CN113049573B - Rubidium or cesium ion detection reagent combination, kit and detection method - Google Patents
Rubidium or cesium ion detection reagent combination, kit and detection method Download PDFInfo
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- CN113049573B CN113049573B CN201911382141.3A CN201911382141A CN113049573B CN 113049573 B CN113049573 B CN 113049573B CN 201911382141 A CN201911382141 A CN 201911382141A CN 113049573 B CN113049573 B CN 113049573B
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- 238000001514 detection method Methods 0.000 title claims abstract description 116
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052701 rubidium Inorganic materials 0.000 title claims abstract description 66
- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 37
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 80
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000010931 gold Substances 0.000 claims abstract description 65
- 229910052737 gold Inorganic materials 0.000 claims abstract description 65
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 54
- -1 cesium ions Chemical class 0.000 claims abstract description 51
- 239000003446 ligand Substances 0.000 claims abstract description 47
- 239000003607 modifier Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 34
- JKCQOMAQPUYHPL-UHFFFAOYSA-N dibenzo-21-crown-7 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 JKCQOMAQPUYHPL-UHFFFAOYSA-N 0.000 claims abstract description 17
- DZWYQRMUCPSDQK-UHFFFAOYSA-N 2,5,8,11,14,17,20-heptaoxabicyclo[19.4.0]pentacosa-1(25),21,23-triene Chemical compound O1CCOCCOCCOCCOCCOCCOC2=CC=CC=C21 DZWYQRMUCPSDQK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004458 analytical method Methods 0.000 claims abstract description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 191
- 239000000523 sample Substances 0.000 claims description 70
- 238000012360 testing method Methods 0.000 claims description 55
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 54
- 239000011259 mixed solution Substances 0.000 claims description 47
- QPOZGXKWWKLJDK-UHFFFAOYSA-N 6-nitro-3h-1,3-benzothiazole-2-thione Chemical compound [O-][N+](=O)C1=CC=C2NC(=S)SC2=C1 QPOZGXKWWKLJDK-UHFFFAOYSA-N 0.000 claims description 22
- 239000003638 chemical reducing agent Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 150000002343 gold Chemical class 0.000 claims description 12
- 238000000862 absorption spectrum Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000012488 sample solution Substances 0.000 claims description 11
- 239000012279 sodium borohydride Substances 0.000 claims description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 230000031700 light absorption Effects 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 5
- AUVSUPMVIZXUOG-UHFFFAOYSA-N (4-sulfanylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(S)C=C1 AUVSUPMVIZXUOG-UHFFFAOYSA-N 0.000 claims description 4
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000009825 accumulation Methods 0.000 claims description 2
- 238000010668 complexation reaction Methods 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims 1
- 238000010998 test method Methods 0.000 claims 1
- 238000004737 colorimetric analysis Methods 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 41
- 239000007864 aqueous solution Substances 0.000 description 17
- 229910001419 rubidium ion Inorganic materials 0.000 description 17
- 238000002835 absorbance Methods 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 15
- 229910021642 ultra pure water Inorganic materials 0.000 description 14
- 239000012498 ultrapure water Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- 239000012267 brine Substances 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000012496 blank sample Substances 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 238000004611 spectroscopical analysis Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004442 gravimetric analysis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 238000009614 chemical analysis method Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 229910001417 caesium ion Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PFAGKWKLTYQJPZ-UHFFFAOYSA-K gold(3+) trichlorite Chemical compound [Au+3].Cl(=O)[O-].Cl(=O)[O-].Cl(=O)[O-] PFAGKWKLTYQJPZ-UHFFFAOYSA-K 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003297 rubidium Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- XZPVPNZTYPUODG-UHFFFAOYSA-M sodium;chloride;dihydrate Chemical compound O.O.[Na+].[Cl-] XZPVPNZTYPUODG-UHFFFAOYSA-M 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
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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
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1813—Specific cations in water, e.g. heavy metals
-
- 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
- G01N2021/775—Indicator and selective membrane
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Abstract
The application discloses a rubidium or cesium ion detection reagent combination, a kit and a detection method, wherein the detection reagent combination comprises a component (a): the gold nanoparticle solution modified by the modifier or the reagent component for forming the gold nanoparticle solution modified by the modifier, wherein the modifier is a sulfydryl compound containing a benzene ring; a component (b): a ligand solution, or a reagent component for forming the ligand solution; the ligand solution is at least one selected from dibenzo-21-crown ether-7 solution, dialkyl dibenzo-21-crown-7 solution and benzo-21-crown-7 solution. The rubidium or cesium ion detection method provided by the application only adopts naked eye colorimetry, namely, the rubidium or cesium ion detection method and the naked eye colorimetry can reach minimum 1 × 10 ‑5 Lower limit of detection of mol/L; the method provided by the invention can be combined with an instrument analysis means, can also detect rubidium or cesium ions with lower concentration, and has very high sensitivity.
Description
Technical Field
The application relates to a rubidium or cesium ion detection reagent and a detection method thereof, belonging to the field of heavy dilute alkali metal ion detection.
Background
Rubidium and cesium are extremely important rare noble metal elements, and the electrical conductivity and the thermal conductivity of the rubidium and cesium are the best of all the known materials at present. Cesium and rubidium have excellent photovoltaic properties and are the best materials for manufacturing phototubes, photovoltaic cells and also essential materials for infrared technology. China has abundant rubidium and cesium resources, complete types and is distributed nationwide. Salt lake brine in Qinghai and Tibet contains abundant rubidium and cesium, and is a future rubidium and cesium resource in China to be developed.
The method for detecting rubidium or cesium ions in salt lake brine mainly comprises a chemical analysis method and an instrument analysis method. The chemical analysis methods include gravimetric analysis and volumetric analysis. Rubidium or cesium ions have no obvious complexing ability, so that the method is not suitable for a capacity analysis method, but a multi-purpose gravimetric analysis method is adopted, but the detection of three ions of potassium, rubidium and cesium in the gravimetric analysis method can interfere with each other. The instrumental analysis method includes atomic absorption spectrometry, atomic emission spectrometry, inductively coupled plasma mass spectrometry, X-ray fluorescence spectrometry, electrochemical analysis, flame spectrophotometry, and the like. Instrumental assays generally suffer from the disadvantages of high detection cost, time consumption and complex operation.
