KR101653454B1 - JULOLIDINE-IMIAZOLE BASED COMPOUNDS, AGENT FOR SELECTING Zn(II), Al(III), Fe(II) AND Fe(III) ION USING THE SAME, DETECTING METHOD AND DETECTING DEVICE THEREOF - Google Patents

Abstract

The present invention relates to novel (E) -9 - ((3- (1H-imidazol-1-yl) propyl) imino) methyl) -2,3,6,7-tetrahydro- , 1-ij] quinolin-8 -ol compound and this, using a zinc ion (Zn ^{2 +),} aluminum ion (Al ^{3 +),} iron divalent ions (Fe ^{2 +)} or iron trivalent ions (Fe ^{3 +)} A detecting method, and a detecting apparatus of the present invention.

Description

TECHNICAL FIELD The present invention relates to a julolidine-imidazole compound, a zinc ion, an aluminum ion, an iron divalent ion, and a ferric trivalent ion detector using the same, (III), Fe (II) and Fe (III) ION USING THE SAME, DETECTING METHOD AND DETECTING DEVICE THEREOF}

The present invention relates to novel line Lowry Dean-imidazole-based compound, a zinc ion including the compound (Zn ^{2 +),} aluminum ion (Al ^{3 +),} iron divalent ions (Fe ^{2 +)} and iron trivalent ion ( Fe ^{+ 3)} detection agent, which is less selective to specific to relate to this detection method and a detection device using the same.

Due to its importance in recent chemical, biotechnological and environmental engineering processes, the development of selective detection agents capable of detecting metal ions has emerged as a hot topic in the environmental and biological fields. Efforts have been made to develop a single compound capable of detecting one or more metal ions and development of a device capable of detecting various metal ions by other detection methods such as fluorescence or color change is also being studied. Among them, fluorescence sensors are known as good ion detection tools because they have advantages such as high sensitivity and selectivity, fast reaction speed and simple operation method. In addition, the color change chemical sensor is also attracting a great deal of attention because it is cheap and does not need a separate device for detection such as easy detection of target ion by the naked eye.

Zinc is the second most abundant and essential element in the human body. Zinc ions play an important role in many basic biological processes such as gene transcription, regulation of metal enzymes, neuronal signaling, apoptosis, DNA binding or recognition. However, excessive amounts of zinc in the human body can cause serious diseases such as Alzheimer's disease, Friedreich's ataxia, Parkinson's disease.

Since zinc ions are colorless in aqueous solution, do not have unpaired electrons, and are intended to remain in a bivalent oxidation state (+2), it is not easy to detect zinc ions in a living environment. In addition, since zinc and cadmium belong to the same group of the periodic table and have similar properties, the distinction between the two is also difficult. Thus, there is a need to develop an easy and efficient zinc detection sensor capable of distinguishing zinc ions from cadmium and having a high selectivity for zinc ions.

Aluminum is the most abundant metallic element in the crust and aluminum compounds are used in many fields such as the textile industry, pharmaceuticals (antacids), bleach, paper industry, food additives, aluminum industry, storage / cooking utensils and light alloy production. However, the toxicity of aluminum is known to pose a risk to the central nervous system of the human body. For example, it can cause Alzheimer's, Parkinson's, and even breast cancer. Therefore, the development of chemical sensors for aluminum is required. Nevertheless, the detection of aluminum ions suffers from disadvantages in spectroscopic properties and lack of organizing ability compared to other transition metals. Therefore, the design and synthesis of new detection materials with excellent selectivity for aluminum ions is increasingly required for environmental and biological research.

Iron is the most abundant transition metal in both plants and animals. It also plays an important role in cell metabolism and enzyme catalysis, as a cofactor of oxygen transport and many enzymatic reactions of hemoglobin. However, iron imbalance in the body leads to the development of various diseases such as anemia, liver and kidney damage, diabetes and heart disease. In addition, since the Fe ^{2 +} / Fe ^{3 +} state is one of the important redox pairs in biological systems, the distinction between iron trivalent ions and iron divalent ions is very important to understand the iron-regulated biological function. Therefore, it is required to develop a sensor capable of detecting and distinguishing both iron ions and iron ions.

