KR20220009690A - New diacetylene compounds, polymers thereof and sensor for detection of cadmium - Google Patents

Abstract

The present invention relates to a novel diacetylene compound, a polymer thereof and a sensor for detecting cadmium, and more specifically, to a diacetylene compound represented by Formula 1 below, a polydiacetylene polymerized with the diacetylene compound as a monomer, and a sensor using the same. Further, the present invention relates to a composition comprising a diacetylene compound and/or polydiacetylene and a method for detecting cadmium using the same: [Formula 1], wherein the definition of formula 1 is as set forth in claim 1.

Description

NEW DIACETYLENE COMPOUNDS, POLYMERS THEREOF AND SENSOR FOR DETECTION OF CADMIUM

The present invention relates to novel diacetylene compounds, polymers thereof and sensors for the detection of cadmium.

Heavy metals refer to heavy metals with a specific gravity of about 4.0 or more. When discharged to the environment, they move through the food chain to humans while circulating in the biosphere, and accumulate in the human body and accumulate for a long time depending on the type. Among them, cadmium is widely used for plating and pigment manufacturing, and it has effects on the human body such as fatigue, loss of concentration and memory, hypertension, loss of smell, prostate cancer, pulmonary edema, and pneumonia.

Heavy metals accumulate in air, water and soil and are not biodegradable, and the sensitive and selective detection and quantitation of toxic heavy metals plays an important role in heavy metal pollution control. Among these toxic heavy metals, cadmium has been given priority in the field of water policy by Directive 2008/105/EC of the European Union Parliament and of the European Council on environmental quality standards.

Cadmium is a major hazardous substance in this list, and in this regard, considerable efforts have been made to develop heavy metal detection methods for industrial process and environmental monitoring. However, standard and traditional techniques for the analysis of trace amounts of Cd ²⁺ require expensive analytical techniques such as atomic absorption spectrometry (AAS), inductively coupled plasma mass spectrometry (ICP-MS), fluorescence sensors and colorimetric analysis.

Many fluorescent sensors for cadmium have been reported in the past few years. However, due to similar physical and chemical properties, only a few probes have higher selectivity for cadmium than for zinc. This is because they are in the same group on the periodic table. Therefore, it is necessary to develop ^{a Cd 2+} selective sensor that can discriminate ^{Cd 2+} and Zn ²⁺ with high sensitivity and selectivity under physiological conditions. The most widely used approach in the development of metal ion chemical sensors is to incorporate fluorophores (signal subunits) with appropriate ionophore groups capable of binding to other metal ions.

Therefore, it is necessary to develop a sensor for qualitative and quantitative analysis of cadmium for cadmium.

The inventors of the present invention, the self-assembly ability of polydiacetylene (PDA) and environmental factors (stimulus ), designed and designed a sensor and system by utilizing the color change of the blue PDA, and made a surprising discovery that it is not only a colorimetric sensor with high selectivity and sensitivity to cadmium but also a fluorescent sensor. .

In order to solve the above-mentioned problems, the present invention provides a novel diacetylene compound having a selective optical property change with respect to cadmium.

The present invention is to provide a novel polydiacetylene in which the diacetylene compound according to the present invention is polymerized as a monomer and has a selective optical property change with respect to cadmium.

The present invention is to provide a composition comprising the diacetylene compound and/or polydiacetylene according to the present invention, having an optical change when in contact with cadmium, and can be utilized as a colorimetric and fluorescent sensor.

An object of the present invention is to provide a chemical sensor that contains the diacetylene compound and/or polydiacetylene according to the present invention, has selectivity to cadmium and excellent sensitivity, and can be utilized as a colorimetric and fluorescent sensor.

The present invention provides an analysis method for detecting or detecting cadmium using a diacetylene compound and/or polydiacetylene according to the present invention.

However, the problems to be solved by the present invention are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

According to an embodiment of the present invention, it relates to a diacetylene compound represented by the following formula (1).

[Formula 1]

(Here, R is an alkyl ^{having 1 to 30 carbon atoms, R 1} is an alkylene having 1 to 30 carbon atoms, R ² is represented by the following formula 1a,

[Formula 1a]

In Formula 1a, R ³ to R ⁹ are each hydrogen, halogen, straight-chain or branched-chain alkyl having 1 to 10 carbon atoms; It is selected from alkenyl having 2 to 10 carbon atoms and aryl having 6 to 10 carbon atoms.)

According to one embodiment of the present invention, in the formula 1 R is an alkyl having 3 to 20 carbon atoms, R ¹ is an alkylene of 3 to 20 carbon atoms, wherein R ¹ is the number of carbon atoms is more alkylene than R, the In Formula 1a, R ¹ to R ⁶ are, respectively, hydrogen, halogen, straight-chain alkyl having 1 to 5 carbon atoms; and alkenyl having 2 to 5 carbon atoms.

According to an embodiment of the present invention, the diacetylene compound exhibits a change in optical properties when combined with cadmium, and the change in optical properties may be at least one of color, fluorescence wavelength, fluorescence intensity, and absorbance.

According to an embodiment of the present invention, it relates to polydiacetylene, which is a polymer of diacetylene monomers represented by Chemical Formulas 1 and 2 below.

