydrogen atom, a halogen atom, a carbonyl group, an azo group, or An alkyl group having an electronegative substituent, and R ² and R ⁵ , R ⁴ and R ⁶ , and R ⁵ and R ⁶ may be linked by an alkylene chain which may have a substituent, R ^{a to} R ^d are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, or a carbonyl group, and R ^a and R ^b , R ^c and R ^d may have a substituent. An ionophore for a transition metal ion is provided which is composed of a [14] azaannulene derivative represented by (which may be linked by an alkylene chain).

Secondly, the invention of this application has the following formula (II):

[0010]

[Chemical 4]

(Wherein R ^{1 to} R ⁴ are the same or different and each is a hydrogen atom or an alkyl group, and R ⁵ and R ⁶ are the same or different and are a hydrogen atom, a halogen atom, a carbonyl group, an azo group, or An alkyl group having an electronegative substituent, and R ² and R ⁵ , R ⁴ and R ⁶ , and R ⁵ and R ⁶ may be linked by an alkylene chain which may have a substituent, R ^{a to} R ^d are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, or a carbonyl group, and R ^a and R ^b , R ^c and R ^d may have a substituent. An ionophore for a halogen ion comprising a [14] azaannulene cation represented by (which may be linked by an alkylene chain).

Thirdly, the invention of this application provides a sensitive film for a transition metal ion, which comprises the ionophore of the first invention.

Fourthly, the invention of this application provides a sensitive film for a halogen ion, characterized by containing the ionophore of the second invention.

Further, the invention of this application is, fifthly, an ion sensor characterized by having at least one of the sensitive films, and sixthly, having at least one of the sensitive films. Provided is an ion-selective field effect transistor, and seventhly, an ion-selective field effect transistor having at least one of the sensitive films described above.

Eighth, the invention of this application also provides an ion exchange membrane containing any one of the above ionophores.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The inventors of the present application show that a [14] azaannulene derivative having a structure similar to that of a biomolecule, porphyrin, exhibits a saddle type, unlike metal porphyrin which shows a rigid plane in a metal complex. Paying attention to
The inventors of the present invention have made extensive studies on the ion selectivity and arrived at the present invention.

That is, the ionophore of the invention of this application has the following formula (I):

[0018]

[Chemical 5]

(Wherein R ^{1 to} R ⁴ are the same or different and each is a hydrogen atom or an alkyl group, and R ⁵ and R ⁶ are the same or different and are a hydrogen atom, a halogen atom, a carbonyl group, an azo group, or An alkyl group having an electronegative substituent, and R ² and R ⁵ , R ⁴ and R ⁶ , and R ⁵ and R ⁶ may be linked by an alkylene chain which may have a substituent, R ^{a to} R ^d are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, or a carbonyl group, and R ^a and R ^b , R ^c and R ^d may have a substituent. The present invention provides an ionophore composed of a [14] azaannulene derivative represented by (which may be linked by an alkylene chain).

As described above, the ionophore means an ion transport carrier, and refers to a molecule that forms a complex with certain ions. Various types of such ionophores are known, and are used in ion sensors for measuring the concentration of free ions. However, as described above, it is difficult for the conventionally known ionophore to distinguish ions such as transition metal ions having similar ionic radii and coordination morphologies.

The ionophore composed of the [14] azaannulene derivative of the invention of the present application exhibits high selectivity for transition metal ions, particularly copper ions, as will be shown in Examples described later.

The [14] azaannulene derivative itself represented by the formula (I) is a known compound, but such a compound has a high selectivity for a transition metal ion and has a high utility value as an ionophore. It has not been reported so far, and it was clarified by the inventors' earnest research.

[14] Azaannulene generally means a compound in which a part of carbon atoms of 14-membered ring annurene is substituted with nitrogen atoms. Here, annulene is a monocyclic hydrocarbon, which is a general name for a compound having a structure in which single bonds and double bonds are alternately arranged, that is, a monocyclic conjugated polyene. And [14] azaanurene derivative is [14]
It has another atom or a substituent at the hydrogen atom site on azaannulene.

