CN114136934B - Fluorescent probe and method for detecting copper ion concentration by using same - Google Patents
Fluorescent probe and method for detecting copper ion concentration by using same Download PDFInfo
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 62
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 48
- 238000001514 detection method Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000003651 drinking water Substances 0.000 claims abstract description 9
- 235000020188 drinking water Nutrition 0.000 claims abstract description 9
- 239000002096 quantum dot Substances 0.000 claims abstract description 7
- -1 3-mercaptopropionic acid-indium Chemical compound 0.000 claims abstract description 5
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 3
- 239000000523 sample Substances 0.000 claims description 22
- 239000012086 standard solution Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 6
- 239000008363 phosphate buffer Substances 0.000 claims description 5
- 235000014171 carbonated beverage Nutrition 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- 235000015203 fruit juice Nutrition 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 235000020124 milk-based beverage Nutrition 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 235000013305 food Nutrition 0.000 abstract description 3
- 239000010949 copper Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010791 quenching Methods 0.000 description 7
- 230000000171 quenching effect Effects 0.000 description 7
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 235000013361 beverage Nutrition 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000011088 calibration curve Methods 0.000 description 3
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 3
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- CEKJAYFBQARQNG-UHFFFAOYSA-N cadmium zinc Chemical compound [Zn].[Cd] CEKJAYFBQARQNG-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
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- 230000006870 function Effects 0.000 description 2
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- 238000011534 incubation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 239000003642 reactive oxygen metabolite Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- NPAWNPCNZAPTKA-UHFFFAOYSA-M sodium;propane-1-sulfonate Chemical compound [Na+].CCCS([O-])(=O)=O NPAWNPCNZAPTKA-UHFFFAOYSA-M 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 206010019663 Hepatic failure Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000001647 Renal Insufficiency Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 206010000059 abdominal discomfort Diseases 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000019522 cellular metabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 201000006370 kidney failure Diseases 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 208000007903 liver failure Diseases 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000006540 mitochondrial respiration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- FDIOSTIIZGWENY-UHFFFAOYSA-N n-[bis(diethylamino)phosphanyl]-n-ethylethanamine Chemical compound CCN(CC)P(N(CC)CC)N(CC)CC FDIOSTIIZGWENY-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 210000002569 neuron Anatomy 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
Classifications
-
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- 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
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N2021/6417—Spectrofluorimetric devices
Abstract
The invention relates to the field of food detection, in particular to a fluorescent probe and a method for detecting the concentration of copper ions by using the fluorescent probe. The fluorescent probe comprises an aqueous solution of 3-mercaptopropionic acid-indium phosphide/zinc sulfide shell core quantum dots MPA-InP/ZnS QDs. The fluorescent probe provided by the invention can be used for rapidly detecting the concentration of trace copper ions in environmental water, drinking water and drinks, is simple and rapid, and is easy to use.
Description
Technical Field
The invention relates to the field of food detection, in particular to a fluorescent probe and a method for detecting the concentration of copper ions by using the fluorescent probe.
Background
Copper is one of essential trace elements essential for human health, and has effects in regulating hemoglobin level, neuron function, mitochondrial respiration, and cellular metabolism. However, high concentrations of Cu in humans 2+ Can react with molecular oxygen to produce Reactive Oxygen Species (ROS), resulting in protein, fat and nucleic acid degradation. Short term exposure to high concentrations of Cu 2+ Substances cause gastrointestinal discomfort and prolonged exposure may lead to liver and kidney failure. Drinking water is considered to be Cu in humans 2+ Is the main source of (C) and the U.S. Environmental Protection Agency (EPA) prescribes Cu in drinking water 2+ The content should not exceed 20. Mu.M. Furthermore, cu 2+ As a heavy metal ion, even at a sub-micromolar level, it causes serious damage to some microorganisms such as fungi and algae in water, thereby making it impossible to make the entire aquatic ecosystemReverse damage. Due to high concentration of Cu 2+ Is harmful to Cu 2+ The rapid and simple detection has important significance for food safety and water quality monitoring.
