CN116514901B - Double-response fluorescent iron nanocluster probe and preparation method and application thereof - Google Patents
Double-response fluorescent iron nanocluster probe and preparation method and application thereof Download PDFInfo
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- CN116514901B CN116514901B CN202310808039.5A CN202310808039A CN116514901B CN 116514901 B CN116514901 B CN 116514901B CN 202310808039 A CN202310808039 A CN 202310808039A CN 116514901 B CN116514901 B CN 116514901B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 227
- 239000000523 sample Substances 0.000 title claims abstract description 124
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 77
- 230000004044 response Effects 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000000243 solution Substances 0.000 claims abstract description 75
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims abstract description 62
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 55
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 49
- 108010024636 Glutathione Proteins 0.000 claims abstract description 38
- 239000007864 aqueous solution Substances 0.000 claims abstract description 33
- 230000009977 dual effect Effects 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 27
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 9
- 239000012498 ultrapure water Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000000017 hydrogel Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims 2
- 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 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 47
- 238000010791 quenching Methods 0.000 abstract description 9
- 230000000052 comparative effect Effects 0.000 description 21
- 239000012086 standard solution Substances 0.000 description 20
- 229960003180 glutathione Drugs 0.000 description 12
- 230000005284 excitation Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
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- 239000002184 metal Substances 0.000 description 9
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- 238000010521 absorption reaction Methods 0.000 description 8
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- 238000006243 chemical reaction Methods 0.000 description 7
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- 230000000171 quenching effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000012491 analyte Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001917 fluorescence detection Methods 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000003902 lesion Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 238000001871 ion mobility spectroscopy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- OIGNJSKKLXVSLS-VWUMJDOOSA-N prednisolone Chemical compound O=C1C=C[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OIGNJSKKLXVSLS-VWUMJDOOSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K5/00—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof
- C07K5/02—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing at least one abnormal peptide link
- C07K5/0215—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing at least one abnormal peptide link containing natural amino acids, forming a peptide bond via their side chain functional group, e.g. epsilon-Lys, gamma-Glu
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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
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- C09K2211/18—Metal complexes
- C09K2211/187—Metal complexes of the iron group metals, i.e. Fe, Co or Ni
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- 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"
- G01N2021/6432—Quenching
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Abstract
The invention relates to the technical field of environment detection, in particular to a dual-response fluorescent iron nanocluster probe and a preparation method and application thereof. A preparation method of a dual-response fluorescent iron nanocluster probe comprises the following steps: 1) Adding ferrous salt aqueous solution into reduced glutathione aqueous solution, stirring to obtain reduced glutathione-Fe 2+ A precursor solution, wherein the molar ratio of the reduced glutathione in the reduced glutathione aqueous solution to ferrous ions in the ferrous salt aqueous solution is (3.6-4.6): 1, a step of; 2) To the reduced glutathione-Fe obtained in step 1) 2+ And adding a reducing agent into the precursor solution, and stirring and reacting for 30-120min at 15-35 ℃ to obtain the double-response fluorescent iron nanocluster probe. The dual-response fluorescent iron nanocluster probe has low preparation and use cost, can simultaneously generate fluorescent response to ammonia and hydrogen sulfide, and can quench the fluorescence by the ammonia and strengthen the fluorescence by the hydrogen sulfide.
Description
Technical Field
The invention relates to the technical field of environment detection, in particular to a dual-response fluorescent iron nanocluster probe and a preparation method and application thereof.
Background
Malodorous gas is an atmospheric pollutant which is extremely harmful to human health, and after people inhale malodorous gas, people not only can cause the reduction of life quality, but also can cause diseases such as dyspnea, central nervous disorder, tissue organ lesion, acute poisoning and the like, and can also cause various chronic lesions, even cancers. Therefore, the development of monitoring and controlling malodorous gas pollutants in environmental systems is an important task in the field of environmental protection. Currently, common malodorous gases in the ecological environment are mainly divided into two main types of nitrogen-containing malodorous gases and sulfur-containing malodorous gases, including ammonia, amide, trimethylamine, indole, hydrogen sulfide, methyl mercaptan, methyl sulfide, dimethyl disulfide, carbon disulfide and the like. The pollutant sources are wide, the material composition is complex, the related pollution discharge industries are numerous, industrial pollution sources such as petroleum refining, chemical industry, pharmacy, rubber, papermaking, food processing and the like are available, service industry pollution sources such as sewage treatment plants, livestock and poultry cultivation, catering lampblack and the like are available, and meanwhile, the detection and identification methods of bad odor in the pollution sources are also various.
