JP6934183B2 - Colorimetric fluorescence detection type anion sensor - Google Patents

Description

The present invention relates to a colorimetric fluorescence detection type anion sensor containing a poly (diphenylacetylene) compound having a unidirectionally wound spiral structure, and a method for identifying anion species and a method for determining anion concentration using the same.

Inorganic anions such as chloride ions and sulfate ions, and anionic substrates having carboxy groups, phosphate groups, etc. are only substances related to life activities in the living body such as energy metabolism, membrane transport, and osmotic pressure regulation inside and outside cells. However, it is known to be one of the important indicators for environmental pollution such as soil pollution, eutrophication of rivers and lakes, and acid rain. Therefore, since such selective detection of anion species leads to the discovery of various diseases and environmental pollution, it is indispensable to develop a simple and highly accurate analysis method for anion species.

Ion chromatography, high performance liquid chromatography (HPLC), gas chromatography (GC) and the like are mainly known as analytical methods for detecting anion species, but all of these require a large-scale device. Therefore, there are problems such as time and cost required for measurement. In recent years, as a simple screening before performing precise instrumental analysis, the development of a sensor that can identify anion species contained in a sample solution by a simple and quick method such as visual inspection by changing the color and fluorescence intensity of the sample solution has attracted attention. Is collecting.

So far, several organic molecules or metal complexes that function as colorimetric or fluorescence detection type anion sensors have been reported.
As a fluorescent sensor capable of detecting anions in an aqueous solution (one or more anions selected from the group consisting of pyrophosphate ions, phosphate ions, citrate ions, halogen ions, and nucleotides), the coumarin moiety is used as a side chain. A metal complex of a cyclic polyamine (cadmium (II) complex) having a cyclic polyamine has been reported (Patent Document 1).
Bicoordination is possible as a sensor capable of colorimetrically detecting perchlorate ion, tetrafluoroborate ion, nitrate ion, hexafluorophosphate ion, trifluoroacetate ion, iodide ion, bromide ion, chloride ion, etc. A metal complex having a specific organic ligand (copper (II) complex) has been reported (Patent Document 2).
A colorimetrically-detecting cyanide ion sensor containing a triarylmethane dye-type complex (zinc, cadmium, or mercury complex) has been reported (Patent Document 3).
It has been reported that caricpyrrole into which a fluorescent probe has been introduced exhibits anion recognition ability (Non-Patent Document 1).
A π-conjugated organic boron polymer has been reported as a colorimetric or fluorescence detection type fluoride ion sensor (Non-Patent Document 2).
As a colorimetric detection type anion sensor, a polyacetylene derivative having a specific chiral amino acid side chain has been reported (Non-Patent Document 3).

However, the above-mentioned known sensors have many problems in their practical use, such as the need for multiple steps in their synthesis, the use of expensive and harmful heavy metals, and the low sensitivity of distinguishing anion species. Was there.

The present inventors have recently described the following equation having a unidirectionally wound helical structure:

[During the ceremony,
^{R 1, R 1 ', R} 2, R 2', R 3, R 3 ', R 4 and ^{R 4'} are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, substituted Indicates a cycloalkyl group which may be present, an alkoxy group which may be substituted, an alkylthio group which may be substituted, a tri-substituted silyl group, a tri-substituted siloxy group or an acyloxy group which may be substituted; Indicates an integer of 10 or more. ]
When an optically active chiralamine compound is condensed and amidated with each carboxy group of the poly (diphenylacetylene) compound represented by, the difference in optical purity and absolute configuration of the optically active chiralamine compound used as a raw material in a specific solvent is obtained. It was reported that the compound exhibited completely different color tone and fluorescence characteristics (Patent Document 4). However, there are no reports of such an amidated poly (diphenylacetylene) compound being used as an anion sensor.

Japanese Unexamined Patent Publication No. 2003-254909 Japanese Unexamined Patent Publication No. 2013-36924 Japanese Unexamined Patent Publication No. 2016-16695 Japanese Unexamined Patent Publication No. 2016-155781

Miyaji, H. et al., Angew. Chem. Int. Ed., 2000, 39, No.10, p.1777-1780 Miyata, M. et al., Polym. J., 2002, 34, No.12, p.967-969 Sakai, R. et al., Macromolecules, 2011, 44, p.4249-4257

Against this background, a practical anion sensor that can be easily synthesized without the use of toxic heavy metals and can quickly and sensitively identify anion species without the use of large measuring instruments. Development is increasingly required.

An object of the present invention is to utilize an amidated optically active poly (diphenylacetylene) compound obtained by condensing a poly (diphenylacetylene) compound having a unidirectionally wound spiral structure with optically active chiral amines having different optical purity. Thus, various types of anion species can be quickly identified and quantified by utilizing visible changes in color tone and / or fluorescence intensity without the use of large equipment, which is convenient and practical. To provide an anion sensor.

As a result of diligent studies under such circumstances, the present inventors have the following formula (I): which has a unidirectionally wound spiral structure.

[During the ceremony,
^{R 1, R 1 ', R} 2, R 2', R 3, R 3 ', R 4 and ^{R 4'} are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, a substituted Indicates a cycloalkyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, a tri-substituted silyl group, a tri-substituted siloxy group or an acyloxy group which may be substituted;
R, R'and R'' are independently hydrogen atoms, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, optionally substituted alkoxycarbonyl groups, and substituted, respectively. Indicates a optionally aryl group or an optionally substituted heteroaryl group;
^{Carbon atoms marked with *} indicate asymmetric carbon atoms; and n represents an integer greater than or equal to 10. However, R, R'and R'' all represent different groups. ]
The optically active poly (diphenylacetylene) compound represented by (hereinafter, also referred to as “compound (I)”) or a salt thereof, or a solvate thereof visually distinguishes various anion species quickly and easily. For the first time, they have found that they are useful as a practical anion sensor that can be quantified, and have completed the present invention.

That is, the present invention is as follows.
[1] Equation (I) having a one-way spiral structure:

[During the ceremony,
^{R 1, R 1 ', R} 2, R 2', R 3, R 3 ', R 4 and ^{R 4'} are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, a substituted Indicates a cycloalkyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, a tri-substituted silyl group, a tri-substituted siloxy group or an acyloxy group which may be substituted;
R, R'and R'' are independently hydrogen atoms, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, optionally substituted alkoxycarbonyl groups, and substituted, respectively. Indicates a optionally aryl group or an optionally substituted heteroaryl group;
^{Carbon atoms marked with *} indicate asymmetric carbon atoms; and n represents an integer greater than or equal to 10. However, R, R'and R'' all represent different groups. ]
A colorimetric fluorescence detection type anion sensor containing an optically active poly (diphenylacetylene) compound represented by (diphenylacetylene), a salt thereof, or a solvate thereof.
[2] In [1] above, R, R'and R'' are independently hydrogen atoms, C _1-4 alkyl groups, C _3-8 cycloalkyl groups or C _6-10 aryl groups, respectively. The specific color fluorescence detection type anion sensor described.
[3] The above-mentioned [1] or [2] for detecting a carboxylate ion, a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a tetraphenylborate ion, and / or a phosphate ion. Colorimetric fluorescence detection type ion sensor.
[4] A step of preparing a sample solution containing the anion to be identified in a solvent containing tetrahydrofuran at ^{a concentration of 10-4} M or more and dividing it into m pieces, m pieces having different optical purity, unidirectional winding. Equation (I) having a helical structure:

[During the ceremony,
^{R 1, R 1 ', R} 2, R 2', R 3, R 3 ', R 4 and ^{R 4'} are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, a substituted Indicates a cycloalkyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, a tri-substituted silyl group, a tri-substituted siloxy group or an acyloxy group which may be substituted;
R, R'and R'' are independently hydrogen atoms, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, optionally substituted alkoxycarbonyl groups, and substituted, respectively. Indicates a optionally aryl group or an optionally substituted heteroaryl group;
^{Carbon atoms marked with *} indicate asymmetric carbon atoms; and n represents an integer greater than or equal to 10. However, R, R'and R'' all represent different groups. ]
In the step of preparing m sensor solutions 1 to m in which each of the optically active poly (diphenylacetylene) compounds represented by (1) is dissolved in a solvent containing tetrahydrofuran, the sensor solution 1 is added to each of the m sample solutions. In the step of preparing m test solutions 1 to m by adding any of 1 to m, each solution containing n'specified anions in a solvent containing tetrahydrofuran at the same concentration as the sample solution. A step of preparing m of each anion species and adding any of the sensor solutions 1 to m to each of them to prepare n'sets of m standard sample solutions 1 to m, and the test solutions 1 to 1. The step of identifying the type of anion to be identified by comparing and observing m and the color tone and / or fluorescence intensity of each of the standard sample solutions 1 to m is included, and m is an integer of 2 to 10. A method for identifying an anion species, wherein n'is an integer of 2 to 7.
[5] The method according to [4] above, wherein m is an integer of 3 to 5.
[6] The method according to the above [4] or [5], wherein the solvent containing tetrahydrofuran is a mixed solvent of tetrahydrofuran, tetrahydrofuran and acetone, or a mixed solvent of tetrahydrofuran and chloroform.
[7] The anion to be identified is selected from the group consisting of carboxylate ion, fluoride ion, chloride ion, bromide ion, iodide ion, tetraphenylborate ion, and phosphate ion [4]. The method according to any one of [6].
[8] A step of dividing a sample solution containing an anion having an unknown concentration in a solvent containing tetrahydrofuran into m'pieces, a formula (I) having a unidirectionally wound spiral structure of m'pieces having different optical purity:

[During the ceremony,
^{R 1, R 1 ', R} 2, R 2', R 3, R 3 ', R 4 and ^{R 4'} are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, a substituted Indicates a cycloalkyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, a tri-substituted silyl group, a tri-substituted siloxy group or an acyloxy group which may be substituted;
R, R'and R'' are independently hydrogen atoms, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, optionally substituted alkoxycarbonyl groups, and substituted, respectively. Indicates a optionally aryl group or an optionally substituted heteroaryl group;
^{Carbon atoms marked with *} indicate asymmetric carbon atoms; and n represents an integer greater than or equal to 10. However, R, R'and R'' all represent different groups. ]
In the step of preparing m'sensor solutions 1 to m'in which each of the optically active poly (diphenylacetylene) compounds represented by is dissolved in a solvent containing tetrahydrofuran, in each of the m'sample solutions, In the step of preparing m'test solutions 1 to m'by adding any of the sensor solutions 1 to m', a solution containing the anion in a solvent containing tetrahydrofuran at different specific concentrations is n. '' Seeds are prepared, each solution of n'' species is divided into m'pieces, and any of the sensor solutions 1 to m'is added to each of the m'pieces of standard sample solutions 1 to m'. By comparing and observing the color tone and / or fluorescence intensity of the test solution 1 to m'and each standard sample solution 1 to m'in the process of preparing the n''set, the anion concentration contained in the sample solution can be determined. A method for determining an anion concentration, which comprises a step of determining, wherein m'is an integer of 2 to 10 and n'' is an integer of 2 to 10.
[9] The method according to [8] above, wherein m'is an integer of 3 to 5, and n'' is an integer of 3 to 5.
[10] The method according to the above [8] or [9], wherein the solvent containing tetrahydrofuran is a mixed solvent of tetrahydrofuran, tetrahydrofuran and acetone, or a mixed solvent of tetrahydrofuran and chloroform.
[11] The method according to any one of [8] to [10] above, wherein the anion is a carboxylate ion, a fluoride ion, a chloride ion, a bromide ion, an iodide ion or a phosphate ion.

