CN111380861B - Detection reagent combination and detection method for cesium ions - Google Patents
Detection reagent combination and detection method for cesium ions Download PDFInfo
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- CN111380861B CN111380861B CN201811620199.2A CN201811620199A CN111380861B CN 111380861 B CN111380861 B CN 111380861B CN 201811620199 A CN201811620199 A CN 201811620199A CN 111380861 B CN111380861 B CN 111380861B
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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
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/29—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands using visual detection
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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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
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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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
- G01N2021/3155—Measuring in two spectral ranges, e.g. UV and visible
Abstract
The application discloses a reagent combination for detecting cesium ions and a detection method. The reagent combination comprises a citrate ion modified gold nanoparticle solution and a ligand solution. The method comprises the following steps: 1) obtaining a sample to be detected; 2) preparing gold nano detection solution; 3) optimizing experimental conditions; 4) mixing a sample to be detected with the gold nano detection solution, and determining the condition of cesium ions according to the color change of the reaction solution under the optimal experimental condition; the method for detecting the cesium ions in the sample has the characteristics of quick detection, simple experimental conditions, accurate result and the like.
Description
Technical Field
The invention relates to the field of radioactive ion detection, in particular to a detection reagent for cesium ions and a detection method thereof.
Background
Cesium is an extremely important, strategically important group of rare noble metal elements. Cesium and its compounds have shown great application prospects and important scientific and commercial values in the fields of aerospace, energy and defense industry, etc., and the application requirements for cesium and its compounds are increasing in recent years. Cesium is an indispensable material for manufacturing atomic clocks and global satellite positioning systems. Cesium is highly ionizable and can be used as a dielectric for solid-state batteries. Researchers are vigorously developing research works of rubidium and cesium on ion engines, magneto-current generators, thermoelectric transducers and the like. Cesium and its compounds also have excellent photoelectric characteristics, electrical conductivity, thermal conductivity and strong chemical activity. Cesium antimony coatings are commonly used on photomultiplier tube cathodes for radiation detection devices, medical imaging devices, and night vision devices. China has a considerable amount of cesium resources, but the cesium resources are distributed and dispersed in the crusta of the earth and usually accompany other minerals, so that pure cesium minerals are not found yet. Currently, the solid minerals which can be exploited mainly include lepidolite, pollucite and the like, but with the annual depletion of the solid minerals, the search for and development of a new caesium mineral is imminent. The salt lake brine contains abundant cesium resources, and although the average mass concentration of cesium in the brine is low (0.034mg/L), the total reserve is considerable, and the cesium resources in the salt lake brine are expected to be the key point of cesium resource development in the future. Researchers have detected more than 60 chemical components from Chinese salt lake brine, and the compositions are quite complexHetero, in which K is present in higher concentrations and has properties similar to those of rubidium or caesium + 、Ca 2+ 、Na + 、Mg 2+ And the metal ions exist, and the existence of the metal ions can seriously interfere the quantitative determination of trace cesium contained in the brine. The concentration of cesium in brine determines a specific method for extracting and separating cesium from brine and the exploitation value, so that the method for detecting cesium in salt lake brine and high-salt-concentration water is a hot spot of research of scholars at home and abroad.
Current methods of detecting and quantifying cesium ions are based on radiation detectors and flash detectors. However, these techniques do not have spatial resolution and therefore it is difficult to identify the radionuclide. Meanwhile, most of the detection methods need to be completed by large or expensive precise instruments, so that the field timeliness is poor, and the cost is too high.
Therefore, there is a need to develop a new method for easily detecting Cs + Ion technology.
In summary, there is still no method for rapidly, timely, on-site and simply detecting low-concentration cesium ions in an aqueous solution in the field.
Disclosure of Invention
According to one aspect of the application, the detection reagent and the detection method thereof are provided, wherein the detection reagent can be used for quickly, timely, on-site and simply detecting low-concentration cesium ions in a salt lake. The method can rapidly, accurately and simply detect the Cs in the aqueous solution system in real time + The method is not only suitable for detecting water environment samples, but also can be used for detecting water solution samples and salt lake brine which are obtained by processing solid environment samples or dust floating in the atmosphere and the like. According to actual needs, the method can be used for treating Cs + Performing qualitative analysis, and optionally analyzing Cs + Quantitative analysis was performed. When qualitative analysis is carried out, judgment can be made only by observing the color change of the solution; when performing quantitative analysis, the absorbance value A at a specific absorption wavelength and concentration can be obtained by using a standard 650nm And A 525nm Calculating the ratio, and substituting the ratio into the equation to obtain the Cs of the sample to be measured + And (4) content. If it is to be measuredAfter a series of pre-treatments or pre-treatments, the sample can be subjected to a back-stepping method to finally obtain Cs in the sample to be detected + And (4) content.
The detection reagent combination of cesium ions is characterized by comprising:
component (a): the reagent component is used for forming the gold nanoparticle solution modified by the citrate ions;
a component (b): a ligand solution, or a reagent component for forming the ligand solution; the ligand solution is selected from at least one of a Prussian blue solution, a methyl blue solution and a methylene blue solution.