[Formula 1]

(Here, R is an alkyl ^{having 1 to 30 carbon atoms, R 1} is an alkylene having 1 to 30 carbon atoms, R ² is represented by the following formula 1a,

[Formula 1a]

In Formula 1a, R ³ to R ⁹ are each selected from hydrogen, halogen, straight or branched chain alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, and aryl having 6 to 10 carbon atoms.)

[Formula 2]

(Here, R is alkyl ^{having 1 to 30 carbon atoms, and R 1} is alkylene having 1 to 30 carbon atoms.)

According to an embodiment of the present invention, the molar ratio of the monomer represented by Formula 1 to the monomer represented by Formula 2 in the polydiacetylene may be 1: 9 to 1: 100.

According to an embodiment of the present invention, it may be formed by photopolymerizing the double-layer self-assembly of the monomers represented by Chemical Formulas 1 and 2 above.

According to an embodiment of the present invention, the polydiacetylene may be represented by the following formula (3).

[Formula 3]

(In Formula 3, m and y are each selected from 1 to 29, and n is 1 or more.)

According to one embodiment of the present invention, it relates to a composition comprising the diacetylene compound according to the present invention, the polydiacetylene according to the present invention, or both.

According to an embodiment of the present invention, the composition includes water, an organic solvent, or both, and the diacetylene compound, the polydiacetylene, or the two in the composition, each containing more than 0 to 100% by weight it could be

According to an embodiment of the present invention, the composition may be used for cadmium detection.

According to an embodiment of the present invention, the composition further includes a buffer solution, and the composition may have a pH of 6 to 8.

According to an embodiment of the present invention, the composition exhibits a change in optical properties upon contact with cadmium, and the change in optical properties may be at least one of color, fluorescence wavelength, fluorescence intensity, and absorbance.

According to an embodiment of the present invention, the diacetylene compound according to the present invention, a sensing unit comprising polydiacetylene or both according to the present invention; including, relates to a chemical sensor.

According to an embodiment of the present invention, the chemical sensor, cadmium detection or quantitative and qualitative analysis of cadmium may be made.

According to an embodiment of the present invention, after the step of contacting the analyte sample with the diacetylene compound according to the present invention, the polydiacetylene or both according to the present invention and the contacting step, the diacetylene compound or polydiacetylene It relates to a method of detecting cadmium, comprising the step of observing an optical change.

According to an embodiment of the present invention, the analysis sample may be maintained at a pH of 6 to 8.

According to an embodiment of the present invention, the observing may include observing at least one of a color, a fluorescence wavelength, absorbance, and fluorescence intensity of the diacetylene compound and polydiacetylene.

According to an embodiment of the present invention, it relates to a kit for detecting cadmium, including a chemical sensor according to the present invention.

According to an embodiment of the present invention, the kit may further include an absorbance meter, a fluorescence meter, or both.

The present invention provides a novel diacetylene compound capable of selectively detecting cadmium and a polymer of the diacetylene compound, and can exhibit high selectivity for cadmium and sensitive colorimetric and fluorescence changes.

ADVANTAGE OF THE INVENTION This invention is excellent in the detection performance of cadmium, and can implement|achieve the qualitative and quantitative analysis of cadmium by a simple method.

Since the present invention exhibits excellent sensitivity due to a low detection limit for cadmium, it is possible to provide a colorimetric sensor having excellent detection performance of cadmium and capable of qualitative and quantitative analysis of cadmium, and an analysis method of cadmium using the same.

1 is, according to an embodiment of the present invention, a self-assembly of PCDA-HP and PCDA according to the present invention, a polymerization process thereof, and an analysis process of ^{Ca 2+ using PDA-HP according to the present invention by way of example} will be.
2 shows the colorimetric reaction of PDA-HP (200 μM) in the presence of 2.0 eq of various metal ions in HEPES buffer (10 mM, pH 7.4) according to an embodiment of the present invention.
3 shows the colorimetric titration of PDA-HP (200 μM) in the presence of ^{various amounts of Cd 2+} in HEPES buffer (10 mM, pH 7.4 or pH 6.8) according to an embodiment of the present invention.
FIG. 4 shows PDA-HP (100 μM) in the presence of ^{various amounts of Cd 2+} in HEPES buffer (10 mM) at (a) pH 7.4 and (c) pH 6.8, according to an embodiment of the present invention. UV/Vis spectra are shown, and PDA-HP by ^{Cd 2+} in HEPES buffer (10 mM) at (b) pH 7.4 and (d) pH 6.8 (excitation at 530 nm, slit: 5 nm/5 nm) ( The results of fluorescence titrations of 100 μM) are shown.
^{FIG. 5 is a partial 1} H NMR of PCDA-HP (2 mM) with addition of Cd ²⁺ (Cd(ClO ₄ ) _2· xH _{2 O in (CD 3} ) ₂ CO, in accordance with an embodiment of the present invention. The spectrum (400 MHz) is shown.

