KR20120062221A - Compound for detecting mercury ion, preparation method of the same and fluorogenic chemodosimetric system using the same - Google Patents
Compound for detecting mercury ion, preparation method of the same and fluorogenic chemodosimetric system using the same Download PDFInfo
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- KR20120062221A KR20120062221A KR1020100123385A KR20100123385A KR20120062221A KR 20120062221 A KR20120062221 A KR 20120062221A KR 1020100123385 A KR1020100123385 A KR 1020100123385A KR 20100123385 A KR20100123385 A KR 20100123385A KR 20120062221 A KR20120062221 A KR 20120062221A
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- C—CHEMISTRY; METALLURGY
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- C07D339/08—Six-membered rings
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
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- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
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- G—PHYSICS
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
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Abstract
Description
The present invention relates to a compound for detecting mercury ions and a fluorescence chemical detection system including the same. More specifically, a compound for detecting mercury ions capable of effectively detecting the presence and concentration of mercury based on an intermolecular reaction and a novel method using the same One fluorescence chemical detection system.
Recently, due to the harmful effects of heavy- and transition-metal (HTM) ions on living organisms and the environment, there is a growing interest in the detection and quantification of these metals. At low concentrations in the environment, it is highly toxic.Methylmercury, when ingested by humans, is known to cause serious diseases including diseases of the sensory, muscular and nervous systems.
BACKGROUND OF THE INVENTION Fluorescent chemosensors have been developed as a number of precise analytical methods for detecting mercury ions. Recently, the chemodometer approach has received a high interest due to its simplicity, high sensitivity, high selectivity and irreversibility. have. Most of these detection techniques are designed based on mercury-induced desulfurization.
However, there is a need for development of a fluorescent dye and a fluorescence chemical detection system using the same to detect mercury ions more effectively in the desulfurization reaction.
The problem to be solved by the present invention is to provide a compound for detecting mercury ions, a method for producing the same that can more effectively detect the presence and concentration of mercury ions based on the intermolecular reaction.
In addition, another object of the present invention is to provide a fluorescence chemical detection system and a detection method using the mercury ion detection compound.
In order to solve the above problems, the present invention provides a compound for detecting mercury ions represented by the following formula (1).
[Formula 1]
In another aspect, the present invention provides a method for producing a compound for detecting mercury ions of
In another aspect, the present invention provides a mercury ion detection fluorescent chemical system comprising the compound of
The present invention also provides a method for selectively detecting mercury ions using the mercury ion detection fluorescence chemistry system.
The fluorescent chemical detection system according to the present invention can effectively detect mercury ions using the compound represented by
1 is a graph showing fluorescence emission intensity when mercury ions are added to a fluorescence chemical detection system according to an embodiment of the present invention.
2 is a graph showing color change and UV-vis spectrum when various metal ions are added to a fluorescence chemical detection system according to an embodiment of the present invention.
3 is a graph showing fluorescence enhancement when various metal ions are added to a fluorescence chemical detection system according to an embodiment of the present invention.
FIG. 4 is a graph showing a process of partially changing the 1 H NMR (300 MHz) spectrum of
Figure 5 is a graph showing the change in fluorescence Hg 2 + (1 eq.) Compound (20 μM) of the formula (1) after a review of UV (365 nm) for 5 minutes in the presence of and o- phenylenediamine (3 eq.) to be.
6 is Hg 2 + (1 eq.) Compound of Formula (20 μM) and of o- 1 when no irradiation with the case examining the UV (handhold UV lamp, 365 nm ) in the presence of the phenylenediamine (3 eq. ) Is a graph showing the fluorescence reaction.
7 is a graph showing the fluorescent reaction of CH 3 CN from the Hg + 2 and the present compounds of formula (1) the absence of the ion (20μM) (20μM) and o- phenylenediamine detection system according to a molar ratio of diamine. (λ ex = 380 nm) The emission intensity change at 492 nm according to the molar ratio of
8 is Hg + 2 ions are 1 H NMR (300 MHz) spectrum of o- phenylenediamine changes with the addition of (1 eq.) In CD 3 CN is a graph illustrating a process in part.
9 is a graph showing the fluorescent reaction of formula (3) compound (10 μM) in accordance with the addition of Hg 2 + ions (0-100 eq) in CH 3 CN. (λ ex = 380 nm) A ratiometric calibration curve of I 454 / I 492 is inserted as a function of the molar ratio function of Formula 3 and mercury ions.
10 is Hg + 2 ions are 1 H NMR (300 MHz) spectrum of compound (4 mM) of formula (3) changes with the addition of (0.2-1 eq.) In CD 3 CN is a graph illustrating a process in part.
11 is a graph showing the fluorescence of the compounds (10 μM) of formula (3) When the addition of Hg 2 + ions and o-PDA in different concentrations in CD 3 CN).
12 is a CH 3 CN from among Ag +, Ba 2 +, Ca 2 +,
13 is a CH 3 CN in Hg 2 + Ag + in the presence of (1 eq.), Ba 2 +,
14 is Hg + 2 under the presence of Cu 2 (1 eq.) + (4 eq.) To contain a high concentration and, o -PDA (7 eq.) Was further added when the present invention system (I (20 μM) and o- PDA (3 eq.)) are graphs showing the fluorescence spectrum.
15 is a graph showing the 1 H NMR spectrum of the compound of Formula 3 measured in CDCl 3 .
Hereinafter, the present invention will be described in more detail.
The inventors have designed and synthesized a novel system for detecting mercury ions using mercury-desulfurization.
