KR102110888B1 - Novel rhodamine-fluorene-rhodamine based compounds and chemosensor for selective detection of mercury ions comprising the same - Google Patents

Abstract

The present invention relates to a novel rhodamine-fluorene-rhodamine compound and a method for detecting mercury ions using the same, wherein the rhodamine-fluorene-rhodamine compound has improved sensitivity and selectivity to harmful mercury ions present in an aqueous solution, thereby being able to detect mercury ions in a water-soluble analysis sample with high selectivity by more quickly and simply identifying colorimetric or fluorescent signals.

Description

Novel RHODAMINE-FLUORENE-RHODAMINE BASED COMPOUNDS AND CHEMOSENSOR FOR SELECTIVE DETECTION OF MERCURY IONS COMPRISING THE SAME}

The present invention relates to a novel rhodamine-fluorene-rhodamine compound, a composition for detecting mercury ions comprising the same, and a method for detecting mercury ions using the same. In addition, the present invention relates to an ink composition for detecting mercury ions containing the rhodamine-fluorene-rhodamine compound, a test strip for detecting mercury ions using the same, and a method for detecting mercury ions using the same. In addition, the present invention relates to a chemical sensor for detecting mercury ions, including the rhodamine-fluorene-rhodamine compound, a composition for detecting mercury ions, or a test strip for detecting mercury ions.

The development of chemical sensors for the detection of metal ions has recently attracted attention due to their potential role in biological, environmental and medicinal applications.

Mercury is ranked as the heavy metal with high environmental and health priorities in terms of occurrence frequency, toxicity, and human hazard, and is the third most common according to the list of the Agency for toxic substances and disease registry (ATSDR). It is a heavy metal that is found and exhibits the second highest toxicity.

The World Health Organization (WHO) limits the mercury tolerance in drinking water standards to 0.001 mg / L. In particular, a mercury ion harmful toxic transition metal in the human body (Hg ^{2 +)} is is water methylmercury compounds (CH ₃ HgX, X = Cl, such as ^-, Br ^{- -,} AcO) neurotoxicity by the bacteria in the water system easier as It can be incorporated into lipophilic chemical species, including organic mercury species that are not absorbed or released well.

Specifically, mercury is converted into an ionic form (Hg ^{2 +} ) that is well soluble in water, causing water pollution, and easily accumulates in fish that survive in the contaminated water, or agricultural products produced using the water quality. That is, ionic mercury accumulates in humans through the food chain, and the amount of contamination accumulated in humans, the last stage of the food chain, becomes quite high.

Mercury absorbed in the human body is combined with blood and protein in the tissue, making it difficult to discharge mercury outside the body and accumulating in the human body. Symptoms caused by short-term exposure of mercury affect the central nervous system, causing ataxia, cognitive impairment, optic nerve disorders, hearing nerve damage, and nervous system development disorders in infants, and neurosensitization, depression, and personality disorders in long-term exposure. It is known to show symptoms of. In addition, it has been reported that genotoxic processes can occur when exposed to relatively low concentrations of mercury for a long time.

Therefore, interest in chemical sensors for monitoring the presence or absence of very low concentrations of mercury ions (Hg ^{2 +} ) in aqueous systems has increased.

Accordingly, research on various separation and analysis methods has been continuously conducted for the past several decades to selectively quantitatively analyze trace amounts of mercury. In general, methods developed for quantitative analysis of mercury include atomic absorption spectroscopy, voltammetry spectrophotometry, and inductively coupled plasma-ductivemass spectroscopy (ICP-MS). However, this method requires expensive equipment, is time consuming, and involves a difficult process that can only be performed by trained professionals.

On the other hand, optical detection through colorimetric and fluorescence changes is useful for Hg ^{2 +} ion detection due to its high sensitivity, instant response time and low detection limit.

Rhodamine derivatives are excellent chromophores or fluorophores, and are of great interest due to their very good photophysical properties such as long absorption and emission wavelengths, large absorption coefficients and high fluorescence quantum yield. Has become the subject of.

Derivatives containing spirolactam in the structure of rhodamine do not exhibit color and fluorescence, but they form complexes with metal ions and, when the spirolactam ring is opened, a distinct color and strong fluorescence emission occur. Rhodamine frame work is particularly suitable for designing off-on fluorescent or colorimetric chemical sensors due to its unique structural features. From these changes, studies are being conducted to quantitatively detect metal ions using a rhodamine derivative.

Conventionally, various chemical sensors for selectively recognizing mercury ions have been proposed. Specifically there may be mentioned the mercury ions with the phosphorescent compound (Hg ^{+ 2)} detecting chemical sensor, or a mercury ion with a fluorescent compound (Hg ^{+ 2)} detecting the chemical sensor or the like (see Patent Documents 1 and 2).

However, the chemical sensors have a problem in that they cannot detect mercury ions below a ppm unit or selectively detect mercury ions when they are interfered with by other metal ions. Therefore, the development of a chemical sensor having a high selectivity for mercury ions is still in demand.

The currently reported sensor material for mercury ions is difficult to apply to the environment and bio fields due to low selectivity to mercury ions, sensitivity, and solubility in water.

Chemical sensors for mercury ions (Hg ^{2 +} ) should not be affected by metals other than mercury, must be sensitive to mercury ions at low concentrations and below ppm, and must have a certain amount of It also needs to work in solutions containing water.

Republic of Korea Patent Publication No. 2010-0106005 Republic of Korea Patent Publication No. 2009-0070860 Republic of Korea Registered Patent No. 10-1642406

The object of the present invention is to provide a novel rhodamine-fluorene-rhodamine compound.

It is also an object of the present invention to provide a composition for the detection of mercury ions containing the rhodamine-fluorene-rhodamine compound.

It is also an object of the present invention to provide a method for detecting mercury ions using the rhodamine-fluorene-rhodamine compound or a composition for detecting mercury ions.

It is also an object of the present invention to provide an ink composition for the detection of mercury ions containing the rhodamine-fluorene-rhodamine compound.

It is also an object of the present invention to provide a test sheet for detecting mercury ions using the ink composition for detecting mercury ions.

It is also an object of the present invention to provide a method for detecting mercury ions using a test strip for detecting mercury ions.

It is also an object of the present invention to provide a chemical sensor for detecting mercury ions, including the rhodamine-fluorene-rhodamine compound, a composition for detecting mercury ions, or a test strip for detecting mercury ions.

