Polyol-cyclic compound complex, boron detection reagent, and method for boron detection

Abstract

To provide a novel polyol-cyclic compound complex capable of forming an electrochemically active complex with boron, enabling measurement at a low potential and highly sensitive measurement.SOLUTION: The present invention relates to a polyol-cyclic compound complex including: a cyclic compound having encapsulation capability for an electrochemically active species; and a polyol having binding capability for boric acid.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a polyol-cyclic compound conjugate, a boron detection reagent, and a boron detection method. [Background technology]

[0002] Ultrapure water, essential for the semiconductor manufacturing process, is highly purified water with impurity concentrations reduced to approximately 0.1 ppt (parts per trillion) or less. When used in the semiconductor manufacturing process, ultrapure water must have a high level of boron removed. Furthermore, boron is one of the substances that is difficult to remove in the ultrapure water manufacturing process. Therefore, the boron concentration must be monitored at various stages in the ultrapure water manufacturing process. There are also standards for the boron concentration in tap water, and standards have also been established for the boron concentration in wastewater. Thus, it is necessary to monitor the boron concentration in water, not just ultrapure water.

[0003] Patent Document 1 discloses that adding hydrochloric acid as a sensitizer to a sample solution containing boron and measuring the result by inductively coupled plasma mass spectrometry (ICP-MS) enables analysis of trace amounts of boron in the solution with an accuracy of the order of several ppt. Patent Document 2 discloses a more sensitive method than that disclosed in Patent Document 1, in which electrochemically inactive boric acid is converted into an electrochemically active boric acid-tiron complex and this is measured by voltammetry. Patent Document 3 discloses a more simple method than that disclosed in Patent Document 2, in which a complex of boric acid and azomethine H is formed and this is measured by voltammetry. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-325380 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-150836 [Patent Document 3] Japanese Patent Application Laid-Open No. 2011-163888 Summary of the Invention [Problem to be solved by the invention]

[0005] However, even if boron in a sample is measured by voltammetry as an electrochemically active complex, problems arise, such as a decrease in measurement sensitivity due to the influence of interfering substances when the observed potential is high, and the measurement takes a long time.

[0006] Therefore, an object of the present disclosure is to provide a novel polyol-cyclic compound complex that can convert boron into an electrochemically active complex, can be measured at low potential, and can be measured with high sensitivity, a boron detection reagent, and a boron detection method. [Means for solving the problem]

[0007] In order to achieve the above-mentioned object, the present inventors conducted extensive research and discovered that a polyol-cyclic compound composite capable of forming a complex with boric acid, which encapsulates an electrochemically active species, can be used to measure the complex at low potential with high sensitivity, thereby completing the present disclosure. That is, the present disclosure includes the following aspects.

[0008] <1> A polyol-cyclic compound composite comprising a cyclic compound having an inclusion ability for electrochemically active species and a polyol having a binding ability for boric acid. <2> The polyol has an aromatic diol group capable of forming a complex with boric acid. <1> The polyol-cyclic compound complex according to claim 1. <3> The aromatic diol group is an aromatic diol group selected from the group consisting of a catechol group having hydroxy groups on adjacent carbon atoms of a benzene ring, a naphthalenediol group having hydroxy groups on adjacent carbon atoms of a naphthalene ring, and a naphthalenediol group having hydroxy groups on the 1st and 8th positions of a naphthalene ring. <2> The polyol-cyclic compound complex according to claim 1. <4> The polyol is one polyol selected from the group consisting of 3,4-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, and 3,4-dihydroxycinnamic acid. <1> ~ <3> 10. The polyol-cyclic compound conjugate according to any one of the above items. <5> The cyclic compound is a sugar cyclic compound. <1> ~ <4> 10. The polyol-cyclic compound conjugate according to any one of the above items. <6> The sugar cyclic compound is a cyclodextrin or a cyclodextrin derivative. <1> ~ <5> 10. The polyol-cyclic compound conjugate according to any one of the above items. <7> For detecting boron <1> ~ <6> 10. The polyol-cyclic compound conjugate according to any one of the above items. <8> The electrochemically active species is ferrocene or a ferrocene derivative. <1> ~ <7> 10. The polyol-cyclic compound conjugate according to any one of the above items. <9> <1> ~ <8> and an electrochemically active species that is included in the cyclic compound in the polyol-cyclic compound complex. <10> The electrochemically active species is ferrocene or a ferrocene derivative. <9> The boron detection reagent according to claim 1. <11> <1> ~ <8> a step of mixing the polyol-cyclic compound complex according to any one of the above, a boron detection reagent containing an electrochemically active species included in the cyclic compound in the polyol-cyclic compound complex, and a test sample; detecting an electrochemical signal; A boron detection method for detecting boron contained in the test sample based on a change in an electrochemical signal. <12> The electrochemically active species is ferrocene or a ferrocene derivative. <11> The boron detection method according to claim 1. <13> The amount of boron contained in the test sample is determined based on the change in the detected electrochemical signal. <11> or <12> The boron detection method according to claim 1. [Effects of the Invention]