To date, cu is detected 2+ There are many methods such as atomic absorption spectrometry, electrochemical analysis, and fluorescence. Atomic absorption spectrometry has high accuracy and can measure various elements, but the method requires specialized equipment and long test time. Electrochemical analysis has the advantages of simplicity, low cost and portability, but is susceptible to interference from other metal ions. Fluorescence has fast response, high spatial resolution and safety for remote processing. With the development of nano technology, cu with simple design and environmental friendliness is designed 2+ Detection methods are becoming more and more interesting. The nano material such as nano tube and quantum dot has the advantages of low toxicity, good selectivity and the like, and is widely applied to Cu 2+ Fluorescent detection of (2).
In recent years, several fluorescence sensing strategies have been successfully used to detect Cu 2+ . Yi et al (dio: 10.1016/S1872-2040 (20) 60054-8) synthesized polyethylphenylimine functionalized carbon quantum dots (PEI-CQDs) and achieved Cu based on complexation 2+ The method has a wide detection range but the detection limit is 80nM and is not applicable to Cu in seawater 2+ Ultra-sensitive detection. Ali et al (dio: 10.1007/s 00216-019-02362-4) constructed dual function sensors based on complexation with polyamino carbon dots to Cu for pipeline water, tap water and mineral water 2+ And S is 2- The method is reusable but specific to other metal ions such as Fe 3+ ，Pb 2+ ，Co 2+ ，Ba 2+ Further investigation is required for the interference immunity of (a). InP/ZnS QDs exhibit low cytotoxicity, good biocompatibility and band gap that can cover the entire visible range. There is no current information about the use of InP/ZnS QDs for detecting Cu in beverages 2+ Is reported in (3). The existing detection method for copper ions is complex in operation process, long in test time consumption, and difficult to rapidly detect trace copper ions in water or drinks. Develop a method capable of detecting trace copper ions in water or beverageIs a difficult problem to be solved urgently at present, and has important significance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a fluorescent probe and a method for detecting the concentration of copper ions. The fluorescent probe provided by the invention can be used for rapidly detecting the concentration of trace copper ions in environmental water, drinking water and drinks, is simple and rapid, and is easy to use.
Specifically, the invention firstly provides a fluorescent probe which comprises an aqueous solution of 3-mercaptopropionic acid-indium phosphide/zinc sulfide shell core quantum dots (MPA-InP/ZnS QDs).
The inventor discovers that the fluorescent probe provided by the invention is used for rapidly detecting copper ions based on a fluorescence quenching principle caused by static quenching, has extremely high sensitivity and selectivity, and is suitable for trace detection. The fluorescent probe mainly comprises MPA-InP/ZnS core-shell quantum dots, and the MPA-InP/ZnS QDs are prepared by a thermal solvent method and have carboxyl end capping. In particular, the MPA-InP/ZnS QDs prepared by the method contains a large number of carboxyl groups on the surface, and the surface is complexed with copper ions to generate a ground state complex in the presence of the copper ions, so that the MPA-InP/ZnS QDs probe has better sensitivity.
According to the fluorescent probe provided by the invention, the MPA-InP/ZnS QDs take indium chloride as an indium source, zinc chloride as a zinc source, hexaethylphosphoramidite as a phosphorus source and sodium propane sulfonate as a sulfur source, and 3-mercaptopropionic acid (MPA) as a ligand; the molar ratio of the indium chloride to the zinc chloride to the MPA is 1:1:1 to 1:20:20, preferably 1:15:15. according to the invention, the MPA ligand is adopted, so that the surface of the synthesized MPA-InP/ZnS QDs has rich functional groups in the dosage proportion, and the selectivity and sensitivity to copper ions are further improved.
According to the fluorescent probe provided by the invention, the pH of the MPA-InP/ZnS QDs aqueous solution is 7.0-9.0.
According to the fluorescent probe provided by the invention, the concentration of MPA-InP/ZnS QDs in the aqueous solution of MPA-InP/ZnS QDs is 10-14 nM.
According to the fluorescent probe provided by the invention, the MPA-InP/ZnS QDs aqueous solution is configured in phosphate buffer solution.
The invention firstly provides a method for detecting the concentration of copper ions by using a fluorescent probe, and the concentration of copper ions is detected based on the fluorescent probe.
