JPH05170707A - Fluorescent calix(4)arene derivative - Google Patents

Abstract

PURPOSE:To provide a new fluorescent calix[4]arene derivative suitable for the analysis of metal ion e.g. by a fluorescent probe for the analysis of sodium ion. CONSTITUTION:The calix[4]arene derivative of formula I [A is fluorescent atomic group of formula II to formula V, etc.; B is quenching atomic group of formula VI, formula VII, etc.; X1 to X4 are atomic groups for giving a void- forming part for Na ion, e.g. (CH2)n-COO and (CH2)n-CO; Y and Z are arbitrary atomic groups or functional groups free from lowering action on the function of the calixarene derivative], e.g. the compound of formula VIII. The exemplified compound of formula VIII can be produced by reacting a compound of formula IX with ethyl bromoacetate in acetone solvent in the presence of potassium carbonate, reacting the reaction product with 4-nitrobenzyl bromoacetate in N,N-dimethylformamide solvent in the presence of calcium hydride and finally reacting the product with 1-pyrenylmethyl bromoacetate in acetone solvent in the presence of potassium carbonate.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a calixarene derivative, and more particularly to a fluorescent calix [4] arene derivative suitable for use in the analysis of metal ions.

[0002]

[Prior art and its problems] Analysis of metal ions including alkali metals is carried out for environmental analysis of rivers and seawater, composition analysis of various industrial products such as cement, glass and tableware, or blood test from a clinical point of view. It is important in various fields such as drug monitoring and pharmacokinetics.

[0003] In particular, the analysis of sodium ion concentration has been required more and more because of its relation to diagnosis of diseases and interest in health foods. In addition, the concentration measurement of sodium ion is important from the viewpoint of treating many industrial processes that must control it and its wastewater.

[0004] The main techniques for analysis of metal ions are emission spectroscopy, flame spectroscopy and atomic absorption spectroscopy, but all of them require a relatively large instrument and are troublesome to operate. Therefore, practically, a simple and rapid analysis method using a light or small device is used. They can be divided into an electrochemical analysis method and an optical analysis method, and the typical method of the latter is a fluorescence method.

The fluorescence method analyzes metal ions using a substance (fluorescent probe) that fluoresces by forming a complex with metal ions, and is expected to have high sensitivity and specificity. ing.

[0006] Conventionally used fluorescent probes are
It has a chemical structure in which (1) a part that recognizes and captures a metal ion and (2) a part that emits fluorescence (converts to fluorescence) by being perturbed by this ion trapping exist in a single compound. is doing. Of these, taking fluorescent probes of alkali and alkaline earth metal ions as an example, as the part (1), a crown (cyclic polyether) compound or an azacrown (nitrogen-containing cyclic polyether) compound is used. In particular, the one using the azacrown compound is excellent in terms of sensitivity. Further, as the portion (2), various fluorescent substances or molecular groups can be used, but those having a phenolic hydroxyl group are excellent in terms of sensitivity and selectivity. Some of the typical ones of such fluorescent probes that have been conventionally used are the following chemical compounds 21, 22, and 23.

[0007]

[Chemical 21]

[0008]

[Chemical formula 22]

[0009]

[Chemical formula 23]

However, since the nitrogen atom contained in the fluorescent probe using the azacrown compound as the portion (1) is strongly basic, hydrogen ions are strongly trapped in addition to the alkali metal ion to cause fluorescence. Emit. Therefore, in a sample in which an inorganic acid such as hydrochloric acid or an organic acid such as an acetic acid derivative coexists, the target metal ion cannot be analyzed due to the influence of these acids. Also (2)
A compound having a phenolic hydroxyl group as a portion of fluoresces due to proton dissociation in the basic region. Therefore, in a sample in which an inorganic base such as alkali hydroxide or an organic base such as an amine derivative coexists, the target metal ion cannot be analyzed due to the influence of these bases. Further, in the analysis of a water-containing sample, there is a constraint that it is affected by the hydrogen ion concentration in the sample, that is, the pH. Moreover, these fluorescent probes using crown compounds were not always sufficiently selective for specific metal ions.