[0009] According to the present disclosure, it is possible to provide a novel polyol-cyclic compound composite capable of converting boron into an electrochemically active complex, as well as a boron detection reagent and a boron detection method using the same. The polyol-cyclic compound composite of the present disclosure forms a complex with boric acid, and in a state in which an electrochemically active species is encapsulated, it is possible to exhibit an electrochemical signal with a large change in magnitude at low potential. Therefore, the polyol-cyclic compound composite and the boron detection reagent and boron detection method using the same of the present disclosure can measure the boron to be detected at low potential with high sensitivity. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a synthesis scheme of 3,4-DHBA-β-CyD. [Figure 2] 1 is a synthesis scheme of 3,4,5-THBA-β-CyD. [Figure 3] 1 is a synthesis scheme of 3,4-DHCA-β-CyD. [Figure 4] 1 is a synthesis scheme of 2,3-DHBA-β-CyD. [Figure 5] 1 is a synthesis scheme of BA-β-CyD. [Figure 6] 1 is a synthesis scheme of 2-HBA-β-CyD. [Figure 7] 1 is a synthesis scheme of 3-HBA-β-CyD. [Figure 8] 1 is a synthesis scheme of 4-HBA-β-CyD. [Figure 9] 1 is a synthesis scheme of 2,5-DHBA-β-CyD. [Figure 10]1 is a synthesis scheme of 2,6-DHBA-β-CyD. [Figure 11] 1 is a synthesis scheme of 3,5-DHBA-β-CyD. [Figure 12] FIG. 1 is a characteristic diagram showing an overlay of cyclic voltammograms measured using 3,4-DHBA-β-CyD and each boron aqueous solution. [Figure 13] FIG. 10 is a characteristic diagram showing the relationship between the boron concentration in an aqueous boron solution and the measured current value. [Figure 14] FIG. 1 is a characteristic diagram showing an overlay of cyclic voltammograms measured using 3,4-DHBA-β-CyD and low-concentration aqueous boron solutions. [Figure 15] FIG. 10 is a characteristic diagram showing the relationship between the boron concentration in an aqueous boron solution and the measured current value. [Figure 16] FIG. 1 is a characteristic diagram showing a cyclic voltammogram measured using BA-β-CyD. [Figure 17] FIG. 1 is a characteristic diagram showing a cyclic voltammogram measured using 4-HBA-β-CyD. [Figure 18] FIG. 1 is a characteristic diagram showing a cyclic voltammogram measured using 3,4-DHBA-β-CyD. [Figure 19] FIG. 1 is a characteristic diagram showing a cyclic voltammogram measured using 3,5-DHBA-β-CyD. [Figure 20] FIG. 1 is a characteristic diagram showing a cyclic voltammogram measured using a boron detection reagent containing 3,4-DHBA-β-CyD but not containing ferrocene. [Figure 21] FIG. 1 is a characteristic diagram showing a cyclic voltammogram measured using 3,4,5-THBA-β-CyD. [Figure 22] FIG. 1 is a characteristic diagram showing a cyclic voltammogram measured using 3,4-DHCA-β-CyD. DETAILED DESCRIPTION OF THE INVENTION

[0011] The following describes the embodiments in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, the components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure. For example, the present disclosure allows addition, omission, substitution, modification, etc. of the number, amount, position, ratio, material, configuration, type, order, etc., within the scope of the spirit of the present disclosure.

[0012] In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, combinations of preferred aspects are more preferred aspects. In the present disclosure, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.

[0013] <<Polyol-cyclic compound composite>> The polyol-cyclic compound composite of the present disclosure comprises a cyclic compound capable of inclusion of electrochemically active species and a polyol capable of binding to boric acid. The polyol-cyclic compound composite of the present disclosure can be used to detect boron present in the form of boric acid. In the polyol-cyclic compound composite of the present disclosure, electrochemically inactive boric acid binds to two hydroxyl groups contained in the polyol, and the electrochemically active species is enclosed within the cyclic compound. In the polyol-cyclic compound composite of the present disclosure, the electrochemical signal resulting from the oxidation of the two hydroxyl groups changes between the state in which boric acid is bound to the two hydroxyl groups and the state in which boric acid is not bound. In the polyol-cyclic compound composite of the present disclosure, the two hydroxyl groups binding the boric acid are in close proximity to the electrochemically active species enclosed within the cyclic compound. Therefore, in the polyol-cyclic compound composite of the present disclosure, the electrochemical signal resulting from the oxidation of the two hydroxyl groups interacts with the electrochemical signal resulting from the electrochemically active species, increasing the intensity of the electrochemical signal. This electrochemical signal can be observed at relatively low potentials.

[0014] (Polyol) In the polyol-cyclic compound composite of the present disclosure, the term "polyol" refers to a moiety containing at least two hydroxy groups for forming a complex with boric acid. Examples of polyols include aromatic polyols having two hydroxy groups at the ortho position as the at least two hydroxy groups for forming a complex with boric acid. In the polyol-cyclic compound composite of the present disclosure, the polyol may also be a moiety having one or more hydroxy groups in addition to the at least two hydroxy groups for forming a complex with boric acid. Preferably, the at least two hydroxy groups for forming a complex with boric acid are cis-diol groups consisting of a pair of hydroxy groups bonded to adjacent carbon atoms.

[0015] In particular, in the polyol-cyclic compound composite of the present disclosure, the polyol preferably contains an aromatic diol group having at least two hydroxy groups for complexing with boric acid, although the polyol in the polyol-cyclic compound composite of the present disclosure is not limited to a moiety having an aromatic diol and may also be a moiety having a cis-diol in a non-aromatic ring structure.

[0016] The aromatic diol group having at least two hydroxy groups is not particularly limited, and examples thereof include aromatic diol groups selected from the group consisting of a catechol group having hydroxy groups on adjacent carbon atoms of a benzene ring, a naphthalenediol group having hydroxy groups on adjacent carbon atoms of a naphthalene ring, and a naphthalenediol group having hydroxy groups at the 1- and 8-positions of a naphthalene ring.

[0017] The polyol-cyclic compound composite of the present disclosure can be obtained by bonding a compound containing a polyol capable of binding to boric acid to the cyclic compound. The bonding mode between the polyol-containing compound and the cyclic compound is not particularly limited, and examples include an ester bond, an ether bond, an amide bond, and the like. For example, if the cyclic compound has an amino group, and the polyol-containing compound has a carboxyl group, the cyclic compound and the polyol-containing compound are bonded via an amide bond, thereby obtaining the polyol-cyclic compound composite of the present disclosure.

[0018] Examples of the polyol-containing compound include 2,3-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,3-dihydroxy-4-methoxybenzoic acid, 3,4,5-trihydroxybenzoic acid, 3,4-dihydroxy-5-methoxybenzoic acid, 3,4-di(hydroxymethyl)benzoic acid, 3-bromo-4,5-dihydroxybenzoic acid, 3-bromo-5,6-dihydroxybenzoic acid, 4-bromo-2,3-dihydroxybenzoic acid, 3-chloro-4, 5-Dihydroxybenzoic acid, 3-chloro-5,6-dihydroxybenzoic acid, 4-chloro-2,3-dihydroxybenzoic acid, 3-fluoro-4,5-dihydroxybenzoic acid, 3-fluoro-5,6-dihydroxybenzoic acid, 4-fluoro-2,3-dihydroxybenzoic acid, D,L-3,4-dihydroxymandelic acid, 3,4-dihydroxyphenylacetic acid, 2,3-dihydroxyphenylacetic acid, 3-(3,4-dihydroxyphenyl)propanoic acid, 3- Examples of aromatic compounds include (3,4-dihydroxyphenyl)acrylic acid, 3-(2,3-dihydroxyphenyl)propanoic acid, 3-(2,3-dihydroxyphenyl)acrylic acid, 2,3-dihydroxycinnamic acid, 3,4-dihydroxycinnamic acid, 3,4-dihydroxy-2-naphthalenecarboxylic acid, 4,5-dihydroxy-2-naphthalenecarboxylic acid, 5,6-dihydroxy-2-naphthalenecarboxylic acid, 6,7-dihydroxy-2-naphthalenecarboxylic acid, 7,8-dihydroxy-2-naphthalenecarboxylic acid, 4,5-dihydroxyquinoline-2-carboxylic acid, 3-(3,4-dihydroxyphenyl)propionic acid, 3,4-dihydroxy-5-methoxybenzaldehyde, 1,2-dihydroxybenzene-3,5-disulfonic acid, 1,8-dihydroxynaphthalene-3,6-disulfonic acid, and cis-1,2-dihydroxy-1,2-dihydro-8-carboxynaphthalene. Among these, the polyol-containing compound is preferably one compound selected from the group consisting of 2,3-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, and 3,4-dihydroxycinnamic acid.