Equation (II) with a unidirectionally wound helical structure:

[During the ceremony,
^{R 1, R 1 ', R} 2, R 2', R 3, R 3 ', R 4 and ^{R 4'} are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, a substituted Shows a cycloalkyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, a tri-substituted silyl group, a tri-substituted siloxy group or an acyloxy group which may be substituted; and n. Indicates an integer of 10 or more. ]
The optically active poly (diphenylacetylene) derivative represented by (hereinafter, also referred to as “compound (II)”) or a salt thereof, or each carboxy group of the solvate thereof, and the formula (III) :.

[During the ceremony,
R, R'and R'' are independently hydrogen atoms, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, optionally substituted alkoxycarbonyl groups, and substituted, respectively. Indicates a optionally aryl group or an optionally substituted heteroaryl group;
^{Carbon atoms marked with *} indicate asymmetric carbon atoms; and R, R'and R'' all represent different groups. ]
The compound (I), which can be easily synthesized by condensation (amidation) with an optically active chiralamine compound represented by (hereinafter, also referred to as “compound (III)”), has an absolute arrangement or optical as a raw material. By using the compound (III) having a different purity, it is possible to easily prepare an optically active substance having a different optical purity. The compounds (I) obtained as optically active substances having different optical purity can be instantly visually identifiable in different color tones and / or in response to the type and concentration of the anion by simply mixing with the anion. It shows a change in fluorescence intensity (enhancement of fluorescence intensity, not quenching). Therefore, according to the present invention, the color tone and fluorescence of a mixture of a plurality of compounds (I) having different optical purity and anion-containing solutions having different types and concentrations can be obtained by using an inexpensive camera or smartphone as a standard sample. By performing image analysis (calibration curve created by RGB analysis) after photography, the color tone and / or fluorescence intensity of the test solution of the test subject can be visually observed by comparing it with those of the standard sample. It is possible to easily and sensitively identify and / or quantify the type and concentration of anions contained in the sample solution. Further, according to the present invention, as described above, the optical purity of the compound (I) can be adjusted only by adjusting the optical purity of the compound (III) used as a raw material. Therefore, the compound (I) can be adjusted. It is possible to freely adjust the non-linear responsiveness in the two-detection system of colorimetric and fluorescence using). Therefore, the present invention has extremely high accuracy as compared with a conventional anion sensor using an organic molecule or a metal complex, which requires identification based only on either color tone or fluorescence intensity, and can visually identify and quantify anions. It is possible to provide a practical anion sensor that is possible.

In FIG. 1, compounds (I-1) (R100), compounds (I-1) (S20), compounds (I-1) (S40) and compounds (I-1) (S60) are dissolved in THF, respectively. to: (1.0 × ^{10 -3} M ^{concentration), AcO -, F -,} Cl -, Br - or BPh ₄ ^- THF solution (concentration (as respective tetra n- butylammonium salt): solution 1. A photograph of the appearance of the mixed solution at 25 ° C. after the addition of 0 × 10 ^{-3 M) is shown.} (A) to (d) of FIG. 2 are compounds (I-1) (R100), compounds (I-1) (S20), compounds (I-1) (S40) and compounds (I-1) (S60). ) to a solution dissolved in THF, respectively ^{(1.0 × 10 -3 M),} AcO - , or BPh ₄ ^- THF solution (concentration (as respective tetra n- butylammonium salt): 1.0 × 10 The CD spectrum and absorption spectrum of the mixed solution at 25 ° C. after the addition of ^{−2 M) are shown.} 3A to 3D are compounds (I-1) (R100), compounds (I-1) (S20), compounds (I-1) (S40) and compounds (I-1) (S60). ) Was dissolved in THF (1.0 × 10 ^-3 M), and AcO ⁻ (as a tetra n-butylammonium salt) in a THF solution (concentration: 0, 0.1 × 10 ^{−) having different concentrations. 3} M, 0.5 × 10 ^-3 M, 1.0 × 10 ^-3 M, 5.0 × 10 ^-3 M, 10 × 10 ^-3 M) of the mixed solution at 25 ° C. The change in the absorption spectrum is shown. In FIGS. 4A to 4D, compounds (I-1) (R100), compounds (I-1) (S20), compounds (I-1) (S40) and compounds (I-1) (S60) are shown. ) Into a solution (1.0 × 10 ^-3 M) dissolved in THF, and a THF solution (concentration: 0, 0.1 × 10 ^{− ) of AcO − (as a tetra n-butylammonium salt) having different concentrations. 3} M, 0.5 × 10 ^-3 M, 1.0 × 10 ^-3 M, 5.0 × 10 ^-3 M, 10 × 10 ^-3 M) of the mixed solution at 25 ° C. A photograph of the appearance is shown. In FIG. 5, compounds (I-1) (R100), compounds (I-1) (S20), compounds (I-1) (S40) and compounds (I-1) (S60) are dissolved in THF, respectively. The solution (1.0 × 10 ^-3 M) and the THF solution (concentration: 0, 0.1 × 10 ^-3 M, 0.5 × 10 ^{) of AcO − (as a tetra n-butylammonium salt) having different concentrations. In} the absorption spectrum of a mixed solution of -3 M, 1.0 × 10 ^-3 M, 5.0 × 10 ^-3 M, 10 × 10 ^-3 M) at 25 ° C., 540 nm with ^{respect to the concentration of AcO −.} A plot of changes in absorption intensity in the vicinity is shown. 6 (a) to 6 (d) are compounds (I-1) (R100), compounds (I-1) (S20), compounds (I-1) (S40) and compounds (I-1) (S60). ) and the solution was dissolved in THF, respectively (concentration: in ^{1.0 × 10 -5 M), AcO} - , or BPh ₄ ^- THF solution (concentration (as respective tetra n- butylammonium salt): 1.0 The changes in the fluorescence spectrum at 25 ° C. when the excitation light is set to 298 nm for the mixed solution after adding × 10 ^{-4 M) are shown.} (A) to (d) of FIG. 7 are compounds (I-1) (R100), compounds (I-1) (S20), compounds (I-1) (S40) and compounds (I-1) (S60). ) Was dissolved in THF (concentration: 1.0 × ^10-5 M) and AcO ⁻ (as a tetra n-butylammonium salt) having different concentrations (concentration: 0, 0.1 ×). About the mixed solution after adding 10 ^-3 M, 0.5 × 10 ^-3 M, 1.0 × 10 ^-3 M, 5.0 × 10 ^-3 M, 10 × 10 ^{-3 M), respectively.} The change in the fluorescence spectrum at 25 ° C. when the excitation light is set to 298 nm is shown. In FIG. 8, compounds (I-1) (R100), compounds (I-1) (S20), compounds (I-1) (S40) and compounds (I-1) (S60) are dissolved in THF, respectively. The solution (1.0 × ^10-5 M) and ^{the THF solution (concentration: 0, 0.1 × 10 -3} M, 0.2 × 10 ^{) of AcO −} (as a tetra n-butylammonium salt) having different concentrations. ^-3 M, 0.5 × 10 ^-3 M, 1.0 × 10 ^-3 M, 2.5 × 10 ^-3 M, 5.0 × 10 ^-3 M, 10 × 10 ^-3 M) mixed solution The change in the fluorescence intensity around 298 nm is plotted against the concentration of ^{AcO −} in the fluorescence spectrum at 25 ° C. In FIG. 9, compounds (I-1) (R100), compounds (I-1) (S20), compounds (I-1) (S40) and compounds (I-1) (S60) are dissolved in THF, respectively. solution and (1.0 × ^{10 -5} M), different BPh ₄ concentrations ^- THF solution (concentration (as tetra n- butylammonium ^{salt): 0,0.1 × 10 -3 M,} 0.2 × Mixing of 10 ^-3 M, 0.5 × 10 ^-3 M, 1.0 × 10 ^-3 M, 2.5 × 10 ^-3 M, 5.0 × 10 ^-3 M, 10 × 10 ^{-3 M)} in the fluorescence spectrum at 25 ° C. under solution, BPh ₄ ^- to concentration, shows a plot of the change in fluorescence intensity near 298 nm. In FIGS. 10 (a) and (b) are respectively compounds (I-1) THF solution (1.0 × ^{10 -5} M) of (S20), the concentration of different AcO ^- or BPh ₄ ^- (tetra n- A THF solution of (as a butylammonium salt) (concentration: 0, 0.1 × 10 ^-3 M, 1.0 × 10 ^-3 M, 2.5 × 10 ^-3 M, 10 × 10 ^-3 M) was added. It is a photograph of the appearance showing the degree of fluorescence of the later mixed solution at 25 ° C.

The details of the present invention will be described below.

