KR20110081697A - Compounds having al(iii) ion selectivity and chemosensor using the same - Google Patents

Abstract

PURPOSE: A compound containing a triazole group, having aluminum ion selectivity and a chemical sensor using the same are provided to effectively detect aluminum ion in a sample. CONSTITUTION: A compound having aluminum ion(Al^3+) selectivity is denoted by chemical formula 1. The compound of chemical formula 1 is prepared from a compound of chemical formula 2 according to reaction formula 1. An aluminum ion is selectively detected in a sample using the compound of chemical formula 1. The detection is performed by measuring change of fluorescence wavelength and UV/Vis by addition of aluminum ion. The sample is a solution, acetonitrile solution. A chemical sensor for detecting aluminum ion is operated using the compound of chemical formula 1.

Description

Compound having aluminum ion selectivity and chemical sensor using the same {Compounds having Al (III) ion selectivity and chemosensor using the same}

The present invention relates to a compound having aluminum ion selectivity, a method for preparing the same, and a method and a chemical sensor for detecting aluminum ion using the same, and more particularly, UV / Vis that appears when a compound having aluminum ion selectivity reacts with aluminum ions. And a method of detecting aluminum ions using a change in fluorescence wavelength.

Aluminum is the most abundant metal among the metals, and is the second most abundant element among oxygen and silicon. It is also widely used in many industrial fields such as automobile and computer manufacturing.

On the other hand, Al ³⁺ ions are known to be associated with Alzheimer's disease from a biochemical point of view regarding toxicity. It is also known that 40% of soil acidification is due to aluminum toxicity. Nevertheless, only a few chemical sensors related to the detection of Al ³⁺ have been reported, which are also limited in the selectivity and sensitivity of Al ³⁺ ions compared to other metal cations.

The first problem to be solved by the present invention is to react with aluminum ions (Al ^{3 +} ) exhibits a significant UV / Vis absorption and fluorescence wavelength change, in particular to provide a compound having excellent detection performance of aluminum ions in aqueous solution.

The second object of the present invention is to provide a method for preparing the compound for detecting aluminum ions.

The third object of the present invention is to provide a method for detecting aluminum ions using the compound.

A fourth object of the present invention is to provide a high sensitivity chemical sensor for detecting aluminum ions using the compound.

In order to solve the first technical problem, the present invention provides a compound represented by the following formula (1) having aluminum ion selectivity:

(1)

(One)

Also, in order to solve the second technical problem, a method for preparing a compound of formula (1) according to claim 1 is provided from the compound of formula (2) according to Scheme 1 below:

Scheme 1

(2) (1)

According to one embodiment of the present invention, the compound of Formula (2) may be prepared according to the following Scheme 2.

Scheme 2

In order to solve the third technical problem, the present invention provides a method for selectively detecting aluminum ions in a sample using the compound of formula (1).

According to one embodiment of the invention, the method for selectively detecting the aluminum ions can be made by measuring the change in the UV / Vis and fluorescence wavelength in accordance with the addition of aluminum ions, the change in the fluorescence wavelength is ICT (excimer / It may be due to exciplex formation, intramolecular charge transfer (CHF) and chalced enhanced fluorescence (CHEF).

In addition, according to an embodiment of the present invention, the wavelength of light to be irradiated for measuring the wavelength change is preferably 450 to 480 nm, more preferably 478 nm.

In addition, according to an embodiment of the present invention, the sample may be an aqueous solution, for example, an acetonitrile (CH ₃ CN) solution.

In order to solve the fourth technical problem, the present invention provides a chemical sensor for detecting aluminum ions using the compound according to the formula (1).

The compound chemical sensor including 1,2,3-triazole group according to the present invention shows a clear change in UV / Vis absorption and fluorescence wavelength even when a small amount of aluminum (Al ³⁺ ) is added, even when other metal ions are mixed. Optionally, aluminum ions can be detected and used as a highly sensitive chemical sensor.