Hereinafter, embodiments of the present invention will be described in detail. In describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted. In addition, the terms used in this specification are terms used to properly express a preferred embodiment of the present invention, which may vary depending on the intention of a user or operator or a custom in the field to which the present invention belongs. Accordingly, definitions of these terms should be made based on the content throughout this specification.

Throughout the specification, when a member is said to be located "on" another member, this includes not only a case in which a member is in contact with another member but also a case in which another member exists between the two members.

Throughout the specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components.

The present invention relates to a diacetylene compound, and according to an embodiment of the present invention, the diacetylene compound may be a diacetylene compound represented by Formula 1 below. The diacetylene compound may exhibit a selective colorimetric and/or fluorescence change when combined with cadmium, which has high sensitivity and high selectivity, and can be used as a colorimetric sensor capable of qualitative and quantitative analysis.

[Formula 1]

In Formula 1, R ^{may be an alkyl having 1 to 30 carbon atoms, and R 1} may be an alkylene having 1 to 30 carbon atoms. Preferably, in Formula 1, R is an alkyl having 3 to 20 carbon atoms; 3 to 15 carbon atoms; Or it may be an alkyl group having 8 to 10 carbon atoms. In Formula 1, R ¹ is alkylene having 3 to 20 carbon atoms (-(CH ₂ ) _n -); alkylene having 3 to 15 carbon atoms; It may be an alkylene having 5 to 10 carbon atoms. R ¹ may be an alkylene group having more carbon atoms than R.

In Formula 1, R ² may be represented by Formula 1a below.

[Formula 1a]

In Formula 1a, R ³ to R ⁹ are, respectively, hydrogen, halogen, straight-chain or branched-chain alkyl having 1 to 10 carbon atoms; It may be selected from alkenyl having 2 to 10 carbon atoms and aryl having 6 to 10 carbon atoms. Preferably, R ³ to R ⁹ are each hydrogen, halogen, straight-chain alkyl having 1 to 5 carbon atoms; and alkenyl having 2 to 5 carbon atoms, more preferably hydrogen and alkyl having 1 to 2 carbon atoms in consideration of selectivity and/or sensitivity to the detection target, more preferably hydrogen. .

^{R 2} represented by Formula 1a corresponds to a chelate moiety for detection of cadmium, and may induce a selective colorimetric and/or fluorescence change in the presence of cadmium.

For example, the diacetylene compound exhibits a change in optical properties when combined with cadmium, and the change in optical properties may be at least one of color, fluorescence wavelength, fluorescence intensity, and absorbance.

According to an embodiment of the present invention, it is possible to provide a self-assembly of diacetylene according to the present invention. The self-assembly is a bilayer structure, and is in the form of particles, liposomes, lines, tubes, films, thin films, sheets, fibers, flakes, etc., and the self-assembly is nano- and/or micro-sized, powders, solutions, slurries, suspensions, etc. etc. can be obtained.

As an example of the present invention, the self-assembly may include the diacetylene compound represented by Chemical Formula 1 and the diacetylene compound represented by the following Chemical Formula 2 according to the present invention.

[Formula 2]

In Formula 2, R and R ¹ may be the same as or different from Formula 1, for example, R and R ¹ are each alkyl ^{having 1 to 30 carbon atoms, and R 1} may be alkylene having 1 to 30 carbon atoms. . Preferably, in Formula 1, R is an alkyl having 3 to 20 carbon atoms; 3 to 15 carbon atoms; Or it may be an alkyl group having 8 to 10 carbon atoms. In Formula 1, R ¹ is alkylene having 3 to 20 carbon atoms; alkylene having 3 to 15 carbon atoms; It may be an alkylene having 5 to 10 carbon atoms. R ¹ may be alkylene having more carbon atoms than R.

In one embodiment of the present invention, the ratio (molar ratio) of the monomers of the diacetylene compound represented by Formula 1 to the diacetylene compound represented by Formula 2 in the self-assembly is 1: 9 to 1: 100; 1: 9 to 1: 50; 1: 9 to 1: 20; Or 1: 9 to 1: 15 may be. When included within the above range, high selectivity and sensitivity to cadmium may be exhibited.

The present invention relates to polydiacetylene, which is a polymer of diacetylene according to the present invention.

According to an embodiment of the present invention, the polydiacetylene is a polymer of the diacetylene monomers represented by Chemical Formulas 1 and 2, preferably a polymer of self-assembly thereof.

In one embodiment of the present invention, the polydiacetylene is added to the diacetylene compound represented by Chemical Formulas 1 and 2 as a monomer for at least 1 minute; 1 minute to 30 minutes; Alternatively, it is formed by photopolymerization by irradiation with UV light for 1 to 10 minutes, and this polymerization process may use a diacetylene compound or a self-assembled diacetylene compound.

As an example of the present invention, referring to FIG. 1 , the polydiacetylene is formed by photopolymerizing a mixture of diacetylene monomers represented by Chemical Formulas 1 and 2 or the self-assembly, and the polydiacetylene is conjugated. It is a polymer, which can be used for the detection of cadmium. More specifically, referring to FIG. 1 , after the diacetylene compound and the diacetylene compound having a chelate moiety are self-assembled in a predetermined ratio, a conjugated polymer may be formed by photopolymerization.