The method for detecting the copper ion concentration by using the fluorescent probe provided by the invention comprises the following steps: mixing a sample to be detected with the fluorescent probe, reacting at room temperature, obtaining the fluorescent intensity of the fluorescent probe, and determining the concentration of copper ions in the sample to be detected.
According to the method for detecting the copper ion concentration by using the fluorescent probe, provided by the invention, the method further comprises the steps of calibrating the fluorescent probe, mixing a copper chloride standard solution with the fluorescent probe, reacting at room temperature to obtain the fluorescent intensity of the fluorescent probe, and establishing the linear relation between the fluorescent intensity of the fluorescent probe of the copper chloride standard solution with different concentrations and the copper ion concentration.
According to the method for detecting the copper ion concentration by using the fluorescent probe provided by the invention, the detection conditions of the fluorescent intensity comprise: the excitation light λex is 245 to 255nm, and the slit width is 3 to 7nm.
According to the method for detecting the copper ion concentration by using the fluorescent probe, the reaction time is 10-15 min; the volume ratio of the fluorescent probe to the sample to be detected is 20:1-10:1.
According to the method for detecting the copper ion concentration by the fluorescent probe provided by the invention, the sample to be detected comprises one or more of mineral water, drinking water, carbonated beverage, fruit juice and milk beverage; preferably, when the sample to be measured is a carbonated beverage or juice, the method further comprises pretreating the sample to be measured; preferably, the sample to be tested is sonicated at room temperature for 10-20 min and then filtered through a 0.22 μm filter paper.
The invention has the advantages that: according to the invention, MPA-InP/ZnSQDs are used as probes, and the characteristic of static quenching of fluorescence is utilized by utilizing a ground state compound generated by the reaction of copper ions and MPA-InP/ZnSQDs, so that the trace copper ion concentration in the beverage is detected.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will briefly explain the drawings needed in the embodiments or the prior art, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the degree of fluorescence quenching (λex=250 nm) after copper ions are added to buffers of different pH in the examples of the present invention;
FIG. 2 is a graph showing fluorescence intensity of MPA-InP/ZnS QDs at different concentrations (λex=250 nm) in an optimal pH buffer in an embodiment of the present invention;
FIG. 3 is a graph showing the change in fluorescence intensity at 1 minute intervals (λex=250 nm) of the fluorescent probe of MPA-InP/ZnS QDs in the example of the present invention after adding a copper ion standard sample of a fixed concentration;
FIG. 4 shows fluorescence spectra (λex=250 nm) of fluorescent probes of MPA-InP/ZnS QDs of the present invention after incubation for 15 minutes with copper ion standard samples of different concentrations;
FIG. 5 is a graph showing the linear relationship between the fluorescence intensity of MPA-InP/ZnS QDs and the concentration of the standard solution of copper ions (A is 0-1000nM, B is 0-50 nM) when the standard solution of copper ions is added to the fluorescent probe of MPA-InP/ZnS in the example of the present invention;
FIG. 6 shows the change in fluorescence intensity of MPA-InP/ZnS QDs fluorescent probes with the addition of solutions of different metal ions (1000 nM) and copper ions (10 nM) in the examples of the present invention;
FIG. 7 is a graph showing the relationship between the fluorescence intensity of the fluorescent probe and the concentration of copper ions in the comparative example of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, which are used for illustrating the present invention but are not intended to limit the scope of the present invention. The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
Example 1
This example provides the synthetic procedure for MPA-InP/ZnS QDs used:
1) 100mg of indium chloride, 300mg of zinc chloride, 0.5mL (1.6 m mol/L) of tris (diethylamino) phosphine and 200mg of sodium propane sulfonate are respectively taken and added into 5mL (15 mol/L) of industrial oleylamine, and the mixture is reacted for 30 minutes at 180 ℃ to obtain a mixed solution;
2) 1mL of saturated MPA (2.2 mol/L) was added to the mixed solution, heated to 260℃and reacted for 40h;
3) Finally, the above product was washed 3 times with chloroform and ethanol to obtain the MPA-InP/ZnS QDs.
