KR20100019906A - Turn-on type signaling method of hg(ii) ions by rhodamine based fluorophores - Google Patents

Abstract

PURPOSE: A method for detecting Hg(II) ions is provided to selectively and efficiently detect Hg^2+ ions using a rhodamine-based hydrazide compound as a selective chemical dosimeter. CONSTITUTION: A method for detecting Hg(II) ions comprises the steps of: dissolving compounds represented by chemical formulas 1-3 in water single, a polar organic solvent single, or a mixed solvent of water and solvent; adding a sample in the prepared solution; and detecting mercury ions by performing selective Hg^2+ induction hydrolysis for a lamtam ring of a rhodamine-based hydrazide and detecting the fluorescence spectrum to detect Hg(II) ions.

Description

Turn-on type signaling method of Hg (II) ions by rhodamine based fluorophores}

The invention turns with the loader mingye fluorophore-signaling by selective Hg ^{2 +} induced hydrolysis of the present invention relates to one type of mercury (Ⅱ) detection method of the ions, and more particularly to a loader lactam ring of mingye hydrazide It is a method using behavior.

Recently, numerous fluorescent signaling systems have been developed for the selective and efficient measurement of important species ((a) Desvergne, JP; Czarnik, AW Chemosensors of Ion and Molecule Recognition Kluwer: Dordrecht, 1997; (b) Fluorescent Chemosensors for Ion and Molecule Recognition Czarnik, AW, Ed .; American Chemical Society: Washington, DC, 1992; (c) de Silva, AP; Gunaratne, HQN; Gunnlaugsson, T .; Huxley, AJM; McCoy, CP; Rademacher, JT; Rice, TE Chem . Rev. 1997, 97 , 1515). Among the widely used syntheses, chemodosimeters in particular attract a lot of attention due to their advantages such as the high selectivity usually achieved by specifically designed reactions and the characteristic cumulative effects for the measurement of analytes. (A) Jimenez, D .; Martinez-Manez, R .; Sancenon, F .; Ros-Lis, JV; Benito, A .; Soto, J. J. Am. Chem . Soc . 2003, 125 , 9000 (b) Yang, YK; Yook, KJ; Tae, J. J. Am. Chem . Soc . 2005, 127 , 16760. (c) Ko, S.-K .; Yang, Y.-K .; Tae , J .; Shin, I. J. Am. Chem . Soc . 2006, 128 , 14150. (d) Song, KC; Kim, JS; Park, SM; Chung, K.-C .; Ahn, S .; Chang, S.-K. Org . Lett . 2006, 8 , 3413. (e) Lee, MH; Wu, J.-S .; Lee, JW; Jung, JH; Kim, JS Org . Lett . 2007, 9 (F) Wu, J.-S .; Hwang, I.-C .; Kim, KS; Kim, JS Org . Lett . 2007, 9 , 907. (g) Kim, SY; Hong, J. -I. Org . Lett . 2007, 9 , 3109). A stoichiometric reaction is performed by reacting stoichiometrically with an analyte such as a metal cation, which is a detection target, to detect an analyte through a chemical reaction, and after detection, the stoichiometry is changed into a different structure to distinguish it from a chemical sensor capable of reversible detection. do.

Cu ^{2 +} - a, the number of unique signaling system due to the hydrazide derivatives of Rhodamine B as in the classical example of a selective fluorescent chemical dosimeter has been developed (Dujols, V .; Ford, F .; Czarnik, AW J. Am. Chem . Soc . 1997, 119 , 7386). Of the formula 1 is the Czarnik Cu ^{2 +} - a selective fluorescent chemical dosimeter.

<Formula 1>

In addition, rhodamine B Hyde large lifting analysis of chromium (Ⅵ) in water (Xiang, Y .; Mei, L .; Li, N .; Tong, A. Anal. Chim. Acta 2007, 581 , 132) and sensitive measurements of hydrogen peroxide and glucose (Chen, X .; Zou, J. Microchim . Acta 2007, 157 , 133). Aqueous medium (media) within the Hg ^{2 +} chemical dosimetry of ions fluorescein (fluorescein) of thio semicarbazide (thiosemicarbazide) irreversibly desulfurization (desulfurization) to the oxadiazole (oxadiazole) of the corresponding derivatives thereof reaction (This represents an efficient chromogenic and fluorogenic signal) (Yang, X.-F .; Li, Y .; Bai, Q. Anal. Chim . Acta 2007, 584 , 95).