The colorimetric detection method for the noble metal nanoparticles has the advantages of high sensitivity, good selectivity, simplicity in operation, rapidness in reaction and the like, is widely researched and applied by people, and is applied to rapid colorimetric detection of heavy metal ions, organic small molecules, DNA, inorganic anions and the like at present.
In conclusion, it is necessary to develop a rapid, timely and simple detection method for rubidium or cesium ions, and on one hand, whether a certain salt lake has development and utilization values can be rapidly judged; on the other hand, after rubidium or cesium ions are adsorbed, the degree of desorption of rubidium or cesium ions can be rapidly judged by a colorimetric method.
Disclosure of Invention
According to one aspect of the present invention, there is provided a reagent combination for detecting rubidium or cesium ions, which can detect rubidium or cesium ions at a low concentration in an aqueous solution quickly, in time, in a real-time manner, and easily.
The rubidium or cesium ion detection reagent combination comprises:
component (a): the gold nanoparticle solution modified by the modifier or the reagent component for forming the gold nanoparticle solution modified by the modifier, wherein the modifier is a sulfydryl compound containing a benzene ring;
a component (b): a ligand solution, or a reagent component for forming the ligand solution; the ligand solution is at least one selected from dibenzo-21-crown ether-7 solution, dialkyl dibenzo-21-crown-7 solution and benzo-21-crown-7 solution.
The ligand solution has selective complexation effect on rubidium or cesium ions, and the molecular structure of the ligand solution contains benzene rings which can be gathered together with the benzene rings on the 2-mercapto-6-nitrobenzothiazole attached to the surface of the gold nanoparticles through pi-pi accumulation effect.
Optionally, the reagent component for forming the modifier-modified gold nanoparticle solution in component (a) comprises:
(i) gold nanoparticle precursors;
(ii) a reducing agent; and
(iii) a modifier.
Optionally, the gold nanoparticle precursor is a soluble gold salt.
Optionally, the gold nanoparticle precursor is selected from at least one of gold chloride, gold chlorite, potassium chloroaurate and sodium chloroaurate.
Optionally, the reducing agent is at least one of sodium borohydride, potassium borohydride, citric acid and citrate, preferably sodium borohydride; the modifier is at least one of 2-mercapto-6-nitrobenzothiazole, 4-mercaptobenzoic acid and 4-mercaptophenylboronic acid;
alternatively, the modifier-modified gold nanoparticle solution is prepared by the following steps:
providing an aqueous solution in which the gold nanoparticle precursor is dissolved;
adding the reducing agent into the aqueous solution to obtain a gold nanoparticle solution;
optionally, adding the reducing agent to the gold nanoparticle solution under stirring; the stirring speed is preferably 500-900 r/min;
and adding the solution containing the modifier into the gold nanoparticle solution according to a certain proportion, uniformly stirring, and reacting for 20-30 minutes. Optionally, the molar concentration of the gold nanoparticle solution is 0.4-1 mM, the molar concentration of the solution containing the modifier is 0.2-0.8 mM, and the volume ratio of the gold nanoparticle solution to the solution containing the modifier is 1000: 1-2000: 1.
optionally, the concentration of gold nanoparticles in the gold nanoparticle solution modified by the modifier is 0.4-1 mM based on the molar amount of gold element; the solvent in the ligand solution can be at least one selected from DMF, pyridine and formic acid, and the concentration of the ligand in the ligand solution is 100-300 mu M. The volume ratio of the gold nanoparticle solution to the ligand solution is 6-10: 1.
Optionally, the detection reagent combination further comprises 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.
According to a second aspect of the present application, there is provided a rubidium or cesium ion detection kit comprising at least one of the rubidium or cesium ion detection reagent combinations described in any one of the above.
Optionally, the kit comprises:
component (a): the gold nanoparticle solution modified by the modifier or the reagent component for forming the gold nanoparticle solution modified by the modifier, wherein the modifier is a sulfydryl compound containing a benzene ring;
optional component (b): a ligand solution, or a reagent component for forming the ligand solution; the ligand solution is at least one selected from dibenzo-21-crown ether-7 solution, dialkyl dibenzo-21-crown-7 solution and benzo-21-crown-7 solution; and
instructions describing a method for detecting rubidium or cesium ions by using components (a) and (b).
Optionally, the reagent composition comprises:
(i) gold nanoparticle precursors;
(ii) a reducing agent; and
(iv) optionally (iii) a modifying agent.
Optionally, the ligand solution is selected from at least one of dibenzo-21-crown-7 solution, dialkyl dibenzo-21-crown-7 solution and benzo-21-crown-7 solution.
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, potassium chloroaurate and sodium chloroaurate.
Optionally, the reducing agent is at least one of sodium borohydride, potassium borohydride, citric acid and citrate, preferably sodium borohydride; the modifier is at least one of 2-mercapto-6-nitrobenzothiazole, 4-mercaptobenzoic acid and 4-mercaptophenylboronic acid;
alternatively, the modifier-modified gold nanoparticle solution is prepared by the following steps:
providing an aqueous solution in which the gold nanoparticle precursor is dissolved;
adding the reducing agent into the aqueous solution to obtain a gold nanoparticle solution;
adding the reducing agent into the gold nanoparticle solution under the condition of stirring; the stirring speed is preferably 500-900 r/min;
and adding the solution containing the modifier into the gold nanoparticle solution according to a certain proportion, uniformly stirring, and reacting for 20-30 minutes. Optionally, the molar concentration of the gold nanoparticle solution is 0.4-1 mM, the molar concentration of the solution containing the modifier is 0.2-0.8 mM, and the volume ratio of the gold nanoparticle solution to the solution containing the modifier is 1000: 1-2000: 1.
optionally, the concentration of gold nanoparticles in the gold nanoparticle solution modified by the modifier is 0.4-1 mM based on the molar amount of gold element; the solvent in the ligand solution can be at least one selected from DMF, pyridine and formic acid, and the concentration of the ligand in the ligand solution is 100-300 mu M.
