KR101213053B1 - The Detection of Actinide metal ion - Google Patents

Abstract

The present invention is analyzed by measuring the absorbance generated during complex formation by reacting an organic compound ligand comprising at least one functional group containing an element selected from the group consisting of oxygen, sulfur and selenium forming complexes with actinide-based metal ions A method for detecting actinide metal ions present in a subject.
The spectroscopic detection method according to the present invention is useful when implementing hand-held in situ optical analysis equipment, and actinide metals including uranium released from medical samples, weapons, and nuclear fuels, which are mine or discarded artificial radioactive materials. It can be usefully used to quantify ions.

Description

The detection of actinide metal ion

The present invention relates to a method for detecting actinide metal ions.

Actinide elements are present in trace amounts in nature. However, the use of actinide in concentrated form is currently on the rise because it is recognized as a useful resource as an energy source or by-product related to nuclear power generation, or as a material having useful chemical / physical properties or radioactivity. Therefore, when these substances are exposed to the natural or human environment, social interest in their effects is increasing and the importance of basic research is increasing.

Currently, various methods have been developed to detect actinides present in the environment and to quantify their concentrations, and to track changes in actinide chemical structure according to environmental conditions. In particular, various assays can detect traces (<μM) of species to understand the decomposition, leaching, chemical reactions, and the pathways of their migration along the groundwater stream, that make up the spent nuclear fuel. Have been developed, typically laser-induced fluorescence spectroscopy, SERS and ICP-MS.

The laser-induced fluorescence spectroscopy is an analysis method using fluorescence obtained when laser light is irradiated to a fluorescent material. Since the laser is used as an excitation light source, it is possible to obtain high spatial sensitivity with high sensitivity.

SERS is Raman scattering, which means that when a material is irradiated with a constant frequency of light, light scattered at a frequency changed by the molecular natural vibration, rotational energy, or crystal lattice vibration energy. When light passes through a medium, part of the light deviates from its direction of propagation and travels in a different direction, called scattering. Scattered light retains its original energy but is less than or equal to the energy of the original light. Some have a lot of energy. Rayleigh scattering is the process of scattering while maintaining the original energy of the scattered light. The process of scattering while losing or gaining energy is called Raman scattering. An analysis method that can be used to infer.

In addition, ICP-MS is an inductively coupled plasma mass spectrometer, which is used to analyze elements in a sample by ionizing elements with argon plasma and separating ions with a mass spectrometer.

These methods have the advantage of providing information about the species present, as well as the concentration of trace amounts of actinide material, but are required in real time because they require sample pretreatment, significant instrument size, and analyst skill. There are disadvantages not suitable for field analysis.

Therefore, it is necessary to develop an analysis method suitable for field analysis, that is, a small / light weight of an analytical device, and a method for collecting analytical results quickly with minimal sample preparation.

Absorption spectroscopy is based on measuring the extent to which light transmits through the medium containing the sample, depending on the wavelength. In recent years, small and light commercial devices using optical fiber optical components and semiconductor device detectors (photodiode assemblies or CCDs) capable of performing the absorption spectroscopy have been widely used. Therefore, it is considered that the method of detecting trace amount of actinide ions using the absorption method may be an alternative to rapid in situ analysis.

In addition, the limit of detection of the absorbance method depends on the molar absorptivity of the target ion species.

Since the extinction coefficient of actinide ion itself in aqueous solution is not large (<several hundred M ^-1 cm ^-1 ) in the useful wavelength range, the detection limit is known to be μM level by the conventional absorption method.

As shown in FIG. 1, only salicylic acid among the ligands having a carboxyl group shows significant absorption in the 350 to 550 nm wavelength region after complex reaction with uranium (U (VI)) ions, and as shown in FIG. 2, similar to the salicylic acid. It can be seen that thiosalicylate, a sulfur compound having a structure, exhibits absorption in a broader wavelength range than salicylic acid.

Accordingly, the present inventors induce an actinide metal complex formation reaction having high light absorption properties based on the above-described light absorption properties of the complex and fluorescence of uranium, and use the method for quantifying actinide metal ions. Developed to complete the present invention.