More recently, Zheng, such as the spiro-lactam (spirolactam) one to an oxygen atom substituted by a sulfur atom thio hydrazide Cu ^{2 +} of the hydrazide of Formula 1 by in generating a (thiohydrazide) a-selective signal characteristic is Hg ²⁺ it reported an interesting discovery that can be effectively switched to selective (Zheng, H .; Qian, Z. -H .; Xu, L .; Yuan, F.-F .; Lan, L.-D .; Xu , J.-G. Org . Lett . 2006, 8 , 859). Salicylic Rhodamine B Hydrazone (Xiang, Y .; Tong, A .; Jin, P .; Ju, Y. Org . Lett . 2006, 8 , 2863) and Fluorescein Hydrazide (Chen, X Ma, H. Anal. Chim, Acta . Exhibited a selective color development properties, and fluorescent signal - via an induced hydrolytic cleavage ^{Cu 2 + - 2006, 575,} 217) of the other optional metal ion of the derivative is the amide bond associated.

On the other hand, the selection and efficient Hg ^{2 +} development of chemical sensors is very important in chemistry, biology and environmental science, there is a need for constant attention and research ((a) Nolan, EM; ... Lippard, SJ J. Am Chem Soc . 2003, 125, 14270 and references therein. (b) Guo, X .; Qian, X .; Jia, L. J. Am. Chem. Soc. 2004, 126, 2272. (c) Chen, P .; He (C) J. Am. Chem . Soc . 2004 , 126 , 728. (d) Ono, A .; Togashi, H. Angew . Chem. Int . Ed . 2004 , 43 , 4300. (e) Yoon, S. Albers, AE; Wong, AP; Chang, CJ J. Am. Chem . Soc . 2005 , 127 , 16030. (f) Ros-Lis, JV; Marcos, MD; Martinez-Manez, R .; Rurack, K. ; Soto, J. Angew Chem Int Ed 2005, 44, 4405. (g) Kim, SH;.... Youn, NJ; Park, JY; Choi, MG;. Chang, S.-K. Bull Korean Chem. Soc . 2006 , 27 , 1553. (h) Kim, JS; Choi, MG; Song, KC; No, KT; Ahn, S .; Chang, S.-K. Org . Lett . 2007 , 9 , 1129. i) Yang, H .; Zhou, Z .; Huang, K .; Yu, M .; Li, F .; Yi, T .; Huang, C. Org . Lett . 2007 , 9 , 4729).

The present inventors fluorescein or rhodamine hydrazide for the development of the new signal system according to the preparation of azide derivatives, well-known Cu ^{2 +} mentioned above - an outstanding Hg ^{2 +} selectivity under a selective chemical dosimeter other adapted condition Found out. A further continue the study, rhodamine hydrazide of related compounds also Hg ^{2 +} proposed in the present invention have found the possibility as an optional chemical dosimeter.

Therefore, in the present invention, we propose a chemical quantitative for selective and efficient Hg ^{2 +} detection, and to propose their more optimized conditions.

The present invention for this purpose is a chemical dosimeter containing a rhodamine-based fluorescent substance represented by the following formulas (1) to (3) to selectively detect mercury ions.

<Formula 1>

<Formula 2>

<Formula 3>

(In Formula 3, R ₁ is Et, R ₂ is H, R ₃ is Me, R ₁ is H, R ₂ is H, R ₃ is H, or R ₁ is Me, R ₂ is H, R ₃ Is one of cases where H is

In addition, the selective chemimetry for the mercury ion is a chemi-dose, characterized in that it uses the signaling behavior by selective Hg ^{2 +} induced hydrolysis of the lactam ring of the rhodamine-based hydrazide of the formula (1) to (3).