Compared with the traditional malodorous gas analysis and detection methods such as gas chromatography, spectrophotometry, ion mobility spectrometry, electronic nose method, chromatography-mass spectrometry and the like, the fluorescence spectrometry has become a powerful means for constructing an accurate, rapid, efficient and sensitive analysis and detection method for malodorous gas pollutants in a complex environment medium due to the advantages of high sensitivity, good reproducibility, simplicity, convenience, rapidness, low analysis cost and the like. Fluorescent metal nanoclusters (Metal naonoclusters, MNCs) are small clusters formed by stacking several to hundreds of metal atoms, have a size of about 1-2 nm or less, and have discontinuous energy band structures and are separated into different energy levels, so that the fluorescent metal nanoclusters show chemical and optical properties of molecules with high water solubility, high dispersibility, fluorescence adjustability and the like, play an important role in the fields of fluorescence sensing, environmental monitoring, biological imaging and the like, and can be used for detecting malodorous gases such as ammonia, hydrogen sulfide and the like.
However, the existing fluorescent metal nanocluster environment detection probes have some bottleneck problems in the development and application process. On one hand, the fluorescent metal nanocluster probes which are mature in application are only four of gold, silver, platinum and copper, the types are fewer, noble metals are used as main materials, and the preparation and use costs are high; on the other hand, in the existing fluorescent metal nanocluster probes, the same probe can rarely generate signal response to a plurality of targets, so that the development and the application of the fluorescent metal nanocluster probes are greatly limited.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that the fluorescent metal nanocluster environment detection probe in the prior art is high in cost and cannot respond to ammonia signals and hydrogen sulfide signals, so that the dual-response fluorescent iron nanocluster probe and the preparation method and the application thereof are provided.
The invention provides a preparation method of a double-response fluorescent iron nanocluster probe, which comprises the following steps:
1) Adding ferrous salt aqueous solution into reduced glutathione aqueous solution, stirring to obtain reduced glutathione-Fe 2+ A precursor solution, wherein the molar ratio of the reduced glutathione in the reduced glutathione aqueous solution to ferrous ions in the ferrous salt aqueous solution is (3.6-4.6): 1, a step of;
2) To the reduced glutathione-Fe obtained in step 1) 2+ And adding a reducing agent into the precursor solution, and stirring and reacting for 30-120min at 15-35 ℃ to obtain the double-response fluorescent iron nanocluster probe.
It can be understood that the prepared dual-response fluorescent iron nanocluster probe is a dual-response fluorescent iron nanocluster probe solution.
Preferably, the mass concentration of the reduced glutathione in the reduced glutathione aqueous solution in the step 1) is 10-15mg/mL.
Preferably, the molar concentration of ferrous ions in the ferrous salt aqueous solution is 0.07-0.15 mol/L;
and/or the ferrous salt aqueous solution is FeCl 2 An aqueous solution.
Preferably, the adding mode of the ferrous salt aqueous solution in the step 1) is dropwise adding;
optionally, the dropping is dropwise adding.
Preferably, the stirring time in step 1) is 10-20 min.
Preferably, the reducing agent in step 2) is NaBH 4 ；
And/or the molar ratio of the reducing agent to ferrous ions in the ferrous salt aqueous solution is (2-7): 1.
preferably, the water used for preparing the reduced glutathione aqueous solution is high-purity water;
and/or the water used for preparing the ferrous salt aqueous solution is at least one of high-purity water and distilled water.
Preferably, the reduced glutathione-Fe 2+ The precursor solution is in a light yellow hydrogel shape;
the dual-response fluorescent iron nanocluster probe is a reddish brown fluorescent iron nanocluster solution.
The invention provides a double-response fluorescent iron nanocluster probe which is prepared by the preparation method.
The invention also provides a dual-response fluorescent iron nanocluster probe prepared by the preparation method or application of the dual-response fluorescent iron nanocluster probe in ammonia and/or hydrogen sulfide detection.