For the above-mentioned purpose, a rhodamine-fluorene-rhodamine compound represented by the following formula (1) is provided.

[Formula 1]

(In the formula 1,

R ₁ and R ₂ are each independently hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, halo C1-C20 alkyl or C6-C20 aryl;

L ₁ and L ₂ are each independently C6-C20 arylene;

R ₃ to R ₆ are each independently hydrogen, C1-C20 alkyl, C2-C20 alkenyl or C2-C20 alkynyl;

R ₇ and R ₈ are each independently hydrogen or C1-C20 alkyl.)

The compound of Formula 1 according to an embodiment of the present invention, wherein R ₁ and R ₂ are each independently C1-C20 alkyl; L ₁ and L ₂ are each independently C6-C20 arylene; R ₃ to R ₆ are each independently hydrogen or C1-C20 alkyl; R ₇ and R ₈ may each independently be hydrogen or C 1 -C 20 alkyl.

The compound of Formula 1 according to an embodiment of the present invention, L ₁ and L ₂ may be each independently phenylene, naphthalene, biphenylene or anthracenylene.

The compound of Formula 1 according to an embodiment of the present invention, wherein R ₁ and R ₂ are C1-C10 alkyl; R ₃ and R ₅ are hydrogen; R ₄ and R ₆ are each independently C1-C7 alkyl; R ₇ and R ₈ may each independently be hydrogen or C 1 -C ₇ alkyl.

The compound of Chemical Formula 1 according to an embodiment of the present invention may be represented by the following Chemical Formula 2.

[Formula 2]

(In the formula 2,

R ₁ and R ₂ are C1-C10 alkyl;

R ₄ and R ₆ are each independently C1-C4 alkyl;

R ₇ and R ₈ are each independently hydrogen or C1-C4 alkyl.)

The compound of Formula 1 according to an embodiment of the present invention may be for the detection of mercury ions.

In addition, the present invention provides a composition for the detection of mercury ions comprising the rhodamine-fluorene-rhodamine compound of Formula 1 above.

In addition, the present invention comprises the steps of contacting an analytical sample with a composition for detecting a rhodamine-fluorene-rhodamine compound of Formula 1 or the mercury ion; And confirming an optical change of the compound or the composition.

In the method for detecting mercury ions according to an embodiment of the present invention, the optical change may be confirmed through at least one of a color change, an absorbance change, and a fluorescence intensity change of the compound.

In the method for detecting mercury ions according to an embodiment of the present invention, the analysis sample may be a water-based analysis sample.

In addition, the present invention is a rhodamine-fluorene-rhodamine compound of Formula 1; And it provides an ink composition for the detection of mercury ions containing a solvent.

In the ink composition according to an embodiment of the present invention, the solvent is water, ethanol, glycerol, N, N-dimethylformamide, dichloromethane, chloroform, dimethylsulfoxide, ethyl acetate, acetonitrile, methanol and tetra It may be one or more selected from hydrofuran.

In addition, the present invention provides a test sheet for detecting mercury ions in which the ink composition for detecting mercury ions is printed on a substrate.

In addition, the present invention comprises the steps of producing a test sheet for detecting mercury ions by printing the ink composition for detecting mercury ions on a substrate; Contacting the test sample with the test strip; And identifying an optical change. A method of detecting mercury ions is provided.

In the method for detecting mercury ions according to an embodiment of the present invention, the substrate may be selected from the group consisting of filter paper, paper, and cellulose paper.

In the method for detecting mercury ions according to an embodiment of the present invention, the optical change may be confirmed through at least one of a color change, an absorbance change, and a fluorescence intensity change of the compound.

In the method for detecting mercury ions according to an embodiment of the present invention, the analysis sample may be a water-based analysis sample.

In addition, the present invention provides a chemical sensor for detecting mercury ions, including a rhodamine-fluorene-rhodamine compound of Formula 1, a composition for detecting mercury ions, or a test strip for detecting mercury ions.

Fluorene-Rhodamine Rhodamine compound according to the invention in spite of a novel compound, as well as having a high selectivity with respect to the aqueous medium in the mercury ion (Hg ^{+ 2),} a very small amount of mercury ions (Hg ²⁺⁾ concentration And since colorimetric or fluorescence changes can be confirmed, the presence or absence of mercury ions can be easily detected with the naked eye or fluorescence.

In addition, the rhodamine-fluorene-rhodamine compound according to the present invention has excellent solubility in water due to the fluorene moiety, so it is eco-friendly and advantageous for application in the environment and bio fields.

In addition, the rhodamine-fluorene-rhodamine compound according to the present invention can be used as a dye for an ink composition for digital printing, and a test paper for mercury ion detection by printing in a predetermined pattern on a paper substrate using an ink composition containing the same Can be produced. Portable, that is the prepared test and can be selectively detected at any time, and detects the ionic mercury (Hg ^{+ 2)} in various locations to show high sensitivity and selectivity for mercury ions.

In addition, by using the chemical sensor containing the rhodamine-fluorene-rhodamine compound according to the present invention, the presence or absence of mercury ions can be visually confirmed, so that colorimetric or fluorescent signals are faster and simpler without the need for additional complicated equipment. By checking, mercury ions in an aqueous medium can be detected.

Figure 1-shows the ability to detect mercury ions (Hg ^{2 +} ) in aqueous solution of the receptor R of Example 1, showing the reaction result when a 2 × 10 ^-5 M cation and a 1 × 10 ^-5 M receptor R are present Photo [Top: As a result of visual observation, Bottom: As a result of irradiating a UV lamp (λex = 360nm)]
Figure 2-UV-vis absorption spectrum change of receptor R (1 × 10 ^-5 M) for mercury ions at various concentrations (0-2.0 eqv.)
Figure 3-Fluorescence spectrum change of receptor R (1 × 10 ^-5 M) for mercury ions at various concentrations (0-2.0 eqv.)
Figure 4-Graph showing metal ion selectivity of receptor R (UV-vis absorption)
Fig. 5-Graph showing metal ion selectivity of receptor R (fluorescence)
Figure 6-Receptor R (bottom) and Receptor R + 2eqv. Hg ^{2 + 1} H NMR (above)
Figure 7-Receptor R (bottom) and Receptor R + 2eqv. Hg ^{2 +} (top) ¹³ C NMR
Figure 8-MALDI-TOF mass spectrum of complex of receptor R and mercury ion in DMF-d ₇ of Example 5
Figure 9-FT-IR spectrum of the complex of receptor R and mercury ions in DMF-d ₇ of Example 5 [bottom: receptor R, top: complex of receptor R and mercury ion]
Figure 10-SEM image [A: pure polyurethane nanofibers, B: receptor R / polyurethane electrospinning nanofibers]
Figure 11-Fluorescent confocal image of receptor R-blended electrospun nanofibers before and after the addition of mercury ions
12-Color and fluorescence change photographs of test strips composed of receptor R-blended electrospun nanofibers before and after the addition of mercury ions
Fig. 13-Overall process of digital printing using receptor R
Figure 14-Photo of color and fluorescence changes before and after the addition of mercury ions on filter paper digitally printed with Receptor R