Io represented by the formula (I) of the invention of this application
R at Nofor¹~ R⁶And R ^a~ R^dIs the above
It is Ri. R¹~ R^FourWhen is an alkyl group, these are methyl
Selected from amongst, ethyl, propyl, butyl and the like. Well
R^Five, R⁶When is a halogen atom, chlorine, bromine,
When iodine or the like is a carbonyl group, -COCH₃,
-COC₆H_Five, -COpC₆H_FourNO₂, -COpC₆H_FourN₂
C₆H_FiveAnd the like is an azo group, -N₂pC₆H_FourNO₂,
-N₂pC₆H_FourOCH₃, -N₂pC₆H_FourCl, etc.
In the case of an alkyl group having an electronegative group, -CH₂
CN, -CH₂CO ₂CH₂CH₃Are exemplified. Furthermore
And R²And R^Five, R^FourAnd R⁶Are linked together
Is, as a connecting chain,-(CH₂)_n-(Where n =
3, 4) are preferably exemplified. Also, R^FiveAnd R⁶Is connected
In the case of₂)_nC
O- (however, n = 3, 5) is preferable. one
One, R ^a~ R^dFor, for a halogen atom, chlorine,
Preferred examples include bromine and iodine, and in the case of an alkyl group
Is a methyl group or an ethyl group, and is an alkoxyl group
Methoxy group, ethoxy group, etc.
In some cases, -COC₆H_FiveEtc. And R^a
And R^b, R^cAnd R^dMay have a substituent linking
As the alkylene chain, benzene and substituted benzene are preferred.
It can be mentioned correctly.

In the invention of this application, the cation of the [14] azaannulene derivative as described above, that is, the following formula (II)

[0026]

[Chemical 6]

(However, R ^{1 to} R ⁴ , R ⁵ and R ⁶ , R ^a
˜R ^d are as described above) also provides an ionophore consisting of the [14] azaanurene cation.

Such ionophore is a counter
NiCl as Nion_Four ^2-And [PF₆ ^-]₂Have
Just do it. According to the research of the inventors, such [14]
The ionophore consisting of the annurene cation is described below.
As shown in the examples, halogen ions, especially
It shows a high selectivity for the iodine ion.

As described above, the ionophore of the invention of this application exhibits a significantly higher ion selectivity than conventionally known ionophores, and is therefore expected to be applied to ion sensors and ion exchange membranes.

Therefore, the invention of this application also provides an ion-sensitive membrane characterized by containing the ionophore as described above. Such ion-sensitive membranes include copper ions, iodine ions, protons, ammonium ions,
Lithium ion, sodium ion, potassium ion,
Ion sensor for magnesium ion, calcium ion, manganese ion, cobalt ion, nickel ion, silver ion, zinc ion, lead ion, cadmium ion, bromine ion, chlorine ion, among others, ion selection for copper ion, iodine ion ion concentration measuring instrument It is useful as an ion-selective film in a conductive electrode or an ion-selective field effect transistor, or as an ion-exchange film for H ⁺ or Cl ⁻ .

In the invention of this application, the form of the sensitive film is not particularly limited. It may be appropriately selected depending on the environment in which it is used. Specifically, known polymers such as polyvinyl chloride, silicone rubber, polyvinylidene chloride, polyurethane, photoresist, and lacquer are used as the film material [14]. ] An azaannulene derivative or [14] azaannulene cation may be supported. For example, the above-mentioned [14] azaannulene derivative or [14] azaannulene cation is mixed with a film material in an arbitrary composition, dissolved in a solvent and cast, or the above-mentioned [14] azaannulene derivative or [14] azaannule derivative. A liquid film can be obtained by mixing a len cation and a film material together with a plasticizer and, if necessary, dissolving or dispersing it in a solvent to form a film. Also, a solid film can be obtained by a known method such as a solvent casting method or baking. In the invention of this application, a liquid membrane that can realize high ion selectivity in applications such as an ion sensor and an ion exchange membrane is preferable.