[0011]

Means for Solving the Problems and Effects of the Invention The object of the present invention is to eliminate the above-mentioned drawbacks in the prior art and to provide a novel fluorescent substance suitable for the analysis of metal ions, especially sodium ions. To provide.

As a result of repeated studies, the present inventor has found that a calixarene derivative having a specific structure can fulfill the above-mentioned purpose.

The calixarene is a cyclic oligomer in which a plurality of phenol units are bonded by a methylene group. Recently, as the characteristic structure of the oligomer is analyzed,
It has attracted the attention of researchers as the subject of host / guest chemistry research. At the same time, the application of calixarene as a functional material has begun to be studied.

This calixarene is often found in a cup with the side with phenolic OH groups as the lower rim and the opposite side as the upper rim. The present inventor has found that a calixarene having four phenol units, that is, a calix [4] arene derivative in which a specific atomic group is arranged on the bottom edge side of the calix [4] arene is suitable as a fluorescent probe.

Thus, according to the present invention, a cavity forming portion for providing a cavity suitable for trapping a metal ion, a fluorescent atomic group, and the fluorescent atom on the bottom edge side of the calix [4] arene molecule. There is provided a calix [4] arene derivative characterized by the presence of a quenching group for the group.

Such a calixarene derivative is
Due to the structural hardness of the calix [4] arene itself, compared to the conventionally used crown compounds,
It is suitable for capturing metal ions, especially alkali metal ions. Thus, by disposing an appropriate atomic group according to the metal ion to be detected and providing a cavity forming portion on the bottom edge side of the calix [4] arene, a high selectivity for the metal ion can be realized. ..

Further, in the case of a fluorescent probe based on a conventional crown compound, as described above, due to the structure of the compound, there is no choice but to be influenced by the acid / base coexisting in the sample and the pH of the sample. There wasn't. That is,
In the presence of an inorganic acid such as hydrochloric acid and an organic acid such as an acetic acid derivative, and an inorganic base such as an alkali hydroxide and an organic base such as an amine derivative, the objective is to emit fluorescence in response to these acids and bases. Unable to analyze metal ions. In addition, a water-containing sample is affected by the pH of the sample.

On the other hand, the fluorescent compound of the present invention is based on the calix [4] arene so that the entire molecule becomes neutral, so that the cavity forming part for the metal, the fluorescent atomic group and the quenching atom are formed. Since it has a structure in which groups are arranged, it provides a fluorescent probe which is not restricted by coexisting acid / base and pH at the time of use and is selective and sensitive to a specific metal ion.

Examples of atomic groups suitable for providing a cavity forming moiety are those having a functional group such as ether, ester, ketone and amide. A polycyclic fused aromatic compound is preferable as the fluorescent atomic group, and nitrobenzenes are preferable as the quenching atomic group for the fluorescence.

According to a particularly preferred embodiment of the present invention, a calix [4] arene derivative represented by the following general formula 24 is provided. This calix [4] arene derivative is particularly suitable as a fluorescent probe for sodium ion analysis.

[0021]

[Chemical formula 24] However, in the formula, A is a fluorescent atomic group and is selected from the following chemical formulas 25, 26, 27, 28, 29, 30 and 31.

[0022]

[Chemical 25]

[0023]

[Chemical formula 26]

[0024]

[Chemical 27]

[0025]

[Chemical 28]

[0026]

[Chemical 29]

[0027]

[Chemical 30]

[0028]

[Chemical 31]

B is a quenching atomic group for A and is selected from the following chemical formulas 32, 33 and 34.

[0030]

[Chemical 32]

[0031]

[Chemical 33]

[0032]

[Chemical 34]

X ₁ , X ₂ , X ₃ and X ₄ are void-forming portions that provide voids suitable for trapping sodium ions. X < ₁ >, X < ₂ >, X < ₃ > and X < ₄ > may be the same as or different from each other and are selected from the following atomic groups 35 to 38.