Optionally, the dual response fluorescent iron nanocluster probe needs to be diluted 50-1000 times when being used for detecting ammonia and/or hydrogen sulfide. The probe concentration depends on the concentration of the analyte, and when the concentration of the analyte is low, too high the probe concentration does not quench significantly, which affects the detection sensitivity. Molecular fluorescence has an internal filtering effect and a self-priming phenomenon, and the fluorescence intensity of a probe with larger concentration is low; the double-response fluorescent iron nanocluster probe is controlled to be diluted by 50-1000 times when ammonia or hydrogen sulfide is detected, the fluorescence intensity of the probe is proper, and the detection sensitivity can be effectively improved.
Optionally, the method for detecting ammonia comprises the following steps: construction of NH at different concentrations 3 Fluorescence signal quenching Rate (DeltaF/F) of standard solution to double-response fluorescent iron nanocluster probe 0 ) Is expressed as fluorescence signal quenching rate (DeltaF/F) 0 ) On the ordinate, NH 3 Drawing a standard curve by taking the concentration of the standard solution as the abscissa, and measuring NH in the sample to be measured according to the standard curve 3 Is a concentration of (2);
wherein Δf=f 0 -F，F 0 To not add NH 3 Double-response fluorescence intensity of fluorescent iron nanocluster probe in standard solution, wherein F is added NH 3 The standard solution is followed by dual response to the fluorescence intensity of the fluorescent iron nanocluster probe.
Optionally, the method applied to detecting hydrogen sulfide comprises the following steps: construction of different concentrations of H 2 Fluorescence signal enhancement (F-F) of S standard solution to dual-response fluorescent iron nanocluster probe 0 ) Is modeled as a fluorescence signal enhancement (F-F) 0 ) On the ordinate, H 2 Drawing a standard curve by taking the concentration of the S standard solution as the abscissa, and measuring H in the sample to be measured according to the standard curve 2 Concentration of S;
wherein F is 0 To not add H 2 Double-response fluorescence intensity of fluorescent iron nanocluster probe in S standard solution, F is added H 2 And (3) double-responding to the fluorescence intensity of the fluorescent iron nanocluster probe after the S standard solution.
The technical scheme of the invention has the following advantages:
the preparation method of the double-response fluorescent iron nanocluster probe provided by the invention comprises the following steps: 1) Adding ferrous salt aqueous solution into reduced glutathione aqueous solution, stirring to obtain reduced glutathione-Fe 2+ A precursor solution, wherein the molar ratio of the reduced glutathione in the reduced glutathione aqueous solution to ferrous ions in the ferrous salt aqueous solution is (3.6-4.6): 1, a step of; 2) Step toReduced glutathione-Fe obtained in step 1) 2+ And adding a reducing agent into the precursor solution, and stirring and reacting for 30-120min at 15-35 ℃ to obtain the double-response fluorescent iron nanocluster probe. The dual-response fluorescent iron nanocluster probe can generate fluorescent response to ammonia and hydrogen sulfide, and the fluorescence of the dual-response fluorescent iron nanocluster probe can be quenched by the ammonia and enhanced by the hydrogen sulfide. The double-response iron nanocluster probe provided by the invention is formed by directly reducing inorganic ferrous salt into zero-valent iron atoms in aqueous solution and accumulating the zero-valent iron atoms on a reduced glutathione template, wherein the molar ratio of reduced glutathione to ferrous ions is controlled to be (3.6-4.6): 1 and reduced glutathione-Fe 2+ The precursor solution and the reducing agent have specific reaction temperature and reaction time to form a new double-response fluorescent iron nanocluster probe, and the double-response fluorescent iron nanocluster probe can form a specific probe-ammonia compound after ammonia addition, so that the absorption of the probe at an excitation light position is reduced, and the fluorescence of the probe is quenched; after adding hydrogen sulfide to the probe, S 2- The reducibility of ions makes up the surface defect of the probe, so that the fluorescence of the probe is enhanced, the probe can simultaneously have sensitive fluorescence response to two environmental pollutants of ammonia and hydrogen sulfide, and the high-selectivity and high-sensitivity fluorescence detection of ammonia and hydrogen sulfide can be realized by only adopting one probe without an additional functional modification process. Meanwhile, the source of the iron element in the double-response fluorescent iron nanocluster probe is wide, noble metals are cheap and easy to obtain, and the preparation and use cost of the double-response fluorescent iron nanocluster probe is greatly lower than that of noble metal nanocluster fluorescent probes such as gold and silver.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a field emission transmission electron micrograph of a dual response fluorescent iron nanocluster probe according to example 1 of the present invention;