[0019] (cyclic compounds) In the polyol-cyclic compound composite of the present disclosure, the cyclic compound is a compound that binds the polyol containing at least two hydroxy groups for forming a complex with boric acid and encapsulates the electrochemically active species. Examples of cyclic compounds include sugar cyclic compounds. Furthermore, organic compounds with hydrophobic interiors can be used as cyclic compounds that have the ability to encapsulate electrochemically active species with low water solubility. Such cyclic compounds are not limited to sugar cyclic compounds, but also include crown ethers, calixarenes, cyclophanes, cucurbiturils, pillararenes, and derivatives thereof. Among these, cyclodextrins or cyclodextrin derivatives, as described below, are preferred as cyclic compounds from the viewpoint of high water solubility and other properties.

[0020] The sugar ring compound is preferably cyclodextrin or a cyclodextrin derivative. Examples of cyclodextrin include α-cyclodextrin (6 glucose residues), β-cyclodextrin (7 glucose residues), γ-cyclodextrin (8 glucose residues), δ-cyclodextrin (9 glucose residues), and ε-cyclodextrin (10 glucose residues). Alternatively, cyclodextran may be used as the sugar ring compound.

[0021] The sugar cyclic compound may also be a cyclodextrin derivative derived from these cyclodextrins. The cyclodextrin derivative includes compounds obtained by chemically modifying the above-mentioned cyclodextrins (chemically modified cyclodextrins), compounds in which at least one hydroxyl group selected from the primary and secondary hydroxyl groups of the above-mentioned cyclodextrins has been substituted with a hydrogen atom (deoxycyclodextrins), and the like. Examples of chemical modifications in chemically modified cyclodextrins include the introduction of low molecular weight structures such as methyl groups or ethyl groups, or polymer structures such as dendrimers, and the introduction of charged structures such as amino groups or carboxyl groups. The cyclodextrin derivative may also be a chemically modified cyclodextrin in which at least one hydroxyl group selected from the primary and secondary hydroxyl groups has been substituted with a hydrogen atom.

[0022] In particular, in the polyol-cyclic compound composite of the present disclosure, the cyclic compound contains a functional group for binding the above-mentioned polyol-containing compound. For example, when the cyclic compound in the polyol-cyclic compound composite of the present disclosure is cyclodextrin or a cyclodextrin derivative, the polyol-containing compound may be bound to a primary hydroxyl group or a secondary hydroxyl group of glucose constituting the cyclodextrin, or the polyol-containing compound may be bound to a functional group introduced into the cyclodextrin.

[0023] When the polyol-containing compound has a carboxyl group, it is preferable to use a cyclodextrin derivative having a functional group capable of reacting with the carboxyl group introduced into the molecule. Examples of functional groups capable of reacting with the carboxyl group include an amino group and a mercapto group. Among these, it is preferable to use a cyclodextrin derivative having an amino group introduced therein. A cyclodextrin derivative having an amino group can form an amide bond with the polyol-containing compound having a carboxyl group. In other words, the polyol-cyclic compound composite of the present disclosure can be produced by forming an amide bond between the carboxyl group in the polyol-containing compound and the amino group in the cyclodextrin derivative.

[0024] Furthermore, examples of functional groups that can bond with the polyol-containing compound include a carboxyl group, a carboxylic acid group, a sulfonic acid group, an amino group, an aminoalkyl group, a hydroxyl group, etc. That is, in the polyol-cyclic compound composite of the present disclosure, the cyclodextrin derivative used as the cyclic compound is preferably one into which at least one functional group selected from the group consisting of a carboxyl group, a carboxylic acid group, a sulfonic acid group, an amino group, an aminoalkyl group, and a hydroxyl group has been introduced.

[0025] Here, examples of cyclodextrin derivatives having a functional group capable of binding to a compound containing a polyol include (2 A S,3 A S)-3 A -amino-3 A -deoxy-β-cyclodextrin, 2-amino-2-deoxy-β-cyclodextrin, 3-amino-β-cyclodextrin, 6-amino-β-cyclodextrin, 3 A -amino-3 A -deoxy-(2 A S,3 A S)-α-cyclodextrin, 3 A -amino-3 A -deoxy-(2 A S,3 AS)-γ-cyclodextrin and the like.

[0026] (Synthesis of Polyol-Cyclic Compound Composites) The polyol-cyclic compound composite of the present disclosure can be synthesized from the above-described polyol-containing compound and a cyclic compound. As an example, the polyol-cyclic compound composite of the present disclosure can be synthesized by a condensation reaction between the above-described polyol-containing compound and a cyclic compound. Specifically, the above-described polyol-containing compound and the cyclic compound are each dissolved in an appropriate solvent, and the two resulting solutions are mixed in the presence of a condensing agent.

[0027] The condensing agent used in the condensation reaction is not particularly limited, and examples thereof include 4-(4,6-dimethoxy-1,3,5-triazine)-4-methylmorpholinium (DMT-MM), N,N'-carbonyldiimidazole (CDI), N,N'-dicyclohexylcarbodiimide (DCC), N-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline (EEDQ), 2-benzotriazole-1,1,3,3-tetramethyluronium tetrafluoroborate (TBTU), 3 ... ,4-dihydro-3-hydroxy-4-oxo-1,2,3-benzotriazine (HODhbt), benzotriazole-1-oxy-tris-pyrrolidino-phosphonium hexafluorophosphate (PyBOP), benzotriazole-1-yl-oxy-tris(dimethylamino)phosphonium hexafluorophosphate (BOP), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), N-hydroxysuccinimide (NHS), and the like.