Hereinafter, the present invention will be described in more detail. Unless otherwise defined in the technical terms and scientific terms used at this time, those skilled in the art to which this invention belongs have meanings that are commonly understood, and the following description unnecessarily obscures the subject matter of the present invention. Descriptions of possible known functions and configurations are omitted.

As used herein, the term “alkyl” refers to a functional group derived from a straight-chain or pulverized hydrocarbon. In addition, the alkyl and alkyl-containing substituents according to the present invention is preferably a short chain having 1 to 7 carbon atoms, and may be preferably selected from methyl, ethyl, propyl and butyl, but is not limited thereto.

Also, the term “alkenyl” in the present specification means a functional group derived from a straight-chain or pulverized hydrocarbon containing one or more double bonds, and “alkynyl” is a straight-chain or pulverized form containing one or more triple bonds. It means a functional group derived from hydrocarbon.

The present invention relates to a novel rhodamine-fluorene-rhodamine compound and a chemical sensor for the detection of mercury ions containing the same, the harmful mercury ions present in an aqueous solution using the rhodamine-fluorene-rhodamine compound It is intended to be highly selective.

Hereinafter, the rhodamine-fluorene-rhodamine compound of the present invention and its application will be described in detail.

The novel rhodamine-fluorene-rhodamine compound according to the present invention may be a compound represented by Formula 1 below.

[Formula 1]

(In the formula 1,

R ₁ and R ₂ are each independently hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, halo C1-C20 alkyl or C6-C20 aryl;

L ₁ and L ₂ are each independently C6-C20 arylene;

R ₃ to R ₆ are each independently hydrogen, C1-C20 alkyl, C2-C20 alkenyl or C2-C20 alkynyl;

R ₇ and R ₈ are each independently hydrogen or C1-C20 alkyl.)

The rhodamine-fluorene-rhodamine compound of Chemical Formula 1 has a dual channel structure in which rhodamine derivatives are bonded to both sides through a fluorene linking group, thereby increasing the solubility in the water-based medium, thereby improving selectivity for mercury ions in the water-based medium. Increased.

From the side to allow a good solubility in the aqueous medium for the implementation, Rhodamine of Formula 1-fluorene-rhodamine compounds wherein R ₁ and R ₂ may be each independently a C1-C20 alkyl. That is, in the rhodamine-fluorene-rhodamine compound of Chemical Formula 1, an alkyl group is introduced at the 9th position of the fluorene linking group to further improve the solubility in the aqueous medium and at the same time to receive a significant amount of water from the solvent of the analyte sample. Was made possible.

Specifically, the rhodamine-fluorene-rhodamine compound of Chemical Formula 1 has R ₁ and R ₂ each independently being C ₁ -C 20 alkyl; L ₁ and L ₂ are each independently C6-C20 arylene; R ₃ to R ₆ are each independently hydrogen or C1-C20 alkyl; R ₇ and R ₈ may each independently be hydrogen or C 1 -C 20 alkyl.

In addition, the rhodamine-fluorene-rhodamine compound of Chemical Formula 1 may have L ₁ and L ₂ each independently being phenylene, naphthalene, biphenylene, or anthracenylene.

In terms of enabling selective detection of mercury ions in an aqueous medium, the rhodamine-fluorene-rhodamine compound of Formula 1 is wherein R ₁ and R ₂ are C 1 -C 10 alkyl; R ₃ and R ₅ are hydrogen; R ₄ and R ₆ are each independently C1-C7 alkyl; R ₇ and R ₈ may each independently be hydrogen or C 1 -C ₇ alkyl.

More preferably, the rhodamine-fluorene-rhodamine compound of Chemical Formula 1 may be a rhodamine-fluorene-rhodamine compound represented by the following Chemical Formula 2.

[Formula 2]

(In the formula 2,

R ₁ and R ₂ are C1-C10 alkyl;

R ₄ and R ₆ are each independently C1-C4 alkyl;

R ₇ and R ₈ are each independently hydrogen or C1-C4 alkyl.)

More specifically, the rhodamine-fluorene-rhodamine compound of Formula 1 may be a compound having the following structure, but is not limited thereto.

The rhodamine-fluorene-rhodamine compound of Chemical Formula 1 is a novel compound having high sensitivity and selectivity to mercury ions, and is capable of selectively detecting mercury ions by forming a mercury-complex upon contact with mercury ions It is a chromosome.

In detecting mercury ions, a mercury-complex is formed by reacting with mercury ions in the rhodamine-fluorene-rhodamine compound analysis sample of Chemical Formula 1, and a change in color may be exhibited by the mercury-composite. As shown in Scheme 1 below, the compound (a) can react with 2 equivalents of mercury ions (Hg ^{2 +} ) to form a mercury ion-R complex (b). The mercury ion-R complex (b) can provide optical properties that are distinct from compound (a).

[Scheme 1]

The rhodamine-fluorene-rhodamine compound of Chemical Formula 1 may be prepared by reacting a rhodamine hydrazide compound (ii) with a fluorene derivative compound (v), as shown in Scheme 1 below. The rhodamine hydrazide compound (ii) can be prepared by reacting a rhodamine derivative compound (i) with hydrazine in an alcohol solvent, and the fluorene derivative compound (v) is halofluorene derivative compound (iii) and formyl It can be prepared by reacting a ronic acid derivative compound (iv-1, iv-2). More details are described in Example 1 below. However, the method for preparing the rhodamine-fluorene-rhodamine compound of the present invention is not limited to the following scheme 1, and it can be synthesized by various methods using a known organic reaction.

[Scheme 1]

(In Reaction Scheme 1, R ₁ to R ₈ , L ₁ and L ₂ are the same as defined in Formula 1.)