Optionally, the ligand Prussian blue can coat the gold nanoparticles and has the capacity of adsorbing cesium ions, and the binding force of the ligand Prussian blue to the cesium ions is greater than that of the ligand Prussian blue to the gold nanoparticles modified by the citrate ions.
Optionally, the pH value of the gold nanoparticle solution modified by the citrate ions is 5-9.
Optionally, the pH value of the gold nanoparticle solution modified by the citrate ions is 6-8.
Optionally, the pH of the gold nanoparticle solution modified by the citrate ions is 6.5-7.5.
Optionally, the concentration of gold nanoparticles in the gold nanoparticle solution containing citrate ion modification is 2.5 nM-100 nM.
Optionally, the concentration of gold nanoparticles in the gold nanoparticle solution containing citrate ion modification is 10 nM-40 nM.
Optionally, the concentration of the ligand in the ligand solution is 0.1M to 0.15M.
Optionally, the reagent components for forming the solution of gold nanoparticles containing citrate ion modifications in component (a) include:
(i) gold nanoparticle precursors;
(ii) a reducing agent; and
(iii) and (4) a protective agent.
Optionally, the combination of reagents for detecting cesium ions further includes: a pH regulator.
Optionally, the pH adjusting agent is a strong acid and/or a strong base.
Optionally, the pH adjusting agent is selected from at least one of sodium hydroxide, potassium hydroxide, sulfuric acid, hydrochloric acid.
Optionally, the gold nanoparticle precursor is a soluble gold salt.
Optionally, the gold nanoparticle precursor is selected from at least one of gold chloride, aurous chloride, chloroauric acid, potassium chloroaurate and sodium chloroaurate.
Optionally, the reducing agent is citric acid and/or a citrate salt.
Optionally, the reducing agent and the protecting agent are the same.
Alternatively, the solution of gold nanoparticles containing citrate ion modifications may be a pre-formed reagent, such as purchased from a commercial source, or may be prepared on-site, such as by a method comprising the steps of:
providing an aqueous solution in which the gold nanoparticle precursor is dissolved;
and adding the reducing agent into the aqueous solution to obtain the gold nanoparticle solution modified by the citrate ions.
Optionally, the reducing agent is added under stirring and/or heating to boiling.
According to another aspect of the present application, there is provided a kit for detecting cesium ions, characterized by comprising at least one of the reagent combinations.
Optionally, the kit further comprises a pH adjusting reagent.
Optionally, the kit comprises:
component (a): a citrate ion modified gold nanoparticle solution, or a reagent component for forming the citrate ion modified gold nanoparticle solution;
optional component (b): a ligand solution, or a reagent component for forming the ligand solution; and instructions describing a method for detecting cesium ions by using components (a) and (b).
Optionally, the reagent composition comprises:
(i) gold nanoparticle precursors;
(ii) a reducing agent; and
(iii) optionally (iii) a protective agent.
Optionally, the ligand solution is selected from the group consisting of: at least one of Prussian blue solution, methyl blue solution and methylene blue solution.
Optionally, the gold nanoparticle precursor is selected from at least one of soluble gold salts.
Optionally, the gold nanoparticle precursor includes at least one of gold chloride, gold chlorite, chloroauric acid, potassium chloroaurate, and sodium chloroaurate.
Optionally, the reducing agent is selected from at least one of sodium borohydride, potassium borohydride, citric acid and citrate.
Optionally, the protective agent is at least one selected from tween 20 and polyvinylpyrrolidone.
Optionally, the kit further comprises a pH adjusting agent.
Optionally, the pH adjusting agent is a strong acid and/or a strong base.
Optionally, the pH adjusting agent is selected from at least one of sodium hydroxide, potassium hydroxide, sulfuric acid, and hydrochloric acid.
Optionally, the reducing agent and the protecting agent are the same.
According to a further aspect of the present application, there is provided the use of a combination of agents consisting of:
component (a): a citrate ion modified gold nanoparticle solution, or a reagent component for forming the citrate ion modified gold nanoparticle solution; and
a component (b): a ligand solution, or a reagent component for forming the ligand solution;
and the reagent is combined to prepare a kit or a reagent for detecting cesium ions.
According to another aspect of the present application, a method for detecting cesium ions is provided, wherein the detection is performed by using the reagent combination or the kit.
Optionally, the method comprises:
(s1) providing a sample solution to be tested;
(s2) obtaining a gold nanoparticle solution modified by citrate ions;
(s3) mixing the sample solution to be detected with the citrate ion modified gold nanoparticle solution and the ligand solution to form a detection mixed solution;
(s4) detecting the spectroscopic characteristics of said test mixture, thereby obtaining a test result.
Optionally, the method further comprises: and adjusting the pH of the gold nanoparticle solution modified by citrate ions and/or the sample solution to be detected by using a pH regulator.
Optionally, the spectroscopic characteristics are selected from at least one of color, visible absorption intensity, absorption spectrum peak.
Optionally, the method further comprises: and observing the color of the detection mixed solution by naked eyes.
Optionally, the method further comprises: and detecting the color of the detection mixed solution by using an instrumental analysis method.
Optionally, the method further comprises: the spectroscopic characteristics of the test mixture were measured instrumentally.
Optionally, the instrumental analysis method is selected from the group consisting of: spectrophotometric detection, ultraviolet-visible absorption spectroscopy.