In other words, the development of chemical sensors for detecting these metal ions (Zn ^{2 +} , Al ^{3 +} , Fe ^{2 +} , Fe ^{3 +} ) is considered to be a very important research task due to their important roles in medicines, have. In particular, fluorescence and / or color chemistry sensors have great advantages due to their good sensitivity, simplicity, selectivity and easy handling. Therefore, it is required to develop a compound and a sensor for detecting various metal ions having advantages such as a potential cost efficiency and a reduction in analysis time.

K. B. Kim, H. Kim, E. J. Song, S. Kim, I. Noh, C. Kim, Dalton Trans. 42 (2013) 16569-16577

The present invention is a zinc ion from a number of metal ions (Zn ^{2 +),} aluminum ion (Al ^{3 +),} iron divalent ions (Fe ^{2 +)} and the iron 3 is selectively recognized by the ions (Fe ^{3 +)} fluorescence or color And to provide a compound that exhibits a change.

It is another object of the present invention to provide a zinc ion, an aluminum ion, an iron divalent ion or an iron trivalent ion detector, a detection method and a detection apparatus using the above compound.

In order to achieve the above object,

The present invention relates to (E) -9 - ((3- (1H-imidazol-1-yl) propyl) imino) methyl) -2,3,6,7-tetrahydro- , 2,1-ij] quinolin-8-ol.

[Chemical Formula 1]

The present invention also relates to a process for the preparation of 8-hydroxyjulolidine-9-carboxaldehyde and 1- (3-aminopropyl) imidazole by reaction with 8-hydroxyjulolidine- And then reacting the compound of formula (1).

The present invention is a zinc ion (Zn ^{2 +),} aluminum ion (Al ^{3 +),} iron divalent ions (Fe ^{2 +)} or iron trivalent ions (Fe ^{3 +)} detection comprising the compound of formula 1 of claim Lt; / RTI >

The present invention is a zinc ion (Zn ^{2 +),} aluminum ion (Al ^{3 +),} iron divalent ions (Fe ^{2 +)} or iron trivalent ions (Fe ^{3 +)} detection method using the compound of formula 1 .

In addition, the present invention the zinc ion (Zn ^{2 +),} aluminum ion (Al ^{3 +),} iron divalent ions (Fe ^{2 +)} or iron trivalent ions (Fe ^{3 +)} zinc ion containing the detection agent (Zn ^{2 +} ), aluminum ion (Al ^{3 +} ), iron divalent ion (Fe ^{2 +} ) or iron trivalent ion (Fe ^{3 +} ).

The compounds of general formula (I) of the present invention is manufactured by a simple metal ion among the zinc ion (Zn ^{2 +),} aluminum ion (Al ^{3 +),} iron divalent ions (Fe ^{2 +)} or iron trivalent ions (Fe ^{3 +} ) To selectively detect the metal ions. Thus, the zinc ions with the compound of general formula (I) of the present invention (Zn ^{2 +),} aluminum ion (Al ^{3 +),} iron divalent ions (Fe ^{2 +)} or iron trivalent ions (Fe ^{3 +)} detection agent, detection A method and a detection apparatus can be provided.