The present invention provides a composition for the detection of mercury ions comprising the rhodamine-fluorene-rhodamine compound of Formula 1 above.

According to one embodiment, the composition may be a composition comprising a rhodamine-fluorene-rhodamine compound of Formula 1 and a solvent.

The solvent may be used without limitation as long as it is a solvent capable of dissolving the compound. For example, methanol, ethanol, isopropanol, n-propanol, n-butanol, tert-butanol, benzene, toluene, xylene, diethyl Ether, diisopropyl ether, tetrahydrofuran (THF), ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, acetone, trichloroethylene, 1,2-dichloroethane, tetrachloromethane, chloroform, dichloromethane (DCM), Acetamide, dimethylacetamide, N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), water, ethyl acetate, and the like.

Preferably, it may be one or more solvents selected from dichloromethane, chloroform, dimethylformamide (DMF), dimethylsulfoxide (DMSO), ethyl acetate, water, acetonitrile, methanol, ethanol and tetrahydrofuran. More preferably, it can be water. When water is used as the solvent, toxicity by an organic solvent may be lowered, and it may be advantageous for applications in bio and environmental fields such as cells.

The present invention provides a rhodamine-fluorene-rhodamine compound / polyurethane electrospinning nanofiber by electrospinning the rhodamine-fluorene-rhodamine compound of Formula 1 with polyurethane.

The spinning solution and the electrospinning method for this are not particularly limited, and those conventionally used in the art may be used.

The present invention provides a method for detecting mercury ions using a composition for detecting a rhodamine-fluorene-rhodamine compound of Formula 1 or mercury ions.

More specifically, the detection method comprises the steps of contacting an analytical sample with a composition for detecting a rhodamine-fluorene-rhodamine compound or mercury ion of Formula 1; And confirming the optical change of the compound or the composition.

The analysis sample may be an aqueous analysis sample, and when a mercury compound is present in the analysis sample by contacting the analysis sample with the compound or the composition, the compound and mercury ions may react to form a mercury-complex. .

The optical change is an optical change that occurs when the mercury-composite is formed in the compound or the composition, and can be confirmed through at least one of a color change, an absorbance change, and a fluorescence intensity change of the compound or the composition. More specifically, qualitative and quantitative analysis of mercury ions can be performed by visually observing the color change of the compound or the composition to confirm the presence of a mercury compound or by using a UV-Vis spectrometer or the like to observe absorption band changes and fluorescence changes. Can be.

For example, when mercury ions are present in the analytical sample, the color of the compound or the composition changes from colorless to pink, and thus the presence of mercury ions can be visually detected, and the absorbance according to the UV-Vis spectrometer In the measurement, the intensity of the absorption band in the 537 nm region is increased. In addition, the yellow fluorescent light is emitted by the excitation light, and the emission peak in the 553 nm region can be confirmed by the excitation light. In addition, by changing the intensity of the absorption band and the emission peak of the compound according to the present invention according to the concentration of mercury ions, it can be used for quantitative and qualitative analysis of mercury ions.

The present invention provides an ink composition for the detection of mercury ions comprising the rhodamine-fluorene-rhodamine compound of Formula 1 above.

According to one embodiment, the composition may be a composition comprising a rhodamine-fluorene-rhodamine compound of Formula 1 and a solvent.

The rhodamine-fluorene-rhodamine compound of Chemical Formula 1 may be used as a dye for an ink composition for digital printing.

The solvent may be used without limitation as long as it is a solvent capable of dissolving the compound, but preferably, a polar protic solvent may be used. The polar quantum solvent may be water, alcohol or a combination thereof. For example, the solvent may be a mixed solvent of water and alcohol. The alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. For example, the alcohol may be methanol, ethanol, isopropanol, n-propanol, n-butanol, tert-butanol, ethylene glycol or glycerol. Preferably, it may be a mixed solvent of water, ethanol and glycerol.

The present invention provides a test sheet for detecting mercury ions, wherein the ink composition for detecting mercury ions comprising the rhodamine-fluorene-rhodamine compound of Formula 1 is printed on a substrate.

A test paper for detecting mercury ions may be prepared by printing in a predetermined pattern on a paper substrate using a digital printing ink composition containing the rhodamine-fluorene-rhodamine compound of Formula 1 as a dye.

The present invention provides a method for detecting mercury ions using a test strip for detecting mercury ions, wherein an ink composition for detecting mercury ions comprising the rhodamine-fluorene-rhodamine compound of Formula 1 is printed on a substrate.

More specifically, the detection method is to print a composition for detecting mercury ions by printing an ink composition for detecting mercury ions containing the rhodamine-fluorene-rhodamine compound of Formula 1 in a predetermined pattern on a substrate. To do; Contacting the test sample with the test strip; And confirming the optical change.

The substrate may be selected from the group consisting of filter paper, paper and cellulose paper.

In one example, after injecting the ink composition into the cartridge, applying an ink in a predetermined pattern shape on a substrate using an inkjet printer; And it may include a step of drying completely to produce a test sheet for mercury ion detection. It is natural that the predetermined pattern shape can be printed as desired by the user.

In one example, the predetermined pattern printed with the ink composition containing the rhodamine-fluorene-rhodamine compound of Chemical Formula 1 is colorless and fluorescence, but detects mercury ions upon contact with an analysis sample containing mercury ions Instantaneous color change, absorbance change or fluorescence intensity change can be exhibited. Therefore, the prepared test strip is easy to carry and exhibits high sensitivity and selectivity to mercury ions, so that mercury ions can be selectively detected and detected at any time in various places.

The analysis sample may be a water-based analysis sample, rhodamine-fluorene of Formula 1 in a predetermined pattern printed on the test sheet when a mercury compound is present in the analysis sample by contacting the test sample with the test sheet Rhodamine compounds can react to form mercury-complexes.

The optical change is an optical change that occurs when the mercury-composite is formed on the test sheet, and can be confirmed through at least one of a color change, an absorbance change, and a fluorescence intensity change of a predetermined pattern printed on the test sheet. More specifically, the color change of the predetermined pattern printed on the test sheet is visually observed to confirm the presence of a mercury compound or the absorption band change and fluorescence change are observed using a UV-Vis spectrometer, etc. Quantitative analysis is possible.