1 is a schematic diagram showing the light emission principle of a chemical sensor according to the present invention.
2A and 2B show Li ⁺ , Na ⁺ , K ⁺ , Ag ⁺ , Mg ²⁺ , Ca ²⁺ , Co ²⁺ , Ba ²⁺ , Sr ²⁺ , Cu ²⁺ , Hg ²⁺ , in CH ₃ CN; Fluorescence spectrum of the compound of Formula 1 (50 μM) when ClO ₄ ⁻ salt of Pb ²⁺ , In ³⁺ , Ru ⁺ , Cd ²⁺ and Al ³⁺ (50 equiv) is added.
3 is a fluorescence spectrum of the compound of formula 1 (50.0 mM) in CH ₃ CN when 50 equivalents of Al ³⁺ ions are added in the presence of ClO ₄ ⁻ salts of various cations.
4 is Li ⁺ , Na ⁺ , K ⁺ , Ag ⁺ , Mg ²⁺ , Ca ²⁺ , Co ²⁺ , Ba ²⁺ , Sr ²⁺ , Cu ²⁺ , Hg ²⁺ , Pb ²⁺ , In ³⁺ Fluorescence and UV / Vis spectra of the compound of Formula 1 in CH ₃ CN containing various metal ions (50 equivalents, perchlorate) such as, Ru ⁺ , Cd ²⁺ .
5 is a differential pulse voltammogram of 0.2 mM compound 1 (free) (compound 1: Al ³⁺ = 1: 0).
6A and 6B are ¹ H NMR and ¹³ C NMR graphs of Formula 1, and FIGS. 6C and 6D are ¹ H NMR and ¹³ C NMR graphs of Formula 2.
7 is a view showing a Job Plot / Benesi-Hildebrand method of the compound of Formula 1.
8 is a graph showing the UV / Vis spectrum of the compound of formula 1 in the presence of metal ions.
9 is a graph showing the UV / Vis Al ³⁺ titration spectrum of the compound of Formula 1.
10 is a graph showing the results of a competitive ion test (UV / Vis spectrum of Formula 1).
11 is a graph showing the DPV of a compound of Formula 1 in the presence of alkali metal ions.
12 is a graph showing the DPV of the compound of formula 1 in the presence of alkaline earth metal ions.

The inventors synthesized chemical sensors comprising 1,2,3-triazole ring spacers and investigated the optical / electrochemical properties that appear when various metal ions are added.

The addition of Al ³⁺ to the compounds according to the invention results in a significant change in fluorescence intensity, which is due to the excimer / exciplex formation, intramolecular charge transfer (ICT) and chalation enhanced fluorescence due to 1,2,3-triazole rings. ) Seems to be due to the effect. In addition, the electrochemical properties of the compounds according to the invention in the presence of Al ³⁺ ions showed a significant change compared to other metal ions.

On the other hand, anthraquinone is used as a chemical sensor for metal ions and anions due to its high extinction coefficient and visual observation. Moreover, it has been used in electroanalytical chemistry because of the quinone system comprising two consecutive electron reduction processes in which Q ^1- is formed followed by Q ^2- . Therefore, the host molecule associated with the anthraquinone group as the sensing unit is considered to be very useful for the detection of metal cations due to the unique electrochemical reaction to the target analyte.

The 1,2-dipolar cycloaddition reaction through alkyne and azide copper Cu (I) catalysts has been adopted as a direct molecular binding strategy in a wide range of synthetic applications. The 2,3-triazole skeleton has also been used as a binding site for metal ions and anions. Also recently, synthesis of 1,2,3-triazole-derived Calix [4] crown has been reported as a binding site for alkali / transition metal ions.

Taking advantage of the advantages of including both triazole and anthraquinone groups in the host-guest recognition reaction, the inventors synthesized a chemical sensor 1 and studied the electrochemical properties of various metal ions.