[0028] The amount of the condensing agent used is usually 1 to 4 equivalents, preferably 1 to 2 equivalents, more preferably 1.05 to 1.5 equivalents, and even more preferably 1.05 to 1.3 equivalents, relative to the amount of the polyol-containing compound and the cyclic compound.

[0029] In the condensation reaction, an additive may be further added, such as 1-hydroxybenzotriazole (HOBt), 1-hydroxy-7-azabenzotriazole (HOAt), 1-hydroxy-1H-1,2,3-triazole-4-ethyl carboxylate (HOCt), 3-hydroxy-1,2,3-benzotriazin-4(3H)-one (HOOBt), N-hydroxysuccinimide (HOSu), N-hydroxyphthalimide (HOPht), N-hydroxy-5-norbornene-2,3-dicarboximide (HONb), pentafluorophenol, ethyl cyanohydroxyiminoacetate (Oxyma), and the like.

[0030] The amount of the additive used is usually 0.1 to 2 equivalents, preferably 0.2 to 1.5 equivalents, and more preferably 0.3 to 1.0 equivalents, relative to the amount of the polyol-containing compound and cyclic compound.

[0031] The solvent for dissolving the polyol-containing compound or cyclic compound is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, gamma butyrolactone, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, etc. These may be used alone or in combination as needed.

[0032] The amount of solvent used is not particularly limited as long as the reaction proceeds, but is usually an amount such that the concentration of the polyol-containing compound or cyclic compound dissolved therein is 0.1 mM to 1 M, and preferably 0.1 mM to 0.5 mM.

[0033] The reaction temperature is a temperature generally used in condensation reactions such as amide bonding, and is usually within the range of, for example, −20° C. to 40° C., and preferably 0° C. to 30° C. The reaction time is usually 0.5 hours to 30 hours.

[0034] The polyol-cyclic compound conjugate of the present disclosure synthesized by the above-described reaction can be stored as a powder by freeze-drying, or as an aqueous solution.

[0035] (Detection of boron using the complex) The polyol-cyclic compound composite of the present disclosure described above can be used for detecting boron. That is, the polyol-cyclic compound composite of the present disclosure can be used as a boron detection reagent for detecting boron. The boron detection reagent of the present disclosure contains the above-mentioned polyol-cyclic compound composite and an electrochemically active species encapsulated in the polyol-cyclic compound composite. By using the boron detection reagent of the present disclosure, boron contained in water can be detected. Note that, since boron is contained in water in the form of boric acid, detecting boron contained in water is synonymous with detecting boric acid contained in water.

[0036] In particular, the boron detection reagent of the present disclosure can detect trace amounts of boron in water. The lower limit of the boric acid concentration in the water to be detected is, for example, 0.005 mM or more, preferably 0.01 mM or more, more preferably 0.05 mM, even more preferably 0.1 mM, and even more preferably 0.5 mM. The boron detection reagent of the present disclosure can detect boric acid with high sensitivity and quantitatively as long as the boric acid content in water is above this range.

[0037] Here, the electrochemically active species included in the cyclic compound portion of the polyol-cyclic compound composite is a substance that has the function of increasing the electrochemical signal of the composite. Examples of such substances include metallocenes. Metallocenes that can be used as the electrochemically active species are not particularly limited, but an example is ferrocene (also known as bis(cyclopentadienyl)iron). The electrochemically active species is not limited to ferrocene, but includes ferrocene derivatives, cobaltocene, ruthenium complexes, and the like. Examples of ferrocene derivatives include acetylferrocene, benzoylferrocene, n-butylferrocene, ferrocene monocarboxylic acid, butyrylferrocene, cyclohexylferrocene, cyclopentenylferrocene, dimethylaminomethylferrocene, ethylferrocene, hexanoylferrocene, hexylferrocene, octanoylferrocene, pentanoylferrocene, pentylferrocene, and propionylferrocene. Ferrocene, Propylferrocene, 1,1'-Diacetylferrocene, 1,1'-Dibutylferrocene, 1,1'-Dibutyrylferrocene, 1,1'-Diethylferrocene, 1,1'-Dihexanoylferrocene, 1,1'-Dihexylferrocene, 1,1'-Dipropylferrocene, 4-Ferrocenoylbutyric acid, 4-Ferrocenoylbutyric acid ester, 3-Ferrocenoylpropionic acid, 3-Ferrocenoylpropionic acid ester Examples of metallocenes include ferrocenylacetic acid, ferrocenylacetonitrile, 4-ferrocenylbutyric acid, 4-ferrocenylbutyric acid ester, ferrocenylcarboxaldehyde, ferroenylcarboxylic acid, ferrocenylethanol, ferrocenylmethanol, 5-ferrocenylvaleric acid, 5-ferrocenylvaleric acid ester, catocene-(2,2-bis(ethylferrocenyl)propane), aminoferrocene, formamidoferrocene, isocyanoferrocene, isothiocyanatoferrocene, and diphosphine-1;1'-bis(diphenylphosphino)ferrocene. These metallocenes, such as ferrocene, are generally water-insoluble or have low water solubility. However, since the metallocenes used as electrochemically active species are included in the cyclic compound in the polyol-cyclic compound composite of the present disclosure, they can be used as boron detection reagents for detecting boron in water.

[0038] By using the boron detection reagent of the present disclosure, a boron detection method can be provided that can detect boron at low potential and with high sensitivity. The boron detection method of the present disclosure includes the steps of mixing the boron detection reagent of the present disclosure with a test sample and detecting an electrochemical signal, and detecting boron contained in the test sample based on a change in the electrochemical signal. Here, the test sample refers to an aqueous sample that may contain boron, but it may also be a sample that does not contain boron. Examples of test samples include aqueous samples obtained from the surrounding environment, such as rainwater, river water, seawater, lake water, tap water, and sewage, as well as treated water whose water quality has been altered by water treatment technology.

[0039] One example of a water treatment technology is a water treatment technology for producing ultrapure water used in semiconductor device manufacturing processes. In this water treatment technology, it is necessary to monitor impurities such as boron contained in water during the process of treatment until ultrapure water is obtained. In particular, boron can cause pn junction defects in semiconductors and is an element that is difficult to completely remove, so it is preferable to monitor boron contained in water during treatment or in the produced ultrapure water. Therefore, in the boron detection method disclosed herein, it is preferable to use water during treatment in the water treatment technology for obtaining ultrapure water or the produced ultrapure water as the test sample.