An object of the present invention is to measure the absorbance generated during complex formation by reacting an organic compound ligand comprising at least one functional group containing an element selected from the group consisting of oxygen, sulfur and selenium forming complexes with actinide-based metal ions It is to provide a method for detecting actinide metal ions present in the analysis target.

In order to achieve the above object, the present invention is to form a complex by reacting an organic compound ligand containing at least one functional group containing an element selected from the group consisting of oxygen, sulfur and selenium to form a complex with actinide-based metal ions The present invention provides a method for detecting actinide metal ions present in analytes by measuring the absorbance generated.

Actinide metal ion spectroscopy according to the present invention is useful when implementing hand-held in situ optical analysis equipment and extracts uranium from medicinal samples, weapons, and fuels, which are mine or discarded artificial radioactive materials. It can be usefully used to quantify actinide metal ions, including.

Figure 1 shows the absorption spectrum of the uranium-carboxylic acid complex according to an embodiment of the present invention.
Figure 2 shows the absorption spectrum of the uranium-thiosalicylic acid complex according to an embodiment of the present invention.
Figure 3 shows the calibration curve of the mixed ligand complexes of uranium-salicylic acid, uranium-thiosalicylate group PEI (SSal-PRI) and uranium-thiosalicylic acid and the selenium compound ebeselen according to an embodiment of the present invention .

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention is to measure the absorbance generated during complex formation by reacting an organic compound ligand comprising at least one functional group containing an element selected from the group consisting of oxygen, sulfur and selenium to form a complex with actinide-based metal ions Provided is a method for detecting actinide metal ions present in analyte.

The actinide-based metal ions are actinium (Ac), thorium (Th), protitanium (Pa), uranium (U), nepthenium (Np), americium (Am), curium (Cm), and californium (Cf) It may be selected from the group consisting of.

In addition, the organic compound ligand preferably has a hydroxy (-OH), thiol (-SH), selenol (-SeH) functional group, and is located at the beta (β) position from the hydroxy, thiol or selenol functional group. Carbon may additionally be present with oxygen, nitrogen, sulfur or selenium elements covalently bonded.

The organic compound having the hydroxy, thiol, and selenol groups participates in the formation of complex bonds with metal ions, which causes the absorption band of the existing molecules to shift. Therefore, it is possible to measure the absorbance change occurring in the complex formation process and use it for quantification of metal ions. In addition, as shown in FIGS. 1 and 2, in the wide wavelength region of 350 nm or more, since the self-absorption of the salicylic acid compound having a hydroxy group and the thiosalicylic acid compound having a thiol group is small, the background signal is small and the detection limit can be lowered. have.

In addition, the presence of covalent bonds including oxygen, nitrogen, sulfur or selenium elements increases the absorbance, so that the absorbance can be measured even with a trace amount of the organic compound ligand.

The organic compound ligand is an aromatic compound ligand, which is a multiconjugated compound in which the hydroxy, thiol or selenol functional group is an element that participates in multiple conjugate bonds, carbon, nitrogen, oxygen or sulfur, and the multiconjugated compound. In the case of an organic compound ligand including a bond, it may have a high extinction coefficient of 10 ⁴ to 10 ⁵ M ⁻¹ cm ⁻¹ . Aromatic compounds which are preferred multiconjugated binding compounds are phenyl, benzyl, naphthyl, anthracenyl, quinyl, pyridyl, pyrimidinyl, pyrrolic, furanyl, thiophenyl, imidazolic, oxa Zolik, indolic, indenyl, purinyl, quinolinyl, adenyl, guanyl, cytosyl, uracil, thyminyl derivatives and the like.

The organic compound ligand may be used alone or in combination to form a complex with actinide-based metal ions.

In addition, the organic compound ligand may include all intermediate compounds capable of generating hydroxy, thiol or selenol functional groups through various chemical reactions including oxidation-reduction reactions occurring in the process of detecting actinide-based metal ions. .

Furthermore, the organic compound ligand may be a monomolecular body or an oligomer body or a polymer body combined with an oligomer or a polymer, which is a polymer or particulate polymer chemically attached to the surface of inorganic carbon, quartz, silica, glass, gold or silver. It can be used in the form attached to the support surface consisting of.