Optionally, the method further comprises: and providing a control mixed liquor, and judging whether cesium ions exist in the sample and/or the content of the cesium ions in the sample by comparing the spectroscopic characteristics of the detection mixed liquor and the control mixed liquor.
Optionally, the method further comprises: and adjusting the pH value of the solution of the sample to be detected to 5-9 by using a pH adjusting reagent.
Optionally, the sample solution to be tested is adjusted with a pH adjusting reagent to a pH value of 6-8, preferably 6.5-7.5.
As an embodiment, the method comprises the steps of:
and comparing the detection mixed solution with a standard sample, and judging whether cesium ions exist in the sample to be detected and/or judging the concentration of the cesium ions in the sample to be detected.
Optionally, the method comprises: and carrying out spectral analysis on the detection mixed solution, and comparing the obtained result with a preset standard curve.
Optionally, the method comprises: and comparing the detection mixed solution with a standard colorimetric card.
Optionally, the standard curve is prepared by:
(I) providing a plurality of cesium ion aqueous solutions with different concentrations, and adding the gold nanoparticle solution and the ligand solution into the solutions to obtain corresponding standard samples with known concentrations;
(II) measuring the spectroscopic characteristic parameters of each detection mixed solution;
(III) drawing a curve of spectroscopic characteristic parameters of the detection mixed solution-cesium ion concentration, or drawing a spectrum of visible light relative absorption value-cesium ion concentration as a standard spectrum;
in another preferred embodiment, the UV-visible absorption spectrum is measured at a wavelength of 400-800nm, preferably at a wavelength of 500-700 nm.
Alternatively, the UV-VIS absorption spectrum is measured at wavelengths around 525 and 650 nm.
Optionally, the sample solution is a solution prepared by pretreating a sample selected from the group consisting of: an environmental water sample, a salt lake water sample, a solid environmental sample, a food product, a cosmetic product, industrial waste water, a blood sample, or a combination thereof.
According to another aspect of the application, the detection reagent combination of cesium ions and/or the kit and/or the method for detecting cesium ions are provided for detecting cesium ions in an aqueous solution system.
Optionally, the aqueous solution system is a solution prepared by pretreating a sample selected from the group consisting of: an environmental water sample, a salt lake water sample, a solid environmental sample, a food product, a cosmetic product, industrial waste water, a blood sample, or a combination thereof.
The beneficial effects that this application can produce include:
1) the application provides a method for detecting Cs in aqueous solution + The method of (1) directly discriminating the change of the solution color by naked eyes to realize the Cs in the solution + The Cs in the solution system can be rapidly detected through simple instrument and equipment + The content of the cesium ions in the detected liquid is reduced, and qualitative and quantitative detection of the cesium ions in the detected liquid is realized.
2) The detection method provided by the application is simple and convenient to operate, quick, low in cost and high in sensitivity, can be operated on site, is suitable for river, lake and ocean water quality investigation, enterprise factory drainage water quality self-checking, monitoring and detection of domestic water and various water samples obtained after treatment, and has wide application value.
3) The detection method of cesium ions provided by the application can achieve minimum 3 × 10 by only naked eye colorimetry -5 Lower limit of detection of mol/L; the method provided by the invention can be combined with an instrument analysis means, can also be used for detecting the cesium ion aqueous solution sample with lower concentration, and has very high sensitivity.
Drawings
FIG. 1 shows the different concentrations of Cs contained in the present application + The colorimetric detection result map of the detection mixed solution.
FIG. 2 is a diagram showing the UV-VIS absorption spectrum of the standard mixed solution obtained in the present application.
FIG. 3 is a graph showing the relative value of absorption of visible light versus the concentration of cesium ions in a standard mixture according to the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials in the examples of the present application were all purchased commercially.
The analysis method in the examples of the present application is as follows:
ultraviolet absorbance detection and analysis are carried out by utilizing an ultraviolet visible spectrophotometer (model number T10CS) provided by Beijing Puproud analysis general instruments Co. (the brand and model of the ultraviolet-visible absorption spectrometer commonly used in the market can be used, and the wavelength range of the light source is 300-900nm)
The application provides a detection reagent combination of cesium ions, which is characterized by comprising:
component (a): the reagent component is used for forming the gold nanoparticle solution modified by the citrate ions;
a component (b): a ligand solution, or a reagent component for forming the ligand solution; the ligand solution is selected from at least one of a Prussian blue solution, a methyl blue solution and a methylene blue solution.
The application provides a detection kit for cesium ions, which is characterized by comprising at least one of the reagent combinations.
The application provides a method for detecting cesium ions, which is characterized in that the reagent combination or the kit is adopted for detection.
As an embodiment, the method comprises:
(s1) providing a sample solution to be tested;
(s2) mixing the sample solution to be detected with the gold nanoparticle solution and the ligand solution to form a detection mixture;
(s3) detecting a spectroscopic characteristic of said test mixture, thereby obtaining a test result.
Optionally, the spectroscopic feature is selected from at least one of color, visible light absorption intensity, absorption spectrum peak.
As an embodiment, the method comprises: and setting a standard sample with known concentration, and comparing the spectroscopic characteristics of the standard sample and the detection mixed solution to obtain the concentration of the sample to be detected.