Compound 1 was synthesized according to the following procedure. 1,8-dihydroxyanthraquinone, 2.1 equivalents of propargyl bromide and K ₂ CO ₃ were reacted with acetone as a solvent to obtain 1,8-bis (prop-2-ynyloxy) anthraquinone of the formula (2). . The cycloaddition reaction of Chemical Formula 2 using copper Cu (I) as a catalyst was carried out to obtain the compound of Chemical Formula 1 according to the present invention in 35% yield.

Scheme 1

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention should not be construed as being limited thereto.

Example 1 Synthesis of Compound of Formula 2

1,8-dihydroxyanthraquinone (500 mg, 2.1 mmol), propargyl bromide (620 mg, 5.3 mmol) and K ₂ CO ₃ (360 mg, 3.2 mmol) in acetone solvent (100 mL) for 18 h. It was refluxed. The solution was washed with water and the organic layer was dried over anhydrous sodium sulfate. The organic solvent was removed in vacuo and subjected to silica gel column chromatography to give 110 mg of the compound of formula 2 as a yellow solid (yield 17%).

mp: 83-88 ° C. ¹ H-NMR (400 MHz, CDCl ₃ ): d 7.92 (dd, 2H, Ar H , J = 7.68 Hz), 7.67 (t, 2H, Ar H , J = 7.80 Hz) , 4.94 (d, 4H, OCH ₂ , ³ J = 2.40 Hz), 2.55 (t, 2H, C CH , ³ J = 2.40 Hz). ¹³ C-NMR (100 MHz, CDCl ₃ ): 157.4, 135.1, 134.0, 121.2, 120.5, 78.2, 57.5 ppm. FAB MS m / z (M ⁺ ): calcd, 316.07; found, 317.4. IR (KBr pellet, cm ⁻¹ ): 2125, 1710.

Example 2 Synthesis of Compound of Formula 1

Compound of formula 2 (250 mg, 0.78 mmol), 1,2-bis (2-azidoethoxy) ethane (174 mg, 0.86 mmol), copper iodide (I) (catalyst amount), and DMF at room temperature for 1 day Was stirred. The solvent was removed in vacuo and the residue was washed with water and CH ₂ Cl ₂ . The organic layer was filtered, dried over anhydrous sodium sulfate and evaporated. Silicagel column chromatography gave 143 mg of the compound of formula 1 as a yellow solid (yield 35%).

mp: 258 ^o C. ¹ H-NMR (300 MHz, CDCl ₃ ): d 8.16 (s, 2H, Ar _triazole H ), 7.86 (d, 2H, Ar _anthra H , J = 7.57 Hz), 7.65 ( t, 2 H, Ar _anthra H , J = 7.67 Hz), 7.55 (d, 2 H, Ar _anthra H , J = 8.34 Hz), 5.45 (s, 4 H, OC H ₂ ), 4.58 (t, 4 H , N CH ₂ CH ₂ O, J = 4.60 Hz), 3.88 (t, 4 H, NCH ₂ CH ₂ O, J = 5.01 Hz), 3.59 (s, 4 H, O CH ₂ CH ₂ O). ¹³ C-NMR (100 MHz, CDCl ₃ ): 183.8, 182.9, 157.9, 135.0, 134.3, 125.3, 121.1, 120.3, 70.7, 69.8, 64.3, 50.6 ppm. FAB MS m / z (M ⁺ ): calcd, 516.51; found, 517.6. IR (KBr pellet, cm ⁻¹ ): 1693, 1668, 1587.

Test Example 1: Photophysical Properties

CH ₃ CN solvent from ^{Li +, Na +, K +} , Ag +, Mg 2+, Ca 2+, Co 2+, Ba 2+, Sr 2+, Cu 2+, Hg 2+, Pb 2+, In The photophysical properties of Formula 1 were investigated by observing changes in absorbance and fluorescence when perchlorates of various cations including ³⁺ , Ru ⁺ , Cd ²⁺ and Al ³⁺ were added. UV / Vis and fluorescence changes are shown in FIGS. 2A and 8, respectively. According to the figure, the compound of Formula 1 shows a band centered at 380 nm corresponding to the anthraquinone site, and when various metal cations are added, it is observed that the UV band of the anthraquinone moiety is significantly shifted.