In another aspect, the present invention is a method for selectively detecting mercury ions, water, or a polar organic solvent mixed well with water alone, or a mixed solvent of water and the solvent is dissolved in the compounds represented by the formula (1) then made to a solution, an optional Hg ^{2 +} induced hydrolysis for the addition of the sample to be analyzed, and the mercury ions contained in the sample to the lactam ring of rhodamine hydrazide represented by the above Chemical formulas 1 to 3 It is a method of detecting mercury ions by measuring the fluorescence spectrum generated through.

The solvent well mixed with water is preferably selected from the group consisting of acetonitrile, dioxane, methanol, acetone, THF, and DMSO, and the solution is selected from the group consisting of acetate buffer, HEPES buffer, and Tris buffer. Preferably buffered. And the concentration of the buffer is preferably 10 mM to 100 mM.

The pH ranges from 4.0 to 5.9 when the buffer is acetate buffer, the pH ranges from 6.0 to 7.9 for HEPES buffer, and the pH ranges from 7.0 to 8.9 for Tris buffer.

In addition, the water content ratio of the solvent is preferably from 90 to 100% (v / v), the concentration of the compound is preferably from 10 ^-7 M to 10 ^-4 M.

The chemical reaction shown signal dosimeter for a Hg ^{2 +} ions present in the present invention is optional and also sensitive to Hg ^{2 +} ions with respect to the relevant metal ion interference with other common biological and chemical environment. Thus, for a simple analysis of the Hg ^{+ 2} ions in the micromolar concentration range in half aqueous conditions (semi-aqueoes media) through the present invention but it presented a special availability of useful rhodamine hydrazide derivative.

Hereinafter, the present invention will be described in more detail, and in describing the present invention, detailed descriptions of related well-known technologies or well-known structures will be omitted in order not to obscure the subject matter of the present invention.

Due to the induction hydrolysis-chemical dosimeter for the detection of Hg ^{+ 2} of the present invention is hydrazide lactam selective Hg ^{+ 2} of the ring, as can be seen in the following Scheme 1.

<Scheme 1>

Some characteristics were studied in order to test the possibility of chemical dosimeter for the detection of this type of Hg ^{+ 2.} First, the absorption and fluorescence spectra were measured to study the signal properties of Formula 1 for typical alkali, alkaline earth and transition element ions. UV-Vis properties of Formula 1 were measured in the presence of various metal ions in aqueous 10% methanol solution (H ₂ O: CH ₃ OH = 90:10, v / v) buffered at pH 5.0 (acetate buffer, 10 mM). It was. The indicated pH value represents the pH of the H ₂ O portion before the addition of methanol. Figure 1 shows the UV characteristics of the formula 1 for a variety of metal ions, [Formula 1] = 5.0 * 10 ^-6 M, the concentration of the metal ion [M ^{n +} ] = 5.0 * 10 ^-4 M. As can be seen from FIG. 1, Formula 1 shows almost no absorption above 450 nm due to the presence of a spiro ring in lactam form. However, only Hg ^{+ 2} ions only shows the intensive absorption band centered at 556 ㎚ (λmax). This increase in absorption at 556 nm is very pronounced, and for mercury ions, the absorption ratio A / Ao of Formula 1 in the presence and absence of metal ions is 70.5. On the other hand, the other metal ions did not induce almost any change in the absorption spectrum of the formula (A / Ao = 1.1-2.0). Specific to, HEPES main target of Cu ^{2 +} ions that were released in the conventional dose for the chemical cues by the buffer in the general formula (1) did not induce any perceptible change has a A / Ao = 1.8. At this time, the solution had changed from pink to colorless, this made it possible to detect with the naked eye of Hg ^{2 +} ions. Standard Cu ^{2 +} a hydrazide - as reported in the signal process of (... Dujols, V .; Ford, F .; Czarnik, AW J. Am Chem Soc 1997, 119, 7386), rapid OFF of the signal changes in the shape selective -ON Hg ^{+ 2} in the lactam ring of a hydrazide-due to induce hydrolysis. These results show that for Hg ^{2 +} You can check the optional properties.