In obtaining a liquid film, the composition of ionophore / membrane material / plasticizer (or curing agent) is not particularly limited. Preferably, the ionophore is 0.2 to 20 relative to the total amount.
wt%, more preferably 1 to 5 wt% and the film material to 20 to
30 wt%, 50-80 wt% plasticizer, more preferably
60 to 70% by weight (however, the total amount is 100% by weight).

In such a liquid film, the plasticizer is not particularly limited as long as it is generally used in producing a membrane electrode. Specifically, 2-nitrooctyl ether (NPOE), 4-nitrophenyl phenyl ether (NPPE), bis (1-butylpentyl) adipate
(BBPA), dibutyl sebacate (DBS), dibutyl phthalate (DBP), dioctyl phthalate (DOP), dioctyl phenyl phosphate (DOPP), dioctyl sebacate (DO
S), 2-nitrophenyl phenyl ether (NPPE),
Examples thereof include dibenzyl ether (DBE), decanol, 2-nitrophenyl dodecyl ether, 2-fluoro-2′-nitrodiphenyl ether and the like. Of these, NPOE is preferable because the plasticizer itself has good electrode response and high compatibility with the ionophore. Further, in such a liquid film, potassium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate (KTFPB), in order to prevent the incorporation of ions (counterions) other than the target ions into the film, Sodium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate (NaTFPB), potassium tetrakis (4-chlorophenyl) borate (KTpClPB), sodium tetrakis (4-chlorophenyl) borate (NaTpClP)
B), potassium tetrakisphenylborate (KTPB), sodium tetrakisphenylborate (NaTPB), potassium tetraphenylborate (KTPB), sodium tetraphenylborate (NaTPB), tetrakis [3,5-bis (1,1) , 1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] sodium salt such as borate may be added.

The invention of this application further includes an ion sensor (ion-selective electrode, ion-selective field effect transistor, etc.) having the sensitive film as described above.
And an ion exchange membrane is also provided.

The ion sensor has a feature that the concentration of a specific ion in a solution can be quantified, and is used in a wide field such as a concentration monitor of a specific ion and water quality analysis. A preferable example of the ion sensor is an ion selective electrode.

The structure of the ion-selective electrode is not particularly limited and is generally known (eg Katsutaka, Chemical Sensor, Vol. 17,
No.1, 12-21 (2001); Nobuhiko Ishibashi, Akinori Jo, Bunseki, 21
0-218 (1978); Nobuhiko Ishibashi, Bunseki, 209-219 (1976), etc.). Specifically, [reference electrode] / [sample solution] / [ion-selective electrode] = [Ag-AgC
An example is one having a structure of l / 3.3 M KCl / 0.1 M CH ₃ COOLi] / [sample solution] / [sensitive film / internal solution / Ag-AgCl]. Such an ion-selective electrode is a known ion-selective electrode containing the ionophore of the above-mentioned invention of this application as an ionophore. The above [1
By using a sensitive film containing a [4] azaannulene derivative or a [14] azaannulene cation, high transition metal selectivity and halogen ion selectivity, which have hitherto not been realized, are realized. Such an ion-selective electrode can be easily assembled using, for example, a commercially available ion electrode kit (manufactured by DKK, etc.).

An example of the ion-selective electrode of the invention of this application is shown in FIG. For example, when the ion selective electrode (1) has the above-mentioned structure, the sensitive membrane (11) is brought into contact with the internal solution (12). The internal solution (12) is not particularly limited, but examples thereof include an aqueous solution of a metal salt such as an aqueous solution of potassium chloride and an aqueous solution of copper chloride, and a mixed solution of an aqueous solution of potassium chloride and another aqueous solution of a metal salt. The reference electrode may be selected without limitation from known electrodes such as hydrogen electrode, saturated calomel electrode, silver-silver chloride electrode and the like.