Wherein, the preparation method of the standard sample comprises the following steps:
and comparing the detection mixed liquor with a standard sample, and judging whether the monovalent cesium ions exist in the sample to be detected and/or judging the concentration of the monovalent cesium ions in the sample to be detected.
Optionally, the method comprises: and carrying out spectral analysis on the detection mixed solution, and comparing the obtained result with a preset standard curve.
Optionally, the method comprises: and comparing the detection mixed solution with a standard colorimetric card.
Optionally, the standard curve is prepared by:
(I) providing a plurality of monovalent cesium ion aqueous solutions with different concentrations, and adding the gold nanoparticle solution and the ligand solution into the solutions to obtain corresponding standard samples with known concentrations;
(II) measuring spectroscopic characteristic parameters of each test mixture;
(III) drawing a curve of spectroscopic characteristic parameters of the detection mixture-monovalent cesium ion concentration, or drawing a spectrum of relative ultraviolet visible light absorption value-monovalent cesium ion concentration as a standard spectrum;
in a preferred embodiment of the present invention, the absorbance (A) of a mixture containing cesium ions of different concentrations is determined by using the concentration of each of the known cesium ions as the abscissa (X) 650nm ) Absorbance of blank mixture (A) 525nm ) Ratio of (A) 650nm /A 525nm ) That is, the "relative ultraviolet-visible absorption value" is taken as the ordinate (Y), and a scatter diagram is obtained, and the linear relationship between the two is calculated. The results of one exemplary embodiment are shown in fig. 3.
When measuring a detection solution of unknown concentration, the absorbance (A) of a mixture containing cesium ions of each concentration is used 650 ) Absorbance with blank mixture (A) 525 ) Ratio of (A) 650 /A 525 ) And substituting the formula Y in figure 3 to obtain the concentration value of cesium ions.
Optionally, the UV-visible absorption is determined at a wavelength of 400-800nm, preferably at a wavelength of 500-700 nm.
Optionally, the uv-vis absorption is measured at wavelengths around 525nm and 650 nm.
In the present invention, the kind of the sample aqueous solution is not particularly limited, and may be a solution prepared by including (but not limited to) a sample selected from the following group with or without pretreatment: an environmental water sample, a salt lake water sample, a solid environmental sample, a food product, a cosmetic product, industrial waste water, a blood sample, or a combination thereof.
In the present invention, a preferred detection method comprises the steps of:
(1) adding a proper amount of soluble gold salt into the aqueous solution, adding a citric acid compound as a reducing agent under the conditions of heating and stirring, and reacting for a period of time to prepare a detection solution containing gold nanoparticles modified and protected by citrate ions; and preparing a Prussian blue solution with a certain concentration.
(2) Preparing an aqueous solution without cesium ions as a blank solution, comparing the blank solution with a reference solution in volume to be detected, and adjusting the solution to be weak acid/weak alkaline. Measuring two detection liquid samples with the same volume from the detection liquid prepared in the step (1), and adding the two detection liquid samples into a blank solution and a detected solution with the same volume to form a first mixed solution and a second mixed solution;
(3) and (3) adding the same amount of the prussian blue solution prepared in the step (1) into the first mixed solution and the second mixed solution in the step (2). Comparing the color or the change of the ultraviolet-visible absorption intensity and the peak value of the second mixed solution and the first mixed solution, and judging whether the detected solution has Cs or not + 。
In the above detection process, the first detection mixture (no Cs) + ) Is grayish blue, when the color of the second detection mixed solution changes to red or red relative to the color of the first detection mixed solution, it is determined that the sample to be detected contains Cs + And Cs + Is greater than or equal to 3X 10 -5 mol/L. If there is no color change, the sample to be tested does not necessarily contain Cs + . Further measuring the spectrum data of the detection mixed solution which is not discolored, thereby further determining whether the sample to be detected existsCs + 。
Optionally, providing a solution capable of reflecting Cs in aqueous solution + Comparing the ultraviolet-visible absorption intensity of the second mixed solution obtained by the method with the standard curve chart of the relation between the concentration and the ultraviolet-visible absorption intensity to obtain the Cs in the second mixed solution + The concentration of (c). The specific drawing method of the standard curve chart is as follows:
preparing a series of different Cs according to the preparation method of the second mixed solution + Scanning the ultraviolet visible absorption intensity of the standard mixed solution with the concentration within the wavelength range of 400-800nm, taking the ultraviolet visible absorption intensity of the mixed solution as a vertical coordinate, and taking Cs contained in the mixed solution + The concentration is plotted on the abscissa, i.e. a standard curve graph is obtained, as shown in fig. 3; FIG. 2 is a graph of UV-VIS absorption spectra of standard mixtures of different concentrations. Standard curve is determined by measuring corresponding Cs + A at concentrations of 0. mu.M, 5. mu.M, 10. mu.M, 30. mu.M, 50. mu.M, 70. mu.M, 90. mu.M, 100. mu.M, 200. mu.M, respectively 650nm /A 525nm Value, then as Cs + Concentration is in the abscissa, A 650nm /A 525nm And drawing a scatter diagram as a vertical coordinate, and obtaining a standard curve through fitting, wherein the standard curve is shown in figure 3.