(Definition)

As used herein, the term "halogen atom" means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the present specification, the "alkyl (group)" means a linear or branched alkyl group having one or more carbon atoms, and is preferably C when there is no particular limitation on the carbon number range. _{It is a 1-20} alkyl group, with a C _1-12 alkyl group being more preferred and a C _1-6 alkyl group being particularly preferred.

In the present specification, "C _1-20 alkyl (group)" means an alkyl group having 1 to 20 carbon atoms in a linear or branched chain, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl. , Se-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, eikosyl and the like.

In the present specification, "C _1-12 alkyl (group)" means an alkyl group having 1 to 12 carbon atoms in a linear or branched chain, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl. , Se-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , Octyl, nonyl, decyl, undecyl, dodecyl and the like.

In the present specification, "C _1-6 alkyl (group)" means an alkyl group having 1 to 6 carbon atoms in a linear or branched chain, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl. , Se-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, etc. Can be mentioned.

In the present specification, the “cycloalkyl (group)” means a cyclic alkyl group, and is preferably a C _3-8 cycloalkyl group unless the carbon number range is particularly limited.

In the present specification, "C _3-8 cycloalkyl (group)" means a cyclic alkyl group having 3 to 8 carbon atoms, and for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like. Can be mentioned. Of these, the C _3-6 cycloalkyl group is preferable.

In the present specification, "alkoxy (group)" means a group in which a linear or branched alkyl group is bonded to an oxygen atom, and the carbon number range is not particularly limited, but C _1-6 alkoxy is preferable. It is a group.

In the present specification, "C _1-6 alkoxy (group)" means an alkoxy group having 1 to 6 carbon atoms in a linear or branched chain, and for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, and the like. Examples thereof include isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy and the like. Of these, the C _1-4 alkoxy group is preferable.

In the present specification, the "alkoxycarbonyl (group)" means a group in which the alkoxy group is bonded to an oxygen atom and a carbonyl group, and the carbon number range is not particularly limited, but C _1-6 alkoxy- is preferable. It is a carbonyl group.

In the present specification, "alkylthio (group)" means a group in which an alkyl group of a linear or branched chain is bonded to a sulfur atom, and the carbon number range is not particularly limited, but C _1-6 alkylthio is preferable. It is a group.

In the present specification, "C _1-6 alkylthio (group)" means an alkylthio group having 1 to 6 carbon atoms in a linear or branched chain, and for example, methylthio, ethylthio, propylthio, isopropylthio, butylthio, and the like. Examples thereof include isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, hexylthio and the like. Of these, a C _1-4 alkylthio group is preferable.

In the present specification, the "alkylsulfonyl (group)" means a group in which a linear or branched alkyl group is bonded to a sulfonyl group, and the carbon number range is not particularly limited, but C _{1-6 is preferable.} It is an alkylsulfonyl group.

In the present specification, the “C _1-6 alkyl sulfonyl (group)” means a group in which an alkyl group having 1 to 6 carbon atoms in a straight chain or a branched chain is bonded to a sulfonyl group. Ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl, isohexylsulfonyl, 1 , 1-Dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl, 2-ethylbutylsulfonyl and the like.

In the present specification, the "arylsulfonyl (group)" means a group in which an aryl group is bonded to a sulfonyl group, and the carbon number range is not particularly limited, but a C _6-10 arylsulfonyl group is preferable.

In the present specification, "C _6-10 aryl sulfonyl (group)" _{means a group in which "C 6-10} aryl group" is bonded to a sulfonyl group, for example, phenylsulfonyl, 1-naphthylsulfonyl, 2-. Examples include naphthylsulfonyl.

In the present specification, the "alkylsulfonyloxy (group)" means a group in which an alkylsulfonyl group is bonded to an oxygen atom, and the carbon number range is not particularly limited, but a C _1-6 alkylsulfonyloxy group is preferable. Is.

In the present specification, "C _1-6 alkyl sulfonyloxy (group)" _{means a group in which a C 1-6} alkyl sulfonyl group is bonded to an oxygen atom, and for example, methyl sulfonyloxy, ethyl sulfonyl oxy, propyl sulfonyl. Oxy, isopropylsulfonyloxy, butylsulfonyloxy and the like can be mentioned.

In the present specification, the "arylsulfonyloxy (group)" means a group in which an arylsulfonyl group is bonded to an oxygen atom, and the carbon number range is not particularly limited, but a C _6-10 arylsulfonyloxy group is preferable. Is.

In the present specification, "C _6-10 arylsulfonyloxy (group)" _{means a group in which a C 6-10} arylsulfonyl group is bonded to an oxygen atom, for example, phenylsulfonyloxy, 1-naphthylsulfonyloxy, and the like. 2-naphthylsulfonyloxy and the like can be mentioned.

In the present specification, the "acyl" means an alkanoyl or an aloyl, and the carbon number range is not particularly limited, but a C _1-7 alkanoyl group or a C _7-11 aloyl is preferable.

In the present specification, the “C _1-7 alkanoyl (group)” is a linear or branched formyl or alkylcarbonyl having 1 to 7 carbon atoms, and is, for example, formyl, acetyl, propionyl, butyryl, and the like. Examples thereof include isobutyryl, pentanoyl, hexanoyl, heptanoyle and the like.

In the present specification, "C _7-11 aloyl (group)" is an arylcarbonyl having 7 to 11 carbon atoms, and examples thereof include benzoyl and the like.

In the present specification, the "acyloxy (group)" means an alkanoyl group or a group in which an aroyl group is bonded to an oxygen atom, and the carbon number range is not particularly limited, but a C _1-7 alkanoyloxy group or a C 1-7 alkanoyloxy group is preferable. C _7-11 Alloyloxy group.

In the present specification, "C _1-7 alkanoyloxy (group)" includes, for example, formyloxy, acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyl. Oxy, tert-butylcarbonyloxy, pentylcarbonyloxy, isopentylcarbonyloxy, neopentylcarbonyloxy, hexylcarbonyloxy and the like can be mentioned.

In the present specification, _{examples of the "C 7-11} aloyloxy (group)" include benzoyloxy, 1-naphthoyloxy, 2-naphthoyloxy and the like.

In the present specification, "aryl (group)" means a monocyclic or polycyclic (condensed) hydrocarbon group exhibiting aromaticity, and specifically, for example, phenyl, 1-naphthyl, and the like. It shows a _C6-14 aryl group such as 2-naphthyl, biphenylyl, 2-anthryl and the like. Of these, a C _6-10 aryl group is preferable.

As used herein, the term "heteroaryl (group)" refers to monocyclic, bicyclic or polycyclic aromatic groups in which at least one ring atom is a heteroatom and the remaining ring atoms are carbon. means. The monocyclic heteroaryl group is, but is not limited to, a cyclic aromatic group having 5 or 6 ring atoms, in which at least one ring atom is a heteroatom and the remaining ring atoms are carbon. Cyclic aromatic groups can be mentioned. The nitrogen atom may be arbitrarily quaternized and the sulfur atom may be optionally oxidized. The heteroaryl groups of the present invention include furan, imidazole, isothiazole, isooxazole, oxazole, oxazole, 1,2,3-oxadiazole, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrolin, thiazole, 1 , 3,4-Thiazole, triazole, and tetrazole are derived from, but are not limited to. A "heteroaryl" is one or two in which the heteroaryl ring is independently selected from the group consisting of an aryl ring, a cycloalkyl ring, a cycloalkenyl ring, and another monocyclic heteroaryl or heterocycloalkyl ring. Bicyclic or tricyclic rings fused to one ring are also included, but not limited to. These bicyclic or tricyclic heteroaryls include benzo [b] furan, benzo [b] thiophene, benzimidazole, imidazole [4,5-c] pyridine, quinazoline, and thieno [2,3-c]. Pyridine, Thieno [3,2-b] Pyridine, Thieno [2,3-b] Pyridine, Indridin, Imidazo [1,2-a] Pyridine, Kinolin, Isoquinolin, Phthalazine, Kinoxalin, Naftilidine, Kinolidine, Indol, Iso Indole, indazole, indolin, benzoxazole, benzopyrazole, benzothiazole, imidazole [1,5-a] pyridine, pyrazolo [1,5-a] pyridine, imidazole [1,2-a] pyrimidine, imidazole [1,2] -C] pyrimidine, imidazo [1,5-a] pyrimidine, imidazo [1,5-c] pyrimidine, pyrolo [2,3-b] pyridine, pyrolo [2,3-c] pyridine, pyrolo [3,2] -C] Pyridine, Pyrrolo [3,2-b] Pyridine, Pyrrolo [2,3-d] pyrimidine, Pyrrolo [3,2-d] pyrimidine, Pyrrolo [2,3-b] Pyrazine, Pyrazolo [1,5 -A] Pyridine, Pyrrolo [1,2-b] pyridazine, Pyrrolo [1,2-c] pyrimidine, Pyrrolo [1,2-a] pyrimidine, Pyrrolo [1,2-a] pyrazine, Triazo [1,5 -A] Pyridine, pteridine, purine, carbazole, aclysine, phenazine, phenothiazene, phenoxazine, 1,2-dihydropyrrolo [3,2,1-hi] indol, pyrido [1,2-a] indol, and 2 ( 1H) -Pyridineone-derived, but not limited to. Suitable heteroaryls (groups) include, for example, those derived from indole (indrill (group)), those derived from imidazole (imidazolyl (group)) and the like.

In the present specification, "C _6-10 aryl (group)" means, for example, phenyl, 1-naphthyl, 2-naphthyl, and phenyl is particularly preferable.

In the present specification, "aralkyl (group)" means a group in which an aryl group is substituted with an alkyl group, and the carbon number range is not particularly limited, but C _7-14 is preferable.

In the present specification, "C _7-14 aralkyl (group)" _{means a group in which "C 1-4} alkyl group" is substituted with "C _6-10 aryl group", for example, benzyl, 1-phenyl. Ethyl, 2-phenylethyl, (naphthyl-1-yl) methyl, (naphthyl-2-yl) methyl, 1- (naphthyl-1-yl) ethyl, 1- (naphthyl-2-yl) ethyl, 2-( Examples thereof include naphthyl-1-yl) ethyl, 2- (naphthyl-2-yl) ethyl and biphenylylmethyl.