The potential difference between the two electrodes may be measured by immersing the ion-selective electrode having the sensitive film as described above together with the reference electrode in the sample solution according to a conventionally known method.

In the ion sensor having the sensitive membrane using the ionophore of the invention of this application, even when a plurality of ions are present in one solution, there is a large difference in the ion selection coefficient between them or there is a difference in the size of the ions. It is possible to measure the ion concentration at the same time for some of the compounds having a different affinity with the [14] azaanurene compound.

The ion sensor of the invention of this application as described above may also be an ion selective effect transistor. Such an ion selective effect transistor is
It can be used as a portable pH meter or the like, and for example, the sensitive film portion of a commercially available product can be replaced with the sensitive film of the present invention. Further, if the ionophore of the invention of this application has a fluorescent property, signals such as quenching and sensitization are emitted by capturing ions. Therefore, the ion sensor of the invention may be an optical sensor. .

Further, the invention of this application also provides an ion exchange membrane containing an ionophore as described above.
Although such an ion exchange membrane may be obtained by any method, it can be easily produced, for example, by binding the ionophore of the present invention to the terminal of a known ion exchange resin. Furthermore, in such an ion exchange membrane, the membrane material and composition are not particularly limited.
By using such an ion exchange membrane, it becomes possible to remove these ions from a solution system containing transition metal ions and halogen ions.

Hereinafter, the invention of this application will be described in more detail with reference to Examples. Needless to say, the invention of this application is not limited to the following examples.

[0043]

Example <Reference example 1> 1,8-Dihydro-5,7,12,14-tetr
amethyldibenzo [b, i] [1,4,8,11] tetraazacyclotetradec
Synthesis of a-4,6,11,13-tetraene derivative (A) [14] The synthesis of an azaannulene derivative was carried out by using nickel ion as a template from a number of synthetic reactions known as general synthetic methods for heterocyclic compounds. It was carried out by utilizing a cyclocondensation reaction in which enamine and imine formation is the reaction type. (1) 5,7,12,14-tetramethyldibenzo [b, i] [1,4,8,11] t
Synthesis of etraazacyclotetradecahexaenato-nikel (II) First, the compound (A) was synthesized using the template effect of nickel.

[0044]

[Chemical 7]

100 mL eggplant-shaped flask was charged with anhydrous methanol
_{50 mL, Ni (OAc) 4} · 4H 2 O 4.9 g (20mmol), acetylacetone 4.0 g (40 mmol) and o- phenylenediamine
4.3 g (40 mmol) was added, and the mixture was refluxed and stirred under N ₂ atmosphere for 2 hours. After the reaction, the mixture was cooled in an ice bath and suction filtered. At this time, it was washed 2-3 times with methanol at 0 ° C. and dried under reduced pressure. It was confirmed by TLC that o-phenylenediamine did not remain, and when it remained, it was separated by silica gel column chromatography using dichloromethane as a solvent.

The product (A) was 1.5 g as a dark green powder.
(Yield 19%) was obtained. The melting point was 254-256 ° C.

The identification results are shown in Table 1.

[0048]

[Table 1]

(2) 1,8-Dihydro-4,11-diimonium-5,7,1
2,14-tetramethyldibenzo [b, i] [1,4,8,11] tetraazacycl
otetradeca-4,6,11,13-tetraene tetrachloronickelate
(II) Synthesis of (B) Next, the nickel central atom of the compound (A) was converted to a tetrachloronickel anion with hydrogen chloride gas to obtain a derivative (B).

[0050]

[Chemical 8]

[14] Azaanurene derivative (A) 1 g (2.5
in absolute ethanol (50 ml) solution of mmol), under stirring, it was introduced HCl gas generated from conc.H ₂ SO ₄ and conc.HCl at room temperature in a fume hood. A precipitate formed and the dark green reaction mixture turned white first. Further, HCl gas was introduced until a turquoise color was obtained, the mixture was cooled in an ice bath, and the precipitate was suction filtered. At that time, it was washed 2-3 times with ethanol at 0 ° C. Since the product changed to white due to the water content in the air, it was quickly placed in a desiccator and dried under reduced pressure.