FIG. 2 is a graph showing fluorescence emission spectra of the dual-response fluorescence iron nanocluster probe of example 1 of the present invention before and after adding the target ammonia, the target hydrogen sulfide, and the respective reaction raw material mixtures;
FIG. 3 is a graph showing fluorescence emission spectra of the dual-response fluorescence iron nanocluster probe of example 2 of the present invention before and after adding the target ammonia, the target hydrogen sulfide, and the respective reaction raw material mixtures;
FIG. 4 is a graph showing fluorescence emission spectra of the dual-response fluorescence iron nanocluster probe of example 3 of the present invention before and after adding the target ammonia, the target hydrogen sulfide, and the respective reaction raw material mixtures;
FIG. 5 is a standard graph of ammonia building for GSH-Fe NCs probe detection in example 4 of the present invention;
FIG. 6 is a standard graph of construction of GSH-Fe NCs probe for detecting hydrogen sulfide in example 5 of the present invention;
FIG. 7 is a graph showing the fluorescence intensity of the probe of comparative example 1 of the present invention before and after the addition of the target;
FIG. 8 is a graph showing the comparison of fluorescence intensity of the probe of comparative example 2 of the present invention before and after the addition of the target;
FIG. 9 is a graph showing the fluorescence intensity of the probe of comparative example 3 of the present invention before and after the addition of the target;
FIG. 10 is a graph showing the ultraviolet-visible absorption spectrum of test example 1 of the present invention;
FIG. 11 is a graph showing the comparison of fluorescence quenching rates of the probes of example 1 and comparative example 1 according to the present invention after adding ammonia at different concentrations;
FIG. 12 is a graph showing the comparison of fluorescence enhancement rates of the probes of example 1 and comparative example 1 of the present invention after hydrogen sulfide was added at different concentrations.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a dual-response fluorescent iron nanocluster probe, which comprises the following steps:
1) Dissolving 0.1200. 0.1200 g reduced glutathione in 10 mL high purity water, stirring at room temperature until it is completely dissolved to form reduced glutathione water solution, dropwise adding 1. 1mL FeCl with concentration of 0.1 mol/L into reduced glutathione water solution 2 Stirring the high-purity water solution for 15 min to obtain light yellow hydrogel-like reduced glutathione-Fe 2+ A precursor solution;
2) To the reduced glutathione-Fe in step 1) 2+ Adding 0.0180 g reducing agent NaBH into the precursor solution 4 Stirring and reacting for 90 min at 25 ℃ to obtain reddish brown double-response fluorescent iron nanocluster probe solution.
Dispersing the double-response fluorescent iron nanocluster probe (marked as GSH-Fe NCs) of the embodiment into high-purity water, uniformly dripping the high-purity water on a copper mesh, airing the copper mesh to prepare an observation sample, and observing the appearance of the observation sample by using a field emission transmission electron microscope. As shown in FIG. 1, GSH-Fe NCs are approximately spherical in shape and uniformly dispersed, small in particle size and uniform in distribution, and the particle size is about 3 nm and the lattice width is about 0.22 nm as seen from an enlarged view.
The fluorescence spectrum of GSH-Fe NCs of this example was measured, and the fluorescence responses to two targets, ammonia and hydrogen sulfide:
the excitation wavelength was set to 510 and nm, and the reduced glutathione-Fe in example 1 was measured by a fluorescence spectrophotometer 2+ Precursor solution (denoted GSH+Fe) 2+ ) Reduced glutathione solution and NaBH in example 1 4 The mixed solution (denoted GSH+NaBH) 4 ) GSH-Fe NCs probe in example 1, 100-fold diluted solution, 500. Mu.L 500 nM ammonia solution +4.5 mL GSH-Fe NCs probe in example 1Fluorescence emission spectra of five test systems, 100-fold diluted solution, 500. Mu.L of 500 nM hydrogen sulfide solution +4.5 mL GSH-Fe NCs probe in example 1, 100-fold diluted solution. The results are shown in FIG. 2, GSH+Fe 2+ Precursor solution and GSH+NaBH 4 The mixture solutions all had no fluorescence emission, which was shown to be due to the newly formed GSH-Fe NCs by chemical reaction, rather than from a simple mixture or complex of the raw materials, only after formation of GSH-Fe NCs, which showed substantial ability as a fluorescent probe, at 695 nm. When the target ammonia and hydrogen sulfide are added into the detection system, the fluorescence of GSH-Fe NCs is obviously quenched by ammonia and enhanced by hydrogen sulfide, which indicates that the GSH-Fe NCs probe has fluorescence response to ammonia and hydrogen sulfide at the same time, and the response directions are opposite, the fluorescence of the GSH-Fe NCs probe can be quenched by ammonia and enhanced by hydrogen sulfide, and the GSH-Fe NCs probe can be effectively distinguished, and the GSH-Fe NCs probe has the capability of carrying out fluorescence detection to ammonia and hydrogen sulfide at the same time.