Optionally, the detection reagent combination further comprises 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.
According to a third aspect of the present application, there is provided a use of a combination of reagents for the detection of rubidium or caesium ions, comprising:
component (a): the gold nanoparticle solution modified by the modifier or the reagent component for forming the gold nanoparticle solution modified by the modifier, wherein the modifier is a sulfydryl compound containing a benzene ring;
a component (b): a ligand solution, or a reagent component for forming the ligand solution; the ligand solution is at least one selected from dibenzo-21-crown ether-7 solution, dialkyl dibenzo-21-crown-7 solution and benzo-21-crown-7 solution;
and the reagent combination is used for preparing a kit or reagent for detecting rubidium or cesium ions.
According to a fourth aspect of the present application, there is provided a method for detecting rubidium or cesium ions, wherein the detection is performed by using at least one of the reagent combination for detecting rubidium or cesium ions and the kit.
Optionally, the method comprises:
(s1) providing a sample solution to be tested;
(s2) obtaining a modifier-modified gold nanoparticle solution;
(s3) mixing the sample solution to be detected with the gold nanoparticle solution modified by the modifier and the ligand solution to form a detection mixed solution;
(s4) detecting a spectroscopic characteristic of said detection mixture, thereby obtaining a measurement;
optionally, the method further comprises: and adjusting the pH value of the sample solution to be detected to be 5-7 and/or adjusting the pH value of the detection mixed solution to be 1-4 by adopting a pH regulator.
Optionally, in the step (s3), mixing the sample solution to be detected with a ligand solution, and then mixing with the modifier-modified gold nanoparticle solution to form a detection mixed solution;
optionally, the spectroscopic feature is selected from at least one of color, visible light absorption intensity, absorption spectrum peak;
preferably, the method further comprises: observing the color of the detection mixed solution by naked eyes;
preferably, the method further comprises: instrumentally detecting spectroscopic characteristics of said test mixture;
optionally, the instrumental analysis method is selected from: spectrophotometric detection, ultraviolet-visible absorption spectroscopy.
Preferably, the method further comprises: and providing a control mixed liquid, and judging whether rubidium or cesium ions exist in the sample to be detected and/or the content of the rubidium or cesium ions in the sample by comparing the spectroscopic characteristics of the detection mixed liquid and the control mixed liquid.
Optionally, the method further comprises: and adjusting the pH value of the detection mixed solution to 1-4 by using a pH regulator.
As an embodiment, the method comprises the steps of:
and comparing the detection mixed solution with a standard sample, and judging whether rubidium or cesium ions exist in the sample to be detected and/or judging the concentration of the rubidium or 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 calibration curve is prepared by the following steps:
(I) providing a plurality of rubidium ion aqueous solutions with different concentrations, adding the ligand solution and the modifier modified gold nanoparticle solution into the aqueous solutions, and adjusting the pH value to obtain corresponding rubidium ion standard samples with known concentrations;
replacing rubidium ions with cesium ions, and obtaining corresponding cesium ion standard samples with known concentrations by the same method;
adding the ligand solution and the gold nanoparticle solution modified by the modifier into ultrapure water, and adjusting the pH value to obtain a blank sample;
(II) measuring spectroscopic characteristic parameters of each standard sample;
(III) drawing a 'spectroscopy characteristic parameter-rubidium ion concentration' curve of a standard sample and a 'spectroscopy characteristic parameter-cesium ion concentration' curve of the standard sample, or drawing a 'visible light relative absorption value-rubidium ion concentration' map and a 'visible light relative absorption value-cesium ion concentration' map as standard maps;
in a preferred embodiment of the present invention, the concentration of each of the known cesium ions or rubidium ions is taken as an abscissa (X), and the absorbance ratio (a) of a mixed solution containing rubidium ions/cesium ions at different concentrations is taken as an abscissa 650 /A 520 ) Absorbance ratio to blank (A) 0 650 /A 0 520 ) Relative value of (A) 650 /A 520 -A 0 650 /A 0 520 )/(A 0 650 /A 0 520 ) As the ordinate (Y), a scatter diagram was obtained, and the linear relationship between the two was calculated. The results of an exemplary embodiment are shown in FIG. 2a (Rb) + ) And FIG. 2b (Cs) + )。
When measuring a detection solution with unknown concentration, the absorbance ratio (A) of a mixed solution containing rubidium/cesium ions with each concentration is used 650 /A 520 ) Absorbance ratio to blank (A) 0 650 /A 0 520 ) Relative value of (A) 650 /A 520 -A 0 650 /A 0 520 )/(A 0 650 /A 0 520 ) Substituting into FIG. 2a (Rb) + ) And FIG. 2b (Cs) + ) In the formula Y, the concentration of rubidium/cesium ions can be obtained.
In another preferred embodiment, the UV-visible absorption spectrum is measured at 300-850nm, preferably at 400-750 nm.
Alternatively, the UV-VIS absorption spectrum is measured at wavelengths of 520nm and 650 nm.
Optionally, the sample solution to be tested 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, industrial wastewater, or a combination thereof.
According to a fifth aspect of the present application, there is provided any one of the rubidium or cesium ion detection reagent combination, the kit, and the method for detecting rubidium or cesium ion, which are used for rubidium or cesium ion detection in an aqueous solution system.
Optionally, the aqueous system is a solution prepared from a sample selected from the group consisting of: an environmental water sample, a salt lake water sample, a solid environmental sample, a food, industrial wastewater, or a combination thereof.