In addition, the polymer is a synthetic polymer selected from the group consisting of polyethyleneimine, polyacrylic acid, polystyrene, polycarbonate and polyurethane; Natural polymers selected from the group consisting of cellulose and dextran; Or a biochemical polymer selected from the group consisting of peptide molecules and proteins.

The method for detecting actinide metal ions according to the present invention quantitatively analyzes actinide-based metal ions included in the analyte by measuring an absorption change generated when complexes are formed between actinide-based metal ions and the organic compound ligand. That's how.

The metal ion detection may include absorption spectroscopy in the ultraviolet, visible or infrared region, absorption spectroscopy using a liquid-core waveguide, spectroscopy using an optode, optoacoustic spectroscopy, fluorescence spectroscopy or spectroscopy. It can be carried out using an electrochemical method, it is preferred to use UV-Vis absorption spectroscopy.

Hereinafter, the present invention will be described in detail with reference to examples.

However, the following examples are illustrative of the present invention, and the present invention is not limited to the following examples.

< Example  1> Single molecule Ligand  Absorbance Measurement Used

First, salicylic acid mother solution 10 mM (pH 4.5, 0.1 M NaClO ₄ ) was prepared. A series of uranium standards was prepared from uranium (U (VI)) mother solution 2 mM (pH 3.5, 0.1 M NaClO ₄ ). The salicylic acid mother solution prepared above and the uranium standard solution were mixed 1: 1, and the final pH was adjusted to 4.5 using 50 mM NaOH and 50 mM HClO ₄ solution. After the mixed solution was placed in a 1-cm spectrocell, the absorbance of the complex solution based on the absorbance of a 0.1 M NaClO ₄ solution having a pH of 4.5 was measured.

The calibration curve obtained by repeating the process of making a mixed solution using the standard solution and measuring the absorbance is shown in Table 1 and FIG. 3.

Uranium Ion Concentration (μM) Relative absorbance (380 nm) 0 0 13.3 0.0133 26.7 0.0275 53.3 0.0527 80 0.0807 107 0.1032 133 0.1187

As shown in Table 1 and Figure 3, according to the uranium ion calibration curve using the complex formation of uranium and salicylic acid, it can be seen that the absorbance also increases as the uranium ion concentration increases.

< Example  2> sulfur containing polymer Ligand  Absorbance Measurement Used

4-Bromothiosalicylic acid was bound to the amine group of polyethyleneimine (PEI) to prepare PEI (SSal-PRI) to which thiosalicylate groups were immobilized. A 1 mg / mL SSal-PEI (pH 5, 0.1 M NaClO ₄ ) mother solution was prepared. A series of uranium standards was prepared from 2 mM uranium mother solution (pH 3.5, 0.1 M NaClO ₄ ). The SSal-PEI stock solution and uranium stock solution were mixed 1: 1, and the final pH was adjusted to 5 using 50 mM NaOH and 50 mM HClO ₄ solution. After the mixed solution was placed in a 1-cm spectrocell, the absorbance of the complex solution based on the absorbance of the 0.1 M NaClO ₄ solution at pH 5 was measured.

The calibration curve obtained by repeating the above process is shown in Table 2 and FIG.

Uranium Ion Concentration (μM) Relative absorbance (400 nm) 0 0 20 0.0488 40 0.0907 60 0.1269 80 0.1682 100 0.2096 120 0.2417

As shown in Table 2 and Figure 3, according to the uranium ion calibration curve using complex formation of PEI (SSal-PRI) in which uranium and thiosalicylate groups are fixed, the absorbance also increases as uranium ion concentration increases. You can check it.

< Example  3> Mixed ligands  Absorbance Measurement Used

A ligand solution was prepared by mixing 10 mM thiosalicylic acid (pH 5, 0.1 M NaClO ₄ ) mother solution with a selenium compound, ebselen (50 mM in DMSO), (5 mM thiosalicylic acid, ebselen 1 mM). . A series of uranium standard solutions were prepared from 2 mM uranium mother solution (pH 3.5, 0.1 M NaClO ₄ ). The thiosalicylic acid and selenium compound mixed solution and uranium mother solution were mixed 1: 1, and the final pH was adjusted to 5 using 50 mM NaOH and 50 mM HClO ₄ solution. After the mixed solution was placed in a 1-cm spectrocell, the absorbance of the complex solution based on the absorbance of the 0.1 M NaClO ₄ solution at pH 5 was measured.