For example, when mercury ions are present in the analytical sample, the color of a predetermined pattern printed on the test strip changes from colorless to pink, so that the presence of mercury ions can be visually detected, and the UV-Vis spectrometer In the measurement of the absorbance, the intensity of the absorption band in the 537 nm region increases. In addition, the yellow fluorescent light is emitted by the excitation light, and the emission peak in the 553 nm region can be confirmed by the excitation light.

The present invention is a rhodamine-fluorene-rhodamine compound of Formula 1, a composition for detecting the mercury ion, a rhodamine-fluorene-rhodamine compound / polyurethane electrospun nanofiber or a test strip for detecting the mercury ion It provides a chemical sensor for the detection of mercury ions containing.

In one example, the chemical sensor may be a chemical sensor that quickly and accurately detects mercury ions known as harmful components in the environment and bio fields with high selectivity and sensitivity.

The rhodamine-fluorene-rhodamine compound and the composition for detecting hydrogen ions comprising the same are applied as a powder, gel, emulsion, or liquid, or a molded article, or an analysis chip, electrical circuit, fiber, pulp, polymer film, It can be applied to the chemical sensor by coating or impregnating on a support such as a glass substrate.

The chemical sensor may qualitatively and / or quantitatively analyze the color change of the rhodamine-fluorene-rhodamine compound, the composition, or the test strip visually or electrically or optically.

The chemical sensor may be in the form of a kit for mercury ion detection, the kit may further include an absorbance, a fluorescence intensity meter, etc., and the meter may be integrated with the kit or may be configured separately.

Hereinafter, examples of the present invention will be described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.

All reagents and solvents were of analytical grade and used without further purification. Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Mg ^{2 +} , Ca ^{2 +} , Fe ^{2 +} , Co ^{2 +} , Ni ^{2 +} , Cu ^{2 +} , Zn ^{2 +} , Ag ⁺ , Cd ^{2 +} , Al ^{3 +} , Fe ^{3 +} and Hg ^{2 +} metal ions were purchased from Aldrich and Alfa Aesar as perchlorate salts and used directly without further purification. Flash column chromatography was performed on chromatography silica gel (230-400 mesh). Structural analysis of the product is ¹ H NMR and ¹³ C NMR (Bruker Avance 300 MHz instrument (1H NMR 300 MHz, 13C NMR 100 MHz), ESI-mass (Thermo Scientific LTQ Orbi-trap XL Fourier transform mass spectrometer), FT-IR (Perkin Elmer Spectrum One spectrophotometer equipped with a diamond probe ATR attachment (neat sample)) The morphology of the nanofibers was confirmed using TESCAN-Vega II / LSU (Czech Republic), and thermal transfer Thermal ink-jet printing was performed using an MG2590 inkjet printer (Canon).

[Example 1] 2,2 ''-(((1E, 1'E)-((9,9-dioctyl-9H-fluorene-2,7-diyl) bis (4,1-phenylene)) bis ( methanylylidene)) bis (azanylylidene)) bis (3 ', 6'-bis (ethylamino) -2', 7'-dimethylspiro [isoindoline-1,9'-xanthen] -3-one) (hereinafter 'receptor R ( receptor R) ')

Step 1: Preparation of rhodamine 6G hydrazide (Compound a1)

Rhodamine 6G (2 g, 4.1 mmol, 1.0 eqv.) And hydrazine hydrate into the _{(NH 2 NH 2 · H 2} O, 0.2 g, 4.1 mmol, 1.0 eqv) in ethanol (EtOH) (50mL) at room temperature (25 ℃ ) For 24 hours. Then, the obtained crude product was purified by column chromatography (eluent: petroleum ether (bp 60-90 ° C) / ethyl acetate = 1/1 v / v) to obtain compound a1 (yield = 95%;).

¹ H NMR (CDCl ₃ , 600 MHz) δ (ppm): 1.252 (t, 6H, J = 7.153 Hz), 1.846 (s, 6H), 3.150 (m, 4H), 3.452 (s, 2H), 3.509 ( s, 2H), 6.189 (s, 2H, 6.318 (s, 2H), 6.989 (m, 1H), 7.383 (m, 2H), 7.889 (m, 1H); ¹³ C NMR (CDCl ₃ , 600 MHz) δ (ppm): 13.74, 15.69, 28.68, 37.34, 65.03, 75.78, 75.99, 76.20, 95.81, 116.97, 122.02, 122.78, 126.67, 127.10, 128.84, 131.56, 146.51, 150.72, 151.21, 165.18; ESI-MS (m / m z) calcd. 428.54, found 429.9 [M + H] ⁺ .

Step 2: 4,4 '-(9,9-dioctyl-9H-fluorene-2,7-diyl) dibenzaldehyde (4,4'-(9,9-dioctyl-9H-fluorene-2,7- Preparation of diyl) dibenzaldehyde, compound a2)

2,7-dibromo-9,9-dioctyl-9H-fluorene (1 g, 1.82 mmol, 1.0 eqv.), (4-formylphenyl) boronic acid ((4- formylphenyl) boronic acid, 0.55 g, 3.64 mmol, 2.0 eqv.) and 2M NaOH were added, stirred at room temperature for 5 hours, and then degassed with nitrogen for 20 minutes. After adding tetrakis (triphenylphosphine) palladium (0) (105 mg, 9 mol%), the mixture was stirred for 24 hours at 90 ° C. under N ₂ atmosphere. Then, the obtained crude product was purified by column chromatography (eluent: petroleum ether (bp 60-90 ° C) / ethyl acetate = 7/3 v / v) to obtain compound a2 (yield = 90%;).

¹ H NMR (CDCl ₃ , 600 MHz) δ (ppm): 0.753 (t, 6H, J = 7.336 Hz), 1.037 (m, 18H), 1.134 (m, 6H), 2.042 (m, 4H), 7.593 ( s, 2H), 7.635 (d, 2H, J = 7.886 Hz), 7.810 (m, 6H), 7.766 (d, 4H, J = 8.253 Hz), 10.057 (s, 2H); ¹³ C NMR (CDCl ₃ , 600 MHz) δ (ppm): 12.99, 21.54, 22.78, 28.11, 28.68, 28.89, 30.72, 39.30, 54.51, 75.78, 75.99, 76.20, 119.50, 120.73, 125.53, 126.70, 129.29, 134.15 , 137.90, 139.93, 146.54, 151.06, 190.84; ESI-MS (m / z) calcd. 598.87, found 599.8 [M + H] ⁺ .