For example, the conjugated polymer is blue and changes color to purple (or red) as it binds to a ^{cadmium target, that is, Cd 2+ at pH 7.4 and pH 6.4, and fluorescence also increases.} This change of the colorimetric may provide a selectively colorimetric and fluorescence changes for the Cd ²⁺ characterized in that reaction with only Cd ²⁺ does not react with other metals.

As an example of the present invention, the ratio (molar ratio) of the monomer represented by Formula 1 to the monomer represented by Formula 2 in the polydiacetylene may be 1: 9 to 1: 100. When included within the above range, high selectivity and sensitivity to cadmium may be exhibited.

As an example of the present invention, the polydiacetylene may be represented by the following formula (3).

[Formula 3]

In Formula 3, m and y are each 1 to 29; or 3 to 20, n is 1 or more; 1 to 10000; 1 to 5000; 10 to 1000; or an integer from 100 to 1000, and is determined according to the molecular weight of the polymer.

In one embodiment of the present invention, the polydiacetylene is a self-assembly, and the self-assembly is a double-layer structure, in the form of particles, liposomes, lines, tubes, films, thin films, sheets, fibers, flakes, etc., and the self-assembly are nano- and/or micro-sized, and can be obtained as a powder, solution, slurry, suspension, or the like.

The present invention provides a composition comprising the compound according to the present invention, wherein the composition comprises at least one of a compound represented by Formula 1 above, a mixture of compounds represented by Formula 1 and Formula 2, self-assembly, and a polymer and may further include a solvent. The solvent includes water and, if necessary, may further include an organic solvent such as an alcohol having 1 to 4 carbon atoms.

In one embodiment of the present invention, the compound is present in an amount of greater than 0 to 100% by weight or less in the composition; 90% by weight or less; 50% by weight or less; 10% by weight or less; 1% by weight or less; 0.1% by weight or less; 0.01% by weight or less; Or 0.001% by weight or less may be included.

In one embodiment of the present invention, the compound is, in the composition, 1 X 10 ^-5 M (mol) or more ^{in the composition, preferably 1 X 10 -5} M (mol) to 1 X 10 ^-2 M (mol), More preferably, it may contain a concentration of 1 X 10 ^-4 M (mol) to 1 X 10 ^-2 M (mol), and if the concentration is ^{less than 10 -5} M (mol), a weak color change of the compound; Due to absorbance, fluorescence intensity, etc., it may not be easy to observe when cadmium is detected.

In one embodiment of the present invention, the composition, pH 6 to 8; pH 6.2 to 7.5; maintained at pH 6.4 to 7.4 or pH 6.8 to 7.4, which can be achieved with a buffer solution.

As an example of the present invention, the detection limit of cadmium in the composition is 10 X 10 ^-5 to 17 X 10 ^-5 ; or 12.2 X 10 ^-5 to 16.4 X 10 ^-5 M (mol), for example, 16.4 X 10 ^-5 at pH 7.4, It may be 12.2 X 10 ^{-5 at pH 6.8.} The detection concentration of the cadmium may be within 100 times the detection limit.

According to an embodiment of the present invention, the composition is used for detection of cadmium, and the detection of cadmium may detect one or more of cadmium ions, cadmium metal, and cadmium compounds. When the composition is in contact with cadmium, optical properties are changed, for example, it is possible to observe a change in at least one of color, fluorescence wavelength, fluorescence intensity, and absorbance. In addition, color transition can be confirmed by visually observing changes in color, etc. without special equipment, and furthermore, it can be used for qualitative and/or quantitative analysis of cadmium using UV-Vis spectroscopy, fluorescence spectroscopy, etc. .

Products and devices for the detection and/or detection of cadmium comprising a compound or composition according to the present invention may be provided.

In one embodiment of the present invention, the compound and the composition may be applied to the product and device in the same manner as described for the chemical sensor. Alternatively, the kit or chemical sensor may be included.

As an example of the present invention, the configuration of the product and device may further include a configuration commonly used without departing from the scope of the present invention, and is not specifically mentioned in this application.

According to an embodiment of the present invention, the chemical sensor relates to a chemical sensor including a sensing unit including the compound or composition according to the present invention.

As an example of the present invention, the chemical sensor may be a colorimetric sensor used for detection and/or detection of cadmium and capable of quantitative and/or qualitative analysis of cadmium.

As an example of the present invention, the compound or composition may include at least one of a compound represented by Formula 1 according to the present invention, a mixture of compounds represented by Formula 1 and Formula 2, self-assembly, and a polymer.

As an example of the present invention, the compound or composition is applied as a powder, gel, emulsion, or liquid, or a molded article, or coated on a support such as an analysis chip, electric circuit, fiber, pulp, polymer film, glass substrate, etc. Alternatively, it can be impregnated and applied to the chemical sensor.

As an example of the present invention, the chemical sensor may perform qualitative and/or quantitative analysis by visually, electrically and/or optically sensing and measuring a color change of the compound or composition. As long as the chemical sensor does not depart from the scope and purpose of the present invention, commonly used analysis equipment may be further mounted, and it is not specifically mentioned in this application.