As used herein, the term "tri-substituted silyl (group)" means a silyl group substituted with _{three identical or different substituents (eg, C 1-6} alkyl group, C _{6-10 aryl group, etc.). However, the groups include a trialkylsilyl group (preferably a triC 1-6} alkylsilyl group) such as a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tert-butyldimethylsilyl group, and a tert-butyldiphenylsilyl. A group, a triphenylsilyl group and the like are preferable.

As used herein, the term "tri-substituted syroxy (group)" means a group in which a tri-substituted silyl group is bonded to an oxygen atom. _{As the group, a trialkylsiloxy group (preferably a triC 1-6} alkylsiloxy group) such as a trimethylsiloxy group, a triethylsiloxy group, a triisopropylsiloxy group and a tert-butyldimethylsiloxy group is preferable.

As used herein, the term "protected amino group" means an amino group protected by a "protecting group". As the "protective group", for example, a protective group for an amino group described in Protective Groups in Organic Synthesis, John Wiley and Sons (1980) can be used, and for example, a C _1-6 alkyl group, C _7-14. Includes protective groups such as aralkyl group, C _6-10 aryl group, C _1-7 alkanoyl group, C _7-14 aralkyl-carbonyl group, tri C _1-6 alkylsilyl group and the like. The above protecting groups _{may be further substituted with halogen atoms, C 1-6} alkyl groups, C _1-6 alkoxy groups or nitro groups. Specific examples of the protecting group for the amino group include methyl, acetyl, trifluoroacetyl, pivaloyl, tert-butoxycarbonyl, benzyloxycarbonyl and the like.

In the present specification, "may be substituted" means that it may have one or more substituents, and the "substituent" includes (1) halogen atom, (2). ) Nitro, (3) cyano, (4) C _1-6 alkyl, (5) C _3-8 cycloalkyl, (6) C _1-6 alkoxy, (7) C _6-10 aryl, (8) C _{7 -14} Aralkyl, (9) C _1-7 Alkanoyloxy, (10) C _7-11 Aloyloxy, (11) C _1-7 Alkanoyl, (12) C _7-11 Alkyl, (13) Azide, (14) C _1-6 alkylthio, (15) C _6-10 arylthio, (16) _{carbamoyl optionally substituted with C 1-6} alkyl group, (17) C _1-6 alkylsulfonyloxy group, (18) C _{6- Examples thereof include a 10} arylsulfonyloxy group, (19) a tri-C _1-6 alkylsilyl group, and (20) a protected amino group. Among them, halogen atom, C _1-6 alkyl, C _1-6 alkoxy, acetyl, formyl, carbamoyl, azide, trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, dimethylamino, acetylamino, tert-butoxycarbonyl. Amino, benzyloxycarbonylamino and the like are preferable, and a halogen atom is particularly preferable. Further, when a plurality of substituents are present, each substituent may be the same or different.

The above-mentioned substituent may be further substituted with the above-mentioned substituent. The number of substituents is not particularly limited as long as it can be substituted, but is preferably 1 to 5, more preferably 1 to 3. When a plurality of substituents are present, each substituent may be the same or different. The substituents are also further C _1-6 alkyl group, C _3-8 cycloalkyl group, C _6-10 aryl group, C _7-14 aralkyl group, halogen atom, protected amino group, carbamoyl group, cyano group, It may be substituted with a nitro group, an oxo group, or the like. The number of substituents is not particularly limited as long as it can be substituted, but is preferably 1 to 5, more preferably 1 to 3. When a plurality of substituents are present, each substituent may be the same or different.

In the present specification, the "one-way winding spiral structure" may be any spiral structure that is biased to either right-handed or left-handed, and is preferably a completely right-handed or left-handed spiral structure. A compound having a "unidirectionally wound helical structure" exhibits optical activity due only to a biased helical structure, even if the molecule does not have an optically active functional group.

In the present specification, "optical activity" means a property of rotating plane polarized light of light, that is, a state having optical rotation ability. Preferably, it is in an optically pure state.

In the present specification, the "chiral amine compound" means an organic chirality compound having central chirality, axial chirality or surface chirality, and specifically, for example, central chirality (asymmetric center). That is, an organic amine compound represented by the above formula (III) having an asymmetric carbon atom) can be mentioned.

In the present specification, the "optically active chiralamine compound" is a compound having a property of rotating the plane polarization of light, that is, an optical rotation ability, and is an organic having central chirality, axial chirality or planar chirality. Examples include amine compounds. Preferably, a primary amine compound represented by the above formula (III) having one optically pure asymmetric carbon atom (that is, compound (III)) having a molecular weight of 500 or less is used in the present invention. Applicable, for example, 1-phenylethylamine, 1-cyclohexylethylamine, 1- (1-naphthyl) ethylamine, 1- (2-naphthyl) ethylamine, sec -Butylamine, 1-phenyl-2- (p-tolyl) ethylamine, 1- (p-tolyl) ethylamine, 1- (4-methoxyphenyl) ethylamine, carboxy group-protected (esterified) amino acids and other chiralamine compounds Examples include optically active substances. Among them, 1-phenylethylamine, 1-cyclohexylethylamine, 1- (1-naphthyl) ethylamine and 1- (2-naphthyl) ethylamine optically active substances are preferable, and 1-phenylethylamine optically active substances are particularly preferable. The "optically active chiralamine compound" includes not only an optically pure compound but also a compound having a low optical purity (a mixture of both optically pure enantiomers at an appropriate compounding ratio).

In the present specification, "ee" is an abbreviation for enantiomeric excess, and represents the optical purity of a chiralamine compound. “Ee” is calculated by subtracting the amount of substance of the smaller enantiomer from the amount of substance of the larger enantiomer, dividing by the total amount of substance, and multiplying by 100, and is represented by “% ee”.

In the present specification, "optically pure" means a state showing an optical purity of 99% ee or more.

As used herein, the term "enantiomer" means an optically antipode that has a different configuration of all asymmetric carbon atoms in an optically active low molecular weight compound, and is mutually exclusive with the optically active low molecular weight compound. It constitutes a pair of optical isomers that are in a relationship between the right hand and the left hand. Specifically, for example, when the optically active compound is (R)-(+)-1-phenylethylamine, the enantiomer is (S)-(-)-1-phenylethylamine.

As used herein, the term "anion sensor" refers to a "anion sensor" that has a sufficiently strong affinity for a specific anion in a sample solution and changes the color tone and / or fluorescence intensity of the molecule by capturing the anion. Means a sensor molecule that has the ability to cause. In the present specification, identifying and quantifying anions using an "anion sensor" is referred to as "anion sensing".

As used herein, the term "sensor solution" means a solution in which an anion sensor containing the compound (I) of the present invention, a salt thereof, or a solvate thereof is dissolved in a specific solvent.

In the present specification, the "optically active poly (diphenylacetylene) compound represented by the formula (I) having m unidirectionally wound spiral structures having different optical purity" is the above-mentioned compound having a unidirectionally wound spiral structure. As a raw material when synthesizing compound (I) by condensation (amidation) of an optically active chiralamine compound (compound (III)) with each carboxy group of compound (II) or a salt thereof, or a mixture thereof. By using m kinds of optically active chiralamine compounds (compound (III)) having different absolute arrangements and optical purity, it is possible to easily prepare them separately. Compounds (III) with different absolute configurations and optical purity are both enantiomers if the enantiomers of compound (III) are available in optically pure form (ie, (R) and (S)). It is possible to prepare the optically active chiralamine compounds having different optical purity only by adjusting the compounding ratio of the body. For example, in order to obtain a 60% ee (S) isomer optically active chiralamine compound, an optically pure (S) isomer and an optically pure (R) isomer are mixed at a blending ratio of 80:20. do it.

In the present specification, "colorimetric detection" means that an anion species to be tested (identified) is changed into a coloring substance, and the degree of coloring is visually or colorimetrically measured by absorbance using visible light of an appropriate wavelength. It is a method of quantification. The "specific color detection" in the present invention also includes a detection method using a visible color change and a detection method using an ultraviolet / visible absorption spectrum.

In the present specification, "fluorescence detection" is a method of changing an anion species to be tested (identified) into a fluorescent substance and quantifying the change in fluorescence intensity by visual inspection or fluorescence spectrum measurement.

In the present specification, "RGB" is a kind of color expression method, and is a kind of additive mixing that reproduces a wide range of colors by mixing three primary colors of red (Red), green (Green), and blue (Blue). be. RGB is an acronym for the three primary colors. It is used for image reproduction with digital cameras and the like.

In the present specification, "non-linear responsiveness" means that the concentration of the anion to be tested (identified) is proportional to the change in the absorbance and / or the fluorescence intensity of the specific absorption region of the anion sensor molecule that has captured the anion. This means that there is no such substance (see FIGS. 5 and 8 described later). Since it is possible to increase the amount of change in absorbance and / or fluorescence intensity in a specific anion concentration region as compared with the case of linear response (when there is a proportional relationship), in order to improve the accuracy of anion sensing. Used as a technique.
In general, it is extremely difficult to predict from the molecular structure whether or not an anion sensor molecule exhibits non-linear responsiveness in a specific anion concentration region. As far as the present inventors know, there are no reported examples of anion sensors capable of precisely controlling non-linear responsiveness.

In the present specification, the "solvent containing tetrahydrofuran" is not particularly limited as long as it is a solvent containing tetrahydrofuran, but is preferably a mixed solvent of tetrahydrofuran, tetrahydrofuran and acetone, or a mixed solvent of tetrahydrofuran and chloroform, more preferably. Is tetrahydrofuran. The solvent containing tetrahydrofuran also includes a mixture of water, alcohol (eg, methanol, ethanol, etc.) in an appropriate amount depending on the solubility of the sensor molecule (compound (I)) or anionic species (metal salt, etc.). Will be done.

(Colorimetric fluorescence detection type anion sensor of the present invention)
The colorimetric fluorescence detection type anion sensor of the present invention has the following formula (I), which has a spiral structure wound in one direction around the compound (I), that is, the polymer main chain.