Hg ^{+ 2,} such as the scheme 1-induced selective conversion was analyzed by UV-Vis, fluorescence, NMR, and Mass spectroscopy measurement. The UV-Vis and fluorescence spectra of formula 1 (5.0 × 10 ^-6 M) treated with 10 equivalents of Hg ^{2 +} ions in the solution of the right compound of Scheme 1 in the presence of 10 eq. Of Hg ^{2 +} ion in the pH 5 It was almost identical to that obtained for. In addition, the structural conversion of the formula (1) was confirmed by NMR. After treatment of Formula 1 with Hg (OAc) ₂ in CD ₃ OD-D ₂ O (4: 1, buffered to pH 5 using deuterated acetate buffer), the ¹ H NMR spectrum of the resulting solution was obtained. Similar to the spectrum of the right compound itself. At 6.4-6.5 ppm the characteristic signal of the xanthene moiety of formula 1 disappeared completely and moved around 7.0-7.2 ppm. The signal of the lactam containing the phenyl ring also showed significant downfield shifts from 7.0-7.9 ppm to 7.4-8.3 ppm. In addition, significant downfield shifts were observed from 1.17 and 3.40 ppm to 1.33 and 3.71 ppm in ethyl protons of diethylamine functional groups, respectively. Although to a small difference exists, however, Hg (OAc) high spectral form of a hydrazide derivative of the general formula (I) obtained after treatment of two equivalents of ₂ under the same conditions as Hg (OAc) Reaction in the presence of 2 equivalents of ₂₁ It is almost identical to the spectrum of the right compound of. ^{In the 13} C NMR spectrum, the 64.7 ppm carbon signal characteristic of the spirolactam ring carbon of Formula 1 disappeared, while another peak of 85.0 ppm corresponding to the same carbon atom of rhodamine B appeared. Mass measurements (EI, DIP) also provided additional evidence that the hydrazide peak disappeared at m / z = 456.25 [M] ⁺ in Formula 1 due to the presence of mercury ions, instead of rhodamine B [M + H] ⁺ it exhibited a strong peak at a specific m / z = 443.23.

In short, such a signal dramatic action by the selective Hg ^{2 +} induced hydrolysis of the lactam ring of Roda mingye hydrazide shows that this can be used as the detection method of the turn-on type for the Hg ^{+ 2.}

Subsequently, in the presence of various metal ions in aqueous 10% methanol solution (H ₂ O: CH ₃ OH = 90:10, v / v) buffered at pH 5.0 (acetate buffer, 10 mM), the fluorescence signal characteristic of Formula 1 Was investigated ([Formula 1] = 5.0 * 10 ^-6 M, metal ion concentration [M ^{n +} ] = 5.0 * 10 ^-4 M). Figure 2 shows the fluorescence spectrum of the compound of formula 1 in the presence of various metal ions, as can be seen from Figure 2, the fluorescence spectrum of formula 1 did not show a significant emission band above 520 nm. However, at the time of a 100 equivalent treatment of a variety of metal ions, formed it is selectively focused emission band at around 578 ㎚ only for Hg ^{2 +} ions. Rate of increase in fluorescence intensity as shown in the presence and absence of the Hg ^{2 +} ions measured at 578 ㎚ the ratio of the fluorescence intensity (I / Io) was 166.2. In addition, when the UV lamp was irradiated, the solution changed from colorless to fluorescent pink. I / Io value for the other metal ions, had a range of 2.81 (Cu ^{+ 2)} from 0.77 (Ca ^{2 +).} In particular, the relative low reactivity for Cu ^{2 +} ions was interesting. In addition, compounds of formula (I) exhibited the Hg ^{2 +} optional signal characteristic, etc. in dioxane (dioxane) or acetonitrile other aqueous solutions as well as Tris or HEPES buffered aqueous methanol solution (acetonitrile) buffered at pH 5 acetate. However, the observed Hg ^{2 +} selectivity is somewhat behind than acetate buffered aqueous 10% methanol solution because of Cu ²⁺ in an enhanced sensitivity of these solvent systems. Trends in selectivity could easily be evaluated by comparing the Hg ^{+ 2} and Cu ^{2 +} formula fluorescence intensity (I _Hg / I _Cu) of 1 in the presence of ions observed in the 578 ㎚. For example, the I _Hg / I _Cu values for the aqueous 10% methanol solution at pH 7 (HEPES) and pH 8 (Tris) were 11.4 and 13.3, respectively, which were much less than 59.1 at pH 5. On the other hand, the I _Hg / I _Cu values in the aqueous 10% acetonitrile and dioxane solutions were 4.4 and 17.5, respectively, which are also much lower than the values (59.1) of the aqueous 10% methanol solution at pH 5. Significant changes in this selectivity are observed depending on the conditions used, but still show very useful Hg ²⁺ selective signaling properties in various solvents and various buffers. That is, the signaling was highly selective and sensitive to Hg2 + ions beyond the possibility of interference of other commonly coexisting biological and environmentally important metal ions.