[0034]

[Chemical 35]

[0035]

[Chemical 36]

[0036]

[Chemical 37]

Or

[Chemical 38] However, n is 0, 1, 2 or 3.

Y and Z are selected from arbitrary atomic groups or functional groups as long as the fluorescence of the calixarene derivative is not impaired. That is, typical examples of Y include saturated and unsaturated, branched / cyclic and straight chain alkyl groups. The two Y's in the formula are generally the same but may be different. Further, as Z, a saturated branched or straight chain alkyl group generally represented by C _n H _{2n + 1} (n = 0,1,2 ...) And a hydrogen atom can be mentioned. When the calixarene derivative of the formula (1) is used by being bound to another molecule via Z, Z is halogen, alkyl halide, unsaturated alkyl, thiol-containing group and aldehyde-containing aldehyde. Composed of atomic groups.

Particularly preferred as the fluorescent atomic group A is
The following are chemical formulas 39, 40, 41 or 42.

[0040]

[Chemical Formula 39]

[0041]

[Chemical 40]

[0042]

[Chemical 41]

[0043]

[Chemical 42] Further, as the quenching atomic group B, the following chemical formula 43 is particularly preferable.

[0044]

[Chemical 43]

The combination of the fluorescent atomic group and the quenching atomic group is preferable in terms of sensitivity and selectivity. That is, the pyrene and anthracene molecules have a light absorption and fluorescence spectrum in a relatively long wavelength region, are not easily affected by other fluorescent impurities mixed in the sample, and thus are capable of selectively analyzing a target metal ion. Is possible. Moreover, since pyrene and anthracene molecules emit extremely strong fluorescence, the use of these fluorescent atomic groups enables very sensitive analysis. Further, as the quenching atomic group, an atomic group having an appropriate quenching ability is necessary, and it is not suitable if the quenching ability is too strong or too weak. For example, benzene and cyanobenzene are too unsuitable for quenching, and di- and trinitrobenzene are rather too quenching, which may lead to a decrease in sensitivity.
In this respect, mononitrobenzene has an appropriate quenching ability and is suitable for providing a highly sensitive fluorescent probe.

Particularly preferred as X ₁ , X ₂ , X ₃ and X ₄ for providing a cavity forming portion for sodium ions are —CH ₂ —COO—, —CH ₂ —CO— or —CH ₂ —CO.
N <.

The reason is that the size of the voids formed by these atomic groups is well suited to the size of sodium ions, and it is possible to impart high selectivity to other ions having different sizes. Because.

The fluorescent calix [4] arene derivative of the present invention can be synthesized by the following method.

That is, halogenated (CH ₂ ) _n COO-
M, halogenated (CH ₂ ) nCO-M, halogenated compound 44, or halogenated (CH ₂ ) nO-M [M, M ₁ and M ₂ are a fluorescent atomic group, a quenching atomic group or the calixarene thereof. An appropriate combination of arbitrary atomic groups or functional groups that do not impair the fluorescence of the derivative] is sequentially reacted with the calix [4] arene in the presence of a base in a solution.

[0050]

[Chemical 44]

Here, as the base, sodium carbonate, potassium carbonate, sodium hydride, calcium hydride, alkali hydroxide, alkaline earth hydroxide, barium oxide, metal alcoholate or the like is preferably used alone or in combination. As the solvent, any solvent may be used as long as it does not inhibit the intended reaction, and particularly acetone, tetrahydrofuran, N, N-dimethylformamide, acetonitrile and the like are preferably used. Although the reaction temperature varies depending on the reactivity of the target reaction, it is usually from room temperature to the boiling temperature of the solvent. Further, in order to avoid an extra side reaction, it is desirable to carry out the reaction under an inert atmosphere such as nitrogen gas. Further, Z in the general formula 24 may be introduced before this reaction or after this reaction.