[During the ceremony,
^{R 1, R 1 ', R} 2, R 2', R 3, R 3 ', R 4 and ^{R 4'} are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, a substituted Indicates a cycloalkyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, a tri-substituted silyl group, a tri-substituted siloxy group or an acyloxy group which may be substituted;
R, R'and R'' are independently hydrogen atoms, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, optionally substituted alkoxycarbonyl groups, and substituted, respectively. Indicates a optionally aryl group or an optionally substituted heteroaryl group;
^{Carbon atoms marked with *} indicate asymmetric carbon atoms; and n represents an integer greater than or equal to 10. However, R, R'and R'' all represent different groups. ]
It is characterized by containing an optically active poly (diphenylacetylene) compound represented by (diphenylacetylene), a salt thereof, or a solvate thereof.

The salt of compound (I) may be any salt as long as it forms a salt with compound (I), for example, a salt with an inorganic acid, a salt with an organic acid, a salt with an inorganic base, and an organic base. Salts, salts with amino acids, etc.
Examples of the salt with the inorganic acid include salts with hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrobromic acid and the like.
As salts with organic acids, for example, oxalic acid, maleic acid, citric acid, fumaric acid, lactic acid, malic acid, succinic acid, tartrate acid, acetic acid, trifluoroacetic acid, gluconic acid, ascorbic acid, methanesulfonic acid, benzenesulfonic acid. , P-Toluene sulfonic acid and the like.
Examples of the salt with the inorganic base include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt and the like.
Examples of salts with organic bases include methylamine, diethylamine, trimethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, tris (hydroxymethyl) methylamine, dicyclohexylamine, N, N'-dibenzylethylenediamine, and guanidine. , Pyridine, picolin, choline, cinconin, meglumine and the like.
Examples of the salt with the amino acid include salts with lysine, arginine, aspartic acid, glutamic acid and the like.

The solvate of compound (I) or a salt thereof is a solvate of compound (I) or a salt thereof in which a molecule of a solvent is coordinated, and hydrates are also included. For example, a hydrate of compound (I) or a salt thereof, a Japanese ethanol product, a Japanese dimethyl sulfoxide product, and the like can be mentioned.

Hereinafter, each group of compound (I) will be described.

^{R 1, R 1 ', R} 2, R 2', R 3, R 3 ', R 4 and ^{R 4'} are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, substituted It represents a cycloalkyl group which may be present, an alkoxy group which may be substituted, an alkylthio group which may be substituted, a tri-substituted silyl group, a tri-substituted siloxy group or an acyloxy group which may be substituted.

^{R 1, R 1 ', R} 2, R 2', R 3, R 3 ', R 4 and ^{R 4'} are preferably each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group , Alkoxy group, trialkylsilyl group or trialkylsiloxy group which may be substituted, more preferably C _1-6 alkyl which may be independently substituted with hydrogen atom, halogen atom and halogen atom, respectively. _{A group, a C 1-6} alkoxy group which may be substituted with a halogen atom, a tri C _1-6 alkylsilyl group or a tri C _1-6 alkylsiloxy group, and among them, a hydrogen atom or a halogen atom is particularly preferable.

^{R 1, R 1 ', R} 2, R 2', R 3, R 3 ', R 4 and ^{R 4',} preferably, ^{R 1} and ^{R 1} ', ^{R 2} and ^{R 2', R 3} and R ³ 'and ^{R 4} and ^{R 4'} are each the same group. ^{R 1, R 1 ', R} 2, R 2', R 3, R 3 all ', ^{R 4} and ^{R 4'} may be the same group.

R, R'and R'' are independently hydrogen atoms, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, optionally substituted alkoxycarbonyl groups, and substituted, respectively. It represents an aryl group which may be substituted or a heteroaryl group which may be substituted, and R, R'and R'' all represent different groups.

R, R'and R'' are preferably independently independent hydrogen atoms, C _1-4 alkyl groups (eg, methyl, ethyl), C _3-8 cycloalkyl groups (eg, cyclohexyl) or C _{6 respectively. It is a -10} aryl group (eg, phenyl, naphthyl) and all of R, R'and R'are different groups. R, R'and R'' are more preferably independently at the hydrogen atom, C _1-4 alkyl group (eg, methyl, ethyl) or C _6-10 aryl group (eg, phenyl, naphthyl), respectively. Yes, and all of R, R'and R'' are different groups.

n is an integer of 10 or more, preferably an integer of 100 or more and 10000 or less.

As the compound (I), the following compounds are suitable.
[Compound (IA)]
^{R 1, R 1 ', R} 2, R 2', R 3, R 3 is ', ^{R 4} and ^{R 4',} independently hydrogen atom, a halogen atom, an optionally substituted alkyl group, substituted which may be an alkoxy group, a trialkylsilyl group or trialkylsiloxy, and ^{R 1} and ^{R 1} ', ^{R 2} and ^{R 2', R 3} is a ^{R 3} 'and ^{R 4} and ^{R 4',} respectively It is the same group;
R, R'and R'' are independently hydrogen atoms, C _1-4 alkyl groups (eg, methyl, ethyl), C _3-8 cycloalkyl groups (eg, cyclohexyl) or C _6-10 aryl, respectively. Compound (I) which is a group (eg, phenyl, naphthyl) and all of R, R'and R'' are different groups; and n is an integer greater than or equal to 10.

A more suitable compound (I) is the following compound.
[Compound (IB)]
^{R 1, R 1 ', R} 2, R 2', R 3, R 3 ', R 4 and ^{R 4'} are each independently a hydrogen atom, a halogen atom, _{C 1} optionally substituted by a halogen atom _{A -6} alkyl group, a C _1-6 alkoxy group optionally substituted with a halogen atom, a tri C _1-6 alkylsilyl group or a tri C _1-6 alkylsiloxy group, and R ¹ and R ¹ ', R. ² and ^{R 2} ', ^{R 3} and ^{R 3'} and ^{R 4} and ^{R 4} 'are, are each the same group;
R, R'and R'' are independently hydrogen atoms, C _1-4 alkyl groups (eg, methyl, ethyl) or C _6-10 aryl groups (eg, phenyl, naphthyl) and R, respectively. , R'and R'' are all different groups; and compound (I), where n is an integer greater than or equal to 10 and less than 10000.

A more suitable compound (I) is the following compound.
[Compound (IC)]
^{R 1, R 1 ', R} 2, R 2', R 3, R 3 ', R 4 and ^{R 4'} are each independently a hydrogen atom or a halogen atom, and ^{R 1} and ^{R 1} ', R ² and ^{R 2} ', ^{R 3} and ^{R 3'} and ^{R 4} and ^{R 4} 'are, are each the same group;
R, R'and R'' are independently hydrogen atoms, C _1-4 alkyl groups (eg, methyl, ethyl) or C _6-10 aryl groups (eg, phenyl, naphthyl) and R, respectively. , R'and R'' are all different groups; and compound (I), where n is an integer greater than or equal to 10 and less than 10000.

The number average degree of polymerization of compound (I) (n) (average number of diphenylethylene units contained in one molecule) is 10 or more, preferably 100 or more, and there is no particular upper limit, but it is 10,000 or less. Is desirable in terms of ease of handling.

Further, Compound (I), isotopes ^{(e.g., 3 H, 2 H (D} ), 14 C, 18 O , etc.) may be labeled with.

The colorimetric fluorescence detection type anion sensor of the present invention may contain compound (I) or a salt thereof, or a solvate thereof, and may be composed of compound (I) alone. Further, as long as the effect of the present invention is not impaired, it may be used in combination with other reagents or the like that can be used for detecting anions.

(Synthesis of compound (I))
The method for producing the compound (I) is not particularly limited, but according to the method known per se or a method similar thereto described in Patent Document 4 (Japanese Unexamined Patent Publication No. 2016-155781) described above, the compound ( It can be produced by a method of reacting II) with compound (III).

(Method for identifying anion species by the anion sensor (Compound (I)) of the present invention)

Compound (I) adjusts the color tone and / or fluorescence intensity of the solution by a non-covalent interaction between the optically active chiralamide site on its side chain and a specific anion to be tested (identified) in the solution. , The type of anion to be tested can be identified because it can be characteristically changed according to the type of anion. Specifically, during the non-covalent interaction, the particular anion responds to slight differences in the absolute configuration and optical purity of the optically active chiralamide site on the side chain of compound (I). Significant changes are observed in the color tone and / or fluorescence intensity of the mixed solution of compound (I) and a particular anion. Then, a remarkable change in the color tone and / or fluorescence intensity of the mixed solution is observed with a camera, a smartphone, or visually, and a mixed solution of a known and specified anion and the compound (I) having the same concentration (standard sample solution). By comparing with the color tone and / or the fluorescence intensity of, it is possible to accurately identify the type of anion to be identified.

The method for identifying the type of anion to be tested (identified) in the present invention is not particularly limited, and includes, for example, the following steps.

(Step 1) A step of preparing a sample solution containing the anion to be identified in a solvent containing tetrahydrofuran at ^{a concentration of 10-4} M or more, dividing the sample solution into m pieces, and preparing sample solutions 1 to m.
(Step 2) A step of preparing m sensor solutions 1 to m in which each of m compounds (I) having different optical purity is dissolved in a solvent containing tetrahydrofuran.
(Step 3) A step of preparing m test solutions 1 to m by adding any of the sensor solutions 1 to m prepared in step 2 to each of the sample solutions 1 to m prepared in step 1.
(Step 4) Each anion type (n'type anion) contains a solution containing n'type of specified anion (type of specified anion) in a solvent containing tetrahydrofuran at the same concentration as the sample solution. A step of preparing n'sets of m standard sample solutions 1 to m by adding any of the sensor solutions 1 to m to each of the m pieces.
(Step 4') A step of creating a calibration curve from the absorbance and / or fluorescence intensity of each standard sample solution prepared in step 4 or the RGB analysis result of a photographic image, and (step 5) the test solution 1 prepared in step 3. Color tone and / or fluorescence intensity of ~ m, color tone and / or fluorescence intensity of each standard sample solution (absorbance and / or fluorescence intensity of each standard sample solution, or RGB analysis of photographic image) by visual inspection or RGB analysis of photographic image. The process of identifying the type of anion to be identified by comparing and observing it with the calibration curve created from the results.
including.