The compounds represented by the formulas (2) to (3) also have the same reaction mechanism. That is due to the selective Hg ²⁺ -induced hydrolysis of the lactam ring of such derivatives of rhodamine hydrazide shows a turn-on signaling behavior. In addition, many similar structures are considered to be capable of signaling using this technical idea, and examples of substitutions or simple modifications within the scope of the present invention are also within the scope of the present invention with respect to those within the scope of the invention.

Hg ^{2 +} -dependence by titrating the compound of Formula 1 to Hg (OAc) ₂ to confirm that it can be used as a novel chemometer for the analysis of Hg ^{2 +} ions of the rhodamine hydrazide derivatives of the present invention The quantitative nature of the signal was investigated. 3 is at _{pH 5 (H 2 O: CH} 3 OH = 90:10, v / v) under the [formula 1] = 2.0 * 10 ^-5 fluorescence of the formula (1) with respect to the M as a function of the concentration of Hg ^{2 +} ions The spectrum is shown. As can be seen in FIG. 3, the fluorescence of Formula 1 increased linearly as a function of [Hg ^{2 +} ]. The detection limit for the measurement of Hg ^{2 +} ions was determined to be 0.2 μM under the same measurement conditions, calculated from three times the standard deviation of the background noise from the calibration curve. The observations indicate that can be used in a manufacturing environment, the water-soluble compound as a novel chemical dosimeter for the analysis of the Hg ^{+ 2} ions in the range of micromolar concentrations.

Hereinafter, the present invention will be described through various test procedures for finding the optimal conditions of the chemical dosimeter of the present invention through the examples. However, the embodiments are not limited to the present invention, and various changes may be added and changed without departing from the spirit of the present invention from the viewpoint of those skilled in the art, as well as other equivalent embodiments, which may be possible. It is within the technical idea of In this embodiment, more specific experimental examples will be shown for the compound of Formula 1 on behalf of the rhodamine hydrazide derivatives of the present invention.

General Information

All solvents were purchased from Aldrich Chemical Co. in 'anhydrous' or 'spectroscopy grade'. Rhodamine B hydrazide represented by Formula 1 is reported procedure (Yang, X.-F .; Guo, X.-Q .; Zhao, Y.-B. Anal. Chim . Acta 2002 , 456 , 121) and reliable samples were purchased from Aldrich Chemical Co. and used without further purification. ¹ H NMR (300 MHz) and ¹³ C NMR (75 MHz) spectra were obtained on a Varian Gemini-2000 spectrometer and were based on the residual solvent signal. Mass spectra were obtained using a Micromass Autospec mass spectrometer using direct insertion probes operating in electron shock ionization mode. UV-Vis spectra were recorded using a Jasco V-550 spectrophotometer equipped with a Peltier thermostat. Fluorescence spectra were measured on an Aminco-Bowman Series 2 Spectrophotometer.

UV- Vis  And fluorescence spectrum measurement

The stock solution of the compound represented by Formula 1 was prepared in methanol (1.0 × 10 ⁻³ M), and metal ions (Na ⁺ , K ⁺ , Ca ^{2 +} , Mg ^{2 +} , Ni ^{2 +} , in perchlorate) were prepared. ^{Cu 2 +, Zn 2 + Cd} 2+, Pb 2 +, was prepared from a stock solution an aqueous solution (0.01 M) of acetate buffer (pH 5.0) of the Ag ⁺ and Hg ^{+ 2).} To a stock solution of Formula 1 (0.03 mL) was added a stock solution of metal ions (0.03 mL), followed by dilution with quantified amounts of methanol and water to obtain an aqueous 10% methanol solution. Final concentrations of Formula 1, metal ions and buffers were 5.0 × 10 ⁻⁶ M, 5.0 × 10 ⁻⁴ M, and 10 mM, respectively. UV-Vis and fluorescence measurements were performed at least 10 minutes after sample preparation.