FIG. 1 is a graph showing fluorescence intensities measured when various metals are added to the compound of Formula 1 in a mixed solvent of acetonitrile and water. FIG.
FIG. 2 is a graph showing the intensity of fluorescence while gradually increasing the concentration of zinc ion (Zn ^{2 +} ) in the compound of Chemical Formula 1. FIG.
FIG. 3 is a graph showing changes in absorbance of a compound of Chemical Formula 1 while gradually increasing the concentration of zinc ions (Zn ^{2 +} ).
FIG. 4 is a graph showing the fluorescence change of Zn (NO ₃ ) ₂ with respect to the compound of Chemical Formula 1 by mole fraction according to Job's plot.
FIG. 5 is a graph showing fluorescence intensities of compounds and zinc ions (Zn ^{2 +} ) when various metal ions are present.
FIG. 6 is a graph showing fluorescence intensities when various metals are added to the compound of Formula 1 under a dimethylformamide solvent. FIG.
7 is a graph showing the intensity of fluorescence while gradually increasing the concentration of aluminum ion (Al ^{3 +} ) in the compound of formula (I).
8 is a graph showing changes in absorbance of the compound of formula (I) while gradually increasing the concentration of aluminum ion (Al ^{3 +} ).
FIG. 9 is a graph showing fluorescence changes of Al (NO ₃ ) ₃ with respect to the compound of Chemical Formula 1 by mole fraction according to Job's plot.
10 is a graph showing fluorescence intensities of compounds and aluminum ions (Al ^{3 +} ) when various metal ions are present.
11 is a spectrum showing ¹ H-NMR spectroscopy of the compound of Chemical Formula 1 resulting from increasing the amount of Zn (NO ₃ ) ₂ under a CD ₃ ON solvent.
12 is a spectrum showing the ¹ H-NMR spectrum of the compound of Chemical Formula 1 due to the gradual increase in the amount of Al (NO ₃ ) ₃ in DMF-d ₇ solvent.
FIG. 13 is a graph showing changes in absorbance when various metals are added to the compound of Formula 1 under a dimethylformamide solvent. FIG.
14 is an image showing the color change ability of the compound of Chemical Formula 1 in the presence of various metal ions.
15 is a graph showing the change in absorbance of the compound of Formula 1 while increasing the concentration of iron divalent ions (Fe ^{2 +} ).
16 is a graph showing fluorescence changes of Fe (ClO ₄ ) ₂ with respect to the compound of Chemical Formula 1 by mole fraction according to Job's plot.
17 is a graph showing changes in absorbance of a compound of Chemical Formula 1 while increasing the concentration of iron trivalent ions (Fe ^{3 +} ).
18 is a graph showing fluorescence changes of Fe (NO ₃ ) ₃ with respect to the mole fraction of Fe (NO ₃ ) ₃ with respect to the compound of formula (1) by Job's plot.
19 is a graph showing the intensity of absorbance of a compound and iron divalent ions (Fe ^{2 +} ) when various metal ions are present.
20 is a graph showing the intensity of absorbance of a compound and iron trivalent ions (Fe ^{3 +} ) when various metal ions are present.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a compound represented by the following general formula (1).

[Chemical Formula 1]

The compound of Formula 1 has a zinc ion (Zn ^{2 +)} from a variety of metal ions, aluminum ions (Al ^{3 +),} iron divalent ions (Fe ^{2 +)} or iron 3 is selectively recognized by the ions (Fe ^{3 +)} Thereby indicating the fluorescence intensity or the color change, whereby the metal ions can be selectively detected.

The compound of formula (I) of the present invention can be prepared by reacting 8-hydroxyjulolidine-9-carboxaldehyde with 1- (3-aminopropyl) imidazole ), And has an advantage that the reaction can be easily performed due to simple reaction conditions. The above reaction is shown in Reaction Scheme 1 below.

[Reaction Scheme 1]

The compounds of general formula (I) of the present invention, various metal ions, e.g., Ag ^+, Al ^{+ _{3, Ca 2 +, Cd 2 +,}} Co 2+, ^{Cr 3 +, Cu 2 +,} Fe 2 +, Fe 3 +, Hg 2 +, K +, Mg 2 +, Mn 2 +, Na +, Ni 2 +, Pb 2 + And Zn ^{2 +,} and the like. However, when the fluorescence intensity changes only when binding with zinc ion (Zn ^{2 +} ) or aluminum ion (Al ^{3 +} ) and when iron divalent ion (Fe ^{2 +} ) or iron trivalent ion (Fe ^{3 +} ) Only a color change is observed. Accordingly, the compounds of the formula I is a zinc ion (Zn ^{2 +),} aluminum ion (Al ^{3 +),} iron divalent ions (Fe ^{2 +)} and iron trivalent ion to the high selectivity is excellent for (Fe ^{3 +)} have.

Using the characteristics, the present invention provides a zinc ion (Zn ^{2 +),} aluminum ion (Al ^{2 +),} iron divalent ions (Fe ^{2 +)} or iron trivalent ion which comprises a compound of Formula 1 (Fe ^{3 +} ) Detection agent. Zinc ion of the present invention (Zn ^{2 +),} aluminum ion (Al ^{3 +),} iron divalent ions (Fe ^{2 +)} or iron trivalent ions (Fe ^{3 +)} detection agent comprises a compound of Formula 1, And may further comprise a solvent.