In the invention, when specific ions (rubidium ions or cesium ions) contained in a sample to be tested are known, the content of the contained ions can be determined by the reagent combination, the kit or the testing method provided by the invention.
Benefits that can be produced by the present application include, but are not limited to:
1) according to the method for detecting rubidium or cesium ions in the aqueous solution, the change of the color of the solution is directly judged through naked eyes to realize semi-quantitative detection of the rubidium or cesium ions in the solution, and the content of the rubidium or cesium ions in the solution system can be rapidly detected through simple instruments.
2) The rubidium and cesium ion detection method provided by the application only adopts naked eye colorimetry, namely, both rubidium and cesium ions can reach minimum 1 × 10 -5 Lower limit of detection of mol/L; the method provided by the invention can be combined with an instrument analysis means, can also detect rubidium or cesium ions with lower concentration, and has very high sensitivity.
3) The detection method provided by the application is simple and convenient to operate, rapid, high in sensitivity and capable of being operated on site, and on one hand, whether a certain salt lake has development and utilization values or not can be rapidly judged; on the other hand, after rubidium or cesium ions are adsorbed, the degree of desorption of rubidium or cesium ions can be rapidly judged by a colorimetric method.
Drawings
Fig. 1a is a colorimetric detection result chart of a detection mixed solution containing rubidium ions with different concentrations in the present application.
FIG. 1b is a chart showing the colorimetric detection results of the detection mixture containing cesium ions at different concentrations in the present application.
Fig. 2a is a graph showing a standard curve of visible light absorption relative value-rubidium ion concentration obtained by detecting standard mixed liquid according to the present application.
FIG. 2b is a graph showing the relative value of visible light absorption versus the standard curve of cesium ion concentration obtained by testing the standard mixed solution according to the present application.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
Wherein the 2-mercapto-6-nitrobenzothiazole is purchased from Aladdin reagent (Shanghai) Co., Ltd, and the dibenzo-21-crown-7, the dialkyl dibenzo-21-crown-7 and the benzo-21-crown-7 are purchased from Hiziai (Shanghai) Industrial development Co., Ltd;
the analytical methods in the examples of the present application are as follows:
the absorbance detection analysis is carried out by using an ultraviolet-visible spectrophotometer (model T10 CS) provided by Beijing Pujingyo general instruments Ltd of China. (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 300-900 nm)
The application provides rubidium, detection reagent combination of cesium ion includes:
component (a): 2-mercapto-6-nitrobenzothiazole modified gold nanoparticle solution;
a component (b): a ligand solution, or a reagent component for forming the ligand solution; the ligand solution is at least one selected from dibenzo-21-crown ether-7 solution, dialkyl dibenzo-21-crown-7 solution and benzo-21-crown-7 solution.
The application provides a rubidium and cesium ion detection kit, which comprises at least one of the reagent combinations.
The application provides a method for detecting rubidium and cesium ions, which adopts the reagent combination or the kit to detect.
As an embodiment, the method comprises:
(s1) providing a sample solution to be tested;
(s2) mixing the sample solution to be detected with the ligand solution and the gold nanoparticle solution modified by 2-mercapto-6-nitrobenzothiazole, and adjusting the pH value 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 solution with a standard sample, and judging whether rubidium ions and cesium ions exist in the sample to be detected and/or judging the concentration of the rubidium ions and 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 calibration curve is prepared by the following steps:
(I) providing a plurality of rubidium and cesium ion aqueous solutions with different concentrations, adding the gold nanoparticle solution and the ligand solution into the solutions, and adjusting the pH value to obtain corresponding rubidium ion standard samples and cesium ion standard samples with known concentrations;
adding the ligand solution and the gold nanoparticle solution modified by 2-mercapto-6-nitrobenzothiazole into ultrapure water, and adjusting the pH value to obtain a blank sample;
(II) measuring spectroscopic characteristic parameters of each standard sample;
(III) drawing a 'spectroscopy characteristic parameter-rubidium ion concentration' curve of a standard sample and a 'spectroscopy characteristic parameter-cesium ion concentration' curve of the standard sample, or drawing a 'relative ultraviolet visible light absorption value-rubidium ion concentration' map and a 'relative ultraviolet visible light absorption value-cesium ion concentration' map as standard maps;
in a preferred embodiment of the present invention, the concentration of each of the known rubidium/cesium ions is taken as an abscissa (X), and the relational expression (a) between the absorbance of a mixed solution containing rubidium/cesium ions at different concentrations and the absorbance of a blank sample is taken 650 /A 520 -A 0 650 /A 0 520 )/(A 0 650 /A 0 520 ) The calculated value of (2) is the ordinate (Y), a scatter diagram of the two is obtained, and the linear relation of the two is calculated. The results of an exemplary embodiment are shown in FIG. 2a (Rb) + ) And FIG. 2b (Cs) + )。
When measuring a detection solution of unknown concentration, the relationship between the absorbance of a mixed solution containing rubidium/cesium ions of each concentration and the absorbance of a blank sample is expressed (A) 650 /A 520 -A 0 650 /A 0 520 )/(A 0 650 /A 0 520 ) Substituted into FIG. 2a (Rb) + ) FIG. 2b (Cs) + ) The concentration of rubidium/cesium ions can be obtained from the formula Y.
Optionally, the UV-visible absorption spectrum is measured at a wavelength of 300-850nm, preferably at a wavelength of 400-750 nm.
Optionally, the UV-VIS spectral absorption is measured at wavelengths of 520nm and 650 nm.
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 sodium borohydride serving as a reducing agent under the stirring condition, reacting for a period of time to obtain a gold nanoparticle solution, then adding a modifier 2-mercapto-6-nitrobenzothiazole, stirring for a period of time, and storing in a refrigerator at 4 ℃; and preparing ligand solution with certain concentration.