Example 2
The embodiment provides a dual-response fluorescent iron nanocluster probe, which comprises the following steps:
1) Dissolving 0.1000g reduced glutathione in 10 mL high purity water, stirring at room temperature until it is completely dissolved to form reduced glutathione water solution, dropwise adding 1.071 mol/L FeCl 1mL 2 Stirring the high-purity water solution for 10 min to obtain light yellow hydrogel-like reduced glutathione-Fe 2+ A precursor solution;
2) To the reduced glutathione-Fe in step 1) 2+ Adding a reducing agent NaBH of 0.01-g into the precursor solution 4 Stirring and reacting for 30 min at 20 ℃ to obtain the reddish brown dual-response fluorescent iron nanocluster probe.
The excitation wavelength was set to 510 and nm, and the reduced glutathione-Fe in example 2 was measured by a fluorescence spectrophotometer 2+ Precursor solution (denoted GSH+Fe) 2+ ) Reduced glutathione solution and NaBH in example 2 4 The mixed solution (denoted GSH+NaBH) 4 ) GSH-Fe NCs Probe thin in example 2Fluorescence emission spectra of 5 test systems, such as 100-fold release solution, 100-fold dilution of GSH-Fe NCs probe in example 2 with 500. Mu.L 500 nM ammonia solution, 100-fold dilution of GSH-Fe NCs probe in example 2 with 4.5 mL with 500. Mu.L 500 nM hydrogen sulfide solution, are shown in FIG. 3 2+ Precursor solution and GSH+NaBH 4 The mixture solution has no fluorescence emission, and only after GSH-Fe NCs are formed, the mixture solution has a strong fluorescence emission peak at 695 and nm, and when target ammonia and hydrogen sulfide are added into a detection system, the fluorescence of GSH-Fe NCs is obviously quenched by ammonia and enhanced by hydrogen sulfide.
Example 3
The embodiment provides a dual-response fluorescent iron nanocluster probe, which comprises the following steps:
1) Dissolving 0.1500 g reduced glutathione in 10 mL high purity water, stirring at room temperature until it is completely dissolved to form reduced glutathione water solution, dropwise adding 1. 1mL FeCl with concentration of 0.13 mol/L into reduced glutathione water solution 2 Stirring the high-purity water solution for 20min to obtain light yellow hydrogel-like reduced glutathione-Fe 2+ A precursor solution;
2) To the reduced glutathione-Fe in step 1) 2+ Adding a reducing agent NaBH of 0.03. 0.03 g into the precursor solution 4 Stirring and reacting for 120min at 30 ℃ to obtain the reddish brown dual-response fluorescent iron nanocluster probe.
The excitation wavelength was set to 510 and nm, and the reduced glutathione-Fe in example 3 was measured by a fluorescence spectrophotometer 2+ Precursor solution (denoted GSH+Fe) 2+ ) Reduced glutathione solution and NaBH in example 3 4 The mixed solution (denoted GSH+NaBH) 4 ) Fluorescence emission spectra of 5 test systems, such as 100-fold diluted GSH-Fe NCs probe in example 3, 500. Mu.L 500 nM ammonia solution, 4.5 mL 100-fold diluted GSH-Fe NCs probe in example 3, 500. Mu.L 500 nM hydrogen sulfide solution, and the like, are shown in FIG. 4 2+ Precursor solution and GSH+NaBH 4 None of the mixture solutions emitted fluorescence, only formedThe GSH-Fe NCs has a strong fluorescence emission peak at 695 and nm, and when the target ammonia and hydrogen sulfide are added into the detection system, the fluorescence of the GSH-Fe NCs is obviously quenched by the ammonia and enhanced by the hydrogen sulfide.