The m represents an integer of 2 to 10, and m is preferably an integer of 3 to 5. Further, n'indicates an integer of 2 to 7, and n'is preferably an integer of 2 to 5.

The anion to be identified is not particularly limited, but the anion selected from the group consisting of a carboxylate ion, a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a tetraphenylborate ion, and a phosphate ion can be selected. It can be identified with good sensitivity. Among them, acetate ion, fluoride ion, chloride ion, or bromide ion can be preferably identified because the change in color tone and fluorescence intensity is remarkable. Further, tetraphenylborate ion is distinguished by the fact that even when mixed with compound (I), no change is observed in either the color tone or the fluorescence intensity of the solution, and the tetraphenylborate ion exhibits characteristics different from those of other anion species. It is possible.
In the method for identifying anion species of the present invention, since it is possible to freely adjust the color tone and fluorescence intensity of the test solution by finely adjusting the optical purity of compound (I), an appropriate sensor molecule ( By selecting the compound (I), it is possible to identify not only one type of anion but also a plurality of types of anions contained in the test solution.

The anion to be identified can be used by dissolving it in a solvent containing tetrahydrofuran in the form of a salt. The type of salt is not particularly limited as long as it is soluble in the solvent, but an alkali metal salt (eg, sodium salt, potassium salt, etc.), a quaternary ammonium salt (eg, ammonium salt, tetraalkylammonium salt, etc.), etc. Is preferable, a quaternary ammonium salt is more preferable, and a tetraalkylammonium salt (eg, tetra n-butylammonium salt) is particularly preferable.

The solvent containing tetrahydrofuran is not particularly limited, but is preferably tetrahydrofuran, a mixed solvent of tetrahydrofuran and acetone, or a mixed solvent of tetrahydrofuran and chloroform, and more preferably tetrahydrofuran. The mixing ratio in the mixed solvent can be appropriately set within a range in which the sample can be dissolved. Further, depending on the solubility of the sample, water, alcohol (eg, methanol, ethanol, etc.) and the like can be further mixed in an appropriate amount.

As described above, the m compounds (I) having different optical purity are those having different absolute configurations and optical purity of the optically active chiralamine compound (compound (III)) as a raw material in the synthesis of the compound (I). It can be easily synthesized by using it in a condensation reaction with compound (II). As described above, the optically active chiralamine compounds (compound (III)) having different absolute arrangements and optical puritys are optically pure forms (that is, (R) and (S)) of both enantiomers of compound (III). ), It is possible to prepare the optically active chiralamine compounds having different optical purity only by adjusting the compounding ratio of both enantiomers.

In the method for identifying anion species of the present invention, low-concentration (1.0 × 10 ^-4 M or more) anion species can be visually identified. Further, most of the known anion sensors tend to quench the fluorescence by the interaction with the anion species, whereas the compound (I) of the present invention has a non-covalent interaction (molecular recognition) with the anion species. ) Makes it possible to identify anion species with high accuracy in that the fluorescence intensity is enhanced.

Further, the method for identifying anion species of the present invention is not only a method by visual inspection or RGB analysis of a photographic image, but also a combination with data of an ultraviolet / visible absorption spectrum, a circular dichroism (CD) spectrum, and / or a fluorescence spectrum. And the method of identification is also included.

As another aspect of the method for identifying anion species of the present invention, each of m compounds (I) having different optical purity is dissolved in a solvent (not particularly limited as long as it is a solvent that dissolves compound (I)). A sensor adsorption test paper was prepared by immersing the test paper in m of the prepared sensor solutions 1 to m, sufficiently adsorbing the compound (I) on the test paper, and then drying the test paper. The anion species can also be identified by using it instead of the sensor solution of the identification method (step 3) and observing changes in the color tone and fluorescence intensity of the sensor adsorption test paper. Specifically, the sensor adsorption test paper is dipped in each of the sample solutions 1 to m, or each of the sample solutions 1 to m is dropped or sprayed onto the sensor adsorption test paper on the test paper. The anion species can be identified by observing changes in color tone and fluorescence intensity in comparison with the test results of a standard sample prepared in advance.

The test paper may be any as long as it can adsorb compound (I), and examples thereof include filter paper, resin, cloth, and the like, but filter paper is preferable.

The present invention can provide a highly practical anion sensing method that can also be used as a test strip.

(Method for quantifying colorimetric fluorescence of anions of unknown concentration by the anion sensor of the present invention (Compound (I)))

Compound (I) adjusts the color tone and / or fluorescence intensity of the solution in solution by a non-covalent interaction between the optically active chiralamide site on its side chain and a specific anion to be tested. It can be characteristically changed according to the concentration of the anion of. Specifically, during the non-covalent interaction, the specific anion, depending on its concentration in solution, has the absolute configuration and optical purity of the optically active chiralamide moiety on the side chain of compound (I). In response to slight differences in, significant changes can occur in the color tone of the solution and / or the fluorescence intensity (particularly the color tone of the solution). Therefore, the concentration (or concentration range) of the anion of the test subject whose concentration is unknown can be easily determined.

The colorimetric fluorescence quantification method (preferably, the colorimetric quantification method) of the anion of the present invention is not particularly limited, and includes, for example, the following steps.

(Step 1) A step of preparing a sample solution 1 to m'by dividing a sample solution containing an anion having an unknown concentration in a solvent containing tetrahydrofuran into m'pieces.
(Step 2) A step of preparing m'sensor solutions 1 to m'by dissolving each of m'compounds (I) having different optical purity in a solvent containing tetrahydrofuran.
(Step 3) Add any of the sensor solutions 1 to m'prepared in step 2 to each of the sample solutions 1 to m'prepared in step 1 to prepare m'test solutions 1 to m'. Process,
(Step 4) A solution containing the anion of the test target at a specific concentration different from each other in a solvent containing tetrahydrofuran was prepared, and each solution of the n'' species was divided into m'types, and each of them was prepared. In the step of adding any of the sensor solutions 1 to m'prepared in step 2 to prepare an n'' set of m'standard sample solutions 1 to m'.
(Step 4') A step of preparing a calibration curve from the absorbance and / or fluorescence intensity of each standard sample solution prepared in step 4 or the RGB analysis result of a photographic image, and (step 5) the test solution 1 prepared in step 3. The color tone and / or the absorbance of ~ m'was determined by visual inspection or RGB analysis of the photographic image, and the color tone and / or the fluorescence intensity of each standard sample solution obtained in step 4 (or each standard sample obtained in step 4'). A step of determining the concentration (or concentration range) of an anion of a test subject by comparative observation with the absorbance and / or fluorescence intensity of a solution or a calibration curve created from the RGB analysis result of a photographic image.
including.

The m'represents an integer of 2 to 10, and m'is preferably an integer of 3 to 5. Further, the n ″ indicates an integer of 2 to 10, and n ″ is preferably an integer of 3 to 5.

The anion to be tested is not particularly limited, and examples thereof include a carboxylate ion, a fluoride ion, a chloride ion, a bromide ion, an iodide ion, and a phosphate ion. Among them, acetate ion, fluoride ion, chloride ion, or bromide ion, in which the change in color tone and fluorescence intensity with respect to the change in concentration is remarkable, is preferable, and acetate ion is particularly preferable.

The anion to be identified can be used by dissolving it in a solvent containing tetrahydrofuran in the form of a salt. The type of salt is not particularly limited as long as it is soluble in the solvent, but an alkali metal salt (eg, sodium salt, potassium salt, etc.), a quaternary ammonium salt (eg, ammonium salt, tetraalkylammonium salt, etc.), etc. Is preferable, a quaternary ammonium salt is more preferable, and a tetraalkylammonium salt (eg, tetra n-butylammonium salt) is particularly preferable.

The solvent containing tetrahydrofuran is not particularly limited, but is preferably tetrahydrofuran, a mixed solvent of tetrahydrofuran and acetone, or a mixed solvent of tetrahydrofuran and chloroform, and more preferably tetrahydrofuran. The mixing ratio in the mixed solvent can be appropriately set within a range in which the sample can be dissolved. Further, depending on the solubility of the sample, water, alcohol (eg, methanol, ethanol, etc.) and the like can be further mixed in an appropriate amount.

In the colorimetric fluorescence quantification method of anions of the present invention, the concentration range of anions in the test solution can be easily determined by visually observing the change in the color tone of the test solution.

Further, the colorimetric fluorescence quantification method of the anion of the present invention includes not only a method by visual or RGB analysis of a photographic image but also data of an ultraviolet / visible absorption spectrum, a circular dichroism (CD) spectrum, and / or a fluorescence spectrum. Also included is a method of quantifying anions in combination with.

As another aspect of the method for quantifying specific color fluorescence of anions of the present invention, each of m'compounds (I) having different optical purity is used as a solvent (there is no particular limitation as long as it is a solvent that dissolves compound (I)). The test paper was dipped in m'sensor solutions 1 to m'dissolved in the test paper, and the compound (I) was sufficiently adsorbed on the test paper and then dried to prepare a sensor adsorption test paper. Paper is used in place of the sensor solution of the specific color fluorescence quantification method (step 3), and the concentration range of the anion to be tested is determined by observing changes in the color tone and fluorescence intensity of the sensor adsorption test paper. You can also do it. Specifically, the test is carried out by immersing the sensor adsorption test paper in each of the sample solutions 1 to m', or dropping or spraying each of the sample solutions 1 to m'on the sensor adsorption test paper. The concentration (or concentration range) of the anion to be tested can be determined by comparing and observing changes in color tone and fluorescence intensity on paper with the test results of a standard sample prepared in advance.

The test paper may be any as long as it can adsorb compound (I), and examples thereof include filter paper, resin, cloth, and the like, but filter paper is preferable.

The colorimetric fluorescence quantification method of anions of the present invention can provide a highly practical anion quantification method that can also be used as a test paper.