Step 3: Preparation of receptor R

Compound a2 (500 mg, 0.84 mmol, 1.0 eqv.) And compound a1 (715 mg, 1.67 mmol, 2.0 eqv.) Were added to ethanol (EtOH) (20 mL) and stirred at room temperature for 12 hours. Then, the obtained crude product was purified by column chromatography (eluent: petroleum ether (bp 60-90 ° C) / ethyl acetate = 1/9 v / v) to obtain the title compound, receptor R (yield = 88%). ;).

¹ H NMR (DMF _d7 , 600 MHz) δ (ppm): 0.731 (t, 6H J = 7.341 Hz), 1.114 (m, 20H), 1.274 (t, 12H J = 7.153 Hz), 1.938 (s, 12H) , 2.192 (s, 4H), 3.249 (m, 8H), 3.493 (s, 4H), 5.069 (t, 4H, J = 5.459 Hz), 6.376 (s, 4H), 6.459 (s, 4H), 7.166 ( d, 2H, J = 7.529 Hz), 7.588 (d, 3H, J = 8.470 Hz), 7.620 (t, 2H, J = 7.529 Hz), 7.661 (t, 2H, J = 7.341 Hz), 7.711 (d, 2H, J = 7.905 Hz), 7.766 (d, 4H, J = 8.282 Hz), 7.885 (s, 2H), 7.941 (d, 2H, J = 8.094 Hz), 7.978 (d, 2H, J = 7.341 Hz) , 8.024 (s, 1H), 9.086 (s, 2H); ¹³ C NMR (CDCl ₃ , 600 MHz) δ (ppm): 13.76, 14.07, 16.17, 22.55, 23.97, 29.11, 29.27, 29.41, 29.55, 29.69, 29.77, 29.82, 29.96, 30.10, 31.75, 34.38, 34.52, 34.66 , 34.80, 34.94, 35.08, 35.21, 38.17, 39.83, 55.67, 66.46, 96.17, 106.11, 118.71, 120.68, 121.71, 123.16, 124.21, 126.13, 127.30, 127.54, 127.64, 128.95, 129.90, 13344. , 142.70, 147.45, 147.47, 151.98, 152.10, 152.15, 162.09, 162.27, 162.47, 164.4; ESI-MS (m / z) calcd. 1419.91, found 1420.8089 [M + H] ⁺ .

[Example 2] Selectivity for mercury ions

Na ⁺ , K ⁺ , Ca ^{2 +} , Li ⁺ , Cs ⁺ , Fe ^{2 +} , Fe ^{3 +} , Co ^{2 +} , Ni ^{2 +} , Cu ^{2 +} , Mg ^{2 +} , Zn ^{2 +} , Ag ⁺ , Cd ^{2 +} , in order to examine the example 1 colorimetric or fluorescence selectivity of the receptor R on the various cations such as Hg ^2+, and Al ^{+ 3,} experiments were performed as follows.

DMF: H ₂ O (2: 8, v / v) in mixed solvents Na ⁺ , K ⁺ , Ca ^{2 +} , Li ⁺ , Cs ⁺ , Fe ^{2 +} , Fe ^{3 +} , Co ²⁺ , Ni ^{2 +} , Various cations including Cu ^{2 +} , Mg ^{2 +} , Zn ^{2 +} , Ag ⁺ , Cd ^{2 +} , Hg ^{2 +} and Al ^{3 +} are respectively introduced into separate vials at a concentration of 2 × 10 ^-5 M, and the various cations After the input of the receptor R of Example 1 to the contained vial at a concentration of 1 × 10 ^-5 M, the color change of the solution in each vial was confirmed by examining the naked eye and a UV lamp (360 nm).

As shown in FIG. 1 (above), only when mercury ions (Hg ^{2 +} ) were present was changed from colorless to pink, and when other metal cations were present, the color of the solution was not changed. In addition, as shown in FIG. 1 (below), only when mercury ions (Hg ^{2 +} ) were present, the color changed from fluorescence to yellow fluorescence, and when other metal cations were present, the color of the solution did not change.

That is, the receiver R according to the invention (Example 1) was found to be highly selective in response to mercury ions (Hg ^{+ 2).}

 [Example 3] UV-vis absorption and fluorescence spectrum observation according to the concentration of mercury ions

In order to observe the UV-vis absorption and fluorescence spectrum of the receptor R according to various concentrations of mercury ions (Hg ^{2 +} ), the experiment was conducted as follows.

DMF: H ₂ O (2: 8, v / v) in a mixed solvent of 1 × 10 ^-5 M concentration of the receptor R, compared to the receptor R mercury ion (Hg ^{2 +} ) 0 to 2.0 equivalents while UV-vis absorption spectra and fluorescence spectra changes of the receptor R in the solution according to mercury ion (Hg ²⁺ ) concentration were measured. The results are shown in FIGS. 2 and 3, respectively.

Figure 2 is a UV-vis absorption spectra, it was confirmed that the intensity of the absorption band increases at 537 nm as the concentration of mercury ions (Hg ^{2 +} ) increases. Figure 3 is a fluorescence spectra, as the concentration of mercury ions (Hg ^{2 +} ) increases, the intensity of the emission peak increases at 553 nm, and at the same time, the luminescence properties of the receptor R are improved with yellow fluorescence due to the addition of mercury ions. I could confirm.

This increase in the intensity of the absorption band and luminescence peak is due to the opening of the spirolactam ring of the rhodamine residue in the receptor R by mercury ions.

[Example 4] Resistance to mercury ions

The possibility of interference due to other metal ions of the receptor R was confirmed through UV-vis absorption and fluorescence spectra change.

DMF: H ₂ O (2: 8, v / v) was added to the receptor R at a concentration of 1 × 10 ^-5 M, and mercury ion (Hg ^{2 +} ) compared to the receptor R was added at 1.0 equivalent, Na ⁺ , K ⁺ , Ca ^{2 +} , Mg ^{2 +} , Li ⁺ , Cs ⁺ , Fe ^{2 +} , Fe ^{3 +} , Co ^{2 +} , Ni ^{2 +} , Cu ^{2 +} , Zn ^{2 +} , Ag ⁺ , Cd ^{2 +} and after in other interfering metal ion such as Al ^{+ 3} to 10.0 equivalents were measured UV-vis absorption and fluorescence spectra change of the receptor R solution. The results are shown in FIGS. 4 and 5, respectively.