[0040] In the boron detection method of the present disclosure, the electrochemical signal is an electrochemical signal that changes in the presence / absence of boron. Methods for measuring electrochemical signals are broadly divided into two categories: methods that measure potential difference and methods that measure current, and examples of such methods include potentiometry, conductometry, AC impedance analysis, cyclic voltammetry, chronopotentiometry, chronoamperometry, and pulse voltammetry. In the boron detection method of the present disclosure, it is preferable to measure the electrochemical signal by cyclic voltammetry.

[0041] In the boron detection method of the present disclosure, in the absence of boric acid, a signal due to the oxidation of the polyol in the polyol-cyclic compound composite is observed in the low potential region; however, when a complex is formed between the polyol and boric acid, the oxidation of the polyol is suppressed, and this is detected as a change in signal intensity. In this case, in the boron detection method of the present disclosure, the electrochemically active species is encapsulated in the cyclic compound portion of the polyol-cyclic compound composite, and the polyol and the electrochemically active species are in close proximity. As a result, the signal observed due to the oxidation of the polyol is increased by the electrochemically active species. Therefore, the boron detection method of the present disclosure can detect trace amounts of boron contained in a test sample at low potential and with high sensitivity.

[0042] In particular, in the boron detection method of the present disclosure, it is preferable to use ferrocene or a ferrocene derivative as the electrochemically active species and a polyol-cyclic compound composite containing an aromatic diol having a cis-diol group as the polyol, because in this case, the signal due to the oxidation of the aromatic diol and the signal due to ferrocene almost coincide with each other, and the effect of enhancing the signal due to the oxidation of the aromatic diol is particularly large.

[0043] Furthermore, the boron detection method of the present disclosure can quantify the amount of boron contained in a test sample based on the change in the detected electrochemical signal. That is, the boron detection reagent of the present disclosure is suitable for quantitative analysis of boron contained in a test sample. In the boron detection method of the present disclosure, for example, a calibration curve prepared in advance is used to quantify the boron concentration contained in a test sample. The calibration curve is obtained by preparing multiple samples with known boron concentrations and measuring the electrochemical signal using these samples as described above. Then, a calibration curve showing the relationship between boron concentration and electrochemical signal can be obtained based on the electrochemical signal obtained for each sample.

[0044] The plurality of samples with known concentrations may include a sample with the lowest boron concentration, for example, a boron concentration of 0.005 mM, 0.01 mM, 0.05 mM, 0.1 mM, or 0.5 mM. The plurality of samples with known concentrations may include a sample with the highest boron concentration, for example, a boron concentration of 5.0 mM, 3.0 mM, 1.0 mM, 0.5 mM, or 0.3 mM. As samples with known concentrations for preparing a calibration curve, two, three, four, five, or six samples with different concentrations within the above-mentioned boron concentration range may be prepared.

[0045] In the boron detection method of the present disclosure, the electrochemical signal measured for the test sample is applied to the calibration curve prepared in advance as described above, thereby making it possible to quantify the boron concentration in the test sample. The boron detection method of the present disclosure is also capable of quantitatively analyzing low concentrations of boron as described above.

[0046] When detecting or quantitatively analyzing boron using the boron detection method of the present disclosure in a method for producing treated water whose quality has been improved by a water treatment technology, either a so-called flow injection analysis system or a sequential injection analysis system can be applied. Either analysis system can be applied to detect or quantitatively analyze boron in a desired step in the production method. [Example]

[0047] The present disclosure will be described in more detail below using examples, but the technical scope of the present disclosure is not limited to the following examples.

[0048] [Example 1] (Synthesis scheme of polyol-cyclic compound composite) 3,4-dihydroxybenzoic acid (3,4-DHBA) via an amide bond (2 A S,3A S)-3 A -amino-3 A A polyol-cyclic compound conjugate modified with β-deoxy-β-cyclodextrin was synthesized as follows.

[0049] 3,4-DHBA (0.24 mmol), condensing agent: N,N'-dicyclohexylcarbodiimide (DCC, 61.5 mg, 0.30 mmol), additive: 1-hydroxybenzotriazole monohydrate (HOBt HO, 46.5 mg, 0.30 mmol) were dissolved in N,N-dimethylformamide (DMF, 10 mL), and the resulting solution was stirred in an ice bath for 30 min. A S,3 A S)-3 A -amino-3 A A solution of β-deoxy-β-cyclodextrin (226.8 mg, 0.20 mmol) in N,N-dimethylformamide (DMF, 10 mL) was prepared. After mixing, the mixture was stirred in an ice bath for 30 minutes and then at room temperature for 24 hours. The solvent was then removed under reduced pressure using a rotary evaporator while heating in a 50°C water bath, and the solution was concentrated to approximately half its original volume.

[0050] The concentrated solution was stored in a refrigerator at 3°C ​​for 3 days to precipitate by-products. After removing the precipitated by-products by cotton filtration, the filtrate was added dropwise to acetone (1.0 L) while stirring. The resulting suspension was suction filtered using a membrane filter (filter code: JHWP). The residue was dissolved in ultrapure water (10 mL) and freeze-dried for 3 days. After freeze-drying, a white substance was obtained. Regarding the resulting white substance: 1 H-NMR, 13 C-NMR, UV-Vis, and elemental analysis confirmed that the product was 3,4-DHBA-β-CyD shown in Figure 1.

[0051] [Example 2] 3,4,5-THBA-β-CyD, shown in Figure 2, was synthesized by a similar procedure using 3,4,5-trihydroxybenzoic acid (3,4,5-THBA, 0.24 mmol) instead of 3,4-DHBA.

[0052] [Example 3] 3,4-DHCA-β-CyD shown in Figure 3 was synthesized by a similar procedure using 3,4-dihydroxycinnamic acid (3,4-DHCA, 0.24 mmol) instead of 3,4-DHBA, except that the synthesis of 3,4-DHCA-β-CyD was carried out at a 1 / 4 scale of that in Example 1.

[0053] [Example 4] 2,3-DHBA-β-CyD shown in Figure 4 was synthesized by a similar procedure using 2,3-dihydroxybenzoic acid (2,3-DHBA, 0.24 mmol) instead of 3,4-DHBA. However, the synthesis of 2,3-DHBA-β-CyD was carried out at a 1 / 4 scale of Example 1.

[0054] [Comparative Example 1] BA-β-CyD, shown in Figure 5, was synthesized by a similar procedure using benzoic acid (BA, 0.24 mmol) instead of 3,4-DHBA.