Meanwhile, when aluminum ions were added, a broad spectrum of absorption bands appeared in the 500 nm region. Also in the emission spectrum, the fluorescence intensity of the compound of formula 1 increased markedly at 557 nm when aluminum ions were added as shown in FIGS. 2A and 2B.

2A and 2B show Li ⁺ , Na ⁺ , K ⁺ , Ag ⁺ , Mg ²⁺ , Ca ²⁺ , Co ²⁺ , Ba ²⁺ , Sr ²⁺ , Cu ²⁺ , Hg ²⁺ , in CH ₃ CN; Fluorescence spectrum of the compound of Formula 1 (50 μM) when ClO ₄ ⁻ salt of Pb ²⁺ , In ³⁺ , Ru ⁺ , Cd ²⁺ and Al ³⁺ (50 equiv) is added.

Test Example 2: Confirmation of Complex Formation Mode

In order to confirm the complex formation ratio of the compound of Formula 1 to aluminum ions, Job plot and Benesi-Hildebrand plot method were used. The maximum point in the job plot was at mole fraction 0.625, which is the typical ligand mole fraction (0.66) with a 2: 1 ratio of ligand to metal complex.

Benesi-Hildebrand plot also confirmed that 2: 1 complexes (Fig. 7). 2b and 5 show the change in absorbance and fluorescence of the compound of formula 1 when the aluminum ions are gradually added, and the binding constant of the formula (1) to aluminum (Calc Ka) was calculated to be 4.52.

¹ H NMR spectroscopy of the compound of Formula 1 and the aluminum ion complex in the compound of Formula 1 and CD ₃ CN was also measured to demonstrate the complex formation mode of the compound of Formula 1 for aluminum ions, the difference in spectrum being shown in FIG. Is shown.

On the other hand, while the signals of other protons showed little change, the signals of H _a , H _b , H _c and H _e were shifted down by about 0.05 ppm. These results show that Al ³⁺ ions, with an anthraquinone group, are bound to two triazole rings in a 2: 1 complex.

From all these spectral data, it can be concluded that the metal binding to the carbonyl group of the anthraquinone causes the absorption band of the compound of formula 1 to be red shifted by intramolecular charge transfer (ICT). Enhancement of the fluorescence intensity of the compound of Formula 1 is presumed to be due to the combination of metals with triazole rings accompanied by chelation-enhanced fluorescence (CHEF), ie PET inhibition. The predictable complexation mode is shown in FIG. 3.

Test Example 3: Competitive Ion Experiment

In addition, in order to use the compound of Formula 1 as an optical / electrochemical ion selective chemical sensor for Al ³⁺ ions, competition experiments with various metal ions were performed. Li ⁺ , Na ⁺ , K ⁺ , Ag ⁺ , Mg ²⁺ , Ca ²⁺ , Co ²⁺ , Ba ²⁺ , Sr ²⁺ , Cu ²⁺ , Hg ²⁺ , Pb ²⁺ , In ³⁺ , Ru ⁺ The fluorescence and UV / Vis spectra of the compound of formula 1 in CH ₃ CN containing various metal ions (50 equivalents, perchlorate), such as Cd ²⁺ , are shown in FIGS. 4 and 10. Even in the presence of other competing metal ions, the complex of the compound of formula 1 and Al 3+ according to the present invention showed a clear change in fluorescence and absorption, indicating that the compound of the present invention can be used as a selective chemical sensor for Al 3+ ions. Shows.

On the other hand, the electrochemical properties of the compound of formula 1 according to the present invention when the presence or absence of Al ³⁺ in CH ₃ CN was investigated by measuring differential pulse voltammetry (DPV). A differential pulse voltammogram of 0.2 mM compound 1 (free) (compound 1: Al ³⁺ = 1: 0) is shown in FIG. 5. Two distinct cathodic peaks were observed at 1.3 and -1.7 V, which show that the two electrons move in succession to the anthraquinone site of formula (1).