The zinc ion detecting agent may include acetonitrile as a solvent, a mixed solution of water and acetonitrile or a mixed solution of HEPES (4- (2-hydroxyethyl) -1-piperazineethanesulfonic acid) buffer solution and acetonitrile The mixed solution of water and acetonitrile or the mixed solution of HEPES buffer and acetonitrile may preferably have a volume of acetonitrile of 9 or more per volume of water or HEPES buffer solution, but is not limited thereto.

The aluminum ions (Al ^{3 +),} iron divalent ions (Fe ^{2 +)} or iron trivalent ions (Fe ^{3 +)} detection agent, but can include dimethylformamide (DMF) as a solvent is not limited to: .

In addition, the present invention is the detection of the zinc ions (Zn ^{2 +),} aluminum ion (Al ^{3 +),} iron divalent ions (Fe ^{2 +)} or iron 3 ions (Fe ^{3 +)} using the compound of formula 1 ≪ / RTI > That is, the compound of formula (I) reacts with zinc ion (Zn ^{2 +} ) or aluminum ion (Al ^{3 +} ) in a ratio of 1: 1 and exhibits fluorescence, and iron divalent ion (Fe ^{2 +} ) or iron trivalent ion ^{3 +} ) is combined with 2: 1 to provide a detection method of color change.

The compound of Formula 1 is bonded with zinc ion (Zn ^{2 +} ) or aluminum ion (Al ^{3 +} ) in a ratio of 1: 1, and iron divalent ion (Fe ^{2 +} ) or iron trivalent ion (Fe ^{3 +} ) 2: 1 can be found through Job's plot and ESI-MS. Thus, the detection of the present invention, zinc ions (Zn ^{2 +)} by using a compound of formula (I), aluminum ions (Al ^{3 +),} iron divalent ions (Fe ^{2 +)} or iron trivalent ions (Fe ^{3 +)} Method can be provided.

In addition, the present invention can provide a fluorescent chemosensor as a zinc ion or aluminum ion detecting apparatus including the zinc ion or aluminum ion detecting agent, and the iron divalent ion or the iron trivalent ion detector And can provide a chromogenic chemosensor as a ferrous or iron trivalent ion detection device. The detection device may be preferably a probe.

That is, the present invention provides a detection apparatus comprising a zinc ion (Zn ^{2 +),} aluminum ion (Al ^{3 +),} iron divalent ions (Fe ^{2 +)} or iron trivalent ions (Fe ^{3 +)} detecting the .

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. These Examples and Experiments are only for illustrating the present invention, and the scope of the present invention is not limited to these Examples and Experimental Examples.

Example  1. Preparation of the compound of formula (1)

8-hydroxyjulolidine-9-carboxaldehyde (230 mg, 1.1 mmol) was dissolved in ethanol (5 mL), and then 1- (3-aminopropyl) (1- (3-aminopropyl) imidazole) (120 mg, 1.0 mmol) was slowly added to the solution, and the mixture was stirred at room temperature for 20 hours. After the solvent of the mixed solution was removed, the resulting yellow oil was purified and separated by column chromatography using dichloromethane.

This was analyzed by ¹ H-NMR, ¹³ C-NMR, HRMS and EA, and it was confirmed to have the structure of the above formula (1).

Yield: 260 mg (80.9%).

_{^{1 H-NMR (CDCl 3,}} 400MHz): δ = 13.71 (s, 1H), 7.94 (s, 1H), 7.44 (s, 1H), 7.06 (s, 1H), 6.91 (s, 1H), 6.61 ( (t, 2H), 3.42-3.39 (t, 2H), 3.22-3.18 (m, 4H), 2.72-2.69 (t, 2H), 2.67-2.64 -2.07 (m, 2H) 1.97-1.89 (m, 4H) ppm.

¹³ C-NMR (CDCl ₃ , 400 MHz):? = 171.08, 163.64, 146.84,136.69,129.98,128.54,128.38,128.27,128.00,127.81,127.49,125.25,124.42,123.63,121.67,204.4,118.92,115.61, 110.57 ppm.

HRMS (ESI): [M + H < ⁺ & gt ^; ]; calcd, 325.43 found, 325.13.

Anal. _{Calcd for C 19 H 24 N 4} O (324.42): C, 70.34; H, 7.46; N, 17.27%. Found: C, 70.39; H, 7.63; N, 17.54%.