According to an embodiment of the present invention, it is possible to provide a kit for detecting cadmium comprising the compound or composition according to the present invention. The kit is portable for use in the laboratory or field use. The kit may contain the compound or composition within the kit in the same manner as described for the chemical sensor above.

As an example of the present invention, the kit can perform qualitative and/or quantitative analysis by visually, electrically or optically detecting and measuring the color change of the compound or composition.

As an example of the present invention, the kit may further include an absorbance, fluorescence intensity meter, and the like, and the meter may be integrated with the kit or configured separately.

As an example of the present invention, if the composition of the kit does not depart from the scope of the present invention, it may further include a composition typically used in a kit, and is not specifically mentioned in this application.

The present invention relates to an analysis method for a detection target using the compound or composition according to the present invention, the analysis method comprising the steps of: contacting an analysis sample; and observing the optical change. The analysis method is a detection and/or detection method of cadmium, and may be utilized for quantitative and/or qualitative analysis of the cadmium.

According to an embodiment of the present invention, in the analysis method, the step of contacting the analyte sample is the step of contacting the analyte sample with the compound or composition according to the present invention.

As an example of the present invention, the compound or composition may include at least one of a compound represented by Formula 1 according to the present invention, a mixture of compounds represented by Formula 1 and Formula 2, self-assembly, and a polymer.

As an example of the present invention, when the detection target, cadmium, for example, one or more of cadmium ions, cadmium metal, and cadmium compounds, preferably cadmium ions are present in the analysis sample, intramolecular structural change of the compound, etc. This can happen.

According to an embodiment of the present invention, the step of observing the optical change is a step of observing the optical change of the compound or composition after the contacting step. Quantitative and qualitative analysis of the detection target, that is, cadmium may be performed.

As an example of the present invention, in the observing, at least one of a color, a fluorescence wavelength, absorbance, and fluorescence intensity of the compound or composition may be observed. That is, the optical change is a change in color, absorbance, or fluorescence intensity, and this optical change may be used for quantitative and qualitative analysis using the naked eye, UV-Vis spectroscopy, fluorescence photometer, or the like. For example, when the presence of cadmium to be detected in the analysis sample, for example, cadmium ions, cadmium and/or cadmium compounds, the color of the composition changes from blue to red, so the presence of cadmium can be detected In the measurement of absorbance according to UV-Vis spectroscopy, the absorption band at 540 nm may increase. In addition, since the absorption band, the intensity of fluorescence emission, etc. are changed according to the concentration of cadmium, quantitative analysis can be performed.

As an example of the present invention, the detection limit of cadmium in the analysis method is 10 X 10 ^-5 to 17 X 10 ^-5 ; or 12.2 X 10 ^-5 to 16.4 X 10 ^-5 M (mol), for example, 16.4 X 10 ^-5 at pH 7.4, It may be 12.2 X 10 ^{-5 at pH 6.8.} The assay sample and/or the composition may have a pH of 6 to 8; pH 6.2 to 7.5; pH 6.4 to 7.4; maintained at about pH 6.8 or about pH 7.4, which can be achieved with a buffer solution. The buffer solution is applicable in the technical field of the present invention, and can be applied without limitation as long as the present invention does not deviate from the purpose.

As follows, although described with reference to preferred embodiments of the present invention, those skilled in the art can variously modify the present invention without departing from the spirit and scope of the present invention as set forth in the claims below. and may be changed.

[Scheme 1]

HP (5-hydroxy-N ^One ,N ³ Synthesis of -bis(pyridin-2-ylmethyl)isophthalamide)

Oxalyl chloride (2.0 mL, 22.9 mmol) in _{CH 3} CN (30 mL) solution containing 5-hydroxyisophthalic acid (5-hydroxyisophthalic acid, 1.0 g, 5.5 mmol) ^{at 0 ° C. under N 2} was dropped After stirring for 1 hour, DMF (0.2 mL) was added to the solution, and the resulting mixture was stirred for 4 hours and then concentrated under reduced pressure to obtain diacyl chloride as a yellow solid, which was CH ₃ CN ( 30 mL) and used directly without purification. _{This solution was added to 10 mL CH 3} CN containing pyridin-2-ylmethanamine (2 mL, 21.8 mmol). The reaction mixture was stirred overnight at room temperature under N _{2 .} This mixture was purified by silica gel column chromatography (CH ₂ Cl ₂ :MeOH = 95:5 to 90:10) as an eluent to obtain a white solid (1.5 g, 75 %).

¹ H NMR (400 MHz, DMSO- d ₆ ) δ10.01 (s, 1H), 9.11 (t, J = 6.0 Hz, 2H), 8.51 (ddd, J = 4.9, 1.9, 0.9 Hz, 2H), 7.90 (t, J = 1.5 Hz, 1H), 7.76 (td, J = 7.7, 1.8 Hz, 2H), 7.45 (d, J = 1.4 Hz, 2H), 7.36-7.23 (m, 4H), 4.56 (d, J = 5.9 Hz, 4H). ¹³ C NMR (100 MHz, DMSO- D ₆ ) δ166.60, 159.22, 157.97, 149.37, 137.28, 136.40, 122.64, 121.46, 117.55, 117.43, 46.08, 45.26. ESI HRMS m/z = 363.1452 [M+H] ⁺ , calc. for C ₂₀ H ₁₈ N ₄ O ₃ =362.38.