[0055] Comparative Example 2 2-HBA-β-CyD shown in Figure 6 was synthesized by a similar procedure using 2-hydroxybenzoic acid (2-HBA, 0.24 mmol) instead of 3,4-DHBA, except that the synthesis of 2-HBA-β-CyD was carried out at a 1 / 4 scale of that in Example 1.

[0056] Comparative Example 3 3-HBA-β-CyD shown in Figure 7 was synthesized by a similar procedure using 3-hydroxybenzoic acid (3-HBA, 0.24 mmol) instead of 3,4-DHBA, except that the synthesis of 3-HBA-β-CyD was carried out at a 1 / 4 scale of that in Example 1.

[0057] Comparative Example 4 4-HBA-β-CyD shown in Figure 8 was synthesized by a similar procedure using 4-hydroxybenzoic acid (4-HBA, 0.24 mmol) instead of 3,4-DHBA, except that the synthesis of 4-HBA-β-CyD was carried out at a 1 / 4 scale of Example 1.

[0058] Comparative Example 5 2,5-DHBA-β-CyD shown in Figure 9 was synthesized by a similar procedure using 2,5-dihydroxybenzoic acid (2,5-DHBA, 0.24 mmol) instead of 3,4-DHBA. However, the synthesis of 2,5-DHBA-β-CyD was carried out at half the scale of Example 1.

[0059] Comparative Example 6 2,6-DHBA-β-CyD shown in Figure 10 was synthesized by a similar procedure using 2,6-dihydroxybenzoic acid (2,6-DHBA, 0.24 mmol) instead of 3,4-DHBA. However, the synthesis of 2,6-DHBA-β-CyD was carried out at a 1 / 4 scale of Example 1.

[0060] Comparative Example 7 3,5-DHBA-β-CyD shown in Figure 11 was synthesized by a similar procedure using 3,5-dihydroxybenzoic acid (3,5-DHBA, 0.24 mmol) instead of 3,4-DHBA, except that the synthesis of 3,5-DHBA-β-CyD was carried out at a 1 / 4 scale of Example 1.

[0061] [Boron detection using each complex] [1] 3,4-DHBA-β-CyD (Example 1) A boron detection reagent was prepared by mixing a methanol solution of ferrocene with an aqueous solution of 3,4-DHBA-β-CyD, phosphate buffer, and sodium chloride dissolved in ultrapure water. The boron detection reagent had a ferrocene concentration of 0.5 mM, a 3,4-DHBA-β-CyD concentration of 1.5 mM, a phosphate concentration of 50 mM, and a sodium chloride concentration of 0.1 M. The methanol:water ratio was 1:9 (v / v), and the pH was 8.6. The pH was adjusted using aqueous sodium hydroxide and aqueous hydrochloric acid.

[0062] Next, boric acid was dissolved in ultrapure water, and various concentrations of boron aqueous solutions (boric acid concentrations of 0.5 mM, 1.0 mM, 1.5 mM, 2.0 mM, or 4.8 mM) were prepared. The boron detection reagent was then added to the boron detection reagent, and the potential range was changed from -1.0 to +1.4 V at a sweep rate of 0.1 Vs. -1 Cyclic voltammetry was performed using a three-electrode system consisting of a glassy carbon electrode (3 mm diameter) as the working electrode, a silver / silver chloride electrode (Ag / AgCl, 3 M, NaCl aq) as the reference electrode, and a platinum wire as the counter electrode. Measurements were performed three times for each boron concentration (n = 3). Before the experiment, the working electrode was polished, and the measurement solution was degassed with argon before each measurement. Graphs and calibration curves were created and analyzed using Microsoft Excel.

[0063] Figure 12 shows an overlay of cyclic voltammograms measured using each boron aqueous solution. Figure 13 shows the relationship between the boron concentration in each boron aqueous solution and the measured current value, based on the results of cyclic voltammetry measured using each boron aqueous solution. The results of Figures 12 and 13 demonstrate that boron in the above concentration range can be quantitatively detected based on the electrochemical signal that appears at a low potential (approximately +0.2 V) by using 3,4-DHBA-β-CyD prepared in Example 1 and ferrocene.

[0064] [2] 3,4-DHBA-β-CyD (Example 1) Analysis by cyclic voltammetry was performed in the same manner as in [1] above, except that boron aqueous solutions with boric acid concentrations of 0.1 mM, 0.2 mM, 0.3 mM, 0.4 mM, or 0.6 mM were used. Figure 14 shows an overlay of cyclic voltammograms measured using each boron aqueous solution. Figure 15 also shows the relationship between the boron concentration in each boron aqueous solution and the measured current, based on the results of cyclic voltammetry measured using each boron aqueous solution. The results in Figures 14 and 15 demonstrate that quantitative detection of boron within the above concentration range is possible using 3,4-DHBA-β-CyD and ferrocene prepared in Example 1, based on the electrochemical signal appearing at a low potential (approximately +0.2 V). From [1] above and this experiment, a single measurement could be performed in approximately several minutes, including solution preparation and argon degassing.

[0065] [3] Example 1, Comparative Example 1, Comparative Example 4, and Comparative Example 7 Next, using a boron aqueous solution with a boron concentration of 4.8 mM, 3,4-DHBA-β-CyD (Example 1), BA-β-CyD (Comparative Example 1), 4-HBA-β-CyD (Comparative Example 4), and 3,5-DHBA-β-CyD (Comparative Example 7) were analyzed by cyclic voltammetry in the same manner as in [1] above. In addition, for comparison, an experiment was also conducted in which analysis by cyclic voltammetry was performed in the same manner as in [1] above, except that a boron detection reagent not containing ferrocene was used.

[0066] The cyclic voltammogram measured using 4-HBA-β-CyD (Comparative Example 1) is shown in Figure 16, the cyclic voltammogram measured using 4-HBA-β-CyD (Comparative Example 4) is shown in Figure 17, the cyclic voltammogram measured using 3,4-DHBA-β-CyD (Example 1) is shown in Figure 18, and the cyclic voltammogram measured using 3,5-DHBA-β-CyD (Comparative Example 7) is shown in Figure 19. In addition, the cyclic voltammogram measured using a boron detection reagent containing 3,4-DHBA-β-CyD (Example 1) but not containing ferrocene is shown in Figure 20.