< Experimental Example >

Experimental Example  1. Zinc ion ( Zn ^{2 +} ) &Lt; / RTI &gt; of compound &lt; RTI ID = 0.0 & Absorbance  analysis

Example 1 various metal ions, a compound of formula (1) prepared in ^{(Mn 2 +, Fe 3 +} , Co 2+, Ni 2 +, Cu 2 +, Zn 2 +, Cd 2 +, Hg 2 +, Na + , K ^+, Mg ^{+ 2,} Fe ^{+ 2,} Ca ^{+ 2,} Al ^{+ 3,} Ga ^{+ 3,} In ^{+ 3} and Cr ^{+ 3} by) and the reaction was analyzed to fluorescent properties.

The compound of Formula 1 (1.62 mg, 0.005 mmol) prepared in Example 1 was dissolved in 1 mL of a mixed solution of acetonitrile and HEPES (= 4- (2-hydroxyethyl) -1-piperazineethanesulfonic acid buffer , v / v), 24 μL of the solution was taken and diluted in a mixed solution of 2.976 mL of acetonitrile and buffer to a final concentration of 40 μM Using a mixed solution of acetonitrile and buffer, Solution was prepared at a concentration of 20 mM and 3.6 μL of the solution was added to the compound of the formula 1. The fluorescence intensity of each solution was measured using a fluorescence instrument (λ _ex = 370 nm) The solution was prepared using nitrate salt.

The results of fluorescence analysis for each metal ion are shown in Fig. As a result, ^{Mn 2 +, Fe 3+, Co} 2 +, Ni 2 +, Cu 2 +, Zn 2 +, Cd 2 +, Hg 2 +, Na +, K +, Mg 2 +, Fe 2 +, Ca 2 A solution containing a metal ion such as ⁺ , Al ^{3 +} , Ga ^{3 +} or In ^{3 +} and the compound of the formula (1) showed little increase in fluorescence intensity. Solution of the compound of formula I chromium ions (Cr ^{+ 3),} iron divalent ions (Fe ^{+ 2)} or iron 3 containing ions (Fe ^{+ 3)} was characterized by a very slight increase in fluorescence. On the other hand, fluorescence intensities were significantly increased in the presence of zinc ions (Zn ^{2 +} ). Therefore, it was found that the compound of formula 1 of the present invention selectively detects zinc ions (Zn ²⁺ ).

Fluorescence intensity was measured while gradually increasing the concentration of zinc ion (Zn ^{2 +} ) to 0 to 1 equivalent in a solution (40 μM) prepared by compounding the compound of Formula 1 prepared in Example 1. The fluorescence intensity increased significantly until 0.3 equivalents were added. The fluorescence intensity increased slightly from 0.4 equivalents, and the maximum value was obtained at 0.6 equivalents. The results are shown in FIG.

Further, the concentration of zinc ion (Zn ^{2 +} ) was changed from 0 to 3.2 equivalents in a solution (40 μM) of the compound of Formula 1 prepared above using a UV-vis instrument (Perkin-Elmer model Lambda 2S UV / vis spectrometer) The absorbance was measured while gradually increasing. As a result, the absorbance decreased at 280 nm and 400 nm, and the absorbance increased at 370 nm.

An isosbestic point was found at 327 nm and 389 nm, and at this point it was found that the compound-Zn ^{2 +} complex of formula 1 was formed (FIG. 3). Further, it was confirmed through Job's plot that the compound of formula (I) and the zinc ion (Zn ^{2 +} ) have a binding ratio of 2: 1 (FIG. 4).

FIG. 5 shows the effect of different metal ions on the fluorescence intensity of the complex of the compound of formula (I) and zinc ion (Zn ^{2 +} ) bound thereto. The manufacture of different metal ions in the compound solutions (40 μM) of Formula ^{1 (Mn 2 +, Fe 3} +, Co 2 +, Ni 2 +, Cu 2 +, Cd 2 +, Hg 2 +, Na +, K + , Mg ^{2 +,} Fe ^{2 +,} Ca ^2+, Al ^3+, Ga ^3+, In ³⁺ or Cr into each ^{3 +)} for as long as 24 μM, then put the zinc ions (Zn ^{+ 2)} 24μM fluorescence Respectively. ^{Mn 2 +, Fe 3 +,} Co 2 +, Cd 2 +, Hg 2 +, Na +, K +, Mg 2 +, Fe 2 +, Ca 2 +, Al 3 +, Ga 3 +, In 3 + and Cr ^{3 +} did not interfere with the interaction between the compound of formula (I) and the zinc ion (Zn ^{2 +} ) and did not affect the fluorescence intensity. However, it has been confirmed that the metal ions such as Ni ^{2 +} and Cu ^{2 +} interfere with the interaction between the compound of formula (1) and the zinc ion (Zn ^{2 +} ) to decrease the fluorescence intensity.