Example 4
This example provides a method for ammonia detection of the dual-response fluorescent iron nanocluster probe of example 1:
1) Preparing ammonia standard solutions with different concentrations: transferring 500 mu L of ammonia water solution with the concentration of 0.1 and M into a 50 mL volumetric flask, adding high-purity water to a constant volume to prepare ammonia high-standard stock solution with the concentration of 50.00 and mL of 1 and mM, and preparing ammonia standard solutions with the concentrations of 10 nM, 1000nM, 5000 and nM, 8000 and nM, 10000 and nM respectively by stepwise dilution based on the stock solution;
2) Diluting the GSH-Fe NCs original solution prepared in the example 1 by 100 times with high-purity water to prepare GSH-Fe NCs diluent;
3) Adding 500 mu L of GSH-Fe NCs diluent in the step 2) and 4.5 mL high purity water into a 5mL centrifuge tube, mixing uniformly, stabilizing for 30 min, and testing the fluorescence intensity of the test solution as the initial fluorescence intensity F of a probe 0 ；
4) Taking 5 centrifuge tubes of 5mL, adding 500 mu L of GSH-Fe NCs diluent and 4.0 mL high purity water in the step 2) into each centrifuge tube, adding 500 mu L of ammonia standard solution with concentration of 10 nM, 1000nM, 5000 nM, 8000 nM and 10000 nM into different centrifuge tubes, at the moment, detecting the ammonia concentration in the detection systems respectively to be 1 nM, 100 nM, 500 nM, 800 nM and 1000nM, shaking up the detection systems, and detecting the fluorescence intensity F of the probe in each system after the ammonia standard solution fully acts with the iron nanoclusters for 30 min;
5) Calculating the fluorescence quenching rate delta F/F of the probe of each system 0 = （F 0 -F）/F 0 And takes the ammonia as an ordinate, and the detection concentration of ammonia [ NH ] of each system 3 ]And drawing a standard curve for the abscissa, and constructing a model.
As shown in FIG. 5, the experimental results show that the quenching rate of GSH-Fe NCs fluorescence intensity and the detection concentration of ammonia show a linear relationship in the range of 1-1000 nM, and the linear equation is DeltaF/F 0 = 0.03588[NH 3 ]+ 0.18285, the detection limit is 0.23 nM. The GSH-Fe NCs can be used for high-sensitivity detection of ammonia as an environmental pollutant.
Example 5
This example provides a method of detecting hydrogen sulfide by the dual-response fluorescent iron nanocluster probe of example 1:
1) Preparation of hydrogen sulfide standard solutions with different concentrations (sodium sulfide aqueous solution is adopted to simulate hydrogen sulfide aqueous solution for ensuring experimental safety): weighing 0.12 g sodium sulfide solid, dissolving in 5mL high-purity water to prepare a high-standard hydrogen sulfide stock solution, and preparing hydrogen sulfide standard solutions with concentrations of 4000 nM, 6000 nM, 8000 nM, 9000 nM and 10000 nM respectively by stepwise dilution based on the stock solution;
2) Diluting the prepared GSH-Fe NCs stock solution by 100 times with high-purity water to prepare GSH-Fe NCs diluent;
3) Adding 500 mu L of GSH-Fe NCs diluent in the step 2) and 4.5 mL high purity water into a 5mL centrifuge tube, mixing uniformly, stabilizing for 30 min, and testing the fluorescence intensity of the test solution as the initial fluorescence intensity F of a probe 0 ；
4) Taking 5 centrifuge tubes of mL, adding 500 mu L of GSH-Fe NCs diluent and 4.0 mL high purity water in the step 2) into each centrifuge tube, adding 500 mu L of hydrogen sulfide standard solution with the concentration of 4000 nM, 6000 nM, 8000 nM, 9000 nM and 10000 nM into different centrifuge tubes, at the moment, detecting the concentration of hydrogen sulfide in detection systems of 400 nM, 600nM, 800 nM, 900 nM and 1000nM respectively, shaking up each detection system, and detecting the fluorescence intensity F of a probe in each system after the hydrogen sulfide standard solution fully acts with iron nanoclusters for 15 min;
5) Calculating the fluorescence enhancement quantity F-F of the probe of each system 0 And takes the hydrogen sulfide as the ordinate and the detection concentration of hydrogen sulfide of each system [ H ] 2 S]And drawing a standard curve for the abscissa, and constructing a model.
