KR101219472B1 - Triphenylamine based dye for detecting heavy metal ions - Google Patents

Abstract

The present invention relates to a triphenylamine dye compound for detecting heavy metal ions and a dye sensor for detecting heavy metal ions comprising the same as an active ingredient. More specifically, the triphenylamine dye compound is combined with mercury + divalent ions, copper + divalent ions or zinc + divalent ions to form a dye metal complex, thereby changing the absorption and emission spectra of the dye compound. It relates to a dye sensor for detecting heavy metal ions through.

Description

Triphenylamine based dye for detecting heavy metal ions

The present invention relates to a triphenylamine dye compound for detecting heavy metal ions and a dye sensor for detecting heavy metal ions comprising the same as an active ingredient. More specifically, the triphenylamine dye compound is combined with mercury + divalent ions, copper + divalent ions or zinc + divalent ions to form a dye metal complex, thereby changing the absorption and emission spectra of the dye compound. It relates to a dye sensor for detecting heavy metal ions through.

The research and development of chemical sensors with good selectivity, sensitivity and simple structure using dye chromophores for heavy metals is one of the important issues in dye molecular chemistry due to their important role in chemistry, biology and environmental systems. Since the initial discovery of these chemical sensors has been reported in chemical sensors such as crown ethers, many researchers' efforts have focused on the design, synthesis and detection of heavy metal ions due to their toxic effects.

Therefore, transition heavy metals such as mercury (Hg ²⁺ ), copper (Cu ²⁺ ) and zinc (Zn ²⁺ ) are very toxic and have problems in their application as they are considered very toxic environmental pollutants. As is well known, mercury and copper are considered very harmful heavy metals in the human body and play an important role in physiological processes due to their severe toxic effects. Moreover, zinc has been reported to be associated with the pathogenesis of Alzheimer's disease due to β-amyloid formation.

In the present invention, the present inventors have devised the present invention by synthesizing dye chromophores based on triphenylamine derivatives as chemical sensors for heavy metal ions, and completed the present invention by measuring metal ion detection characteristics of these dyes. At this time, the metal ion detection value was confirmed by UV-visible absorption and fluorescence measurement in detail. In addition to the metal ion detection property, the molecular energy potentials (HOMO and LUMO energy values) of dye chemical sensors based on triphenylamine derivatives were also determined. Calculated and measured.

An object of the present invention is to synthesize dye chromophores based on triphenylamine derivatives as chemical sensors for heavy metal ions. In addition, the metal ion detection characteristics of these dyes were measured, and the metal ion detection values were determined by UV-Vis absorbance and fluorescence emission measurements, and in addition to the metal ion detection characteristics, the molecular energy potential of the dye chemical sensor based on the triphenylamine derivative ( HOMO and LUMO energy values) are also measured.

An object of the present invention is to provide a dye compound A for heavy metal detection represented by the following formula prepared by reacting a benzoxazole compound with triphenylamine monoaldehyde.

An object of the present invention is to provide a dye compound B for heavy metal detection represented by the following formula prepared by reacting triphenylamine dialdehyde with 2 equivalents of a benzoxazole compound.

Another object of the present invention

Iii) synthesizing triphenylamine monoaldehyde (dye 1) and triphenylamine dialdehyde (dye 2) using triphenylamine as a starting material;

Ii) synthesizing dye compound A by reacting 1 equivalent of dye 1 with a benzoxazole compound (dye 3) in an equivalent amount; or

Iii) synthesizing the dye compound B by reacting 2 equivalents of the benzoxazole compound (dye 3) to the equivalent of dye 2 to provide a method for producing a dye compound A and a dye compound B.

Meanwhile, the dye compound A and the dye compound B are characterized by forming a dye metal complex by combining with mercury +2 ions, copper +2 ions, and zinc +2 ions.

In addition, the dye compound A is characterized in that the mercury +2 in solution exhibits an increased absorption spectrum near 320 nm, a reduced absorption spectrum near 400 nm, and a reduced emission spectrum near 500 nm.

In addition, the dye compound B is characterized in that the mercury +2 in solution exhibits an increased absorption spectrum near 320 nm, a reduced absorption spectrum near 400 nm, and an increased emission spectrum near 500 nm.

Another object of the present invention is to provide a dye sensor for detecting mercury + divalent ions, copper + divalent ions or zinc + divalent ions comprising the dye compound A or the dye compound B as an active ingredient.

The effect of the present invention is to provide dye chromophores based on triphenylamine derivatives as chemical sensors for heavy metal ions. In addition, the metal ion detection characteristics of these dyes were measured, and the metal ion detection values were determined by UV-Vis absorbance and fluorescence emission measurements, and in addition to the metal ion detection characteristics, the molecular energy potential of the dye chemical sensor based on the triphenylamine derivative ( HOMO and LUMO energy levels).