(2) Respectively adding the same volume of ligand solution into the same amount of ultrapure water and the solution to be detected (containing rubidium/cesium) to form a first mixed solution and a second mixed solution;
(3) and (3) adding the same amount of the gold nanoparticle solution modified by the 2-mercapto-6-nitrobenzothiazole in the step (1) into the first mixed solution and the second mixed solution in the step (2), and adjusting the pH to 1-4 to respectively form a third mixed solution and a fourth mixed solution. And comparing the color or the change of the ultraviolet-visible absorption intensity and the peak value of the third mixed solution and the fourth mixed solution, and judging whether rubidium ions and cesium ions exist in the detected solution.
In the above detection process, the third detection mixture (no Rb) + 、Cs + ) Is wine red, and when the color of the fourth detection mixed solution (containing rubidium/cesium) is changed into purple or deep blue relative to the color of the third detection mixed solution, the Rb contained in the sample to be detected is judged + /Cs + And Rb is + /Cs + Is greater than or equal to 1X 10 -5 mol/L. If no color change occurs, the sample to be tested does not necessarily contain Rb + /Cs + . Further measuring the spectral data of the detection mixed solution which is not discolored, thereby further determining whether Rb exists in the sample to be detected + /Cs + 。
Optionally, provision is made to reflect Rb in an aqueous solution + /Cs + Comparing the ultraviolet-visible absorption intensity of the fourth mixed solution obtained by the method with the standard curve graph of the relation between the concentration and the ultraviolet-visible absorption intensity to obtain the Rb in the fourth mixed solution + /Cs + The concentration of (c). The specific drawing method of the standard curve chart is as follows:
preparing a series of Rb containing different compounds according to the preparation method of the fourth mixed solution + /Cs + Scanning the ultraviolet-visible absorption intensity of the standard mixed solution with the concentration within the wavelength range of 400-750nm, taking the numerical relation of the ultraviolet-visible absorption intensity of the mixed solution as a vertical coordinate, and taking Rb contained in the mixed solution as the vertical coordinate + /Cs + The concentration is plotted on the abscissa, i.e. a standard curve is obtained, as shown in fig. 2a and 2 b. Drawing a Standard Curve for Rb to be determined + Respectively in a concentration of0μM、0.5μM、2μM、5μM、10μM、20μM、40μM、50μM，Cs + Concentrations of 0. mu.M, 0.5. mu.M, 2. mu.M, 5. mu.M, 20. mu.M, 30. mu.M, 40. mu.M, 50. mu.M, respectively, were then adjusted to (A) 650 /A 520 -A 0 650 /A 0 520 )/(A 0 650 /A 0 520 ) Value is ordinate, Rb + /Cs + And (4) drawing a scatter diagram with the concentration as a horizontal coordinate, and fitting to obtain a standard curve.
Through experiments, the standard curve graph is drawn along with Rb + /Cs + The detection wavelengths of the ultraviolet-visible absorption intensity at the increased concentration are preferably 520nm and 650 nm.
In the technical scheme, the reaction time is 10 minutes; the detected aqueous solution can be a water sample in the environment, such as river water, lake water, underground brine, seawater and the like; can be solution formed by dissolving other environmental samples in water, such as gaseous environmental samples, solid environmental samples, urine in biomedicine, blood and the like; the method can be used for detecting various water samples such as water quality investigation of lakes and rivers, water quality detection of sewage outfalls, domestic water, enterprise pollution discharge self-detection and the like.
Alternatively, in the step (3), the pH of the resulting mixture is adjusted, and HCl is added to the system in a volume of 50. mu.L-70. mu.L at a concentration of 0.2M. For alkaline detection systems, strong acids are preferred, and the pH is preferably adjusted with hydrochloric acid; for acidic detection systems, strong bases are preferred, and pH adjustment with sodium hydroxide and/or potassium hydroxide solutions is particularly preferred.
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 15mL of 5mM chloroauric acid solution into 100mL of ultrapure water, adding 3.75mL of 0.1M sodium borohydride solution serving as a reducing agent under the condition of stirring, reacting for 30min, preparing a gold nanoparticle solution, and adding 8 mu L of freshly prepared DMF (dimethyl formamide) solution of 2-mercapto-6-nitrobenzothiazole with the concentration of 0.5mM per 10mL of gold nanoparticle solution to prepare a 2-mercapto-6-nitrobenzothiazole modified gold nanoparticle solution with the pH value of 5-7;
preparing a dibenzo-21-crown ether-7 solution with the concentration of 200 mu M, wherein a solvent is DMF;
(2) preparing a standard sample: formulating a series of Rb with ultrapure water and a rubidium salt + A series of Cs were prepared in the order of 0. mu.M, 5. mu.M, 20. mu.M, 50. mu.M, 100. mu.M, 200. mu.M, 300. mu.M, 400. mu.M and 500. mu.M in standard solutions, using ultrapure water and cesium salt + The concentrations were 0. mu.M, 5. mu.M, 20. mu.M, 50. mu.M, 100. mu.M, 200. mu.M, 300. mu.M, 400. mu.M and 500. mu.M in this order.