Time Course Measurements

Time course signal experiments were performed in an aqueous 10% methanol solution buffered at pH 5.0 (10 mM acetate buffer). A measurement solution (1.0 × 10 ⁻⁶ M) was prepared in a cuvette by mixing a freshly prepared stock solution of Formula 1 with a solution of Hg (OAc) ₂ or Cu (OAc) ₂ . Changes in absorption at 556 nm at room temperature or fluorescence intensity at 578 nm were measured.

Also as described in 4, the fluorescence intensity of the formula (1) is increased rapidly during the Hg ^{+ 2} ions and the reaction was reached the constant value within 10 minutes after preparation of the sample, after which was kept flat. However, in the case of Cu ^{2 +} ions, the signaling has been developed very slowly, with only 1% or less of the formula 1-Hg ^{2 +} system after 10 min, and even after the measurement 48 hours was observed to not more than 3%, This is very inefficient compared with the case of Hg ^{2 +} ions. The other metal ions showed little change in the fluorescence spectrum after 48 hours of measurement.

Competitive Experiments on Mercury

Of formula 1 Hg ^{2 +} - were studied selective signal properties under addition of a race condition. Usually it indicated the presence of 100 equivalents of the metal ion present together with Hg ^{+ 2} at the time of the 10 times the amount of processing of the formula (I) ions (5.0 × 10 ^-6 M) by measuring the fluorescence intensity of this histogram (Fig. 5). Although some variations Although observed in the fluorescence intensity of the formula (I), but general formula (1) ^{2 +} Hg-signal characteristic of the system that did not significantly influenced by the metal ion present together. Therefore, Formula 1 can effectively detect Hg ²⁺ ions even in the presence of other common interfering metal ions, such as typical alkali, alkaline earth and transition element ions.

Solvent effect

Signaling is possible among various solvents mixed well with water such as acetonitrile, dioxane, methanol, acetone, THF, and DMSO, but as shown in FIGS. 6A to 6C, the selectivity is excellent among dioxane solvents.

The concentration of the compound may be in the range of 10 ⁻⁷ M to 10 ⁻⁴ M, but the micromolar region is considered to be the most appropriate considering the reproducibility and the intensity of the generated fluorescent signal.

pH effect

Signaling was also possible when the pH conditions of the solution were changed to pH 5 acetate, pH 7 HEPES, pH 8.1 Tris, and the like. These pH conditions will allow some variation.

The concentration of the buffer used may be 10 mM or less but preferably 10-100 mM. In other words, it is appropriate to use more than 10 mM to avoid possible pH changes caused by the various matrices present in the solution and need not be higher than necessary. Of course, it is possible to use a lower concentration, but using a lower concentration is less than the buffer capacity (buffer capacity) to resist changes in pH is preferable to use more than 10 mM.

Water content of the solution

The water content of the solution can be from 100% aqueous solution to 0% aqueous solution (100% organic solvent), but considering the signaling rate and selectivity, it is understood that the optimum behavior is shown in 90-100% aqueous solution.

Figure 1 shows the UV- of formula 1 in the presence of various metal ions in an aqueous 10% methanol solution (H ₂ O: CH ₃ OH = 90:10, v / v) buffered at pH 5.0 (acetate buffer, 10 mM). Vis characteristics were measured, and [Formula 1] = 5.0 * 10 ^-6 M and the concentration of metal ions [M ^{n +} ] = 5.0 * 10 ^-4 M.

FIG. 2 shows the fluorescence signal of Formula 1 in the presence of various metal ions in aqueous 10% methanol solution (H ₂ O: CH ₃ OH = 90: 10, v / v) buffered at pH 5.0 (acetate buffer, 10 mM) It was shown that the characteristics were investigated ([Formula 1] = 5.0 * 10 ^-6 M, the concentration of metal ions [M ^{n +} ] = 5.0 * 10 ^-4 M).