Figure 4 shows the intensity of the 537 nm absorption band of UV-vis absorption spectra, Na ⁺ , K ⁺ , Ca ^{2 +} , Mg ^{2 +} , Li ⁺ , Cs ⁺ , Fe ^{2 +} , Fe ^{3 +} , Co ² The intensity of the absorption band of 537 nm by mercury ions, all with and without 10.0 equivalents of other interfering metal ions such as ⁺ , Ni ^{2 +} , Cu ^{2 +} , Zn ^{2 +} , Ag ⁺ , Cd ^{2 +} and Al ^{3 +} Was able to confirm the strength. Figure 5 shows the intensity of the 533 nm emission peak of the fluorescence spectra, Na ⁺ , K ⁺ , Ca ^{2 +} , Mg ^{2 +} , Li ⁺ , Cs ⁺ , Fe ^{2 +} , Fe ^{3 +} , Co ^{2 +} , Ni ^If there are 10.0 equivalents or not of other interfering metal ions such as ^{2 +} , Cu ^{2 +} , Zn ^{2 +} , Ag ⁺ , Cd ^{2 +} and Al ^{3 +} , the intensity of the 533 nm emission peak is strong by mercury ions. I could confirm.

That is, since the receptor R of the present invention has high selectivity for mercury ions, it can provide high sensitivity applicable to chemical sensors.

[Example 5] Receptor R detection mechanism for mercury ions

In order to investigate the detection mechanism for the mercury ion of the receptor R of the present invention, after the addition of the receptor R (1 × 10 ^-5 M, 1 equivalent) and 2 equivalents of mercury ion to DMF-d ₇ , ¹ H and ¹³ C NMR Changes were confirmed (Figures 6 and 7).

As shown in Figure 6, the ¹ H NMR spectrum of the receptor R showed a peak corresponding to the imine group (-N = CH) at 9.086 ppm, and a peak corresponding to the xanthene proton at 6.376 and 6.459 ppm. If the addition of the receptor R 2 equivalents of mercury ions (Hg ^{+ 2)} the three peaks have moved respectively 9.146, 6.439 and 6.560 ppm. These results indicated that the chemical shift value of -N = CH and xanthene protons of the receptor R was increased due to the addition of mercury ions, indicating that the downfield shift was caused by mercury ions binding to the nitrogen atom, thereby increasing the electron density of the -CH proton. It means that it was significantly reduced. In other words, the binding of mercury ions to nitrogen atoms significantly reduced the electron density of the -CH proton. In addition, it can be seen that the spirolactam ring of the receptor R was opened by deshielding the xanthene proton.

In addition, as shown in Figure 7, the peak at 66.46 ppm in the ¹³ C NMR spectrum for receptor R alone corresponds to the bridged carbon of the spiro isoindoline xanthene ring, but with the addition of mercury ions (2 equivalents). Due to this, the peak disappeared as the ring opened, resulting in simultaneous movement to the aromatic region. From these results, it was found that the mercury ion binds to the receptor R through a spirolactam ring opening reaction.

In addition, complexation of the receptor R with mercury ions was confirmed by MALDI-TOF mass spectrum (FIG. 8), and the binding properties of the receptor R and mercury ions were investigated using the FT-IR spectrum (FIG. 9).

As shown in Fig. 9, in the FT-IR spectrum of the receptor R alone, the stretching frequency of the carbonyl group in the spirolactam unit was located at 1687 cm ^-1 ; In the complex of the receptor R and mercury ions, the frequency disappeared. This is expected because a new peak at 1673 cm ^-1 corresponding to the ring opening of the spirolactam ring and the binding of mercury ions (Hg ^{2 +} ) to oxygen of the spirolactam ring has appeared. In addition, the peak at 1615 cm ^-1 corresponding to -C = N vibration appeared at 1647 cm ^-1 in the spectrum of the product, and the bending vibration of imine -C = N was 3426 after the complex formation of the receptor R and mercury ions. moved from cm ^-1 to 3360 cm ^-1 . These results indicate that the oxygen and nitrogen atoms of the receptor R participate in the binding of mercury ions. The mechanism of binding of the receptor R of the present invention to mercury ions is shown below.

[Example 6] Preparation and sensing characteristics of receptor R / polyurethane electrospinning nanofibers

Acetone (3 g) and DMAc (dimethylacetamide, 2 g) were added to polyurethane (1 g), and then receptor R (22.5 mg) was added and stirred at 25 ° C. for 10 hours to prepare a spinning solution.

The electrospinning apparatus (Chungpa EMT, CPS-40K03VIT, Korea) was used, the voltage was 15 kV, the radiating distance was 15 cm, and the collector (with aluminum foil attached to the collector) was 11 cm in diameter, releasing the prepared spinning solution. It was put in a pipette and electrospun to prepare a receptor R / polyurethane electrospinning nanofiber. The average diameter of the prepared receptor R / polyurethane electrospinning nanofibers was 450 nm.

The prepared receptor R / polyurethane electrospinning nanofibers form a film structure and, as a result of SEM analysis, consists of numerous, randomly arranged, crosslinked nanofibers, and the electrospinning nano blended with receptor R and polyurethane. The surface of the fiber did not show any serious cracking or decomposition. That is, as shown in Figure 10, the shape of the prepared receptor R / polyurethane electrospinning nanofibers (B) was similar to pure polyurethane nanofibers (A).

The coated receptor R / polyurethane electrospinning nanofibers are coated on individual glass slides, immersed in a mercury ion solution, allowed to stand for 1 minute, and then, after drying the solvent, confocal laser scanning microscopy, CLSM ) To confirm the mercury ion sensing properties of the receptor R / polyurethane electrospinning nanofibers. 11 is a fluorescence confocal image, the polyurethane electrospun nanofibers in which the receptor R is blended before the addition of mercury ions do not exhibit fluorescence, while fluorescence was observed after the addition of mercury ions.

[Example 7] Evaluation of properties as an electrospinning test strip

In order to investigate the colorimetric and fluorescence reaction of the test strip for mercury ions, the receptor R / polyurethane electrospinning nanofiber prepared in Example 6 was used as an electrospinning test strip, and DMF: H ₂ O (2: 8, v / v) was immersed in a DMF aqueous solution to observe the characteristics of the presence or absence of mercury ions (Hg ^{2 +} ).