Synthesis of PCDA-HP (3,5-bis((pyridin-2-ylmethyl)carbamoyl)phenyl pentacosa-10,12-diynoate)

Oxalyl chloride, CH ₂ Cl ₂ containing (Oxalyl chloride, 0.7 mL, 5.51 mmol) for 10,12- pentamethyl Kosa diimide acid (10,12-pentacosadiynoic acid, PCDA, 0.5 g, 1.34 mmol) under N ₂ at room temperature (20 mL) was added dropwise to the solution. After stirring for 1 hour, DMF (0.1 mL) was added to the solution, and the resulting mixture was stirred for 4 hours and then concentrated under reduced pressure to obtain PCDA-Cl, which _{was purified by dissolving in CH 3} CN (30 mL). used directly without The solution was 10mL CH ₃ CN 5- hydroxy -N ^1, N ³ - bis (pyridin-2-ylmethyl) isophthalamide (HP, 5-hydroxy-N 1, N 3 -bis (pyridin-2-ylmethyl )isophthalamide) (200mg, 0.55mmol) and triethylamine (0.4mL, 4mmol). The reaction mixture was stirred at room temperature under N ₂ overnight. After evaporation, the crude product was dissolved in water (100 mL) and extracted 3 times with ethyl acetate (100 mL). The organic phase was purified by silica gel column chromatography (CH ₂ Cl ₂ :MeOH = 95:5) followed by Sephadex LH-20 (chloroform:MeOH = 1:1) to a yellow oil (138 mg, 35%) was obtained.

¹ H NMR (600 MHz, DMSO- d ₆ ) δ9.29 (t, J = 6.0 Hz, 2H), 8.51 (ddd, J = 4.9, 1.9, 1.0 Hz, 2H), 8.39 (t, J = 1.5 Hz) , 1H), 7.83 (d, J = 1.5 Hz, 2H), 7.76 (td, J = 7.7, 1.8 Hz, 2H), 7.34 (dt, J = 7.8, 1.0 Hz, 2H), 7.27 (ddd, J = 7.6, 4.8, 1.1 Hz, 2H), 4.59 (d, J = 5.9 Hz, 4H), 3.17 (d, J = 5.3 Hz, 1H), 2.63 (t, J = 7.4 Hz, 2H), 2.26 (q, J = 7.0 Hz, 4H), 1.66 (p, J = 7.5 Hz, 2H), 1.49-1.19 (m, 34H), 0.84 (t, J = 7.0 Hz, 3H). ¹³ C NMR (150 MHz, DMSO- d ₆ ) δ171.75, 164.96, 158.42, 150.40, 148.88, 136.71, 135.83, 123.79, 123.60, 122.13, 121.05, 77.93, 65.34, 48.58, 44.83, 33.99, 31.28 28.93, 28.85, 28.69, 28.55, 28.37, 28.34, 28.26, 28.15, 27.70, 27.67, 24.25, 22.08, 18.26, 13.92. ESI HRMS m/z = 719.4531 [M+H] ⁺ , calc. for C ₂₀ H ₁₈ N ₄ O ₃ = 718.45.

[Scheme 2]

Diacetylene assembly and photopolymerization

A lipid solution in HEPES (hydroxyethyl piperazineethanesulfonic acid) buffer was prepared by the following method. A mixture containing monomer (PCDA-HP) (0.1mmol) and PCDA (6.7mg, 0.9mmol) in a 1:9 ratio was dissolved in CH 2 Cl _{2 in a double-necked round bottom flask.} The organic solvent _{was completely evaporated under N 2} gas and 20 mL of HEPES buffer (10 mM) in different pH (pH 7.4 and 6.8) was added to obtain 1 mM PDA lipid solution. The solution was sonicated at 80 °C for 30 min, passed through a cotton filter to remove lipid aggregates, and the filtrate was incubated at 4 °C overnight. Polymerization of the solution was carried out at room temperature by irradiation with 254 nm UV light (1 mW/cm ^{2 ) for 15 min.}

Cadmium detection characteristics

Recognition of various metal ions by PDA-HP was investigated through colorimetric changes and changes in UV absorption and fluorescence emission of HEPES buffer (10 mM) at pH 7.4 and 6.8. The results are shown in FIGS. 2, 3 and 4 .

Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ , Mg ²⁺ , Ca ²⁺ , Cr ³⁺ , Mn ²⁺ , Fe ²⁺ , Fe ³ _{using perchlorate (ClO 4} ⁻ ) as counter anion in FIG. 2 . The colorimetric response of PDA-HP (200 μM) was investigated using various metal ions of ⁺ , Ni ²⁺ , Cu ²⁺ , Ag ⁺ , Zn ²⁺ , Cd ²⁺ and Hg ^{2+ .} This colorimetric reaction was done at controlled concentrations of 2.0 and 1.0 equivalents in HEPES buffer (10 mM) at pH 7.4 and 6.8. Among the various analytes, ^{only Cd 2+} induced a color transition from blue to red, no change was observed for other metal ions.