A pyrene group was used as the fluorescent atomic group, a nitrobenzene group was used as the quenching atomic group, --CH ₂ COO-- group was used as X ₁ , X ₂ , X ₃ and X ₄ , an ethyl group was used as Y, and a hydrogen atom was used as Z. The synthetic method will be described in more detail with reference to the preferred examples of the calixarene derivative of the present invention. The reaction scheme is shown in FIG.

Compound 2 is obtained by reacting 1 mol of calix [4] arene (compound 1 in the reaction scheme) with ethyl bromoacetate in the presence of 2 molar equivalents of potassium carbonate in an acetone solvent. Then, in a N, N-dimethylformamide solvent, 4-nitrobenzyl bromoacetate is reacted with 4-nitrobenzyl bromoacetate in the presence of 4-molar amount of calcium hydride with respect to 1 mol of compound 2, thereby obtaining compound 3. Furthermore, subsequently, 1-pyrenylmethyl bromoacetate is reacted with 1 mol of compound 3 in the presence of 4 molar equivalents of potassium carbonate in an acetone solvent to obtain the target compound 4, compound 4.

The calixarene derivative of the present invention thus obtained is considered to emit fluorescence by the following mechanism. In the absence of metal ions, the conformation of the calixarene structure is not fixed, and fluorescent groups like pyrene interact catalytically with quenching groups like face-to-face nitrobenzenes. , The fluorescence is quenched. This quenching is based on "photoinduced intramolecular electron transfer". When the metal ion is bound, the conformation is fixed, the fluorescent atomic group and the quenching atomic group are spatially separated from each other, and the interaction disappears, and the function of the fluorescent atomic group is exerted and the fluorescent atomic group is converted into fluorescence. FIG. 2 schematically shows such a mechanism.

Here, the calixarene derivative of the present invention has the flexibility that it can be adjusted to a size capable of selectively binding a specific metal ion due to the inherent hardness of the calixarene structure. In particular, the above-mentioned calix [4] arene derivative of the general formula 24 is extremely selective for Na ⁺ (sodium ion) and serves as a specific fluorescent probe for Na ⁺ . Further, in the fluorescent substance of the present invention based on calix [4] arene, a fluorescent atomic group derived from a polycyclic fused aromatic compound such as pyrene or anthracene, and nitrobenzenes having a strong quenching effect on the atomic group Such quenching atomic groups can be spatially arranged so that effective quenching / fluorescence based on photoinduced electron transfer can be obtained, so that the fluorescence measurement sensitivity is high. That is, a very large fluorescence sensitization is exhibited due to the difference between the quenching state in the absence of the guest (metal ion) and the light emitting state at the time of capturing the guest. Further, in the calixarene structure, the fluorescent substance of the present invention using polycyclic fused aromatic atomic groups and nitrobenzenes is different from conventional fluorescent compounds,
Since it is neutral throughout the molecule, it is not affected by coexisting acid / base substances and pH during use.

The use of a polycyclic fused aromatic atomic group such as pyrene or anthracene as the fluorescent atomic group is chemically stable or has an excitation / fluorescence spectrum in a relatively long wavelength region. Therefore, an excellent fluorescent substance is provided for the reason that it is hardly affected by the coexisting substance and the specificity is high.

There are various modes for using the calixarene derivative of the present invention as a fluorescent probe, and it is not particularly limited. Generally, the calix [4] arene derivative of the present invention is dissolved in a solution containing a metal ion to be measured such as sodium ion, and the fluorescence intensity thereof is measured. It is also possible to dissolve the calix [4] arene derivative of the present invention in a water-insoluble organic solvent, extract metal ions from sample water, and measure the fluorescence intensity of the organic layer. In still another embodiment, the calixarene derivative of the present invention can be mixed with other membrane components to be used as a suitable membrane-like substance, for example, in optrode. Further, the calixarene derivative of the present invention can be used not only as a single compound as it is, but also as a constituent component of another compound, for example, a complex compound chemically bonded to an appropriate polymer chain.