Receptor R have been discolored to pink colorless under visible light by the addition of a blended polyurethane electrospinning check that mercury ions (Hg ^{+ 2),} showed a yellow fluorescence under a UV lamp (12). This color change is because mercury ions are bound to the receptor R / polyurethane nanofibers to induce the opening of the spirolactam ring in the receptor R.

[Example 8] Preparation of ink composition and digital printing using it and detection of mercury ions using printed matter

A solution in which the receptor R was dissolved in ethanol at a concentration of 10 ^-4 M, ethanol, glycerol, and water was dissolved in a ratio of 2: 72: 3: 23% by weight to prepare an ink composition.

A Canon (MG2590) printer cartridge (CL-946) was commercially available, and the cartridge was thoroughly washed with ethanol and water to completely remove the blue ink. Then, the prepared ink composition was injected into the cartridge.

The overall setup of the digital printing process using receptor R is shown in FIG. 13.

The desired image was printed on filter paper and then dried completely in air. The printed image could not be observed under daylight and ultraviolet lamps, but when mercury ions (6.25 × 10 ^-6 M) were dissolved in 100% water and added to the filter paper, the image printed on the filter paper was observed under both visible light and ultraviolet light. Could. That is, the image printed on the filter paper appeared pink under visible light and showed a fluorescent yellow under ultraviolet light (FIG. 14).

As described above, the receptor R of the present invention is a rhodamine-fluorene-rhodamine-based receptor, which can function as a colorimetric and turn-on fluorescent probe that enables the detection and recognition of mercury ions (Hg ^{2 +} ) with the naked eye. have. It exhibits very high selectivity even in the presence of other competing metal ions and is applicable as a chemical sensor for mercury ions (Hg ^{2 +} ). In addition, R receptor of the present invention may be used as a digital print material, the print R receptor seems excellent reaction to detect mercury ions (Hg ^{+ 2)} in a 100% water medium, namely water. That is, since the color change according to the detection of mercury ions (Hg ^{2 +} ) in both visible and ultraviolet light is clear and rapid, the test strip printed with receptor R easily detects mercury ions (Hg ^{2 +} ) in aqueous solution without the need for a separate tool. can do.

Thus, the receptor of the present invention R is very useful for the detection of ionic mercury (Hg ^{+ 2)} in the water and can be seen to advantage.

As described above, the present invention has been described by specific matters and limited embodiments, but these are provided only to help a more comprehensive understanding of the present invention, and the present invention is not limited to the above embodiments, and the field to which the present invention pertains Those skilled in the art can make various modifications and variations from these descriptions.

Accordingly, the spirit of the present invention should not be limited to the described embodiments, and should not be determined, and all claims that are equivalent or equivalent to the scope of the claims as well as the claims to be described later belong to the scope of the spirit of the invention. .

Claims (18)

Rhodamine-fluorene-rhodamine compound represented by Formula 1 below:
[Formula 1]

(In the formula 1,
R ₁ and R ₂ are each independently hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, halo C1-C20 alkyl or C6-C20 aryl;
L ₁ and L ₂ are each independently C6-C20 arylene;
R ₃ to R ₆ are each independently hydrogen, C1-C20 alkyl, C2-C20 alkenyl or C2-C20 alkynyl;
R ₇ and R ₈ are each independently hydrogen or C1-C20 alkyl.) According to claim 1,
R ₁ and R ₂ are each independently C ₁ -C 20 alkyl;
L ₁ and L ₂ are each independently C6-C20 arylene;
R ₃ to R ₆ are each independently hydrogen or C1-C20 alkyl;
R ₇ and R ₈ are each independently hydrogen or C 1 -C 20 alkyl, rhodamine-fluorene-rhodamine compound. According to claim 1,
R ₁ and L ₂ are each independently phenylene, naphthalene, biphenylene or anthracenylene, rhodamine-fluorene-rhodamine compound. According to claim 1,
R ₁ and R ₂ are C1-C10 alkyl; R ₃ and R ₅ are hydrogen; R ₄ and R ₆ are each independently C1-C7 alkyl; R ₇ and R ₈ are each independently hydrogen or C 1 -C ₇ alkyl, rhodamine-fluorene-rhodamine compound. According to claim 1,
The rhodamine-fluorene-rhodamine compound is a rhodamine-fluorene-rhodamine compound, which is a rhodamine-fluorene-rhodamine compound represented by Formula 2 below:
[Formula 2]

(In the formula 2,
R ₁ and R ₂ are C1-C10 alkyl;
R ₄ and R ₆ are each independently C1-C4 alkyl;
R ₇ and R ₈ are each independently hydrogen or C1-C4 alkyl.) According to claim 1,
The rhodamine-fluorene-rhodamine compound is for detection of mercury ions, rhodamine-fluorene-rhodamine compound. A composition for detecting mercury ions, comprising the rhodamine-fluorene-rhodamine compound of claim 1. Contacting the analyte with the composition for detection of the rhodamine-fluorene-rhodamine compound of claim 1 or the mercury ion of claim 7; And
Confirming the optical change of the compound or the composition;
A method of detecting mercury ions comprising a. The method of claim 8,
The optical change is confirmed by at least one of color change, absorbance change and fluorescence intensity change of the compound. The method of claim 8,
The analysis sample is a water-based analysis sample, detection method. The rhodamine-fluorene-rhodamine compound of claim 1; And a solvent, an ink composition for detecting mercury ions. The method of claim 11,
The solvent is at least one selected from water, ethanol, glycerol, N, N-dimethylformamide, dichloromethane, chloroform, dimethyl sulfoxide, ethyl acetate, acetonitrile, methanol and tetrahydrofuran. A test sheet for detecting mercury ions on which the ink composition of claim 11 is printed on a substrate. Using the ink composition of claim 11, printing in a predetermined pattern form on a substrate to produce a test sheet for detecting mercury ions;
Contacting the test sample with the test strip; And
Identifying an optical change;
A method of detecting mercury ions comprising a. The method of claim 14,
The substrate is selected from the group consisting of filter paper, paper and cellulose paper, detection method. The method of claim 14,
The optical change is confirmed by at least one of color change, absorbance change and fluorescence intensity change of the compound. The method of claim 14,
The analysis sample is a water-soluble analysis sample, detection method. A chemical sensor for the detection of mercury ions, comprising a rhodamine-fluorene-rhodamine compound of claim 1, a composition for detecting mercury ions of claim 7, or a test strip for detection of mercury ions of claim 13.

Images