Experimental Example  2. Aluminum ion ( Al ^{3 +} ) For Compound 1  Fluorescence and Absorbance  analysis

Example 1 A variety of metal ions with the use of the compound of formula (1) prepared in ^{(Mn 2 +, Fe 2 +} , Co 2 +, Ni 2 +, Cu 2 +, Zn 2 +, Cd 2 +, Hg 2 +, ^{Na +, K +, Mg 2} +, Ca 2 +, Al 3 +, Cr 3 +, Pb 2 +) and the reaction was observed by fluorescence properties.

The compound of Formula 1 prepared in Example 1 was dissolved in dimethylformamide (DMF) to make 5 mM, and 6 μL of the solution was added to 3 mL of DMF. Various metal ions were dissolved in ^{DMF (Mn 2 +, Fe 2} +, Co 2 +, Ni 2 +, Cu 2 +, Zn 2 +, Cd 2 +, Hg 2 +, Na +, K +, Mg 2+, Ca ^{2 +, Al 3 +, Cr} 3 +, Pb 2 +) solution (20 mM, and then semi-put by 80μM to a solution of the compound of the formula (1) to 1 mL), using a fluorescence instrument to measure the respective fluorescence intensity ( lambda _ex = 374 nm). The results of the fluorescence analysis for each metal ion are shown in Fig. At this time, the metal ion solution was prepared using nitrate salt.

^{Mn 2 +, Fe 2 +,} Co 2 +, Ni 2 +, Cu 2 +, Cd 2 +, Hg 2 +, Na +, K +, Mg 2 +, Ca 2 +, Cr 3 + or Pb ^{2 +,} and The fluorescence intensity of the compound of formula (1) containing the same metal ion was not substantially increased, and a weak fluorescence intensity was observed in the case of containing zinc ion (Zn ^{2 +} ) or gallium ion (Ga ^{3 +} ). On the other hand, when aluminum ion (Al ^{3 +} ) was included, strong fluorescence intensity was increased. Therefore, it was confirmed that the compound of formula (I) of the present invention reacts very selectively with respect to aluminum ion (Al ^{3 +} ).

The compound of Formula 1 prepared in Example 1 was dissolved in dimethylformamide (DMF) to prepare 10 μM. Fluorescence intensity was measured while gradually increasing the concentration of aluminum ion (Al ^{3 +} ) to 0 to 10 equivalents. As the concentration of aluminum ion increased, the intensity of fluorescence increased and showed the maximum value at 8 equivalents. The results are shown in Fig.

The concentration of aluminum ion (Al ^{3 +} ) was gradually increased from 0 to 1.5 equivalents to the solution (10 μM) of the compound of Formula 1 prepared above using a UV-vis instrument (Perkin-Elmer model Lambda 2S UV / vis spectrometer) And the absorbance was measured. As a result, the absorbance decreased at 348 nm and the absorbance increased at 380 nm. In addition, an isosbestic point was found at 290 nm and 357 nm, and it was found that a complex of the compound of formula (1) and aluminum ion (Al ^{3 +} ) was formed at this point (FIG.

Further, it was confirmed through Job's plot that the compound of formula (I) and aluminum ion (Al ^{3 +} ) have a binding ratio of 2: 1 (FIG. 9).

Experiments were conducted to confirm the influence of different metal ions on the fluorescence intensity of the compound of formula (I) of the present invention and the aluminum ion (Al ^{3 +} ) complex. The results are shown in FIG. Other metal ions in solution compound (10 μM) of the formula (1) prepared above ^{(Mn 2 +, Fe 3 +} , Co 2 +, Ni 2+, Cu 2 +, Zn 2 +, Cd 2 +, Hg 2 +, Na ^+, K ^+, Mg ^{2 +,} Fe ^{2 +,} Ca ^{2 +,} Ga ^3+, In ^3+, Ag ^+, Pb ^{2 +,} Cr into ^{3 +)} for as long as 80 μM, and then aluminum ions (Al ^{3 +} ) 80 μM was added to measure the fluorescence intensity. Most of the metal ions did not interfere with the interaction of the compound of formula (1) with aluminum ions (Al ^&lt; ^{3 + &} gt ^; ) and did not interfere with the increase of fluorescence intensity. However, the Cu ^{2 +} or Fe ^{3 +} ion affects the interaction between the compound of formula (1) and aluminum (Al ³⁺ ) to decrease the fluorescence intensity.