The present invention will be described below with reference to examples in order to further clarify the characteristics of the present invention.

[0059]

【Example】

Example 1 The calixarene derivative 4 of the present invention was prepared according to the flowchart of FIG.

Preparation of Compound 2 : Calix [4] arene (3.5 mmol), ethyl bromoacetate (35 mmol), and potassium carbonate (7.0 mmol) were added in acetone (50 ml) and this solution was added. The mixture was stirred at room temperature under a nitrogen stream for 24 hours. The solution was poured into water (500 ml) and extracted with chloroform (150 ml). The organic layer was separated, washed once with 0.1 M hydrochloric acid, then twice with 1 M aqueous NaCl solution, and dried over magnesium sulfate. The solution was concentrated and then treated with n-hexane to give a white solid. This solid content was further recrystallized from a mixed solvent of chloroform and n-hexane to give pure compound 2 (white crystals,
2.8 mmol) was obtained.

Preparation of Compound 3 : Compound 2 (2.5 mmol), 4-nitrobenzyl bromoacetate (3.8 mmol) and calcium hydride (10 mmol) were added to N,
It was added to N-dimethylformamide (25 ml), and the mixture was stirred at 60 ° C. for 48 hours under a nitrogen stream. After filtering this solution, pour water (300 ml) into chloroform (150 ml).
It was extracted with. The organic layer was separated, washed once with 0.1 M hydrochloric acid, then twice with 1 M aqueous NaCl solution, and dried over magnesium sulfate. After concentrating this solution, it was separated and purified by a column packed with silica gel (Wakogel C-300) using a mixed solvent of toluene and chloroform as a developing solvent to obtain pure compound 3 (white powder, 1.2 mmol). ..

Preparation of Compound 4 : Compound 3 (0.9 mmol), 1-pyrenylmethyl bromoacetate (1.1 mmol) and potassium carbonate (3.6 mmol) were added in acetone (20 ml) and nitrogen was added. The mixture was heated under reflux for 24 hours under an air stream. The solution was poured into water (300 ml) and extracted with chloroform (100 ml). Separate the organic layer to 0.1M
The extract was washed once with hydrochloric acid and then twice with a 1 M NaCl aqueous solution, and then dried over magnesium sulfate. After concentrating this solution, it was separated and purified by a column packed with silica gel (Wakogel C-300) using a mixed solvent of chloroform and n-hexane as a developing solvent to obtain pure compound 4 (white powder, 0.1%).
45 mmol) was obtained. The following analysis was performed on the obtained product. (1) Melting point 73 ° C (2) Infrared absorption spectrum ν (COO) 1757cm ^-1 (3) ¹ H-nuclear magnetic resonance spectrum (The results are attached as Fig. 3) Measurement solvent: Deuterated chloroform Proton resonance frequency: 400MHz Standard Substance: tetramethylsilane FIG. 5 shows the peak positions (ppm) in the NMR spectrum and their assignments along the structural formula. In FIG.
(a) 1.1 to 1.2 ppm and 4.1 to 4.2 ppm, (b) 4.5 ppm, (c) 3.2
~ 3.3ppm and 4.7-4.9ppm, (d) 4.8ppm, (e) 5.0 and
5.1ppm, (f) 5.9ppm, (g) 6.2 ~ 6.5ppm and 6.7 ~ 7.0pp
m, (h) 6.9 ~ 7.0ppm, (i) 7.6 ~ 7.7ppm, (j) 8.0 ~ 8.4pp
m. 2 because the signal of (i) overlapped with the signal of (h)
Chemical shifts were determined by the technique of dimensional (COSY) NMR. In addition, the ratio of the amount of hydrogen obtained by the integration coincided with that of the target product.

(4) Mass spectrometric spectrum m / e = 1062 (M ⁺ ) (5) Elemental analysis

[0064]

[Table 1] From the above measurement results, it was confirmed that the product was a pure target product.