Example 2
The embodiment provides an MPA-InP/ZnS QDs fluorescent probe, the construction of which comprises: preparing phosphate buffer solutions with pH of 3.0-11.0, preparing aqueous solutions of MPA-InP/ZnS QDs with different pH with concentration of 10nM by using the buffer solutions, and detecting the fluorescence quenching degree of the solution when 50nM copper ions are added, wherein the fluorescence quenching rate of the MPA-InP/ZnS QDs is maximum when the pH=8.0, namely 8.0 is the optimal detection pH as shown in FIG. 1; in a buffer solution with pH=8.0, preparing MPA-InP/ZnS QDs aqueous solutions with the concentration of 2nM, 4nM, 6nM, 8nM, 10nM, 12nM, 14nM, 16nM and 18nM, recording the fluorescence emission patterns (λex=250 nM) of the solutions, and as shown in FIG. 2, the fluorescence intensity is maximum at the concentration of 14nM, namely, the optimal detection concentration of MPA-InP/ZnS QDs is 14nM; MPA-InP/ZnS QDs fluorescence probe was constructed with pH=8.0 and MPA-InP/ZnS QDs concentration of 14 nM: in a phosphate buffer at ph=8.0, an aqueous MPA-InP/ZnS QDs solution at a concentration of 14nM was prepared.
Example 3
The embodiment provides a calibration method of the fluorescent probe, which comprises the following steps:
1) Preparing copper chloride standard aqueous solutions with different concentrations: 0nM, 3nM, 5nM, 10nM, 15nM, 20nM, 30nM, 50nM,100nM, 150nM, 200nM, 250nM, 300nM, 400nM, 600nM and 1000nM;
2) 100 mu L of copper chloride standard solution with the concentration of 50nM is added into 2mL of MPA-InP/ZnS QDs fluorescent probe described in the example 2, and the fluorescence spectrum of the fluorescent probe is recorded by a fluorescence spectrometer every one minute until the fluorescence emission peak is stable, as shown in FIG. 3, the fluorescence intensity of the fluorescent probe tends to be stable in 10 minutes, and 12 minutes is selected as the reaction time in the example;
3) 100. Mu.L of copper chloride standard solutions with different concentrations are respectively added to 2mL of MPA-InP/ZnS QDs fluorescent probe described in example 2, and after incubation for 12 minutes at room temperature, the fluorescence spectrum (λex=250 nm) of the fluorescent probe is recorded, as shown in FIG. 4;
4) Calibration curves between the fluorescence intensities of MPA-InP/ZnS QDs fluorescence probes added with standard solutions with different copper ion concentrations and the concentrations of the standard solutions with copper ions are established, wherein A and B respectively correspond to 0-1000nM and 0-50nM, and the detection limit is 0.22nM as shown in FIG. 5.
Example 4
The embodiment provides a detection of copper ions in a beverage sample, comprising the following steps:
1) Pretreatment of drink samples: taking 1mL of carbonated beverage (seven happiness, BAIXIAO Co.) and placing into an ultrasonic instrument for ultrasonic treatment at room temperature for 15min, and filtering with 0.22 μm filter paper to obtain treated beverage sample;
2) 100 μl of the pretreated beverage sample was added to 2mL of MPA-InP/ZnS QDs fluorescent probe as described in example 1, incubated for 12 min, and the fluorescence intensity Ia was recorded as 7030896.33 (a.u.);
3) Ia was carried into the calibration curve described in example 3 and the copper ion concentration in the drink samples was calculated to be 4.33.+ -. 0.30nM.
Meanwhile, the concentration of copper ions in a sample detected by adopting an inductively coupled plasma mass spectrometry (ICP-MS) method is 4.07nM, and the error of the method provided by the invention is calculated to be within 6.39%.
Example 4
The embodiment provides a detection of copper ions in a water sample, which comprises the following steps:
1) 100 μl of mineral water and drinking water, respectively, were added to 2mL of MPA-InP/ZnS QDs fluorescent probe as described in example 2, incubated for 12 min, and fluorescence intensities Ib were recorded as 7640335.50 (a.u.), 7777722.83 (a.u.);
2) Ib was carried into the calibration curve described in example 3, and the copper ion concentrations in the water samples were calculated to be 5.16.+ -. 0.40nM and 3.83.+ -. 0.29nM, respectively.