[0067] As can be seen from Figures 16 to 19, it was revealed that when a polyol capable of binding to boric acid is present, boron in an aqueous solution can be detected. Furthermore, as shown in Figures 18 and 20, when an electrochemically active species that is included in a cyclic compound is present, the electrochemical signal is enhanced by the electrochemically active species, making it possible to detect boron in an aqueous solution with high sensitivity. Furthermore, the LOD of this method was calculated using the slope of the calibration curve created from the measurement results and the standard deviation when [boron] = 0 M by the 3σ method, and was found to be 0.16 mgBL -1 It was calculated that:

[0068] [3] Examples 2 to 4 In addition, similar to [1] above, a boron aqueous solution with a boron concentration of 4.8 mM was used, and 3,4,5-THBA-β-CyD (Example 2), 3,4-DHCA-β-CyD (Example 3), and 2,3-DHBA-β-CyD (Example 4) were analyzed by cyclic voltammetry.

[0069] The cyclic voltammogram measured using 3,4,5-THBA-β-CyD (Example 2) is shown in Figure 21, and the cyclic voltammogram measured using 3,4-DHCA-β-CyD (Example 3) is shown in Figure 22. As can be seen from Figures 21 and 22, it was revealed that boron in an aqueous solution can be detected by using a polyol-cyclic compound composite having a polyol capable of binding to boric acid, even if it is other than 3,4-DHBA-β-CyD (Example 1).

[0070] [5] Measurement of actual samples Analysis was performed by cyclic voltammetry in the same manner as in [1] above, except that actual samples (rainwater, river water, or tap water) were used instead of the boron aqueous solution. The actual samples were used after suction filtration using a membrane filter (filter code: JHWP). The measurement results are shown in Table 1. In Table 1, the "added / mM" column indicates the actual boron concentration contained in the actual sample, the "found / mM" column indicates the boron concentration calculated from the measurement results, the "recovery / mM" column indicates the recovery rate indicated by the measurement results relative to the actual boron concentration, the "RSD%" column indicates the standard deviation, and the "Linearity" column indicates linearity.

[0071] [Table 1]

[0072] The results shown in Table 1 demonstrate that even when using actual samples, the boron concentration can be quantitatively measured by using 3,4-DHBA-β-CyD prepared in Example 1 and ferrocene.

[0073] [Reference data] Identification data for the polyol-cyclic compound composites synthesized in Examples 1 to 4 and Comparative Examples 1 to 7 are listed below. Example 1 Yield; 156 mg (0.12 mmol), 61.4 %; HR-MS (ESI-) (calcd for C 49 H 75 NO 37 ): m + / z = ​​1269.40244 (1269.40179); 1 H NMR (500MHz, D2O): δ 7.12-7.2 (t,2H), 6.88 (d,1H), 4.85-5.05 (m,7H), 3.35-4.05 (m,42H); 13C NMR (125MHz, D2O + 0.5 % acetone): δ 170.31, 115.69, 102.032, 101.96, 101.75, 101.84, 101.69, 101.60, 81.24, 81.14, 81.08, 81.01, 80.94, 80.84, 80.79, 80.75, 73.34, 73.32, 73.24, 73.17, 73.00, 72.82, 72.54, 72.16, 71.95, 71.77, 71.69, 71.53, 60.41, 60.24, 60.17, 51.53; UV-Vis (H2O at pH 6.0): λ max / nm(log 10 (ε / mol -1 dm 3 cm -1 )) = 257.5 (4.02), 290.0 (3.77). Example 2 Yield; 249 mg (0.19 mmol), 96.9 %; HR-MS (ESI-) (calcd for C 49 H 75 NO 38 ): m + / z = 1285.40405 (1285.39670); 1 H NMR (500MHz, D2O): δ 6.77-6.83 (s,2H), 4.84-5.07 (m,7H), 3.37-4.07 (m,42H); 13 C NMR (125MHz, D2O + 0.5 % acetone): δ 170.35, 145.13, 137.16, 125.06, 124.93, 124.83, 124.75, 117.67, 111.30, 102.10, 102.05, 101.86, 101.81, 101.68, 101.63, 101.40, 101.15, 81.34, 81.15, 81.03, 80.92, 73.21, 73.13, 72.05, 71.99, 71.88, 71.80, 60.39, 60.30, 60.20, 51.49; UV-Vis (H2O at pH 6.5): λmax / nm(log 10 (ε / mol -1 dm 3 cm -1 )) = 268.0 (3.81). Example 3 Yield; 47 mg (0.04 mmol), 72.6 %; MS (ESI-) (calcd for C 51 H 77 NO 37 ): m + / z = 1295 (1295); 1 H NMR (500MHz, D2O): δ 7.25-7.33 (d,1H), 6.71-6.95 (d and s,3H), 5.31-5.39 (d,1H), 4.85-5.00 (m,7H), 3.20-4.00 (m,42H). Example 4 Yield; 69 mg (0.05 mmol), 54.4 %; HR-MS (ESI-) (calcd for C 49 H 74 NO 37 ([M-H])): m + / z = 1268.2099 (1268.39397); UV-Vis (H2O): λ max / nm(log 10 (ε / mol -1 dm 3 cm -1 )) = 306.5 (3.50). Comparative Example 1 Yield; 171 mg (0.14 mmol), 69.1 %; HR-MS (ESI-) (calcd for C 49 H 74 NO 35 ([M-H])): m + / z = 1236.40793 (1236.40414); 1H NMR (500MHz, D2O): δ 7.50-7.55 (t,2H), 7.61-7.68 (m,3H), 4.90-5.07 (m,7H), 3.35-3.99 (m,42H); 13 C NMR (125MHz, D2O + 0.5 % acetone): δ 170.38, 170.36, 131.85, 128.92, 126.66, 102.89, 102.39, 102.30, 101.99, 101.69, 100.60, 100.57, 81.65, 81.40, 81.20, 81.16, 80.61, 80.41, 73.46, 72.25, 72.14, 72.09, 72.04, 71.92, 60.55, 60.32, 60.28, 60.21, 51.26; UV-Vis (H2O at pH 6.0): λ max / nm(log 10 (ε / mol -1 dm 3 cm -1 )) = 226.5 (3.98); elemental analysis (calculated for C 49 H 75 NO 35 ): C 43.b87 (47.57) %, H 6.56 (6.11) %, and N 1.14 (1.13) %. Comparative Example 2 Yield; 49 mg (0.04 mmol), 78.2 %; HR-MS (ESI-) (calcd for C 49 H 74 NO 36 ([M-H])): m + / z = 1252.39281 (1252.39905); 1 H NMR (500MHz, D2O): δ 7.76-7.80 (d,1H), 7.41-7.47 (t,1H), 6.97-7.04 (t,1H), 6.82-6.87 (d,1H), 4.78-5.05 (m,7H), 3.06-4.03 (m, 42H); UV-Vis (H2O at pH 5.8): λ max / nm(log 10 (ε / mol -1 dm 3 cm -1 )) = 236.5 (3.94), 296 (3.54). Comparative Example 3 Yield; 43 mg (0.03 mmol), 68.61 %; HR-MS (ESI-) (calcd for C 49 H 74 NO 36 ([M-H])): m + / z = 1252.40611 (1252.39905); 1 H NMR (500MHz, D2O): δ 7.28-7.34 (t,1H), 7.10-7.16 (d,1H), 6.98-7.03 (d and s,2H), 4.77-5.01 (m,7H), 3.26-4.01 (m,42H); UV-Vis (H2O at pH 7.0): λ max / nm(log 10 (ε / mol -1 dm 3 cm -1 )) = 291.5 (3.38). Comparative Example 4 Yield; 261 mg (0.21 mmol), 105.0 %; HR-MS (ESI-) (calcd for C 49 H 74 NO 36 ([M-H])): m + / z = 1252.40253 (1252.39905); 1 H NMR (500MHz, D2O): δ 7.53-7.61 (d,2H), 6.8-6.89 (d,2H), 4.85-5.06 (m,7H), 3.31-4.10 (m,42H); 13C NMR (125MHz, D2O + 0.5 % acetone): δ 170.23, 129.32, 115.586, 102.03, 101.97, 101.80, 101.75, 101.75, 101.67, 101.60, 101.57, 101.54, 101.54, 81.25, 81.12, 80.94, 80.89, 80.83, 73.17, 72.14, 71.91, 71.87, 71.68, 71.56, 60.40, 60.30, 60.18, 60.12, 51.52; UV-Vis (H2O at pH 6.0): λ max / nm(log 10 (ε / mol -1 dm 3 cm -1 )) = 253.5 (3.96). Comparative Example 5 Yield; 103 mg (0.08 mmol), 40.5 %; HR-MS (ESI-) (calcd for C 49 H 74 NO 37 ([M-H])): m + / z = 1268.39656 (1268.39397); 1 H NMR (500MHz, D2O): δ 7.28-7.32 (s,1H), 6.98-7.03 (d,1H), 6.71-6.75 (d,1H), 4.85-5.05 (m,7H), 3.35-4.05 (m,42H); 13 C NMR (125MHz, D2O + 0.5 % acetone): δ 121.43, 102.33, 102.09, 101.88, 101.60, 101.49, 100.40, 81.13, 80.77, 73.33, 73.19, 73.08, 72.63, 72.27, 72.19, 72.16, 72.06, 71.99, 71.74, 71.65, 60.64, 60.45, 60.33, 60.24, 60.10, 50.97; UV-Vis (H2O at pH 5.9): λ max / nm(log 10(ε / mol -1 dm 3 cm -1 )) = 322.0 (3.60); elemental analysis (calculated for C 49 H 75 NO 37 ): C 46.10 (46.34) %, H 5.96 (5.95) %, and N 1.19 (1.10) %. Comparative Example 6 Yield; 22 mg (0.02 mmol), 34.7 %; HR-MS (ESI-) (calcd for C 49 H 74 NO 37 ([M-H])): m + / z = 1268.48103 (1268.39397); 1 H NMR (500MHz, D2O): δ 7.09-7.13 (t,1H), 6.24-6.28 (d,2H), 4.85-5.01 (m,7H), 3.2-3.96 (m,42H), 3.35-4.05 (m,42H); UV-Vis (H2O at pH 7.0): λ max / nm(log 10 (ε / mol -1 dm 3 cm -1 )) = 248.0 (3.82), 308.0 (3.45). Comparative Example 7 Yield; 49 mg (0.04 mmol), 77.2 %; HR-MS (ESI-) (calcd for C 49 H 75 NO 37 ): m + / z = 1268.39752 (1268.39397); 1 H NMR (500MHz, D2O): δ 6.57-6.60 (s,2H), 6.50-6.53 (s,1H), 4.86-5.00 (m,7H), 3.23-3.89 (m,42H); UV-Vis (H2O at pH 7.5): λ max / nm(log 10 (e / mol) -1 dm 3 cm -1 )) = 248.5 (3.83), 299.0 (3.47).