Preparation of Comparative Compound 5 : By the same procedure as in the preparation of Compounds 3 and 4, except that benzyl bromoacetate was used in place of 4-nitrobenzyl acetate in the above-mentioned preparation method of Compound 3. The following compound 5 (Chemical formula 45, white powder, melting point 69 ° C.) was obtained.

[0066]

[Chemical 45]

Preparation of Comparative Compound 6 : Phenol (1.0
1-pyrenylmethyl bromoacetate (0.1 mmol).
9 mmol) and potassium carbonate (2.5 mmol) were added in 20 ml of acetone and stirred at room temperature for 20 hours.
After filtering this solution, acetone was distilled off under reduced pressure, and the residue was dissolved in chloroform (100 ml). The solution was washed once with 0.1 M hydrochloric acid and twice with water, and then dried over magnesium sulfate. After chloroform was distilled off under reduced pressure, it was recrystallized from methanol to give compound 6 (Chemical Formula 4)
6, white needle crystals, melting point 94 ° C.) were obtained.

[0068]

[Chemical 46]

Application Example 1 Approximately 8 ml of diethyl ether was placed in a 10 ml volumetric flask, and a 1 milliM chloroform solution 1 of compound 4 was placed in the flask.
0 μl, 10 μl of a 100 mM methanolic solution of alkali metal (lithium, sodium, potassium or cesium) thiocyanate, ammonium thiocyanate, acetic acid, benzoic acid, methylamine or aniline in 300 ml methanol and 300 μl of acetonitrile are injected, and exactly 10 ml is added with diethyl ether. Diluted to. The fluorescence intensity of these solutions was measured under the following conditions. Conditions: spectrofluorometer ・ ・ ・ ・ Hitachi F-2000 type spectrofluorometer cell ・ ・ ・ Quartz 1cm square cell Excitation wavelength ・ ・ ・ 342nm Fluorescence wavelength ・ ・ ・ 378nm Temperature ・ ・ ・ 25 ℃ The fluorescence intensity of each measurement solution was shown as a relative value with respect to the fluorescence intensity of 1.0 when the metal salt was not added. The results are shown in Table 2. In addition, as a comparative example, Table 2 also shows the results of the same test using compounds 5 and 6 instead of compound 4.

[0070]

[Table 2] ─────────────────────────────────── Example Comparative Example No. Metal salt or acid / base Compound 4 Compound 5 Compound 6 ──────────────────────────────────── 1 1.0 1.0 1.0 2 LiSCN 1.0 1.0 1.0 3 NaSCN 6.3 1.0 1.0 4 KSCN 1.1 1.0 1.0 5 CsSCN 1.1 1.0 1.0 6 NH ₄ SCN 1.0 1.0 1.0 7 CH ₃ COOH 1.0 − − 8 C ₆ H ₅ COOH 1.0 − − 9 CH ₃ NH ₂ 1.0 − − 10 C ₆ H ₅ NH ₂ 1.0 − − 11 NaSCN + CH ₃ COOH 6.3 − − 12 NaSCN + CH ₃ NH ₂ 6.3 − − ─────────────────────── ─────────────

From Tables 1 to 6, it is clear that compounds 5 and 6 do not respond to metal salts at all, whereas compound 4 responds specifically to sodium and is an excellent fluorescent probe for sodium. Is. Further, as is clear from Nos. 7 to 10 in Table 2, Compound 4 does not respond to acids such as acetic acid and bases such as methylamine, and as is clear from Nos. 11 and 12 in Table 2, acetic acid and It is a sodium-specific fluorescent probe that responds to sodium without being affected by these factors even in the presence of methylamine.

Application Example 2 In a 10 ml volumetric flask, about 8 ml of diethyl ether was placed, and 1 ml of the compound 4 in 1 mM chloroform solution 1 was placed in the flask.
0 μl, 0, 1, 10, 20, 40, 6 of NaSCN
10 μl of 0, 80, 100 and 200 mM methanolic solution and 300 μl of acetonitrile were injected and diluted correctly to 10 ml with diethyl ether. The fluorescence intensity of these solutions was measured under the same conditions as in Application Example 1 above. The results are shown in FIG. 4 as the relationship between the fluorescence intensity and the added NaSCN concentration.