Respectively taking 0.1mL of standard solutions with different concentrations, respectively adding 0.08mL of dibenzo-21-crown ether-7 solution prepared in the step (1), mixing for 5 minutes, respectively adding 0.74mL of 2-mercapto-6-nitrobenzothiazole modified gold nanoparticle solution prepared in the step (1), adding 0.2M 60 mu L of HCl, and standing for 10 minutes to obtain a standard sample. FIG. 1a shows a group containing different Rb + The color development of the standard sample at the concentration was 50. mu.M, 40. mu.M, 30. mu.M, 20. mu.M, 10. mu.M, 5. mu.M, 2. mu.M, and 0. mu.M, in this order from left to right. FIG. 1b shows a sample containing different Cs + The color development of the standard sample at the concentration is 50. mu.M, 40. mu.M, 30. mu.M, 20. mu.M, 10. mu.M, 5. mu.M, 2. mu.M, and 0. mu.M, in this order from left to right. From FIG. 1a (Rb) + ) And FIG. 1b (Cs) + ) In can be seen, Rb + /Cs + The color is red at the concentrations of 0. mu.M, 2. mu.M and 5. mu.M, and is unchanged; rb + /Cs + The color gradually changed to purple or even blue at concentrations of 10. mu.M, 20. mu.M, 30. mu.M, 40. mu.M, and 50. mu.M. Rb can be judged by naked eye colorimetry + /Cs + Whether the concentration is greater than 1X 10 -5 mol/L。
(3) Drawing a standard curve: for prepared Rb + The standard sample and Cs at concentrations (final concentrations) of 0. mu.M, 0.5. mu.M, 2. mu.M, 5. mu.M, 10. mu.M, 20. mu.M, 40. mu.M, 50. mu.M, respectively + The UV-visible absorption spectrum measurement was carried out on standard samples having concentrations (final concentrations) of 0. mu.M, 0.5. mu.M, 2. mu.M, 5. mu.M, 20. mu.M, 30. mu.M, 40. mu.M, and 50. mu.M, respectively, the change in the UV-visible absorption intensity measured in the interval of 400-750nm was recorded, and the changes at 520nm and 650nm were recordedAbsorbance ratio. With Rb in the Standard sample + /Cs + Concentration as abscissa (A) 650 /A 520 -A 0 650 /A 0 520 )/(A 0 650 /A 0 520 ) The values are taken as the ordinate. The standard curve is shown in FIG. 2a (Rb) + ) And FIG. 2b (Cs) + ) Shown are the absorbance ratio and Rb + The concentration satisfies the formula: y is 0.0074X +0.0019, wherein Y is (A) 650 /A 520 -A 0 650 /A 0 520 )/(A 0 650 /A 0 520 ) Value, X is Rb + Concentration (. mu.M), R 2 0.9949; absorbance ratio and Cs + The concentration satisfies the formula: y ═ 0.0133X +0.0025, where Y is (a) 650 /A 520 -A 0 650 /A 0 520 )/(A 0 650 /A 0 520 ) Value, X is Cs + Concentration (. mu.M), R 2 ＝0.9957。
Ultraviolet-visible absorption Spectroscopy testing of mixtures of different samples
To 100. mu.L of the dibenzo-21-crown-7 solution prepared in step (1), 0.1mL of Rb at each of the above concentrations was added + /Cs + And (3) uniformly mixing the standard solution for 5 minutes, then respectively adding 0.74mL of the 2-mercapto-6-nitrobenzothiazole modified gold nanoparticle solution prepared in the step (1) and 60 mu L0.2M HCl solution, reacting for 10 minutes to obtain a sample mixed solution with the pH value of 1-4, and carrying out ultraviolet-visible absorption spectrum test.
Preparing a 2-mercapto-6-nitrobenzothiazole solution: the concentration was 0.5mM, prepared as solids by weighing, and dissolved in N, N-dimethylformamide.
Preparing a dibenzo-21-crown ether-7 solution: the concentration was 200. mu.M, prepared as solids by weighing, and dissolved in N, N-dimethylformamide.
Example 1 Rb in Water samples of river and lake waters + Detection of (2)
(1) Collecting a water sample to be detected: collecting water samples at certain depths (20-30 cm) of three different places in river water and lake water. In order to ensure good detection effect, the obtained mixed solution needs to be filtered by filter paper to remove impurities, the obtained filtrate is a water sample to be detected, and the pH value is adjusted to be 5.
(2) Preparing a detection solution: adding 15mL of 5mM chloroauric acid solution into 100mL of ultrapure water, adding 3.75mL of 0.1M potassium borohydride aqueous solution serving as a reducing agent under the condition of stirring, reacting for 30min to obtain a gold nanoparticle solution, wherein the volume ratio of the gold nanoparticle solution to the 2-mercapto-6-nitrobenzothiazole solution is 1250: adding a freshly prepared DMF solution of 2-mercapto-6-nitrobenzothiazole with the concentration of 0.5mM into the mixture according to the proportion of 1 to prepare a gold nanoparticle solution modified by the 2-mercapto-6-nitrobenzothiazole; a200. mu.M DMF solution of dibenzo-21-crown-7 was prepared.
(3) Two test tubes A and B of the same specification were prepared, and 100. mu.L of DMF solution of dibenzo-21-crown-7 prepared in (2) was added to each test tube A, 100. mu.L of ultrapure water was added to each test tube A, and 100. mu.L of a sample solution to be tested was added to each test tube B, and they were mixed for 5 minutes.
(4) 750 μ L of 2-mercapto-6-nitrobenzothiazole modified gold nanoparticle solution was added to test tube A and test tube B, respectively, followed by 50 μ L of 0.2M HCl solution. And reacting for 10 minutes to obtain a sample mixed solution with the pH value of 3-4, and observing the color change of the test tube A and the test tube B.
And (3) detection results: after 10 minutes, if the color of the solution in the test tube B changes to purple or even blue, and the color of the solution in the test tube A changes to red, determining Rb in the water sample to be detected + And the concentration is greater than or equal to 1 x 10 -5 mol/L；
If the colors of the solutions in the test tube A and the test tube B are not greatly different and are red, determining that Rb is contained in the water sample to be detected + The concentration is less than 1 × 10 -5 mol/L。
Measuring the UV-visible absorption spectrum of the detection mixture, measuring the change of the UV-visible absorption intensity in the range of 300-850nm, and correlating the absorbance values at 520nm and 650nm (A) 650 /A 520 -A 0 650 /A 0 520 )/(A 0 650 /A 0 520 ) Substituting into FIG. 2a (Rb) + ) Performing comparison calculation to obtain Rb in the liquid to be detected + And (4) concentration.
Example 2 Rb in Water samples of salt lake and chlor-alkali industries + Detection of (2)
(1) Collecting a water sample to be detected: the method comprises the steps of collecting water samples at the sampling position of a wastewater discharge port at intervals of 1h, mixing the water samples in equal amount to form a mixed sample, filtering the solution with filter paper to remove impurities in order to ensure good detection effect, and adjusting the pH value to be 6 to obtain a filtrate to be a water sample to be detected.