It is found through experiments that when a standard curve graph is drawn, the standard curve graph is associated with Cs + The detection wavelengths of the ultraviolet-visible absorption intensity are preferably 525nm and 650nm in increasing concentration. The relative absorption intensity was obtained as a function of the monovalent cesium ion concentration, as shown in FIG. 3.
In the technical scheme, the reaction time is 20 minutes; the detected aqueous solution can be a water sample in the environment, such as river water, lake water, seawater and the like; can be a sample obtained by processing a liquid sample, such as a blood product, a urine product and the like; an aqueous solution obtained by treating an environmental sample (such as food, vegetable product, etc.) which may be in a solid state; or an aqueous solution obtained by treating dust floating in the atmosphere.
Optionally, in the steps (1) and (2), the obtained gold nanoparticle solution and the solution to be detected are subjected to pH adjustment to adjust the pH value to 6.5-7.5, and then the operation of the step (3) is performed, so that not only can the detection time be saved, but also the detection limit and the sensitivity can be improved. For strongly alkaline sample solution to be detected, strong acid is preferred, and the pH value is preferably adjusted by hydrochloric acid; for strongly acidic sample solutions to be tested, strong bases are preferred, and the pH value is particularly preferably adjusted by means of sodium hydroxide and/or potassium hydroxide solutions.
General procedure
Preparation of the Standard Curve
(1) Preparation of the detection solution of the invention: the detection solution can be prepared by the following method:
adding 5mL of 5mM chloroauric acid solution into 91mL of ultrapure water, adding 4mL of 1% sodium citrate solution serving as a reducing agent and a protective agent under the conditions of stirring and heating to boiling, reacting for 15min, and preparing a citrate modified gold nanoparticle solution, wherein the pH value of the citrate modified gold nanoparticle solution is 6; and preparing a Prussian blue aqueous solution with a certain concentration of 0.1M.
(2) Preparing a standard sample: preparing a series of Cs by using deionized water and cesium salt + 0.1mL of each of standard solutions having ion concentrations of 0. mu.M, 50. mu.M, 100. mu.M, 300. mu.M, 500. mu.M, 700. mu.M, 900. mu.M, 1000. mu.M and 2000. mu.M, respectively, was added to each of the test sample solutions having different concentrations, 0.9mL of each of the test sample solutions prepared in step 1, and the Prussian blue solution (10. mu.L) prepared in step (1). And standing for 20 minutes. FIG. 1 shows the results of the different Cs + The color development of the standard sample at the concentration is 0. mu.M, 5. mu.M, 10. mu.M, 30. mu.M, 50. mu.M, 70. mu.M, 90. mu.M, 100. mu.M, and 200. mu.M, in this order from left to right. As can be seen in FIG. 1, Cs + The color is grayish blue at the concentrations of 0 μ M, 5 μ M and 10 μ M, and is not changed; cs + The color gradually turns red at concentrations of 30. mu.M, 50. mu.M, 70. mu.M, 90. mu.M, 100. mu.M, and 200. mu.M. Cs can be judged through naked eye colorimetry + Whether the concentration is more than 3 x 10 -5 mol/L。
(3) Drawing a standard curve: for the Cs prepared above + Standard samples at concentrations (final concentrations) of 0. mu.M, 5. mu.M, 10. mu.M, 30. mu.M, 50. mu.M, 70. mu.M, 90. mu.M, 100. mu.M, and 200. mu.M, respectivelyAnd (3) carrying out ultraviolet-visible absorption spectrum measurement, measuring the change of the ultraviolet-visible absorption intensity within the range of 400-800nm, and recording the absorbance ratio at 525nm and 650 nm. By Cs in the standard sample + Concentration as abscissa, A 650nm /A 525nm The absorbance ratio is plotted on the ordinate. The standard curve is shown in FIG. 3, the absorbance ratio vs. Cs + The concentration satisfies the formula: y is 0.0075X +0.8614, wherein Y is a 650nm /A 525nm Absorbance ratio, X is Cs + Concentration (. mu.M), R 2 ＝0.9933。
Ultraviolet testing of mixtures of different samples
0.9mL of the gold nanoparticle solution, 0.1mL of Cs at each of the above concentrations was added + After mixing, 10uL of Prussian blue solution was added, and the reaction was carried out for 20min for UV-visible absorption spectroscopy, the results are shown in FIG. 2.
Preparing a prussian blue solution: 10mL of aqueous solution containing 1mM FeCl 3 ·6H 2 O,1mMK 3 Fe(CN) 6 0.1M KCl,0.025M HCl, formulated as solids weighed. The prussian blue aqueous solution prepared by the method in the examples has the concentration of 0.1M.
Example 1 Cs in Water samples of river, lake, and tap Water + Detection of (2)
(1) Preparing a detection solution: adding 5mL of 5mM chloroauric acid solution into 91mL of ultrapure water, adding 4mL of 1% sodium citrate solution serving as a reducing agent under the conditions of stirring and heating to boiling, and reacting for 15min to obtain a gold nanoparticle solution modified by citrate; and preparing a prussian blue solution.
(2) Collecting a water sample to be detected: collecting water samples at certain depths (20-50 cm) of three different places in a river or a lake by using a water sample collecting bottle, adjusting the pH of the water samples to be 6-7 by using hydrochloric acid or sodium hydroxide (depending on the pH value of a detection liquid sample) in the obtained mixed solution so as to avoid the influence of impurities on the detection effect, filtering the water samples by using filter paper, and obtaining filtrate which is the water sample to be detected.
