KR102109597B1 - Water-dispersed polyurethane thin film doped with fluorescent porphyrin derivative and method for detecting mercury ion using the same - Google Patents

Abstract

The present invention provides a method for detecting a water-dispersible polyurethane thin film doped with a fluorescent porphyrin derivative and mercury ion using the same.
The water-dispersible polyurethane thin film doped with the fluorescent porphyrin derivative of the present invention and the mercury ion detection method using the same can be conveniently used as a mercury ion specific detection technique in the mercury ion detection field because it is easy to use and easy to carry.

Description

Water-dispersed polyurethane thin film doped with fluorescent porphyrin derivative and method for detecting mercury ion using the same}

The present invention relates to a thin film doped with porphyrin derivatives used for mercury ion detection, and more particularly to a water-dispersible polyurethane thin film doped with fluorescent tetraphenyl porphyrin derivatives and a mercury ion detection method using the same.

Mercury (Hg ²⁺ ) is one of the third most heavily discovered heavy metals in the human body in the list of the United States Agencies for Toxic Substances and Disease Registry (ATSDR). Mercury contamination is widespread and arises from a variety of natural causes. Once introduced into the marine environment, bacteria convert inorganic mercury ions (Hg ²⁺ ) to methylmercury. Like the Itaitai disease, which collectively occurred to residents who ate fish and shellfish containing methylmercury in Minamata, Japan in 1956, methylmercury has severe neurotoxicity, so it can easily cross membranes in living organisms due to its lipophilic nature, making it easier than inorganic mercury. Not only is it absorbed, it accumulates for a long time and acts as a source of mercury associated with irreversible neurological damage. Accordingly, in recent years, interest in a method for selectively detecting mercury ions (Hg ²⁺ ) in the fields of chemistry, biotechnology and environmental engineering has increased.

Common mercury detection methods include inductively coupled plasma mass spectrometry and atomic absorption spectrophotometry. These are low-accuracy and high-accuracy methods that can detect mercury down to mercury levels of ppb (7 to 10% by weight). On the other hand, however, there are disadvantages of using various chemical solvents that are harmful to the human body and requiring a high level of sophisticated analysis procedures, large and expensive equipment, and a high degree of skill of the tester. In addition, fluorescent chemosensors have been developed in recent years, and the chemodometric approach has received very high attention due to its simplicity, high sensitivity, high selectivity, and irreversible properties. Nevertheless, there remains a need for the development of an efficient new detection device with superior mercury simplicity, high selectivity and sensitivity.

Porphyrin (porphyrin) is a macrocyclic compound containing four pyrrole rings as a kind of a compound constituting a pigment component that plays an important role in an oxidation-reduction reaction in vivo. The porphyrin absorbs light of a long wavelength, and thus is used for photodynamic treatment using a laser. In particular, it has been used as a semiconductor material in the application research of organic devices such as organic transistors and organic solar cells with recent developments in the field of organic electronics.

Among various sensor systems that recognize mercury ions, a detection device using a water-dispersible polyurethane thin film has various advantages such as portability, excellent selectivity, low cost, and easy detection, and is used in various fields such as food, medicine, and environment. It is believed that its biological application will be possible. Therefore, there is a need to develop a novel device using a fluorescent chemical sensor that emphasizes portability and convenience.

Republic of Korea Patent Publication No. 10-2010-0062995 (June 10, 2010)

M. Plaschke, et al., Analytica Chimica Acta, 1995, 304, 107-113. (November 7, 1994) Emilio Palomares, et al., Chem. Comm., 2004, 362-363. (December 12, 2003)

The inventors of the present invention were studying various detection methods and apparatuses using fluorescence sensing technology for mercury ion detection, while a thin film doped with tetraphenylporphyrin in water-dispersed polyurethane reacts specifically with mercury ions, reducing absorbance and It exhibited a fluorescence reduction phenomenon, confirming that the reaction specificity was excellent.

Accordingly, an object of the present invention is to provide a water-dispersible polyurethane thin film doped with a fluorescent porphyrin derivative and a mercury ion detection method using the same.

According to an aspect of the present invention, there is provided a water-dispersible polyurethane thin film doped with a fluorescent porphyrin derivative.

In one embodiment, the fluorescent porphyrin derivative may be 5,10,15,20-tetra (sulfonatophenyl) porphyrin. At this time, the fluorescent porphyrin derivative may be doped with 0.1 to 10 parts by weight based on 100 parts by weight of polyurethane.

In one embodiment, the water-dispersible polyurethane thin film may be prepared by reacting a polyester polyol and diisocyanate.