(2) Preparing a detection solution: adding 15mL of 5mM chloroauric acid solution into 100mL of ultrapure water, adding 3.75mL of 0.1M sodium borohydride aqueous solution serving as a reducing agent under the condition of stirring, reacting for 30min to prepare a gold nanoparticle solution, wherein the volume ratio of the gold nanoparticle solution to the 2-mercapto-6-nitrobenzothiazole solution is 1000: adding a 0.4mM DMF solution of freshly prepared 2-mercapto-6-nitrobenzothiazole into the mixture according to the proportion of 1 to prepare a 2-mercapto-6-nitrobenzothiazole modified gold nanoparticle solution; a solution of dibenzo-21-crown-7 in DMF was prepared at a concentration of 300. mu.M.
(3) Two test tubes A and B of the same specification were prepared, and 100. mu.L of a DMF solution of dibenzo-21-crown-7 prepared in (2) was added to each test tube A, 100. mu.L of ultrapure water was added to each test tube A, and 100. mu.L of Rb was added to each test tube B + And mixed for 5 minutes.
(4) 730. mu.L of 2-mercapto-6-nitrobenzothiazole-modified gold nanoparticle solution was added to test tube A and test tube B, respectively, and 70. mu.L of 0.2M HCl solution was added. And reacting for 10 minutes to obtain a sample mixed solution with the pH value of 2-3, and observing the color change of the test tube A and the test tube B.
And (3) detection results: after 10 minutes, if the color of the solution in the test tube B changes to purple or even blue, and the color of the solution in the test tube A changes to red, determining Rb in the water sample to be detected + And the concentration is greater than or equal to 1 x 10 -5 mol/L；
If the colors of the solutions in the test tube A and the test tube B are not greatly different and are red, determining that Rb is contained in the water sample to be detected + The concentration is less than 1 × 10 -5 mol/L。
Measuring the detection mixed solution by ultraviolet-visible absorption spectrum within the range of 300-850nmThe resulting change in UV-visible absorption intensity correlates the absorbance at 520nm and 650nm (A) 650 /A 520 -A 0 650 /A 0 520 )/(A 0 650 /A 0 520 ) Substituting into FIG. 2a (Rb) + ) Performing comparison calculation to obtain Rb in the liquid to be detected + And (4) concentration.
Example 3 Rb in samples of underground brine + Detection of (2)
(1) Collecting a water sample to be detected: collecting an underground brine water sample, filtering the water sample by using filter paper to obtain a mixed solution, and adjusting the pH value to 5, wherein the obtained filtrate is the water sample to be detected.
(2) Preparing a detection solution: adding 15mL of 5mM chloroauric acid solution into 100mL of ultrapure water, adding 3.75mL of 0.1M sodium borohydride aqueous solution serving as a reducing agent under the condition of stirring, reacting for 30min to prepare a gold nanoparticle solution, wherein the volume ratio of the gold nanoparticle solution to the 2-mercapto-6-nitrobenzothiazole solution is 1500: adding a freshly prepared DMF solution of 2-mercapto-6-nitrobenzothiazole with the concentration of 0.7mM into the mixture according to the proportion of 1 to prepare a gold nanoparticle solution modified by the 2-mercapto-6-nitrobenzothiazole; a solution of 100. mu.M dialkyl dibenzo-21-crown-7 in DMF was prepared.
(3) Two test tubes A and B of the same specification were prepared, and 100. mu.L of the DMF solution of benzo-21-crown-7 prepared in (2) was added to each test tube A, 100. mu.L of ultrapure water was added to each test tube A, and 100. mu.L of the sample water to be tested was added to each test tube B, and they were mixed for 5 minutes.
(4) 730. mu.L of 2-mercapto-6-nitrobenzothiazole-modified gold nanoparticle solution was added to test tube A and test tube B, respectively, and 70. mu.L of 0.2M HCl solution was added. And reacting for 10 minutes to obtain a sample mixed solution with the pH value of 2-3, and observing the color change of the test tube A and the test tube B.
And (3) detection results: after 10 minutes, if the color of the solution in the test tube B changes to purple or even blue, and the color of the solution in the test tube A changes to red, determining Rb in the water sample to be detected + And the concentration is greater than or equal to 1 x 10 -5 mol/L；
If the solutions in test tube A and test tube B are not very different in color and are red, thenDetermining Rb in water sample to be detected + The concentration is less than 1 × 10 -5 mol/L。
Measuring the UV-visible absorption spectrum of the detection mixture, measuring the change of the UV-visible absorption intensity in the range of 300-850nm, and correlating the absorbance values at 520nm and 650nm (A) 650 /A 520 -A 0 650 /A 0 520 )/(A 0 650 /A 0 520 ) Substituting into FIG. 2a (Rb) + ) Performing comparison calculation to obtain Rb in the liquid to be detected + And (4) concentration.
Example 4 Rb in seawater sample + Detection of (2)
(1) Collecting a water sample to be detected: collecting a natural seawater sample, filtering the water sample by using filter paper to obtain a mixed solution, and adjusting the pH value to 6, wherein the obtained filtrate is the water sample to be detected.
(2) Preparing a detection solution: adding 15mL of 5mM chloroauric acid solution into 100mL of ultrapure water, adding 3.75mL of 0.1M sodium borohydride aqueous solution serving as a reducing agent under the condition of stirring, reacting for 30min to prepare a gold nanoparticle solution, wherein the volume ratio of the gold nanoparticle solution to the 2-mercapto-6-nitrobenzothiazole solution is 1250: adding a freshly prepared 2-mercapto-6-nitrobenzothiazole DMF solution with the concentration of 0.5mM into the mixture according to the volume ratio of 1 to prepare a gold nanoparticle solution modified by the 2-mercapto-6-nitrobenzothiazole; a solution of dibenzo-21-crown-7 in DMF was prepared at a concentration of 300. mu.M.