(3) The pH of the gold nanoparticle detection solution prepared in the step (1) is adjusted to 6.5 by using 0.05mol/L HCl aqueous solution to serve as a detection solution sample.
(4) Two test tubes A and B of the same specification were prepared, and the same volume (0.9mL) of the test solution sample was added to each of the test tubes A and B.
(5) Adding ultrapure water and a water sample to be detected which are equal in volume (0.1mL) into the test tube A and the test tube B respectively, mixing uniformly, and then adding the prussian blue solution (10uL) prepared in the step (1). The color change of the aqueous solution in test tubes A and B was observed.
And (3) detection results: within 20 minutes, if the color of the aqueous solution in the test tube B changes (turns red) relative to the aqueous solution in the test tube A, the Cs in the water sample to be detected is judged + And the concentration is greater than or equal to 3 x 10 -5 mol/L；
If the color of the aqueous solution in the test tube B relative to the aqueous solution in the test tube A does not change, determining that the Cs in the water sample to be detected is the same as the color of the aqueous solution in the test tube B + The concentration is less than 3 × 10 -5 mol/L。
Measuring the ultraviolet-visible absorption spectrum of the detection mixed solution, measuring the change of the ultraviolet-visible absorption intensity within the range of 400-800nm, substituting the absorbance ratio of 525nm and 650nm into the graph 3 for comparison calculation to obtain the Cs in the solution to be detected + And (4) concentration.
Example 2 Cs in Water samples from Industrial and mining companies, chlor-alkali and salt lake industries + Detection of (2)
(1) Preparing a detection solution: adding 5mL of 5mM chloroauric acid solution into 91mL of ultrapure water, adding 4mL of 1% sodium citrate solution serving as a reducing agent under the conditions of stirring and heating to boiling, and reacting for 15min to obtain a gold nanoparticle solution modified by citrate; and preparing a prussian blue solution.
(2) Collecting a water sample to be detected: collecting water samples at the sampling position of a wastewater discharge port at intervals of 1h, mixing the water samples into mixed samples in equal quantity, filtering the solution by using filter paper, and adjusting the pH of the filtrate to be 6-7 weak acid by using hydrochloric acid (or sodium hydroxide, depending on the pH value of a detection solution sample) so as to avoid influencing the detection effect and obtain a water sample to be detected.
(3) Adjusting the pH of the gold nanoparticle detection solution prepared in the step (1) to 6.5 by using 0.05mol/L HCl aqueous solution to be used as a detection solution sample,
(4) two test tubes A and B of the same specification were prepared, and an equal volume (0.9mL) of the test solution sample was added to each of the test tubes A and B.
(5) Adding ultrapure water and a water sample to be detected into the test tube A and the test tube B respectively in equal volume, uniformly mixing, adding the Prussian blue solution (10uL) prepared in the step (1), and observing the color change condition of the water solution in the test tube A and the test tube B.
And (3) detection results: within 20 minutes, if the color of the aqueous solution in the test tube B changes (turns red) relative to the color of the aqueous solution in the test tube A, the water sample to be detected is judged to contain Cs + And at a concentration of 3X 10 or more -5 mol/L; if the color of the aqueous solution in the test tube B relative to the aqueous solution in the test tube A does not change, determining that the Cs in the water sample to be detected is the same as the color of the aqueous solution in the test tube B + The concentration is less than 3 × 10 -5 mol/L。
Performing ultraviolet-visible light absorption spectrum measurement on the detection mixed solution, measuring the change of ultraviolet-visible absorption intensity within the range of 400-800nm, substituting the absorbance ratio at 525nm and 650nm into the graph 3, and performing comparison calculation to obtain Cs in the solution to be detected + And (4) concentration.
Example 3 Cs in oilfield Water samples, subsurface brine, subsea sediments + Detection of (2)
(1) Preparing a detection solution: adding 5mL of 5mM chloroauric acid solution into 91mL of ultrapure water, adding 4mL of 1% sodium citrate solution serving as a reducing agent under the conditions of stirring and heating to boiling, and reacting for 15min to obtain a gold nanoparticle solution modified by citrate; and preparing a prussian blue solution.
(2) Collecting a water sample to be detected: collecting water samples in three different places of an oil field, underground brine and submarine sediments by using a water sample collecting bottle, adjusting the pH of the water sample of the obtained mixed solution to 6-7 by using hydrochloric acid or sodium hydroxide (depending on the pH value of a detection solution sample) so as to prevent impurities from influencing the detection effect, filtering the water sample by using filter paper, and obtaining filtrate which is the water sample to be detected.
(3) And (3) adjusting the pH of the gold nanoparticle detection solution prepared in the step (1) to 6.5 by using 0.05mol/L HCl aqueous solution to serve as a detection solution sample.
(4) Two test tubes A and B of the same specification were prepared, and the same volume (0.9mL) of the test solution sample was added to each of the test tubes A and B.