Experimental Example  3. Zinc ion ( Zn ^{2 +} ) And the compound of formula (1) In the complex  Proton nuclear magnetic resonance ^One H- NMR ) Titration experiment

¹ H-NMR titration experiments were carried out on CD ₃ CN (FIG. 11) in order to examine the binding state between the compound of formula (1) of the present invention and zinc ion (Zn ^{2 +} ).

0, 0.25 or 0.5 equivalents of zinc ion (Zn ^{2 +} ) was added to the compound of Formula 1 prepared in Example 1, and ¹ H-NMR was measured. NMR peaks corresponding to the hydroxyl groups (-OH) of the compound of formula (1) disappear when 0.5 equivalents of zinc ion (Zn ^{2 +} ) is added, and NMR peaks corresponding to three hydrogens in the imidazole ring, As shown in Fig. Also, it was confirmed that the hydrogen cation of the imine bond moves to the down field.

All these changes were completed when 0.5 equivalents of zinc ions (Zn ^{2 +} ) were added, and it was predicted that the compound of formula (1) and the zinc ion (Zn ^{2 +} ) were bound at a ratio of 2: 1.

Experimental Example  4. Aluminum ions ( Al ^{3 +} ) And the compound of formula (1) In the complex  Proton nuclear magnetic resonance ^One H- NMR ) Titration experiment

The engaged state the ¹ H-NMR titration experiments in DMF-d ₇ was to evaluate the present compound and the aluminum ion of the general formula (I) of the invention (Al ^{3 +)} (Fig. 12).

0, 0.25 or 0.5 equivalents of aluminum ion (Al ^{3 +} ) was added to the compound of Formula 1 prepared in Example 1, and ¹ H-NMR was measured. When the aluminum ion (Al ^{3 +} ) is added to the compound of formula (1), the NMR peak corresponding to the hydroxyl group (-OH) of the compound of formula (1) disappears and the NMR peak corresponding to the hydrogen of the imine migrates to the down field I could confirm.

All of these changes could be expected that the combination was completed when put into the aluminum ions (Al ^{+ 3)} 0.5 equivalent of the compound of formula (1) and through which the ratio of aluminum ions (Al ^{+ 3)} is 2 to 1.

Experimental Example  5. Iron divalent ions ( Fe ^{2 +} ) Or iron trivalent ions ( Fe ^{3 +} 0.0 &gt; 1 &lt; / RTI &gt; Absorbance  analysis

The compound of Formula 1 prepared in Example 1 was dissolved in dimethylformamide (DMF) at a concentration of 40 μM. Various metal ions of one equivalent to the solution ^{(Mn 2 +, Fe 3 +} , Co 2 +, Ni 2 +, Cu 2 +, Zn 2 +, Cd 2 +, Hg 2 +, Na +, K +, Mg 2 ^+, Ca ^{+ 2,} Al ^{+ 3,} Ag ^+, Pb ^{+ 2} or Cr ^{+ 3,} insert), each using a UV-vis the device was measured, the absorbance exhibited an absorbance analysis results are shown in Fig.

As a ^{result, Mn 2 +, Co 2 +} , Ni 2 +, Zn 2 +, Cd 2 +, Hg 2 +, Na +, K +, Mg 2 +, Ca 2 +, Ag +, Pb 2 + , or Cr ^{3 +} , There was almost no change in the absorbance. On the other hand, in the case of the solution of the compound of the formula (1) to which the iron divalent ion (Fe ^{2 +} ) or the iron trivalent ion (Fe ^{3 +} ) was added, the wavelengths increased at 440 nm and 450 nm, respectively.

In addition, iron divalent ions (Fe ^{2 +)} solution of the compound of formula (I) with a solution of the compound of formula (1) added was changed to orange, colorless, iron 3 is the addition of ions (Fe ^{3 +)} is changed to purple colorless Respectively. On the other hand, no color change was observed when other metal ions were added (Fig. 14).