(3) Two test tubes A and B of the same specification were prepared, and 100. mu.L of the DMF solution of benzo-21-crown-7 prepared in (2) was added to each test tube A, 100. mu.L of ultrapure water was added to each test tube A, and 100. mu.L of the sample water to be tested was added to each test tube B, and they were mixed for 5 minutes.
(4) 740. mu.L of 2-mercapto-6-nitrobenzothiazole-modified gold nanoparticle solution was added to test tube A and test tube B, respectively, followed by 60. mu.L of 0.2M HCl solution. And reacting for 10 minutes to obtain a sample mixed solution with the pH value of 2-3.5, and observing the color change of the test tube A and the test tube B.
And (3) detection results: after 10 minutes, if the solution in tube B turns purple or even blue and the solution in tube A turns red, it is determined that the solution is ready to be usedDetecting Rb in water sample + And the concentration is greater than or equal to 1 x 10 -5 mol/L；
If the colors of the solutions in the test tube A and the test tube B are not greatly different and are red, determining that Rb is contained in the water sample to be detected + The concentration is less than 1 × 10 -5 mol/L。
Measuring the UV-visible absorption spectrum of the detection mixture, measuring the change of the UV-visible absorption intensity in the range of 300-850nm, and correlating the absorbance values at 520nm and 650nm (A) 650 /A 520 -A 0 650 /A 0 520 )/(A 0 650 /A 0 520 ) Substituting into FIG. 2a (Rb) + ) Performing comparison calculation to obtain Rb in the liquid to be detected + And (4) concentration.
Example 5 Cs in river and lake Water samples + Detection of (2)
The detection method was substantially the same as in example 1, except that pyridine was used instead of the ligand solvent, and sodium borohydride was used instead of the reducing agent for preparing gold nanoparticles.
Example 6 Cs in Water samples from salt lake and chlor-alkali industries + Detection of (2)
The detection method is basically the same as that of example 2, except that the modifier is 4-mercaptobenzoic acid, the ligand solution is benzo-21-crown-7, and the solvent is pyridine.
Example 7 Cs in samples of underground brine + Detection of (2)
The detection method is basically the same as that of example 3, except that the volume ratio of the gold nanoparticle solution to the modifier is 2000: 1.
EXAMPLE 8 Cs in seawater sample + Detection of (2)
The detection method is basically the same as that of example 4, except that the reducing agent for preparing the gold nanoparticles is citric acid, the modifying agent is 4-mercaptophenylboronic acid, and the concentration of the ligand solution is 200 μ M.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (11)
1. The method for detecting rubidium or cesium ions is characterized in that detection is carried out by utilizing a rubidium or cesium ion detection reagent combination or a rubidium or cesium ion detection kit;
the detection method comprises the following steps:
(s1) providing a sample solution to be tested;
(s2) obtaining a modifier-modified gold nanoparticle solution;
(s3) mixing the sample solution to be detected with the modifier modified gold nanoparticle solution and the ligand solution to form a detection mixed solution;
(s4) detecting a spectroscopic characteristic of said detection mixture, thereby obtaining a measurement;
the spectroscopic characteristics are selected from at least one of color, visible light absorption intensity and absorption spectrum peak;
the rubidium or cesium ion detection reagent combination comprises:
component (a): the gold nanoparticle solution modified by the modifier or the reagent component for forming the gold nanoparticle solution modified by the modifier, wherein the modifier is a sulfydryl compound containing a benzene ring;
a component (b): a ligand solution, or a reagent component for forming the ligand solution; the ligand solution is at least one selected from dibenzo-21-crown ether-7 solution, dialkyl dibenzo-21-crown-7 solution and benzo-21-crown-7 solution;
the ligand solution has selective complexation effect on rubidium or cesium ions, and the molecular structure of the ligand solution contains benzene rings which can be aggregated together with the benzene rings on the modifying agent attached to the surface of the gold nanoparticles through pi-pi accumulation effect;
the detection kit for rubidium or cesium ions comprises at least one of the detection reagent combinations of rubidium or cesium ions.
2. The detection method according to claim 1, wherein the reagent component for forming the modifier-modified gold nanoparticle solution in component (a) comprises:
(i) gold nanoparticle precursors;
(ii) a reducing agent; and
(iii) a modifier.
3. The detection method according to claim 2, wherein the reducing agent is at least one of sodium borohydride, potassium borohydride, citric acid and citrate; the modifier is at least one of 2-mercapto-6-nitrobenzothiazole, 4-mercaptobenzoic acid and 4-mercaptophenylboronic acid.
4. The detection method according to claim 1, further comprising a pH adjuster.
5. The detection method according to claim 1, wherein the concentration of gold nanoparticles in the gold nanoparticle solution modified with the modifier is 0.4 to 1mM in terms of the molar amount of gold element;
the solvent in the ligand solution is at least one selected from DMF, pyridine and formic acid, and the concentration of the ligand in the ligand solution is 100-300 mu M;
the volume ratio of the gold nanoparticle solution modified by the modifier to the ligand solution is 6-10: 1.
6. The detection method according to claim 1, further comprising: and adjusting the pH value of the sample solution to be detected to be 5-7 or adjusting the pH value of the detection mixed solution to be 1-4 by adopting a pH regulator.
7. The method of detecting according to claim 1, further comprising: and observing the color of the detection mixed solution by naked eyes.
8. The detection method according to claim 1, further comprising: instrumental analysis was performed to detect spectroscopic characteristics of the test mixture.
9. The detection method according to claim 1, further comprising: and providing a control mixed liquid, and judging whether rubidium or cesium ions exist in the sample to be detected and/or the content of the rubidium or cesium ions in the sample by comparing the spectroscopic characteristics of the detection mixed liquid and the control mixed liquid.
10. The detection method as claimed in any one of claims 1 to 9 for rubidium or cesium ion detection in an aqueous system.
11. A test kit for carrying out the test method according to any one of claims 1 to 9.
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