FIG. 1 (a) shows the absorption spectrum of dye 4 (dye A) (1.0 × 10 ⁻⁴ M, chloroform) upon addition of divalent metal ions (Zn ²⁺ , Hg ²⁺ and Cu ²⁺ ) and FIG. ) Shows the absorption spectrum of dye 4 (dye A), optionally titrated with Hg ²⁺ .
FIG. 2 (a) shows an absorption spectrum of dye 5 (dye B) (1.0 × 10 ⁻⁴ M, chloroform) upon addition of divalent metal ions (Zn ²⁺ , Hg ²⁺ and Cu ²⁺ ), and FIG. b) shows the absorption spectrum of dye 4 (dye A), optionally titrated with Hg ²⁺ .
FIG. 3 shows the fluorescence emission spectra of dye 4 (dye A) and dye 5 (dye B) (1.0 × 10 ⁻⁴ M, chloroform) titrated with Hg ²⁺ .
4 shows the Job method for Hg ²⁺ addition: dye 4 complex (a) and dye 5 complex (b).
5 shows the geometric optimization and HOMO and LUMO energy values of dyes 4 (dye A), 5 (dye B).
6 is a cyclic voltammetry plot of dyes 4 (dye A) (a) and 5 (dye B) (b) in acetonitrile (0.05 M TBAPF6, Ag / Ag + reference electrode and scan rate 100 mV / s).

The inventors devised and synthesized a triphenylamine-based novel dye sensor and measured the detection function of the dye sensor with excellent selectivity and sensitivity to heavy metal ions. The composite potential for heavy metal ions was characterized by optical characterization using a UV-vis spectrophotometer and spectrofluorometer. Furthermore, the molecular energy values of the designed dye sensors are also computer-generated by density function theory (DFT) as an exchange correction function of local density approximation (LDA) based on Perdew-Wang (PWC) sets and cyclic voltammetry. Optimized and calculated.

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

In the present invention, by using the triphenylamine aldehyde (dye 1) and triphenylamine dialdehyde (dye 2) as a starting material and reacted with the dye 3 of the benzoxazole-based intermediate, dyes dye A (dye 4) and dye B ( Dye 5) was synthesized.

The following scheme shows the synthetic route of the dye A and dye B.

The dyes A and B synthesized in the above-described manner combine with metal ions to form new metal ion complexes, and the metal ion complexes thus formed cause changes in the absorption and emission spectra of the dye.

Absorbance and fluorescence emission spectra were measured to monitor the sensing function of designed dyes 4 (dye A) and 5 (dye B) for heavy metals (Hg ²⁺ , Cu ²⁺ and Zn ²⁺ ).

The absorbance spectra of Dye A and Dye B with three metal ions in chloroform are shown in FIGS. 1 and 2, respectively. The detection properties of Dye A and Dye B for the three metals showed a selective function, especially for Hg ²⁺ ions.

The optical properties of dyes A and B showed increased action near 320 nm and decreased action near 400 nm with increasing Hg ²⁺ concentration. At 350 nm, the iso-absorbance point was clearly observed. This sensing action was caused by the metal bonding reaction.

Figure 3 shows the fluorescence spectra of Dye A and Dye B upon addition of Hg ²⁺ ions. When Hg ²⁺ ions were added to Dye A, the maximum emission band at 500 nm decreased with increasing Hg ²⁺ concentration. However, for Dye B, the maximum emission band at 500 nm increased with increasing Hg ²⁺ concentration. This optical change is explained by MLCT, ie, "charge transfer from metal to ligand." The apparent optical luminescence properties change when a metal bonding reaction occurs. These sensing properties provide an easy way to visually measure metal ion detection properties.

Job methods are widely used to measure complex compositions of host-customer interactions. The relationship of the molar fraction of metal ions to the maximum absorbance peak is shown in FIG. 4. From the results of dyes 4 (dye A) and 5 (dye B) the mole fractions were close to 50% and 65%. These findings confirmed that addition of Hg ²⁺ ions formed 1: 1 and 1: 2 binding complexes, respectively.

Optimization of the molecular geometry and molecular energy potentials of the dye sensors 4 (dye A) and 5 (dye B) were computerized by DFT as an exchange correction function of LDA based on the PWC set using Materials studio 4.2.

FIG. 5 shows that the electron densities of dye sensors 4 (dye A) and 5 (dye B) are distributed within the triphenylamine moiety in the HOMO state and then located within the benzoxazole moiety in the LUMO state. From these findings, HOMO and LUMO energy levels were calculated by -4.61 eV and -2.51 eV (dye sensor 4) and -4.74 eV and -2.82 eV (dye sensor 5). Cyclic voltammetry of these dyes was performed using a conventional three-electrode system. Oxidation and reduction potential values were also used to measure HOMO and LUMO energy level potentials.