(5) Adding ultrapure water and a water sample to be detected which are equal in volume (0.1mL) into the test tube A and the test tube B respectively, mixing uniformly, and then adding the prussian blue solution (10uL) prepared in the step (1). The color change of the aqueous solution in the test tube A and the test tube B was observed.
And (3) detection results: within 20 minutes, if the color of the aqueous solution in the test tube B changes (turns red) relative to the aqueous solution in the test tube A, the Cs in the water sample to be detected is judged + And the concentration is greater than or equal to 3 x 10 -5 mol/L；
If the color of the aqueous solution in the test tube B relative to the aqueous solution in the test tube A does not change, determining that the Cs in the water sample to be detected is the same as the color of the aqueous solution in the test tube B + The concentration is less than 3 × 10 -5 mol/L。
Performing ultraviolet-visible light absorption spectrum measurement on the detection mixed solution, measuring the change of ultraviolet-visible absorption intensity within the range of 400-800nm, substituting the absorbance ratio at 525nm and 650nm into the graph 3, and performing comparison calculation to obtain Cs in the solution to be detected + And (4) concentration.
Example 4 simulation of Cs in brine, Low-concentration brine, Szechwan underground brine samples + Detection of (2)
(1) Preparing a detection solution: adding 5mL of 5mM chloroauric acid solution into 91mL of ultrapure water, adding 4mL of 1% sodium citrate solution serving as a reducing agent under the conditions of stirring and heating to boiling, and reacting for 15min to obtain a gold nanoparticle solution modified by citrate; and preparing a prussian blue solution.
(2) Collecting a water sample to be detected: collecting brine, low-concentration brine and Sichuan underground brine water samples by using a water sample collecting bottle, adjusting the pH of the water sample to 6-7 by using hydrochloric acid or sodium hydroxide (depending on the pH value of a detection liquid sample) in the obtained mixed solution so as to prevent impurities from influencing the detection effect, filtering the water sample by using filter paper, and obtaining filtrate which is the water sample to be detected.
(3) And (3) adjusting the pH of the gold nanoparticle detection solution prepared in the step (1) to 6.5 by using 0.05mol/L HCl aqueous solution to serve as a detection solution sample.
(4) Two test tubes A and B of the same specification were prepared, and the same volume (0.9mL) of the test solution sample was added to each of the test tubes A and B.
(5) Adding ultrapure water and a water sample to be detected which are equal in volume (0.1mL) into the test tube A and the test tube B respectively, mixing uniformly, and then adding the prussian blue solution (10uL) prepared in the step (1). The color change of the aqueous solution in the test tube A and the test tube B was observed.
And (3) detection results: within 20 minutes, if the color of the aqueous solution in the test tube B changes (turns red) relative to the aqueous solution in the test tube A, the Cs in the water sample to be detected is judged + And the concentration is greater than or equal to 3 x 10 -5 mol/L；
If the color of the aqueous solution in the test tube B relative to the aqueous solution in the test tube A does not change, determining that the Cs in the water sample to be detected is the same as the color of the aqueous solution in the test tube B + The concentration is less than 3 × 10 -5 mol/L。
Measuring the ultraviolet-visible absorption spectrum of the detection mixed solution, measuring the change of the ultraviolet-visible absorption intensity within the range of 400-800nm, substituting the absorbance ratio at the position of 525nm and the position of 650nm into the graph 3, and performing comparison calculation to obtain the Cs in the solution to be detected + And (4) concentration.
And within 20 minutes, if the color of the solution in the test tube containing the sample to be detected is observed to change relative to the blank control solution, and the color of the solution in the test tube containing the sample to be detected is changed to red or deep red relative to the blank control solution, judging that the sample to be detected contains Cs + And at a concentration of 3X 10 or more -5 mol/L。
If the color of the solution in the test tube containing the sample to be detected is not changed relative to the blank control solution at 20 minutes, the sample to be detected is judged to contain no Cs + Or at a concentration of less than 3X 10 -5 mol/L。
Example 5 Cs in Natural seawater sample + Detection of (2)
(1) Preparing a detection solution: adding 5mL of 5mM chloroauric acid solution into 91mL of ultrapure water, adding 4mL of 1% sodium citrate solution serving as a reducing agent under the conditions of stirring and heating to boiling, and reacting for 15min to obtain a citrate modified gold nanoparticle solution; and preparing a methyl blue solution.
(2) Collecting a water sample to be detected: collecting a natural seawater sample by using a water sample collecting bottle, adjusting the pH value of the water sample of the obtained mixed solution to 6-7 by using hydrochloric acid or sodium hydroxide (depending on the pH value of a detection solution sample) so as to prevent impurities from influencing the detection effect, filtering the water sample by using filter paper, and obtaining filtrate as the water sample to be detected.
(3) And (3) adjusting the pH of the gold nanoparticle detection solution prepared in the step (1) to 6.5 by using 0.05mol/L HCl aqueous solution to serve as a detection solution sample.
(4) Two test tubes A and B of the same specification were prepared, and the same volume (0.9mL) of the test solution sample was added to each of the test tubes A and B.
(5) Adding ultrapure water and a water sample to be detected in equal volume (0.1mL) into the test tube A and the test tube B respectively, mixing uniformly, and adding the methyl blue solution (10uL) prepared in the step (1). The color change of the aqueous solution in test tubes A and B was observed.