After drying, the product (B) was obtained as turquoise powder in an amount of 0.94 g (yield 94%) and had a melting point of 236-239 ° C. In addition, storage was performed in a desiccator under reduced pressure.

The identification results are shown in Table 2.

[0054]

[Table 2]

(3) 1,8-dihydro-4,11-diimonium-5,7,1
2,14-tetramethyldibenzo [b, i] [1,4,8,11] tetraazacycl
otetradeca-4,6,11,13-tetraene hexafluorophosphate
Synthesis of (C) Further, the obtained tetrachloronickel anion (B)
The PF ₆ ^- was converted to the anion, to give compound (C).

[0056]

[Chemical 9]

[14] into 9 mL deionized water using a 20 mL receiver
Dissolve the azaannulene derivative (B) and add 0.8 g of NH ₄ PF ₆
A H ₂ O (2.0 mL) solution was slowly added dropwise with stirring. After the precipitate formed, it was stirred for another 15 minutes. Then, it was suction filtered and dried under reduced pressure.

The product was 0.5 g as pale yellow powdery crystals.
(Yield 71%) was obtained and the melting point was 199-200 ° C.

The identification results are shown in Table 3.

[0060]

[Table 3]

(4) 1,8-dihydro-5,7,12,14-tetramethy
ldibenzo [b, i] [1,4,8,11] tetraazacyclotetradeca-4,6,
Synthesis and of 11,13-tetraene, PF ₆ by base ^- anion (C) led to cyclic polyamine (D).

[0062]

[Chemical 10]

14 mL of methanol was placed in a 20 mL Erlenmeyer flask, the [14] azaannulene derivative (C) was suspended, and Et ₃ N was slowly added dropwise with stirring at room temperature. The suspension turned deep green to yellow-orange. After stirring for a further 30 minutes, suction filtration and vacuum drying were performed.

The product was 0.7 g as yellowish brown prism crystals.
(Yield 72%) was obtained and the melting point was 226-229 ° C.

The identification results are shown in Table 4.

[0066]

[Table 4]

<Example 1> [Preparation] (1) Preparation of standard solution The following 22 kinds of 10 ^-1 M standard solutions were prepared according to a known method. Cation standard solution: hydrochloric acid, silver nitrate, copper (II) chloride, lead nitrate, potassium chloride, ammonium chloride, zinc chloride, cobalt (II) chloride, sodium chloride, cadmium nitrate,
Manganese (II) chloride, lithium chloride, magnesium chloride, nickel (II) chloride, calcium chloride anion standard solution: potassium iodide, potassium thiocyanate, sodium perchlorate, potassium nitrate, potassium nitrite, potassium bromide, potassium chloride (2 ) Preparation of electrode chip with ion-sensitive membrane Polyvinyl chloride (PVC, molecular weight about 1,100, Wako Pure Chemical Industries 223-
00255) 29.5 wt% of the membrane material is used as a membrane electrode plasticizer.
-Nitrophenyl octyl ether (o-NPOE, Dojindo Laboratories No15, CAS NO [37682-29-4]) 68.5 wt%,

[0068]

[Chemical 11]

2.0 wt% of the compound (D) represented by was mixed and dissolved in an arbitrary amount of tetrahydrofuran (THF), and the mixture was stirred for an arbitrary time. The obtained solution is used as an ion electrolysis kit (D
It was included in Teflon (registered trademark) paper attached to KK and attached to the groove of the tip of the ion electrode kit.