One of the compounds for detecting mercury ions according to the present invention is represented by the following formula (1).
[Formula 1]
In addition, the compound of Formula (1) may be prepared by the following
The present invention provides a mercury ion detection fluorescent chemical system comprising the compound of
The present invention also provides a method for selectively detecting mercury ions using the mercury ion detection fluorescence chemistry system.
Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are only provided by way of example in order to make the present invention easier to understand, and should not be construed as limiting the scope of the present invention.
Synthetic example : Synthesis of Compound of Formula (1)
Mercury ion detection compound (Formula 1) according to the present invention was prepared by the following
The yield of compound (1) produced according to this reaction was quite high, 89%.
Example : Mercury Detection Fluorescence Chemical System
In the mercury ion detection fluorescence chemical system according to the present invention is a specific mechanism for detecting mercury ions are as follows.
In the reaction, 6,10-dithiaspiro-acenaphthene quinine (Compound 1) is chemically reacted with o-phenylenediamine (o-PDA) in the presence of mercury ions. The compound 3 can be formed, and as a result, the fluorescent signal can be amplified.
When mercury ions are added to a mixture of
UV irradiation of the mixture of
In order to optimize the fluorescence chemidetection system according to the invention, the
Fluorescence emission intensity in which mercury ions (0 to 100 μM) was added to a fluorescence chemical detection system (probe represented by Formula 1 (20 μM) and o-PDA (3eq.)) According to the present invention in CH 3 CN is shown in FIG. 1. Shown in
As shown in Figure 1 below, the fluorescent titration curves of
To account for this fluorescence change in the presence of excess mercury ions, the fluorescence spectral change was tested while gradually adding mercury ions to the solution of compound 3. The strong emission at 492 nm of compound 3 gradually blue shifted and reached λ max = 454 nm with a significant increase in fluorescence emission intensity at a mercury ion concentration of 150 μM.
NMR titration experiments were performed to study the mechanism between compound 3 and mercury ions. Comparing the 1 H NMR spectra before and after the addition of mercury ions to compound 3, it can be seen that all protons moved downward. This change in spectrum is due to the complex of metal ions in which mercury ions bind to the nitrogen of the imidazole ring of compound 3. In addition, the complexation between compound 3 and mercury ions is weaker than that for o-PDA. Thus, by adjusting the concentration of o-PDA in solution, the emission intensity and emission wavelength of the sample can be controlled. The change in fluorescence spectral dependence on the concentration of mercury ions indicates that the system according to the invention can not only detect mercuric ions but also its concentration level.
The color change and UV-vis spectrum when various metal ions are added to the fluorescence chemical detection system according to an embodiment of the present invention are shown in FIG. 2. More specifically, various metal ions (Ag + , Ba 2 + , Ca 2 + , Cd 2 + , Co 2 + , Cu 2 + , Cs 2 + , Fe 2+ , K + , Li + , in CH 3 CN Mg 2 +, Na +, Pb 2 +, Rb +,
UV-vis spectral behavior for representative metal ions of the fluorescence chemical detection system according to the present invention was carried out using physiologically important alkali metals, alkaline earth metals and transition metal perchlorates in CH 3 CN. Upon interaction with various metal ions, a significant change in absorption spectrum was observed, especially in the case of copper ions, which was found to readily bind to PDA in the solution, resulting in CuPDA x (ClO 4 ) 2 (x = 1 or 2) This is because it forms a complex. Incidentally, a color change from colorless to brown was also observed.
Fluorescence enhancement when various metal ions were added to the fluorescence chemical detection system according to an embodiment of the present invention is shown in FIG. 3.
In terms of practical applications, interference with other metal ions should be considered. Thus, the fluorescence changes for mercury ions in the presence of other competing metal ions were observed and shown in FIG. 3.
Ag +, Ba 2 +, Ca 2 +,
In conclusion, the fluorescent chemistry detection system according to the present invention can selectively exhibit high fluorescence for mercury ions. Therefore, it can be more usefully used for detecting mercury ions and can be effectively used even in the presence of other competitive metal ions.
Claims (7)
[Formula 1]
[Reaction Scheme 1]
The mercury ion detection fluorescence chemistry system, characterized in that the detection of the mercury ion is carried out by fluorescence intensification of the material generated while the mercury reacts with the compound of formula (1) and o-phenylenediamine.
Mercury ion detection fluorescence chemistry system, characterized in that the detection of the mercury ion is carried out through the following mechanism:
The mercury ion detection fluorescence chemical system, characterized in that the mercury ion detection is carried out in an aqueous solution.
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Cited By (2)
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KR101505467B1 (en) * | 2013-04-16 | 2015-03-25 | 고려대학교 산학협력단 | Chemosensor for detecting divalent mercury ions and method for preparing the same |
CN114105979A (en) * | 2021-11-27 | 2022-03-01 | 大连医科大学附属第二医院 | Application of broad-spectrum fluorescent probe for detecting cytochrome oxidase CYP3A |
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CN110615785A (en) * | 2018-06-20 | 2019-12-27 | 南京大学 | Novel Hg2+Synthesis and application of ion probe |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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KR101505467B1 (en) * | 2013-04-16 | 2015-03-25 | 고려대학교 산학협력단 | Chemosensor for detecting divalent mercury ions and method for preparing the same |
CN114105979A (en) * | 2021-11-27 | 2022-03-01 | 大连医科大学附属第二医院 | Application of broad-spectrum fluorescent probe for detecting cytochrome oxidase CYP3A |
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