3 shows the colorimetric titration of PDA-HP (200 μM) in the presence of ^{varying amounts of Cd 2+} in HEPES buffer (10 mM) at pH 7.4 and 6.8.

That is, the conjugated polymer PDA-HP obtained by polymerizing the monomer PCDA-HP using the chelate HP with PCDA in a ratio of 1:9 is blue and purple (or red) as it binds with ^{Cd 2+ at pH 7.4 and pH 6.4.} The color changes and the fluorescence also increases. ^{The colorimetric change can confirm the detection of Cd 2+ with} the naked eye without any special equipment, and the color change is also observed quickly, and it does not react with other metals and shows selectivity to react ^{only with Cd 2+ .}

We propose the hypothesis that the detection of Cd ^{2+ in} polymers exhibits differences at pH 7.4 and 6.8 at various concentrations due to the contribution of nitrogen atoms of aromatic rings and amide groups as well as stereoscopic effects of HP units in the polymer. Although the reported PDA solution containing only the PCDA monomer does not show color change due to metal ions, the PCDA-HP monomer or polymer according to the present invention can be used as a selective and efficient colorimetric sensor for ^{Cd 2+ detection.} suggests that there is

4 shows UV/Vis spectra and fluorescence titrations, PDA- in the presence of ^{varying amounts of Cd 2+} in HEPES buffer (10 mM) at (a) pH 7.4 and (c) pH 6.8. ^{UV/Vis spectra of HP (100 μM) are shown, and Cd 2} in HEPES buffer (10 mM) at (b) pH 7.4 and (d) pH 6.8 (excitation at 530 nm, slit: 5 nm/5 nm) Fluorescence titrations of PDA-HP (100 μM) by ^+.

As a result of analyzing the change in the UV/Vis absorption spectrum of the PDA-HP aqueous solution in FIG. 4 , the original 640 nm absorption band of the PDA-derivative was pH 7.4 ((a) of FIG. 4) and HEPES buffer solution of pH 6.8 (10 mM) It can be seen that when combined with Cd ²⁺ ions, it decreases with an increase at 540 nm (pH 7.4 ((a) of FIG. 4) and pH 6.8 ((c) of FIG. 4). In addition, of Cd ²⁺ The presence is monitored by an increase in fluorescent emission due to a color transition accompanied by emission: HEPES buffer (10 mM) at pH 7.4 (Fig. 4(b)) and pH 6.8 (Fig. 4(d)). fluorescence (FL) of the PDA-HP (100μM) contained in the Cd ²⁺ at various concentrations were measured in. these values are the strength of the FL PDA-HP (from 0 400) Cd ²⁺ concentration gradually increases with the increase in μM indicates that

In addition, detection limit (LOD) represents an important parameter in molecular recognition. The detection limits of PDA-HP for Cd ²⁺ were calculated using the following equations, resulting in 53.33 μM at pH 7.4 and 30.62 μM at pH 6.8:

(Where δ represents the standard deviation of the blank measurement, and S is the slope of the intensity versus sample concentration curve.)

Job's plots (continuous-variation plots) analysis were performed to confirm the stoichiometry of the binding of the sensor PDA-HP to Cd ^{2+ ions.} The maximum with a mole fraction of about 0.3-0.5 is from 1:1 to 1:2.5 stoichiometry.

The selectivity of PDA-HP ^{could be attributed to the possible interaction of Cd 2+} with the carboxylate carbonyl group of the HP unit and the adjacent PCDA-acid residue. The addition of Cd ²⁺ can perturb the backbone of the PDA polymer to allow release of the strain energy imposed on the alkyl side chains generated during polymerization. The release of side chain strains can cause partial distortion of the ordered p -orbitals, which can lead to the observed changes in optical properties. As shown in FIG. 5 , in order to understand the interaction between ^{PCDA-HP and Cd 2+ , 1} H NMR titration experiment was performed on Acetone- d ₆ ( FIG. 5 ). When Cd ²⁺ was added to the solution of PCDA-HP, the aromatic proton peak shifted downfield, indicating an interaction between the ^{aromatic ring and Cd 2+.}

In addition, broadening of aromatic protons was observed, also supporting heteroatoms that play an important role in ^{Cd 2+ chelation.} In particular, the H _c peak was split into two peaks, and consequently the Cd ²⁺ binding site is flanked in PCDA-HP. This result shows that pyridine; chelidamic acid; The isophthalic acid moieties of PCDA-HP are involved in binding to ^{Cd 2+ .}