The anion sensor of the present invention has the following excellent features as compared with conventionally known sensor molecules.
<1> By using the compound (III) obtained by using both enantiomers in optically pure forms (that is, the (R) form and the (S) form) as raw materials, the compounds (I) having different optical purity are used. ) Can be easily and quickly synthesized.
<2> Compound (I) is a two-detection anion sensor capable of not only colorimetric detection but also more sensitive fluorescence detection.
<3> In fluorescence detection, compound (I) exhibits an enhancement behavior of fluorescence intensity instead of the quenching behavior generally observed due to non-covalent interaction with a specific anion, so that anions can be identified. , It can be performed more easily and accurately than the conventional method.
<4> Compound (I) has a non-linear response to changes in color tone and / or fluorescence intensity with respect to the concentration of anions in the test subject by simply adjusting the absolute configuration and optical purity of the optically active chiralamide site on its side chain. It is possible to freely adjust the sex. Such non-linear responsiveness is a property that is not known in conventional anion sensors, and due to this property, if compound (I) of appropriate optical purity is used as a sensor, the type of anion to be tested can be visually observed. It is possible to identify and determine the concentration (concentration range) of anions contained in the solution easily and accurately.

Hereinafter, the present invention will be described in detail with reference to Examples and Test Examples, but the present invention is not limited thereto.

^{1 The 1} H-NMR spectrum was measured using JMM-ECA 500 manufactured by JEOL Ltd., using tetramethylsilane as an internal standard, and using deuterated chloroform or deuterated dimethyl sulfoxide / heavy water as a solvent. ^{Data for 1 1} H-NMR are reported as chemical shift (δppm), multiplicity (br = broad), integration and allocation.
Average molecular weight is converted to polystyrene by gel permeation chromatography (JASCO High Performance Liquid Chromatography Pump PU-2080, JASCO Ultraviolet Visible Detector UV-970, JASCO Column Oven CO-1560, JASCO Column KF-805L) Calculated in.
Circular dichroism (CD) measurement is JASCO's circular dichroism dispersometer J-725, JASCO's ultraviolet visible spectrophotometer V-650 is used for ultraviolet visible absorption measurement, and JASCO's spectroscopic fluorescence photometer is used for fluorescence measurement. This was done using FP-8500.
For photography, an iPhone (registered trademark) 6S manufactured by Apple Inc. was used. RGB analysis of the captured image was performed using the application Pixel Picker.
"Room temperature" in the following examples usually indicates about 10 ° C to about 25 ° C. The ratio shown in the mixed solvent indicates the volume ratio unless otherwise specified. % Indicates% by weight unless otherwise specified.
Further, the formula (II-1) which is a raw material compound:

A compound having a unidirectionally wound spiral structure (optically active substance) represented by (hereinafter, also referred to as “compound (II-1)”) is described in Patent Document 4 (Japanese Unexamined Patent Publication No. 2016-155781). Was synthesized according to the method described in Example 1. The di-heptyl ester, a synthetic precursor of that time, measurements of gel permeation chromatography number average molecular weight _M n = 1.14 × 10 ^4, the degree of dispersion _M w _{/ M} n = 1.74 (polystyrene basis ) Was used. Further, in the synthesis of the following compound (I-1), when the circular dichroism spectrum is measured as the compound (II-1), the Δε value at 395 nm, which indicates the optical purity, is in the range of 19 to 21. I used the one.

Example 1
Synthesis of compounds (I-1) with different optical purity (typical example)

Compound (II-1) (10.0 mg, 37.6 μmol), 1-phenylethylamine (18.2 mg, 150 μmol) prepared with ee, 4- (4,6-dimethoxy-1,3) in a 5 mL eggplant flask. , 5-Triazine-2-yl) -4-methylmorpholinium chloride (DMT-MM) (41.5 mg, 150 μmol), and THF / water = 4/1 (v / v) (1.0 mL) was added. , Stirred overnight at room temperature. After adding a methanol / water = 1/1 (v / v) solution to the reaction solution and reprecipitating, centrifugation and washing with a methanol / water = 1/1 (v / v) solution are repeated, and then freeze-drying is performed. The title compound (Compound (I-1)) was obtained as a yellow solid. As 1-phenylethylamine prepared by adjusting the above ee, R form (hereinafter referred to as "R100"), 20% ee S form (hereinafter referred to as "S20"), 40% ee S form (hereinafter referred to as "S40"). ”) Or 60% ee S-form (hereinafter referred to as“ S60 ”), and the same operation was carried out to obtain a compound (I-1) into which 1-phenylethylamine of a different ee was introduced. I got each. Hereinafter, the compound (I-1) synthesized by using 1-phenylethylamine (R100, S20, S40 or S60) having different optical purity is prepared as compounds (I-1) (R100) and compound (I-1), respectively. S20), referred to as compound (I-1) (S40) or compound (I-1) (S60).

Test Example 1
Compounds (I-1) with different optical purity (Compounds (I-1) (R100), Compounds (I-1) (S20), Compounds (I-1) (S40) and Compounds (I-1) (S60). ) Is used to identify the anion species compounds (I-1) (R100), compounds (I-1) (S20), compounds (I-1) (S40) and compounds (I-1) (S60), respectively. In the solution (1.0 × 10 ^-3 M), anion (acetate ion (AcO ⁻ ), fluoride ion (F ⁻ ), chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ) or tetraphenylborate ion (BPh 4 _-) ^a) to observe changes in the color tone of the mixed solution after respectively 1 equivalent (1.0 × 10 -3 ^M) was added in the form of tetrabutylammonium salt.

The results are shown in a table in FIG. According to FIG. 1, with respect to the compounds (I-1) and (R100), no change in color tone was observed while the compound (I-1) (R100) remained red regardless of the addition of any of the anions. On the other hand, with respect to the compounds (I-1) (S20), the compounds (I-1) (S40) and the compounds (I-1) (S60), the mixed solutions with other anions other than _{BPh 4} ^{-are all mixed solutions.} Changes to orange and yellow were confirmed. It was also found that the responsiveness to anions improved as the S-form became excessive. Since the recognition ability of anions differs greatly by changing the optical purity of the chiralamide site on the side chain in this way, by combining a plurality of optical purity compounds (I-1), it is possible to visually identify various types of anions. Confirmed that it is possible.

Test Example 2
Compounds (I-1) with different optical purity (Compounds (I-1) (R100), Compounds (I-1) (S20), Compounds (I-1) (S40) and Compounds (I-1) (S60). acetate ion (AcO using) ^-) and tetraphenyl borate ion (BPh ₄ ^- identification compounds of) (I-1) (R100 ), compound (I-1) (S20) , compound (I-1) (S40 ) And Compounds (I-1) and (S60) are dissolved in THF (1.0 × 10 ^-3 M), respectively, after addition of 10 equivalents of anion (AcO ⁻ or BPh ₄ ^−). The CD spectrum and absorption spectrum were measured.

The result is shown in FIG. According to FIG. 2, BPh ₄ ^- in case of adding, in any of the CD spectrum and absorption spectra, while little difference to the case of the anion-free additive was observed, AcO ^- in the case of adding A short wavelength shift (blue shift) was observed.

Test Example 3
Compounds (I-1) with different optical purity (Compounds (I-1) (R100), Compounds (I-1) (S20), Compounds (I-1) (S40) and Compounds (I-1) (S60). acetate ion (AcO using) ^- simple colorimetric compound of) (I-1) (R100 ), compound (I-1) (S20) , compound (I-1) (S40) and the compound (I- ^{1) The absorption spectrum when AcO − having different concentrations was added to the solutions (1.0 × 10 -3} M) in which (S60) was dissolved in THF was measured, and the color tone of the mixed solution was observed. ..

The measurement results of the absorption spectrum and the photographs of the mixed solution are shown in FIGS. 3 and 4, respectively. Further, a solution in which compounds (I-1) (R100), compounds (I-1) (S20), compounds (I-1) (S40) and compounds (I-1) (S60) are dissolved in THF, respectively. FIG. 5 shows a plot of changes in absorption intensity near 540 nm with respect to the amount of ^{AcO −} added in the absorption spectra of a mixed solution of ^{AcO − having} different concentrations of (1.0 × 10 ^{-3 M).} ..
According to FIG. 3, the ^{absorption spectrum gradually shifts to a short wavelength (blue shift) according to the amount of AcO −} added, and as the S-form of compound (I-1) becomes excessive, it becomes sensitive to ^{AcO −.} Was confirmed to respond to.
Further, according to FIG. 4, the compounds (I-1) (S20), the compounds (I-1) (S40) and the compounds (I-1) (S60) are 5 equivalents, 1 equivalent, and 0.5, respectively. By adding an equivalent amount of AcO ⁻ , the color tone of the mixed solution changed from red to yellow. Further, according to FIG. 4, the color tone of the mixed solution of the compounds (I-1) and (R100) ^{changes from red to orange by adding 10 equivalents of AcO −} , and becomes yellow when the addition amount is further increased. Conceivable. ^{Since the change in color tone due to the change in the concentration of AcO −} seen in FIG. 4 can be easily confirmed visually, the optical purity of the chiralamide moiety on the side chain of compound (I-1) is appropriately adjusted. By adjusting the non-linear responsiveness, it was confirmed that compound (I-1) functions as a colorimetric sensor capable of easily and visually quantifying the concentration of the anion to be identified.

Test Example 4
Compounds (I-1) with different optical purity (Compounds (I-1) (R100), Compounds (I-1) (S20), Compounds (I-1) (S40) and Compounds (I-1) (S60). ) Is used to identify anions by changing the fluorescence intensity. Compounds (I-1) (R100), compounds (I-1) (S20), compounds (I-1) (S40) and compounds (I-1) (S60). In the form of tetrabutylammonium salt, 10 equivalents (1.0 × 10 ^-4 M) of anion (AcO ⁻ or BPh ₄ ⁻ ) was added to a solution (1.0 × 10 ^{-5 M) in which each was dissolved in THF.} The fluorescence spectrum of the mixed solution after each addition was measured when the excitation light was set to 298 nm.