The application of the THF solution and the drying were repeated any number of times by the casting method, and the production of the PVC sensitive film was completed when the grooves disappeared. [Experiment] FIG. 1 shows a schematic diagram of the measuring apparatus used. After the PVC film (11) was completely dried, the electrode was immersed in an aqueous solution of potassium chloride of about 10 ^-2 M for one day and for conditioning. Next, the same conditioning solution was used as the internal solution (12), and the selection chip was sufficiently filled. The electrode tip (13) was attached to the ion electrode kit (1) while being completely filled with the internal solution (12). A double-junction type silver-silver chloride electrode (21) is used as a reference electrode (2), a 3.3 M saturated potassium chloride solution is used as an internal solution (22) thereof, and a 10 ^-1 M lithium acetate solution is used as an external solution (23) thereof. Was used.

The silver nitrate standard solution (3) was placed in a constant temperature bath (4) at 25 ° C.
While keeping constant, 10 ^-6 to 10 in order from the low concentration solution
^The potential was measured in the concentration range of ^-1 M. The concentration of the solution was determined by the injection method in which the high concentration solution was added to the low concentration solution.

The obtained potential was defined as the potential of copper ion at 25 ° C. From the obtained results, it was confirmed that the copper ion sensor response result was a linear response in a wide range of 10 ^−6.3 M to 10 ^−3.5 M. Therefore, this electrode was shown to be excellent as an ion-selective electrode for copper ions.

The sensor response at 25 ° C. was measured by the same method with respect to the above 15 kinds of 10 ⁻¹ M cation standard solutions. Similarly, the ion selectivity coefficient was also measured while keeping the temperature at 25 ° C. constant in a constant temperature bath.

The results are shown in FIG.

The ion selectivity coefficient was calculated by the single solution method. There is the following relationship between the ion activity a and the concentration C.

A = f.multidot.C (where f is an activity coefficient) At this time, the activity coefficient f is the Debye-Hückel equation Logf = -0.511Z2√μ / (1 + √μ) (where μ Is the ionic strength). Further, the ionic strength μ is obtained by the following formula μ = ½√C _i Z _i ² (where C _i is the concentration of each ion in the solution and Z _i is the charge of each ion in the solution). .

By measuring the potential differences E _N and E _M , respectively, the selectivity coefficient of N ions with respect to M ions can be obtained. Therefore, seeking a potential difference in the 10 ^-1 M standard solution of each ion, the following equation _{^{logk Pot N, M = ZF (}} E M -E N) /2.303RT-
By using logC _N ^{(ZN-Zm) / ZM} , the selectivity coefficient for each ion is calculated.

From the above, it was confirmed that the ion selective electrode using the compound (A) as an ionophore has the highest selectivity for copper ions and can be used as an ion sensor having a transition metal ion sensing ability.

Example 2 Instead of the compound (D), the following formula

[0080]

[Chemical 12]

Using the anion (B) represented by, an electrode tip was prepared in the same manner as in Example 1.

In the same manner as in Example 1 except that the above 7 kinds of anion standard solutions were used in place of the cation standard solution, the sensor response at 25 ° C. was measured for each of the 7 kinds of anion standard solutions.

The results are shown in FIG.

From FIG. 3, it was confirmed that the electrode acts as an ion-selective electrode having a high ion selectivity with respect to iodine ions.

From the above, it was shown that the ion-selective electrode using the compound (A) as an ionophore had the highest selectivity for iodine ions.

Since it is generally said that the anion sensing ability of the ion-selective electrode follows the permeation sequence of the Hofmeister anion, it is considered difficult to develop an ionophore having a sensing ability away from this permutation. . However, from FIG. 3, it was clarified that it can be used as an ion sensor having an anion sensing function different from the conventional one. <Comparative Example 1> Response potential at 25 ° C in the same manner as in Example 1 using a commercially available copper sulfide-silver sulfide solid film type copper ion selective electrode (8006-10C, Lot 001003 manufactured by Horiba Ltd.), The response speed and the potential stability were measured, and the results of the response potential measurement are shown in FIG.