Claims

1. a cyclic compound having clathration ability for electrochemically active species; a polyol having a binding ability to boric acid; A polyol-cyclic compound composite having the formula:

2. 2. The polyol-cyclic compound composite according to claim 1, wherein the polyol has an aromatic diol group capable of forming a complex with boric acid.

3. The polyol-cyclic compound composite according to claim 2, wherein the aromatic diol group is an aromatic diol group selected from the group consisting of a catechol group having hydroxy groups on adjacent carbon atoms of a benzene ring, a naphthalenediol group having hydroxy groups on adjacent carbon atoms of a naphthalene ring, and a naphthalenediol group having hydroxy groups at the 1- and 8-positions of a naphthalene ring.

4. The polyol-cyclic compound composite according to claim 1, wherein the polyol is one polyol selected from the group consisting of 3,4-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, and 3,4-dihydroxycinnamic acid.

5. The polyol-cyclic compound conjugate according to claim 1, wherein the cyclic compound is a sugar cyclic compound.

6. The polyol-cyclic compound complex according to claim 5, wherein the sugar cyclic compound is a cyclodextrin or a cyclodextrin derivative.

7. The polyol-cyclic compound conjugate according to claim 1, which is used for detecting boron.

8. 2. The polyol-cyclic compound composite according to claim 1, wherein the electrochemically active species is ferrocene or a ferrocene derivative.

9. The polyol-cyclic compound composite according to any one of claims 1 to 8, and an electrochemically active species that is included in the cyclic compound in the polyol-cyclic compound complex.

10. The boron detection reagent according to claim 9, wherein the electrochemically active species is ferrocene or a ferrocene derivative.

11. A step of mixing the polyol-cyclic compound complex according to any one of claims 1 to 8, a boron detection reagent containing an electrochemically active species included in the cyclic compound in the polyol-cyclic compound complex, and a test sample; detecting an electrochemical signal; A boron detection method for detecting boron contained in the test sample based on a change in an electrochemical signal.

12. 12. The method for detecting boron according to claim 11, wherein the electrochemically active species is ferrocene or a ferrocene derivative.

13. The boron detection method according to claim 11, wherein the amount of boron contained in the test sample is determined based on the amount of change in the detected electrochemical signal.

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