And (3) detection results: within 20 minutes, if the color of the aqueous solution in the test tube B changes (turns red) relative to the aqueous solution in the test tube A, the Cs in the water sample to be detected is judged + And the concentration is greater than or equal to 3X 10 -5 mol/L；
If the color of the aqueous solution in the test tube B relative to the aqueous solution in the test tube A does not change, judging that the Cs in the water sample to be detected + The concentration is less than 3 × 10 -5 mol/L。
Measuring the ultraviolet-visible absorption spectrum of the detection mixed solution, measuring the change of the ultraviolet-visible absorption intensity within the range of 400-800nm, substituting the absorbance ratio of 525nm and 650nm into the graph 3 for comparison calculation to obtain the Cs in the solution to be detected + And (4) concentration.
The results show that in each example, the concentration of the sample that did not change color was less than 3X 10 -5 And mol/L indicates that the detection result of the semi-quantitative method is reliable. The concentration of cesium ions in the sample can be further accurately determined by a standard curve calculation methodAnd (4) realizing quantitative detection.
When the minimum acceptable concentration of the sample water sample is more than or equal to 3 multiplied by 10 -5 And when the concentration is mol/L, the color comparison can be carried out by naked eyes, so that whether the cesium ions in the sample water meet the standard or not can be conveniently judged. When the minimum acceptable concentration of the sample water sample is less than 3 multiplied by 10 -5 When the mol/L is higher than the standard, the reagent can be used for analyzing by combining a spectroscopic instrument to judge whether the cesium ions in the sample water meet the standard or not so as to obtain the concentration of the sample. When quantitative analysis is required, the concentration of the sample can be obtained by combining the analysis of a spectroscopic instrument.
The reagent provided by the invention can be used for determining cesium ion-containing water samples from various sources, cannot be interfered by impurities in the water samples, and can accurately and quantitatively determine the concentration of cesium ions in the water samples. Therefore, the reagent has great application value.
Although the present invention has been described with reference to a few preferred embodiments, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (18)
1. A combination of reagents for the detection of cesium ions, comprising:
component (a): the reagent component is used for forming the gold nanoparticle solution modified by the citrate ions;
a component (b): a ligand solution, or a reagent component for forming the ligand solution; the ligand solution is selected from Prussian blue solution;
the prussian blue solution contains potassium ions.
2. The cesium ion detection reagent combination according to claim 1, wherein the pH of the gold nanoparticle solution modified with citrate ions is = 5-9.
3. The cesium ion detection reagent combination according to claim 2, wherein the pH of the gold nanoparticle solution modified with citrate ions is = 6-8.
4. The cesium ion detection reagent combination according to claim 3, wherein the pH of the solution containing citrate ion-modified gold nanoparticles is = 6.5-7.5.
5. The cesium ion detection reagent combination according to claim 1, wherein the concentration of gold nanoparticles in the gold nanoparticle solution modified with citrate ions is 2.5 nM-100 nM.
6. The cesium ion detection reagent combination according to claim 5, wherein the concentration of gold nanoparticles in the citrate ion modified gold nanoparticle solution is 10 nM-40 nM.
7. The cesium ion detection reagent combination according to claim 1, wherein the concentration of the ligand in the ligand solution is 0.1-0.15M.
8. The cesium ion detection reagent combination according to claim 1, wherein the reagent components for forming the citrate ion modified gold nanoparticle-containing solution in component (a) comprise:
(i) gold nanoparticle precursors;
(ii) a reducing agent; and
(iii) and (4) a protective agent.
9. The cesium ion detection reagent combination according to claim 1, further comprising: a pH regulator.
10. A cesium ion detection kit comprising the cesium ion detection reagent combination according to any one of claims 1 to 9.
11. A method for detecting cesium ions, characterized in that detection is performed using the combination of detection reagents for cesium ions according to any one of claims 1 to 9 or the kit according to claim 10.
12. The method of claim 11, wherein the method comprises:
(s1) providing a sample solution to be tested;
(s2) obtaining a gold nanoparticle solution modified by citrate ions;
(s3) mixing the sample solution to be detected with the citrate ion modified gold nanoparticle solution and a ligand solution to form a detection mixed solution;
(s4) detecting the spectroscopic characteristics of said test mixture, thereby obtaining a test result.
13. The method of claim 12, further comprising: and adjusting the pH of the gold nanoparticle solution modified by the citrate ions and/or the pH of the sample solution to be detected by using a pH regulator.
14. The method of claim 12, wherein the spectroscopic characteristics are selected from at least one of color, visible light absorption intensity, absorption spectrum peak.
15. The method of claim 14, further comprising: and observing the color of the detection mixed solution by naked eyes.
16. The method of claim 15, further comprising: instrumental analysis was performed to detect spectroscopic characteristics of the test mixture.
17. The method of claim 16, further comprising: and providing a control mixed liquor, and judging whether cesium ions exist in the sample to be detected and/or the content of the cesium ions in the sample by comparing the spectroscopic characteristics of the detection mixed liquor and the control mixed liquor.
18. The combination of detection reagents for cesium ions of any one of claims 1 to 9 and/or the kit of claim 10 and/or the method for detecting cesium ions of any one of claims 11 to 17 is used for cesium ion detection in an aqueous system.
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