From the comparison of the results of Comparative Example 1 and Example 1, it was confirmed that the ion-selective electrode of Example 1 exhibited a Nernst response and was close to the ideal state. In particular, it was shown that the use of the ion-selective electrode of Example 1 dramatically improved the interfering effect on polymetal ions, which is a problem in ion sensing.

[0088]

As described above in detail, the invention of this application provides an ionophore capable of recognizing copper ions with high accuracy and an ionophore exhibiting excellent sensing for iodine ions. These ionophores are easy to synthesize, and an ion-selective electrode having high sensing ability can be obtained only by mixing with PVC, a membrane solvent, an additive and the like. Further, in the ionophore of the present invention, the property can be appropriately changed by changing the substituent,
High sensing ability can be expected for transition metal ions other than copper.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a potential measuring device used in an example of the invention of this application.

FIG. 2 is a diagram showing ion selectivity coefficients of 15 kinds of 10 ⁻¹ M cation standard solutions obtained by using an ion selective electrode having a [14] azaannulene derivative as an ionophore in an example of the invention of this application. .

FIG. 3 is a diagram showing ion selection coefficients of seven kinds of 10 ⁻¹ M anion standard solutions obtained by using an ion-selective electrode having a [14] azaannulene derivative as an ionophore in an example of the invention of this application. .

FIG. 4 is a diagram showing ion selection coefficients of various cations obtained by using a commercially available copper sulfide-silver sulfide solid membrane type copper ion selective electrode as a comparative example of the invention of this application.

[Explanation of symbols]

1 Ion Selective Electrode, Ion Electrode Kit 11 Sensitive Membrane, PVC Membrane 12 Internal Solution 13 Electrode Tip 14 Silver-Silver Chloride Electrode 2 Reference Electrode 21 Double Junction Type Silver-Silver Chloride Electrode 22 Internal Solution (3.3M KCl) 23 External Solution (0.1M CH ₃ COOLi) 24 Silver-silver chloride electrode 3 Silver nitrate standard solution 4 Constant temperature bath 5 Stirrer

Claims (8)

[Claims] 1. The following formula (I): (However, R ^{1 to} R ⁴ are the same or different and each is a hydrogen atom or an alkyl group, and R ⁵ and R ⁶ are the same or different and are a hydrogen atom, a halogen atom, a carbonyl group, an azo group, or an electronegative substitution. R ² and R ⁵ , R ⁴ and R ⁶ , and R ⁵ and R ⁶ may be linked by an alkylene chain which may have a substituent.
^{a to} R ^d are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, or a carbonyl group, and R ^a and R ^b , R ^c and R ^d are alkylene which may have a substituent. May be linked by chains) [1
4] An ionophore for transition metal ions, characterized by comprising an azaannulene derivative. 2. The following formula (II): (However, R ^{1 to} R ⁴ are the same or different and each is a hydrogen atom or an alkyl group, and R ⁵ and R ⁶ are the same or different and are a hydrogen atom, a halogen atom, a carbonyl group, an azo group, or an electronegative substitution. R ² and R ⁵ , R ⁴ and R ⁶ , and R ⁵ and R ⁶ may be linked by an alkylene chain which may have a substituent.
^{a to} R ^d are the same or different and each is a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, or a carbonyl group, and R ^a and R ^b , R ^c and R ^d are alkylene which may have a substituent. May be linked by chains) [1
4] An ionophore for halogen ions, characterized by comprising an azaanurene cation. 3. A sensitive film for transition metal ions, comprising the ionophore of claim 1. 4. A sensitive film for halogen ions, which contains the ionophore of claim 2. 5. An ion sensor, comprising at least the ion-sensitive film according to claim 3 or 4. 6. An ion-selective electrode comprising at least the ion-sensitive film according to claim 3 or 4. 7. An ion-selective field-effect transistor comprising at least the ion-sensitive film according to claim 3 or 4. 8. An ion exchange membrane containing at least the ionophore according to claim 1 or 2.