As is clear from Application Example 2, the fluorescence intensity of compound 4 increases in proportion to the concentration of sodium ions,
Therefore, the sodium concentration in the test liquid can be analyzed from this fluorescence intensity.

Example 2 An anthracene as a fluorescent atomic group, nitrobenzene as a quenching atomic group, and a calix [4] arene derivative (compound 7) having an ester group and an amide group as a cavity forming part were prepared as in Example 1. Prepared by a similar method. The structural formula of compound 7 is shown below.
Shown in.

[0075]

[Chemical 47]

However, 2-chloro-N, N-diethylacetamide was used in place of ethyl bromoacetate in the preparation of compound 2 in Example 1, and 1 was used in the preparation of compound 4.
9-anthracenemethyl bromoacetate was used instead of -pyrenylmethyl bromoacetate.

Application Example 1 in Example 1 using Compound 7
The fluorescence response to alkali metal ions was examined in the same manner as in. As a result, about 5 times the fluorescence intensity was increased by the addition of sodium, and no response was given to other alkali metal ions.

[Brief description of drawings]

FIG. 1 shows a reaction scheme for synthesizing a calix [4] arene derivative of the present invention.

FIG. 2 shows the mechanism of fluorescence emitted by the calix [4] arene derivative of the present invention.

FIG. 3 shows N of the calix [4] arene derivative of the present invention.
It is an MR spectrum.

FIG. 4 is a graph showing the relationship between fluorescence intensity and NaSCN concentration when the calix [4] arene derivative of the present invention is used.

FIG. 5: N of the calix [4] arene derivative of the present invention
The peak position and its attribution in the MR spectrum are shown along the structural formula.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C09K 11/06 Z 6917-4H G01N 21/78 C 7906-2J 31/00 T 7906-2J 31 / 22 122 9015-2J

Claims (4)

[Claims] 1. A cavity forming part which provides a cavity suitable for trapping a metal ion, a fluorescent atomic group, and a quenching atomic group for the fluorescent atomic group are provided on the bottom edge side of the calix [4] arene molecule. A calix [4] arene derivative characterized by being present. 2. The calix [4] arene derivative according to claim 1, which is represented by the following general formula 1. [Chemical 1] [Wherein A represents a fluorescent atomic group, and
Chemical formula 3, Chemical formula 4, Chemical formula 5, Chemical formula 6, Chemical formula 7, Chemical formula 8 or Chemical formula 2 [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] [Chemical 7] [Chemical 8] B is a quenching atomic group and is represented by the following chemical formula 9, chemical formula 10 or chemical formula 1 below.
Selected from 1, [Chemical 10] [Chemical 11] X ₁ , X ₂ , X ₃ and X ₄ are the same or different atomic groups that provide a cavity forming portion for sodium ions, and are selected from the following Chemical formula 12, Chemical formula 13, Chemical formula 14 or Chemical formula 15 (provided that , N is 0, 1, 2 or 3), and Y and Z are selected from any atomic group or functional group that does not impair the function of the calixarene derivative. ] [Chemical formula 12] [Chemical 13] [Chemical 14] [Chemical 15] 3. The fluorescent atomic group A is represented by the following chemical formula 16 and chemical formula 1.
Selected from the following formulas: [Chemical 17] [Chemical 18] [Chemical 19] The quenching atomic group B is Chemical formula 20, and X ₁ , X ₂ , X ₃ and X ₄ are —CH ₂ —COO—, —CH ₂ —
The calix [4] arene derivative according to claim 2, which is selected from CO- or -CH ₂ -CON <. 4. A fluorescent probe for sodium ion analysis, which comprises the calix [4] arene derivative according to claim 2.