6 shows the redox potential characteristics of the dye sensors 4 (dye A) and 5 (dye B), respectively. HOMO and LUMO energy levels of the dye sensor were measured and compared from the redox potential (Table 1).

HOMO and LUMO energy values were calculated using the following formula:

HOMO or LUMO (eV) = -4.8-( E _{peak potential} - E 1/2 _ferrocene )

E _{peak potential} and E 1/2 _ferrocene are the maximum, minimum peak potential and half wave potential of Ferrocene.

In the present invention we have developed novel dye chemical sensors 4 (dye A) and 5 (dye B) based on triphenylamine. The dye chemistry sensor exhibited selective characteristics of absorbance and fluorescence intensity for Hg ²⁺ . The stable binding function of dyes 4 (dye A) and 5 (dye B) formed 1: 1 and 1: 2 complexes with Hg ²⁺ , which was measured by the Job method. Molecular energy values were calculated using computer optimization and cyclic voltammetry. Synthesized dye sensors 4 (dye A) and 5 (dye B) can be used as good chemical sensors that are selective for Hg ²⁺ ions in chemical, environmental and biological systems.

Hereinafter, the present invention will be described in more detail by way of examples. However, these embodiments are not intended to limit the scope of the present invention.

Material and measurement

All reagents and solvents used in the synthesis of triphenylamine based dye chemical sensors were purchased from Aldrich and used without further purification. The spectroscopic and fluorescence properties of these dyes were investigated and measured using an Agilent 8453 UV-Visible Spectrophotometer and Shimadzu RF-5301 Spectrofluorometer, respectively. ¹ H NMR spectra and elemental analysis were recorded with a JNMAL400 spectrometer and Carlo Elba Model 1106 analyzer operating at 400 MHz NMR, respectively. The electrochemical properties of these dyes were investigated with VersaSTAT3 using platinum wire acting as the working electrode, Ag / Ag ⁺ acting as the reference electrode and carbon acting as the counter electrode. The scan speed was 100 mV / s. Optimization geometry and molecular energy potential were calculated with Materials studio 4.2.

Preparation Example 1 Synthesis of Starting Material Dye 1 and Dye 2

To a mixture of 4 g (16.3 mmol) triphenylamine with 8 ml N, N-dimethylformamide, 7.6 ml was added phosphorus oxychloride at 0 ° C. and the mixture was then stirred at 45 ° C. for 2 hours (dye 1) and 95 The countercurrent was refluxed at 4 ° C. (dye 2). The reaction was cooled to room temperature and the mixture was cooled in 150 ml ice water. The precipitate solution formed was titrated to neutral pH conditions using 4 M sodium hydroxide solution. The solid was filtered and purified by column chromatography by elution with hexane / ethyl acetate. Dye 1, yield: 61.07% (2.72 g); Analytical calculation for C ₁₉ H ₁₅ NO: C, 83.49; H, 5.532; N, 5.12. Found: C, 83.42; H, 5.50; N, 4.995. ¹ H NMR (400 MHz, CDCl ₃ ): δ 7.06 (d, 2H), 7.19-7.25 (m, 6H), 7.38 (t, 4H), 7.7.2 (d, 2H), 9.85 (s, 1H) . Dye 2, yield: 68.27% (2.52 g); Analytical calculation for C ₂₀ H ₁₅ NO ₂ : C, 79.72; H, 5.02; N, 4.65. Found: C, 79.65; H, 5.07; N, 4.65. 1 H NMR (400 MHz, CDCl ₃ ): δ 7.19 (m, 6H), 7.40 (t, 2H), 7.76-7.78 (d, 4H), 9.89 (s, 2H).

Preparation Example 2 Synthesis of Reactive Material Dye 3

Signal unit dye 3 was prepared by condensing 0.998 g (6.52 mmol) of p -aminosalicylic acid and 0.711 g (6.52 mmol) of o -aminophenol. 20 g of polyphosphoric acid was added and heated at 200 ° C. with constant stirring. After 3 hours the reaction was cooled in ice water and stirred for 24 hours. The precipitate solution formed was titrated to neutral pH conditions using 1% sodium carbonate solution. After 3 hours the mixture was filtered several times with distilled water and dried in a 40 ° C. oven. Dye 3, yield: 23.03% (0.34 g); Analytical calculation for C ₁₃ H ₁₀ N ₂ O ₂ : C, 69.02; H, 4.46; N, 12.38: confirmation; C, 69.16; H, 4. 16; N, 12.81. ¹ H NMR (400 MHz, CDCl ₃ ): δ 4.00 (s, 2H), 6.24 (d, 1H), 6.28 (d, 1H), 7.18-7.32 (m, 2H), 7.42-7.50 (m, 1H) , 7.52-7.62 (m, 1 H), 7.30 (d, 1 H), 11.47 (s, 1 H).