However, in the presence of Al ³⁺ ions, the electrochemical properties of Formula 1 have changed significantly. 4 shows that the voltammograms of the compound of formula 1 changed when the Al ³⁺ ion was continuously added. When the concentration ratios of compound 1: Al ³⁺ are 6: 1, 4: 1 and 2: 1, three reduction curves were observed, and one curve observed near −1.3 V is represented by the compound of formula 1 (free Curves corresponding to the first reduction of) and two new curves observed near −0.4 and −0.8 V are curves corresponding to the continuous reduction of the complexes of Formula 1 and Al ³⁺ (2: 1 complex formation). The two new reduction peaks are located on the positive potential side more than the peak corresponding to the compound of formula 1 (free), which is a strong interaction between formula 1 and Al ³⁺ and reduced formula for Al ³⁺ ions compared to the normal state. Reflects an increase in the complexing strength of the compound of 1. When the ratio of the formula 1: Al ³⁺ is 1: 1, no reduction peak of the compound of formula 1 (free) was observed (FIG. 5). This shows that only a small amount of the compound of formula 1 is in the free state and little reduction process occurs in the formation of the 1: Al ³⁺ complex. It is worth noting that an additional reduction peak was observed at -0.2 V of the voltammogram when the concentration ratio was Compound 1: Al ³⁺ = 1: 1 (1: 1 complex formation mode), which is a compound 1: Al ³⁺ complex ( 1: 1 complex formation mode), which is significant as the concentration of 1 is reduced compared to the concentration of Al ³⁺ . The relative intensity of the reducing peak of Free 1 rapidly disappears with the action of [Al ³⁺ ], indicating that 1 and Al ³⁺ form a complex. The electrochemical properties of 1 were also investigated in the presence of alkali metal and alkaline earth metal ions. The results show that the binding force of 1 to the metal ions other than Al ³⁺ is weak (FIGS. 10 and 11). However, it was observed that the binding force to alkaline earth metal is stronger than alkali metal, reflecting the interaction of alkaline earth metal ion with 1,2,3-triazole ring system of formula (1), and the nitrogen atom is related to acid / base hardness. It shows better binding with alkaline earth metals than alkali metals.

In the present invention, a novel chemical sensor including 1,2,3-triazole ring spacer was synthesized and its optical / electrochemical properties were studied. The formation of the complex of the compound of Formula 1 and the Al ³⁺ ion promoted the fluorescence change at 556 nm, which is Al ³⁺ by both 1,2,3-triazole ring and carbonyl group in the 2: 1 complex formation mode. It is thought to be due to the chelation of Formula 1 for ions. In addition, Compound 1 according to the present invention showed a significant change in electrochemical properties when Al ³⁺ ions were added, and thus, Chemical Formula 1 may be used as an optical / electrochemical sensor for Al ³⁺ ions.

Claims (10)

A compound represented by the following formula (1) having aluminum (Al ³⁺ ) ion selectivity:

(One) A process for preparing the compound of formula (1) according to claim 1 from the compound of formula (2) according to Scheme 1 below.
Scheme 1

(2) (1) The method of claim 2,
The compound of formula (2) is prepared according to the following scheme 2.
Scheme 2

A method for selectively detecting aluminum ions in a sample using the compound of claim 1. The method of claim 4, wherein
A method for selectively detecting aluminum ions, characterized by measuring the change in UV / Vis and fluorescence wavelengths according to the addition of the aluminum ions. The method of claim 5,
Wherein the change in fluorescence wavelength is due to ICT and CHEF phenomena. The method of claim 6,
The wavelength of light irradiated for measuring the wavelength change is a method for selectively detecting aluminum ions, characterized in that 450 to 480nm. The method of claim 4, wherein the sample is an aqueous solution. The method of claim 8,
Wherein said aqueous solution is an acetonitrile (CH ₃ CN) solution. A chemical sensor for detecting aluminum ions using a compound according to formula (1) according to claim 1.

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