According to another aspect of the present invention, a method for detecting mercury ions comprising reacting the water-dispersible polyurethane thin film with a sample is provided.

In one embodiment, after adding and mixing 30 to 50% by volume of isopropanol to the sample to be detected, the water-dispersible polyurethane thin film may be reacted with a test agent.

In one embodiment, the water-dispersible polyurethane thin film can be reacted with a sample and absorbance and fluorescence can be measured after 10 to 30 minutes have elapsed.

In one embodiment, measuring absorbance in the visible light wavelength range 300-900 nm, and measuring fluorescence in the fluorescence wavelength range 450-800 nm may be included.

According to another aspect of the present invention, an apparatus for detecting mercury ions using the water-dispersible polyurethane thin film is provided.

In one embodiment, absorbance may be measured in the visible light wavelength range 300-900 nm, and fluorescence may be measured in the fluorescence wavelength range 450-800 nm.

According to the present invention, mercury ions react specifically with a water-dispersible polyurethane thin film doped with a tetraphenylporphyrin sulfonate, a fluorescent porphyrin derivative, exhibiting a decrease in absorbance and fluorescence quenching, thereby exhibiting excellent reaction specificity to mercury ions. The detection limit was measured to be 0.2 mM, which confirmed that the detection sensitivity was excellent.

Accordingly, the polyurethane thin film doped with the fluorescent porphyrin derivative of the present invention and the mercury ion detection method using the same can be conveniently used as a mercury ion specific and practical technique in the field of cation detection because it is easy to use and easy to carry.

1 is a conceptual diagram showing that tetraphenylporphyrin is an excellent ionophore for mercury.
2 is an explanatory view showing that the water-dispersible polyurethane has excellent properties as a coating and film casting material.
3 is a schematic diagram showing the synthesis process of water-dispersible polyurethane.
4 is an explanatory diagram showing a process of manufacturing a thin film.
5 is a result showing the relationship between the thickness of the thin film adjusted according to the number of castings and UV-visible light absorbance.
6 is a change in absorbance spectrum (a) and a change in fluorescence spectrum (b) for mercury ions in a thin film.
7 is a photograph of colorimetric changes in visible light (a) and UV light (b) for mercury ions in a thin film.

The present invention provides a water-dispersible polyurethane thin film doped with a fluorescent porphyrin derivative.

In one embodiment, the fluorescent porphyrin derivative may be 5,10,15,20-tetra (sulfonatophenyl) porphyrin (5,10,15,20-tetra (sulfonatophenyl) porphyrin).

In one embodiment, the water-dispersible polyurethane may be prepared by reacting a polyester polyol with diisocyanate. Tetraphenylporphyrin sulfonate is added to the emulsion containing the polyurethane polymer using the synthesized polyurethane and mixed uniformly, followed by dip casting the polymer emulsion on a glass slide to prepare a water dispersion thin film. At this time, the fluorescent porphyrin derivative may be doped with 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight based on 100 parts by weight of polyurethane. The prepared water-dispersion thin film exhibits an increase in absorbance as the number of castings increases between wavelengths of 300 nm to 700 nm.

In addition, the present invention provides a mercury ion detection method comprising the step of reacting the thin film with a sample. After confirming the ultraviolet absorbance and fluorescence emission of the tetraphenylporphyrin-doped polyurethane thin film itself, add 30 to 50% by volume of isopropanol to a solution containing mercury ions as a sample to be detected, mix it, and then do the polyphenyl doped with tetraphenylporphyrin Urethane thin film is introduced. After 10 to 30 minutes, the color change was observed under visible and ultraviolet wavelengths, and ultraviolet absorbance and fluorescence emission were measured.

In one embodiment, absorbance is measured in the visible light wavelength range 300-900 nm, preferably 380-430 nm, and the fluorescence wavelength range 450-800 nm, preferably 600-695 nm or 700-740 nm, most preferred It may include measuring fluorescence at 620-675 nm or 700-725 nm.

In addition, the present invention provides an apparatus for detecting mercury ions using the water-dispersible polyurethane thin film.

In one embodiment, absorbance is measured in the visible light wavelength range 300-900 nm, preferably 380-430 nm, and the fluorescence wavelength range 450-800 nm, preferably 600-695 nm or 700-740 nm, most preferred Fluorescence can be measured at 620-675 nm or 700-725 nm.