Preparation Example 3 Synthesis of Dye A and Dye B of the Present Invention

Chemical sensor dyes 4 (dye A) and 5 (dye B) were obtained from the intermediates 2 and 3 prepared for the next step synthesis. 0.045 g and 0.090 g (0.2 mmol, 0.4 mmol) of dye 1 were mixed with dyes 2 and 3 (0.2 mmol, 0.054 g, 0.06 g), respectively. The reaction mixture was dissolved in 15 ml of benzene. Five to six drops of piperidine were added dropwise during the reaction and then refluxed for 48 hours. The reaction product was filtered off with benzene and dried.

Dye 4 (dye A), yield: 53.37% (0.052 g); Analytical calculation for C ₃₂ H ₂₃ N ₃ O ₂ : C, 79.81; H, 4.81; N, 8.73. Found: C, 79.26; H, 4.56; N, 8.25. ¹ H NMR (400 MHz, DMSO-d ₆ ): δ 6.07 (s, 4H), 6.26-6.29 (m, 2H), 6.86-6.88 (m, 2H), 7.07-7.19 (m, 1H), 7.32- 7.33 (m, 5 H), 7.69-7.70 (m, 7 H), 9.75 (s, 1 H).

Dye 5 (dye B), yield: 35.81% (0.052 g); Analytical calculation for C ₄₆ H ₃₁ N ₅ O ₄ : C, 76.97; H, 4. 35; N, 9.76. Found: C, 76.94; H, 4. 70; N, 10.31. ¹ H NMR (400 MHz, CDCl ₃ ): δ 6.29-6.34 (t, 4H), 6.29 (s, 4H), 7.52-7.54 (d, 1H), 7.60-7.64 (m, 4H), 7.71-7.78 ( m, 8H), 7.86 (s, 2H), 8.03-8.05 (d, 2H), 8.43 (s, 2H), 9.87-9.89 (d, 2H), 11.58 (s, 2H).

Example 1 Absorption and Fluorescence Measurements

UV-vis absorption and fluorescence spectra were performed by the addition of 0-2 divalent different metal ions (Hg ²⁺ , Cu ²⁺ and Zn ²⁺ ) in 3 ml dye solution (1.0 × 10 ⁻⁴ M).

Example 2 Composition of Metal Composite

4 dye (dye A), 5 (dye B) and the Hg ²⁺ ion solution having different volume ratios with a total concentration of ^{1.0 X 10 -4 M (1:} 9, 2: 8, 3: 7, 4: 6, 5: 5, 6: 4, 7: 3, 8: 2, 9: 1, 10: 0). The mixed solution was characterized by the maximum absorbance value using a spectrophotometer.

Claims (7)

Dye compound A for heavy metal detection represented by the following formula prepared by reacting a benzoxazole compound with triphenylamine monoaldehyde

Dye compound B for heavy metal detection represented by the following chemical formula prepared by reacting triphenylamine dialdehyde with 2 equivalents of benzoxazole compound

Iii) synthesizing triphenylamine monoaldehyde (dye 1) and triphenylamine dialdehyde (dye 2) using triphenylamine as a starting material;
Ii) synthesizing dye compound A by reacting 1 equivalent of dye 1 with a benzoxazole compound (dye 3) in an equivalent amount; or
Iii) synthesizing dye compound B by reacting 2 equivalents of the benzoxazole compound (dye 3) to the equivalent of dye 2; a method for producing dye compound A and dye compound B consisting of

The dye according to claim 1 or 2, wherein the dye compound A and the dye compound B are combined with mercury + divalent ions, copper + divalent ions or zinc + divalent ions to form a dye metal complex. compound
The method of claim 1, wherein the dye compound A is characterized in that the mercury +2 in solution exhibits an increased absorption spectrum near 320 nm, a reduced absorption spectrum near 400 nm and a reduced emission spectrum near 500 nm. Dye Compound A
The method of claim 2, wherein the dye compound B is characterized in that the mercury +2 in solution shows an increased absorption spectrum near 320nm, a reduced absorption spectrum near 400nm and an increased emission spectrum near 500nm Dye Compound B
Dye sensor for detecting mercury + divalent ions, copper + divalent ions or zinc + divalent ions comprising the dye compound A of claim 1 or the dye compound B of claim 2 as an active ingredient

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