Meanwhile, the copper ion concentration in the sample detected by adopting the ICP-MS method is 5.31nM and 3.75nM respectively, and the error of the method provided by the invention is within 2.82% through comparison calculation.
Comparative example 1
This comparative example provides a method comparison (CN 111504962) for detecting ions based on aqueous zinc cadmium fluorescent quantum dots. The detection range of the copper ion detection method provided by the invention CN111504962 is 0.1-0.4 mM; the detection limit of the copper ion detection method proposed in the embodiment 2 of the invention is 0.22nM, and the detection range is 0-1000nM. The U.S. environmental protection agency (USEPA) prescribes that the copper ion concentration in drinking water should not exceed 20 μm, i.e., 0.02mM, and therefore, the copper ion detection method provided by the invention CN111504962 cannot realize nanomolar copper ion detection, especially cannot detect the copper ion concentration in drinking water; in addition, the water phase zinc-cadmium fluorescent quantum dot proposed by the invention CN111504962 has fluorescent response to copper ions and iron ions at 626nm of excitation wave, which indicates that the detection of the copper ions is interfered when the iron ions exist; the copper ion detection method proposed in embodiment 2 of the present invention has strong interference resistance to other metal ions, as shown in fig. 6.
Comparative example 2
This comparative example provides a comparison of copper ion detection at ph=3 for aqueous MPA-InP/ZnS QDs at a concentration of 6 nM.
This comparative example provides an MPA-InP/ZnS QDs fluorescent probe, the construction of which comprises: phosphate buffer at pH 3.0 was prepared, phosphate buffer at MPA-InP/ZnS QDs at a concentration of 6nM was prepared, 100. Mu.L of copper chloride standard solution at 10nM,50nM,100nM and 1000nM was added to the above-mentioned 2mL of MPA-InP/ZnS QDs fluorescent probe, and the fluorescence spectrum of the fluorescent probe was recorded by a fluorescence spectrometer every 12 minutes. As shown in fig. 7, although the fluorescence intensity of the fluorescent probe constructed in this comparative example was quenched with an increase in copper ion concentration, the degree of quenching was not sufficiently remarkable and the linearity was poor as compared with the fluorescent probe constructed in example 2.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (4)
1. A method for detecting the concentration of copper ions by using a fluorescent probe is characterized by comprising the steps of calibrating the fluorescent probe, mixing a copper chloride standard solution with the fluorescent probe, reacting at room temperature to obtain the fluorescence intensity of the fluorescent probe, and establishing a linear relation between the fluorescence intensity of the fluorescent probe of the copper chloride standard solution with different concentrations and the concentration of the copper ions; mixing a sample to be detected with the fluorescent probe, reacting at room temperature, obtaining the fluorescent intensity of the fluorescent probe, and determining the concentration of copper ions in the sample to be detected; the fluorescent probe comprises an aqueous solution of 3-mercaptopropionic acid-indium phosphide/zinc sulfide core-shell quantum dots MPA-InP/ZnS QDs; the pH of the MPA-InP/ZnS QDs aqueous solution is 8; the concentration of MPA-InP/ZnS QDs in the MPA-InP/ZnS QDs aqueous solution is 14nM; the MPA-InP/ZnS QDs take 3-mercaptopropionic acid as a ligand; the molar ratio of the indium source to the zinc source to the MPA is 1:15:15; the detection limit of the concentration of the copper ions is 0.22nM, and the detection range is 0-1000nM.
2. The method for detecting copper ion concentration by using a fluorescent probe according to claim 1, wherein the aqueous MPA-InP/ZnS QDs solution is prepared in a phosphate buffer.
3. The method for detecting the concentration of copper ions by using the fluorescent probe according to claim 1, wherein the reaction time is 10-15 min; the volume ratio of the fluorescent probe to the sample to be detected is 20:1-10:1.
4. A method for detecting copper ion concentration by using a fluorescent probe according to any one of claims 1 to 3, wherein the sample to be detected comprises one or more of mineral water, drinking water, carbonated beverage, fruit juice and milk beverage.
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