The water-dispersible polyurethane thin film doped with the fluorescent porphyrin derivative was reacted with polyester polyol and polyisocyanate to synthesize a polyurethane polymer, and then mixed with tetraphenylporphyrin sulfanate to form a water-dispersible thin film using a glass plate. . In addition, it was confirmed that the absorbance was specifically reduced and the fluorescence was extinguished when applied to mercury ions using the thin film, and a color change in which the color on the thin film was changed from colorless to yellow under visible light was observed. Fluorescence change was observed in which the color on the thin film was changed from red to colorless under the light beam.

Therefore, the mercury ion detection method using a polyurethane thin film doped with fluorescent porphyrin derivatives is a practical technique in the field of cation detection, in which mercury ions and tetraphenylporphyrin derivatives doped on the thin film react specifically and are easy to use and easy to carry. It can be useful.

Hereinafter, the present invention will be described in more detail through examples and test examples. However, the following examples and test examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Example 1. Preparation of thin film of water dispersion

Polyurethane polymer was prepared as shown in the reaction scheme of FIG. 3 by reacting polyester polyol with diisocyanate. After synthesizing the polyurethane polymer, a uniform amount of tetraphenylporphyrin sulfonate equivalent to 1% (w / w) of the weight of the polyurethane polymer is added to the emulsion in which the synthesized polyurethane polymer is present as colloidal particles. Mix well. Thereafter, a polymer dispersion was dip casted on a glass slide to prepare a water dispersion thin film (see FIG. 4).

The prepared aqueous dispersion thin film showed an increase in absorbance as the number of castings increased between the wavelengths of 300 nm to 700 nm (see FIG. 5).

Test Example 1. Evaluation of specificity for mercury ions of a polyurethane thin film doped with tetraphenylporphyrin

First, confirm the ultraviolet absorbance and fluorescence emission of the tetraphenylporphyrin-doped polyurethane thin film, then add 40% by volume of isopropanol to water containing mercury ions, mix, and add the tetraphenylporphyrin-doped polyurethane thin film to the solution. Introduced. After 20 minutes elapsed, color changes were observed under visible and ultraviolet wavelengths, and ultraviolet absorbance and fluorescence emission were measured.

Polyurethane thin films doped with tetraphenylporphyrin exhibited absorbance at 421 nm and fluorescence emission at 651 nm or 717 nm (see FIG. 6). As shown in FIG. 6, when mercury ions were added to the polyurethane film doped with tetraphenylporphyrin, the absorbance decreased at 421 nm and the fluorescence emission decreased at 651 nm or 717 nm.

In addition, as shown in FIG. 7, when mercury ions were added to the polyurethane film doped with tetraphenylporphyrin, a color change in which color on the thin film was changed from colorless to yellow under visible light was observed, and under UV light. A fluorescence change was observed in which the color on the thin film changed from red to colorless.

In the reaction, the mercury ion and the tetraphenyl porphyrin derivative doped with the thin film specifically reacted to exhibit a decrease in absorbance and a decrease in fluorescence, and the porphyrin derivative reacted on the thin film to confirm the color change in visible and UV light.

Test Example 2. Measurement of detection limit for mercury ions of a polyurethane film doped with tetraphenylporphyrin

As a result of measuring the absorbance and fluorescence intensity in the same manner as in Test Example 1 by gradually adding mercury ions, the detection limit for Hg ²⁺ ions of a polyurethane film doped with tetraphenylporphyrin was determined to be 0.2 mM.

Claims (10)

delete delete delete delete In the mercury ion detection method comprising the step of reacting a water-dispersible polyurethane thin film doped with a fluorescent porphyrin derivative with a sample, after adding and mixing 30 to 50% by volume of isopropanol to the sample to be detected, the water-dispersible polyurethane thin film is sampled. And reacting with mercury ions. delete The mercury ion detection method according to claim 5, wherein the absorbent and fluorescence is measured after 10 to 30 minutes after the water-dispersible polyurethane thin film is reacted with a sample. The method of claim 5, comprising measuring the absorbance in the visible light wavelength range 300-900 nm and measuring the fluorescence in the fluorescence wavelength range 450-800 nm. In the apparatus for detecting mercury ions using a water-dispersible polyurethane thin film doped with a fluorescent porphyrin derivative, the device is reacted with a sample after dispersing the water-dispersible polyurethane thin film by adding 30 to 50% by volume of isopropanol to the sample to be detected. A device for detecting mercury ions, which is characterized in that. The apparatus for detecting mercury ions according to claim 9, wherein the absorbance is measured in the visible light wavelength range 300-900 nm and the fluorescence is measured in the fluorescence wavelength range 450-800 nm.

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