The present invention provides a chelating moiety of 10,12-pentacosadiynoic acid and 5-hydroxyisophthalic acid-2-picolylamine (HP). PCDA-HP derived from the reaction was synthesized. A PDA-HP copolymer containing PCDA-HP and PCDA in a ratio of 1: 9 was prepared as an aqueous solution. When bound with Cd ²⁺ ions, PDA-HP exhibits enhanced fluorescence as well as a selective colorimetric shift from blue to red. That is, when the sensor according to the present invention reacted with various metal ions in 200 μM PDA-HP solution (in HEPES buffer/10 mM, pH 7.4 and pH 6.4), the color change occurred only in ^{Cd 2+} and showed high selectivity for ^{Cd 2+ . When reacted with 0~5.0 eq of Cd 2+} in 200 μM PDA-HP solution (in HEPES buffer/10 mM, pH 7.4 and pH 6.4), color change occurred quantitatively, showing excellent detection limit. In addition, the previous Cd ^{2+ sensor detects Cd 2+} using specific equipment, but the PDA-HP can visually confirm the detection of ^{Cd 2+ without any special equipment.}

In addition, the PCDA-HP of the present invention is designed to act as an interaction between a heavy metal and a “Schiff base”, and the interaction between PCDA-HP and Cd ² was confirmed by NMR analysis.

As described above, although the embodiments have been described with reference to the limited embodiments and drawings, various modifications and variations are possible from the above description by those skilled in the art. For example, even if the described techniques are performed in an order different from the described method, and/or the described components are combined or combined in a different form from the described method, or are substituted or substituted by other components or equivalents Appropriate results can be achieved. Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

Claims (18)

A diacetylene compound represented by Formula 1 below:

(Here, R is an alkyl ^{having 1 to 30 carbon atoms, R 1} is an alkylene having 1 to 30 carbon atoms, R ² is represented by the following formula 1a,

[Formula 1a]

In Formula 1a, R ³ to R ⁹ are each hydrogen, halogen, straight-chain or branched-chain alkyl having 1 to 10 carbon atoms; It is selected from alkenyl having 2 to 10 carbon atoms and aryl having 6 to 10 carbon atoms.)
According to claim 1,
In Formula 1, R is an alkyl ^{having 3 to 20 carbon atoms, R 1} is an alkylene having 3 to 20 carbon atoms,
Wherein R ¹ is alkylene having more carbon atoms than R,
In Formula 1a, R ¹ to R ⁶ are, respectively, hydrogen, halogen, straight-chain alkyl having 1 to 5 carbon atoms; and alkenyl having 2 to 5 carbon atoms,
diacetylene compounds.
According to claim 1,
The diacetylene compound exhibits a change in optical properties when combined with cadmium,
The optical property change is at least one of color, fluorescence wavelength, fluorescence intensity and absorbance,
diacetylene compounds.
Polydiacetylene, which is a polymer of diacetylene monomers represented by the following Chemical Formulas 1 and 2:

[Formula 1]

(Here, R is an alkyl ^{having 1 to 30 carbon atoms, R 1} is an alkylene having 1 to 30 carbon atoms, R ² is represented by the following formula 1a,

[Formula 1a]

In Formula 1a, R ³ to R ⁹ are each selected from hydrogen, halogen, straight or branched chain alkyl having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, and aryl having 6 to 10 carbon atoms.)

[Formula 2]

(Here, R is alkyl ^{having 1 to 30 carbon atoms, and R 1} is alkylene having 1 to 30 carbon atoms.)
5. The method of claim 4,
The molar ratio of the monomer represented by Formula 1 to the monomer represented by Formula 2 in the polydiacetylene is 1: 9 to 1: 100,
polydiacetylene.
5. The method of claim 4,
Which is formed by photopolymerizing the double-layer self-assembly of the monomers represented by Formula 1 and Formula 2,
polydiacetylene.
5. The method of claim 4,
The polydiacetylene is represented by the following formula (3), polydiacetylene:
[Formula 3]

(In Formula 3, m and y are each selected from 1 to 29, and n is 1 or more.)
5. The method of claim 4,
The polydiacetylene is in the form of self-assembled liposomes,
polydiacetylene.
The diacetylene compound of claim 1, comprising the polydiacetylene of claim 4 or both,
composition.
10. The method of claim 9,
The composition contains water, an organic solvent, or both,
In the composition, the diacetylene compound, the polydiacetylene, or both of them, each comprising more than 0 to 100% by weight,
composition.
10. The method of claim 9,
The composition is used for cadmium detection,
composition.
10. The method of claim 9,
The composition further comprises a buffer solution,
The composition is of pH 7 to 8,
composition.
10. The method of claim 9,
The composition exhibits a change in optical properties when in contact with cadmium,
The optical property change is at least one of color, fluorescence wavelength, fluorescence intensity and absorbance,
composition.
A detection unit comprising the diacetylene compound of claim 1, the polydiacetylene of claim 4 or both;
containing,
chemical sensor.
15. The method of claim 14,
The chemical sensor, cadmium detection or quantitative and qualitative analysis of cadmium is made,
chemical sensor.
The step of contacting the analysis sample with the diacetylene compound of claim 1, the polydiacetylene of claim 4, or both;
After the step of contacting, observing the optical change of the diacetylene compound or polydiacetylene
containing,
Cadmium detection method.

16. The method of claim 15,
The analysis sample, which is maintained at a pH of 6 to 8,
Cadmium detection method.
17. The method of claim 16,
The observing step is to observe at least one of the color, fluorescence wavelength, absorbance and fluorescence intensity of the diacetylene compound, polydiacetylene,
Cadmium detection method.

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