The calibration curve obtained by repeating the above process is shown in Table 3 and FIG.

Uranium Ion Concentration (μM) Relative absorbance (410 nm) 0 0 20 0.0183 40 0.0385 60 0.0627 80 0.0807 100 0.1032 120 0.1287

As shown in Table 3 and Figure 3, according to the uranium ion calibration curve using the complex formation of uranium with a mixed ligand of thiosalicylic acid and a selenium compound, the selenium compound, the absorbance also increases as the uranium ion concentration increases. You can check it.

Claims (14)

Actinide series metal ions,
Complexes can be formed with the actinide-based metal ions, and the absorbances generated during the formation of the complexes by reacting salicylic acid derivatives containing at least one functional group containing an element selected from the group consisting of oxygen, sulfur and selenium are analyzed. A method for detecting actinide metal ions, which detects actinide metal ions present in a subject.
The method of claim 1, wherein the actinide-based metal ions are actinium (Ac), thorium (Th), protaxinium (Pa), uranium (U), Nepternium (Np), Americium (Am), Curium (Cm) And californium (C f) is selected from the group consisting of actinide metal ion detection method.
The method of claim 1, wherein the functional group of the salicylic acid derivative is hydroxy (-OH), thiol (-SH), or selenol (-SeH).
4. The acti of claim 3, wherein the salicylic acid derivative may be covalently present with an oxygen, nitrogen, sulfur or selenium element in addition to the carbon at the beta (β) position from the hydroxy, thiol or selenol functional group. Method for detecting nit metal ions.
4. The salicylic acid derivative according to claim 3, wherein the salicylic acid derivative is a multiconjugated compound in which the hydroxy, thiol or selenol functional group is bonded to carbon, nitrogen, oxygen or sulfur which is an element participating in multiple conjugate bonds. A method for detecting actinide metal ions.
The method of claim 5, wherein the aromatic compound is a conjugated compound is phenyl, benzyl, naphthyl, anthracenyl, quinyl, pyridyl, pyrimidinyl, pyrrolic, furanyl, thiophenyl ), Imidazolic, oxazolic, indolic, indenyl, purinyl, quinolinyl, adenyl, guanyl, cytosyl, uracil or thyminyl derivatives Method of detecting ions.
The method of claim 3, wherein the salicylic acid derivative is used alone or in combination to form a complex with an actinide-based metal ion.
The method of claim 3, further comprising an intermediate compound capable of generating hydroxy, thiol or selenol functional groups through a chemical reaction including an oxidation-reduction reaction occurring during the detection of actinide-based metal ions. Method for detecting actinide metal ions.
The method of claim 1, wherein the salicylic acid derivative is a monomolecular body, or an oligomer body or a polymer body combined with an oligomer or a polymer.
The actinide metal according to claim 1, wherein the salicylic acid derivative is bound to a support surface composed of a polymer or a particulate polymer chemically attached to a surface of inorganic carbon, quartz, silica, glass, gold or silver. Method of detecting ions.
The method of claim 9, wherein the polymer is a synthetic polymer selected from the group consisting of polyethyleneimine, polyacrylic acid, polystyrene, polycarbonate and polyurethane; Natural polymers selected from the group consisting of cellulose and dextran; Or a biochemical polymer selected from the group consisting of peptide molecules and proteins.
The actinide of claim 1, wherein the detection method measures quantitative analysis of actinide-based metal ions included in an analyte by measuring an absorption change when complexes between actinide-based metal ions and the salicylic acid derivative are formed. Method of detecting metal ions.
The method of claim 1, wherein the actinide-based metal ion is detected by absorption spectroscopy in the ultraviolet, visible or infrared region, absorption spectroscopy using a liquid-core waveguide, and an optode. A method for detecting actinide metal ions, characterized in that it is carried out using spectroscopy, photoacoustic spectroscopy, fluorescence spectroscopy or spectroelectrochemical methods.
The method of claim 13, wherein the actinide-based metal ion is detected using ultraviolet-vis absorption spectroscopy.

Images