3 is at _{pH 5 (H 2 O: CH} 3 OH = 90:10, v / v) under the [formula 1] = 2.0 * 10 ^-5 fluorescence of the formula (1) with respect to the M as a function of the concentration of Hg ^{2 +} ions The spectrum is shown.

The presence of Hg ^{2 +} ions and Cu ^{2 +} ions _{from: (CH 3 OH = 90:10,} v / v H 2 O) 4 pH 5.0 (acetate buffer, 10 mM) in the buffer-treated aqueous 10% methanol solution The fluorescence intensity of the compound of formula 1 is shown at 578 nm as a function of time ((Formula 1] = 5.0 * 10 ⁻⁶ M, concentration of metal ions [M ^{n +} ] = 5.0 * 10 ⁻⁴ M).

5 is shown in Formula 1 in the presence of conventional interfering metal ions in an aqueous 10% methanol solution (H ₂ O: CH ₃ OH = 90:10, v / v) buffered at pH 5.0 (acetate buffer, 10 mM). Shows the selective signal characteristics of Hg ^{2 +} ion ((Formula 1] = 5.0 * 10 ^-6 M, the concentration of conventional interfering metal ion [M ^{n +} ] = 5.0 * 10 ^-4 M, [Hg ^{2 +} ] = 5.0 * 10 ^-5 M).

Figure 6 (a, b, c) shows the fluorescence signal characteristics of Formula 1 in the presence of various metal ions when using acetonitrile, dioxane, methanol solvent, respectively.

Figure 7 (a, b, c) shows the fluorescence signal characteristics of Formula 1 in the presence of various metal ions with pH using acetate buffer, HEPES buffer, Tris buffer, respectively.

Claims (9)

A chemical dosimeter containing a rhodamine-based fluorescent substance represented by the following formulas (1) to (3) to selectively detect mercury ions. <Formula 1>

<Formula 2>

<Formula 3>

(In Formula 3, R ₁ is Et, R ₂ is H, R ₃ is Me, R ₁ is H, R ₂ is H, R ₃ is H, or R ₁ is Me, R ₂ is H, R ₃ Is one of cases where H is The method of claim 1, Selective chemo-dose for the mercury ion is a chemi-dose, characterized in that to use the signaling behavior by selective Hg ^{2 +} induced hydrolysis of the lactam ring of the rhodamine-based hydrazide of Formula 1 to 3. In the method for selectively detecting mercury ions, Water alone, or a polar organic solvent mixed well with water alone, or a solution of the compound represented by the formula (1) to (3) in a mixed solvent of water and the solvent is prepared, and then the sample to be analyzed is added to the sample, Method for detecting mercury ions by measuring the fluorescence spectrum generated by the Hg ^{2 +} induced hydrolysis of the mercury ions contained in the lactam ring of the rhodamine-based hydrazide represented by the formula (1) to (3). <Formula 1>

<Formula 2>

<Formula 3>

(In Formula 3, R ₁ is Et, R ₂ is H, R ₃ is Me, R ₁ is H, R ₂ is H, R ₃ is H, or R ₁ is Me, R ₂ is H, R ₃ Is one of cases where H is The method of claim 3, The solvent well mixed with water is selected from the group consisting of acetonitrile, dioxane, methanol, acetone, THF, and DMSO. The method according to any one of claims 3 to 4, Wherein said solution is buffered selected from the group consisting of acetate buffer, HEPES buffer, and Tris buffer. The method of claim 5, PH is in the range of 4.0 to 5.9 when the buffer is an acetate buffer, pH is 6.0 to 7.9 when the HEPES buffer, pH is 7.0 to 8.9 if the Tris buffer. The method of claim 5, The concentration of the buffer is 10 mM to 100 mM. The method of claim 4, wherein The water content ratio of the solvent is characterized in that 90 to 100% (v / v). The method of claim 4, wherein The concentration of the compound is characterized in that from 10 ^-7 M to 10 ^-4 M.

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