The result is shown in FIG. According to FIG. 6, BPh ₄ ^- in the case of addition of, even in the fluorescence spectrum, whereas little difference to the case of the anion-free additive was observed, AcO ^- when added to the near 510nm Fluorescence intensity increased. Further, according to FIG. 6, the compound (I-1) (R100) is an S-form excess compound (I-1) (S20), compound (I-1) (S40) or compound (I-1) ( Compared with S60), the degree of increase in fluorescence intensity when ^{AcO − was added was small.}

Further, a solution in which compounds (I-1) (R100), compounds (I-1) (S20), compounds (I-1) (S40) and compounds (I-1) (S60) are dissolved in THF, respectively. The change in the fluorescence spectrum of the mixed solution when ^{AcO −} having different concentrations was added to (1.0 × ^10-5 M) was measured.

The result is shown in FIG. Further, a solution in which compounds (I-1) (R100), compounds (I-1) (S20), compounds (I-1) (S40) and compounds (I-1) (S60) are dissolved in THF, respectively. FIG. 8 shows a plot of changes in fluorescence intensity in the vicinity of 510 nm with respect to the amount of ^{AcO −} added in the absorption spectra of the mixed solutions of ^{AcO −} having different amounts of (1.0 × 10 ^{-3 M).} rice field.
According to FIG. 7, it was confirmed that the mixed solution showed a Turn-on type behavior in which the fluorescence intensity of the mixed solution gradually increased ^{according to the amount of AcO − added.} Further, according to FIGS. 7 and 8, it was confirmed that the compound (I-1) having an excess of S-form responded more sensitively when the concentration of ^{AcO − was low.} On the other hand, ^{when the concentration of AcO −} becomes high, the fluorescence intensity of the compound (I-1) having an excess of S-form hardly changes, whereas the fluorescence intensity of the compounds (I-1) and (R100) is remarkable. It was confirmed that it would increase.
As described above, it was confirmed that the optical purity of the chiralamide site on the side chain of compound (I-1) can be appropriately adjusted and the nonlinear responsiveness can be controlled even in the fluorescence spectrum measurement. It was confirmed that (I-1) functions as a fluorescence detection type anion sensor having high detection sensitivity.
Further, as is clear from FIGS. 6 and 7, the fluorescence spectrum of the compound (I-1) has a region of 510 nm in which the change is large and a region of 430 nm in which the change is small depending on the change in the type and concentration of the anion. .. Such behavior suggests that compound (I-1) may be useful for dual-wavelength ratio-type fluorescence anion sensing because it can correct the error of concentration adjustment.

On the other hand, as in the case of the addition of ^{AcO −,} a plot of the change in fluorescence intensity near 510 nm with respect to the addition amount of _{BPh 4} ^{− is shown in FIG.} According to FIG. 9, BPh ₄ ^- against, be used any optical purity of compound (I-1), the correlation was not observed in the fluorescence intensity, substantially no change was observed.
Further, FIG. 10 shows a photograph of the fluorescence of the mixed solution after adding ^{AcO −} or BPh ₄ ^{− to the solution (1.0 × 10-5} M) of the compounds (I-1) and (S20). According to FIG. 10, since it ^{was visually confirmed that the fluorescence intensity of the mixed solution increased after the addition of AcO −} , it was also possible to observe the change in the fluorescence intensity of the compound (I-1). It was found that the types of anion species can be visually identified.

Compounds (I) having different optical purity can be instantly visually recognizable in different color tones and / or fluorescence intensity changes (in quenching) in response to the type and concentration of the anion by simply mixing with the anion. (Enhancement of fluorescence intensity) is shown. According to the present invention, the color tone and fluorescence of a mixture of a plurality of compounds (I) having different optical purity and anion-containing solutions having different types and concentrations are used as standard samples after taking a picture with an inexpensive camera or smartphone. By performing image analysis (calibration curve created by RGB analysis), the color tone and / or fluorescence intensity of the test solution of the test subject can be visually observed in the sample solution simply by comparing and observing with those of the standard sample. It is possible to easily and sensitively identify and / or quantify the type and concentration of anions contained in. Further, according to the present invention, it is possible to adjust the optical purity of the compound (I) only by adjusting the optical purity of the compound (III) used as a raw material in the synthesis of the compound (I). , The non-linear responsiveness can be freely adjusted in the two-detection system of colorimetric and fluorescence using compound (I). Therefore, according to the present invention, the anion can be identified and visually identified with extremely high accuracy as compared with the conventional anion sensor using an organic molecule or a metal complex, which requires identification only by color tone or fluorescence intensity. A practical anion sensor capable of quantification can be provided.

Claims (11)

Equation (I) with a unidirectionally wound helical structure:

[During the ceremony,
^{R 1, R 1 ', R} 2, R 2', R 3, R 3 ', R 4 and ^{R 4'} are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, a substituted Indicates a cycloalkyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, a tri-substituted silyl group, a tri-substituted siloxy group or an acyloxy group which may be substituted;
R, R'and R'' are independently hydrogen atoms, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, optionally substituted alkoxycarbonyl groups, and substituted, respectively. Indicates a optionally aryl group or an optionally substituted heteroaryl group;
^{Carbon atoms marked with *} indicate asymmetric carbon atoms; and n represents an integer greater than or equal to 10. However, R, R'and R'' all represent different groups. ]
A colorimetric fluorescence detection type anion sensor containing an optically active poly (diphenylacetylene) compound represented by (diphenylacetylene), a salt thereof, or a solvate thereof. The colorimetric according to claim 1, wherein R, R'and R'' are independently hydrogen atoms, C _1-4 alkyl groups, C _3-8 cycloalkyl groups or C _{6-10 aryl groups, respectively.} Fluorescence detection type anion sensor. The specific color fluorescence detection type according to claim 1 or 2, for detecting a carboxylate ion, a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a tetraphenylborate ion, and / or a phosphate ion. Ion sensor. A step of preparing a sample solution containing the anion to be identified in a solvent containing tetrahydrofuran at ^{a concentration of 10 -4} M or more and dividing it into m pieces, a spiral structure of m pieces having different optical purity and unidirectional winding. Equation (I):

[During the ceremony,
^{R 1, R 1 ', R} 2, R 2', R 3, R 3 ', R 4 and ^{R 4'} are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, a substituted Indicates a cycloalkyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, a tri-substituted silyl group, a tri-substituted siloxy group or an acyloxy group which may be substituted;
R, R'and R'' are independently hydrogen atoms, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, optionally substituted alkoxycarbonyl groups, and substituted, respectively. Indicates a optionally aryl group or an optionally substituted heteroaryl group;
^{Carbon atoms marked with *} indicate asymmetric carbon atoms; and n represents an integer greater than or equal to 10. However, R, R'and R'' all represent different groups. ]
In the step of preparing m sensor solutions 1 to m in which each of the optically active poly (diphenylacetylene) compounds represented by (1) is dissolved in a solvent containing tetrahydrofuran, the sensor solution 1 is added to each of the m sample solutions. In the step of preparing m test solutions 1 to m by adding any of 1 to m, each solution containing n'specified anions in a solvent containing tetrahydrofuran at the same concentration as the sample solution. A step of preparing m of each anion species and adding any of the sensor solutions 1 to m to each of them to prepare n'sets of m standard sample solutions 1 to m, and the test solutions 1 to 1. The step of identifying the type of anion to be identified by comparing and observing m and the color tone and / or fluorescence intensity of each of the standard sample solutions 1 to m is included, and m is an integer of 2 to 10. A method for identifying an anion species, wherein n'is an integer of 2 to 7. The method according to claim 4, wherein m is an integer of 3 to 5. The method according to claim 4 or 5, wherein the solvent containing tetrahydrofuran is a mixed solvent of tetrahydrofuran, tetrahydrofuran and acetone, or a mixed solvent of tetrahydrofuran and chloroform. Any of claims 4 to 6, wherein the anion to be identified is selected from the group consisting of a carboxylate ion, a fluoride ion, a chloride ion, a bromide ion, an iodide ion, a tetraphenylborate ion, and a phosphate ion. The method described in item 1. A step of dividing a sample solution containing an anion having an unknown concentration in a solvent containing tetrahydrofuran into m'pieces, a formula (I) having a unidirectionally wound spiral structure of m'pieces having different optical purity:

[During the ceremony,
^{R 1, R 1 ', R} 2, R 2', R 3, R 3 ', R 4 and ^{R 4'} are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, a substituted Indicates a cycloalkyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, a tri-substituted silyl group, a tri-substituted siloxy group or an acyloxy group which may be substituted;
R, R'and R'' are independently hydrogen atoms, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, optionally substituted alkoxycarbonyl groups, and substituted, respectively. Indicates a optionally aryl group or an optionally substituted heteroaryl group;
^{Carbon atoms marked with *} indicate asymmetric carbon atoms; and n represents an integer greater than or equal to 10. However, R, R'and R'' all represent different groups. ]
In the step of preparing m'sensor solutions 1 to m'in which each of the optically active poly (diphenylacetylene) compounds represented by is dissolved in a solvent containing tetrahydrofuran, in each of the m'sample solutions, In the step of preparing m'test solutions 1 to m'by adding any of the sensor solutions 1 to m', a solution containing the anion in a solvent containing tetrahydrofuran at different specific concentrations is n. '' Seeds are prepared, each solution of n'' species is divided into m'pieces, and any of the sensor solutions 1 to m'is added to each of the m'pieces of standard sample solutions 1 to m'. By comparing and observing the color tone and / or fluorescence intensity of the test solution 1 to m'and each standard sample solution 1 to m'in the process of preparing the n''set, the anion concentration contained in the sample solution can be determined. A method for determining an anion concentration, which comprises a step of determining, wherein m'is an integer of 2 to 10 and n'' is an integer of 2 to 10. The method according to claim 8, wherein m ′ is an integer of 3 to 5, and n ″ is an integer of 3 to 5. The method according to claim 8 or 9, wherein the solvent containing tetrahydrofuran is a mixed solvent of tetrahydrofuran, tetrahydrofuran and acetone, or a mixed solvent of tetrahydrofuran and chloroform. The method according to any one of claims 8 to 10, wherein the anion is a carboxylate ion, a fluoride ion, a chloride ion, a bromide ion, an iodide ion or a phosphate ion.

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