Accordingly, it was confirmed that the compound of formula (I) of the present invention selectively detects iron divalent ions (Fe ^{2 +} ) and iron trivalent ions (Fe ^{3 +} ).

The concentration of iron divalent ions (Fe ^&lt; ^{2 + &} gt ^; ) was changed from 0 equivalent to 1.0 equivalent to a solution of the compound of Formula 1 (solvent DMF, 40 [mu] M) using a UV-vis instrument (Perkin-Elmer model Lambda 2S UV / vis spectrometer) The absorbance was measured while gradually increasing.

As a result, the absorbance decreased at 349 nm and the absorbance increased at 440 nm. An isosbestic point was found at 327 nm and 358 nm, indicating that the compound-Fe ^{2 +} complex of Formula 1 was formed at this point (FIG. 15). Further, it was confirmed through Job's plot that the compound of Formula 1 and the iron divalent ion (Fe ^{2 +} ) have a binding ratio of 1: 1 (FIG. 16).

In the same manner as above, the absorbance was measured while gradually increasing the concentration of iron trivalent ions (Fe ^{3 +} ) from 0 equivalents to 1.0 equivalents. As a result, at 450 nm, the absorbance increased as the concentration of iron trivalent ion increased, and an isosbestic point was found at 325 nm, indicating that the compound-Fe ^{3 +} complex of formula (1) (Fig. 17). Further, it was confirmed through Job's plot that the compound of Formula 1 and the iron trivalent ion (Fe ^{3 +} ) had a binding ratio of 1: 1 (FIG. 18).

The influence of other metal ions on the binding of the compound of formula (1) to the iron divalent ion (Al ^{2 +} ) or the compound of formula (1) and the iron trivalent ion (Fe ^{3 +} ) is shown in FIGS. 19 and 20.

Solution of the compound of formula (I) with other metal ions to (the solvent ^{DMF, 40 μM) (Mn 2} +, Fe 3 +, Co 2 +, Ni 2+, Cu 2 +, Zn 2 +, Cd 2 +, Hg 2 +, ⁺ Na, K ^+, Mg ^{+ 2,} Fe ^{+ 2,} Ca ^{+ 2,} Ga ^{+ 3,} In ^{+ 3,} Ag ^+, Pb ^{+ 2,} Cr ^{+ 3} was put) as a 40 μM. Thereafter, iron divalent ions (Fe ^{2 +} ) or iron trivalent ions (Fe ^{3 +} ) were added in an amount of 40 μM, respectively, and the absorbance was measured. As a result, it was confirmed that most of the metal ions do not interfere with the interaction between the compound of formula (1) and the iron divalent ion (Fe ^{2 +} ) or the iron trivalent ion (Fe ^{3 +} ) and thus do not decrease the absorbance.

Claims (9)

delete delete An aluminum ion (Al ³⁺ ), iron divalent ion (Fe ²⁺ ) or iron trivalent ion (Fe ³⁺ ) detecting agent comprising a compound of the following formula (1).
[Chemical Formula 1]

delete delete The method of claim 3,
The aluminum ions (Al ^{3 +),} iron divalent ions (Fe ^{2 +)} or iron trivalent ions (Fe ^{3 +)} detection agent may comprise a solvent in addition, the solvent is characterized in that dimethylformamide aluminum ions (Al ^{+ 3),} iron divalent ions (Fe ^{+ 2)} iron or a third detecting ions (Fe ^{+ 3)} according to. A method for detecting an aluminum ion (Al ³⁺ ), iron divalent ion (Fe ²⁺ ) or iron trivalent ion (Fe ³⁺ ) using the compound of Chemical Formula 1 of claim 3. Claim 3 of the aluminum ion (Al ^3+), iron divalent ions (Fe ²⁺⁾ or trivalent iron ion (Fe ³⁺⁾ aluminum ions (Al ^3+), iron divalent ions including a detection agent (Fe ^{2 +} ) Or iron trivalent ion (Fe ³⁺ ) detecting device. The method of claim 8,
(Al ³⁺ ), iron divalent ion (Fe ²⁺ ) or iron trivalent ion (Fe ³⁺ ) detection device, characterized in that the detection device is a probe.

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