As shown in FIG. 6, the experimental result shows that in the range of 400-1000 nM of hydrogen sulfide concentration, the enhancement of GSH-Fe NCs fluorescence intensity and the detection concentration of hydrogen sulfide show a linear relationship, and the linear equation is F-F 0 = 0.03078[H 2 S] + 7.79503, the detection limit is 96 nM. The GSH-Fe NCs can be used for high-sensitivity detection of environmental pollutant hydrogen sulfide.
Comparative example 1
The comparative example provides a fluorescent iron nanocluster probe comprising the steps of:
1) Weighing 0.1000g of reduced Glutathione (GSH) and dissolving in 15mL of high-purity water; 1mL of 0.1M FeCl was removed 2 Adding the high-purity water solution into the GSH solution in the step 1), and fully stirring for 20min;
2) To the above reaction mixture was added 0.0190g of sodium borohydride solid under stirring, and the reaction was stirred at 25℃for 15 minutes, whereby the color of the reaction solution was changed from colorless to pale yellow, to obtain a final product solution.
The fluorescence iron nanocluster probe of the comparative example was diluted 100 times, and then added with ammonia and hydrogen sulfide at different concentrations to control the concentration of the detection substance in the detection system to 200nM, 600nM and 1000nM, and the excitation wavelength was set to 510 nM, and the fluorescence intensity was measured by a fluorescence spectrophotometer. The experimental results are shown in FIG. 7, in which the fluorescence of the probe is not significantly quenched or enhanced.
Comparative example 2
The comparative example provides a dual response fluorescent iron nanocluster probe comprising the steps of:
1) Dissolving 0.1200. 0.1200 g reduced glutathione in 10 mL high purity water, stirring at room temperature until it is completely dissolved to form reduced glutathione water solution, dropwise adding 1. 1mL FeCl with concentration of 0.1 mol/L into reduced glutathione water solution 2 Stirring the high-purity water solution for 15 min to obtain reduced glutathione-Fe 2+ A precursor solution;
2) To the reduced glutathione-Fe in step 1) 2+ Adding 0.0180 g reducing agent NaBH into the precursor solution 4 Stirring and reacting for 15 min at 25 ℃ to obtain the double-response fluorescent iron nanocluster probe.
The fluorescence intensity of the fluorescent iron nanocluster probe of the comparative example was measured by a fluorescence spectrophotometer after the fluorescent iron nanocluster probe was diluted 100 times and the concentrations of the detection substances in the ammonia and hydrogen sulfide control detection systems of different concentrations were 200nM, 600nM and 1000nM, and the excitation wavelength was set to be 510 nM, as shown in fig. 8, and the fluorescence of the probe was not significantly quenched or enhanced.
Comparative example 3
The comparative example provides a dual response fluorescent iron nanocluster probe comprising the steps of:
1) Dissolving 0.1000g reduced glutathione in 10 mL high purity water, stirring at room temperature until it is completely dissolved to form reduced glutathione water solution, dropwise adding 1. 1mL FeCl with concentration of 0.1 mol/L into reduced glutathione water solution 2 Stirring the high-purity water solution for 15 min to obtain reduced glutathione-Fe 2+ A precursor solution;
2) To the reduced glutathione-Fe in step 1) 2+ Adding 0.0180 g reducing agent NaBH into the precursor solution 4 Stirring and reacting for 90 min at 25 ℃ to obtain the double-response fluorescent iron nanocluster probe.
The fluorescence intensity of the fluorescent iron nanocluster probe of the comparative example was measured by a fluorescence spectrophotometer after the fluorescent iron nanocluster probe was diluted 100 times and the concentrations of the detection substances in the ammonia and hydrogen sulfide control detection systems of different concentrations were 200nM, 600nM and 1000nM, and the excitation wavelength was set to be 510 nM, as shown in fig. 9, and the fluorescence of the probe was not significantly quenched or enhanced.
Test example 1
The test example was directed to a 100-fold diluted solution of the fluorescent iron nanocluster probe prepared in example 1, a 100-fold diluted solution of the fluorescent iron nanocluster probe prepared in comparative example 1, and 500. 500 nM NH 3 Solution, 500 nM hydrogen sulfide solution, solution of 4.5 mL fluorescent iron nanocluster probe prepared in example 1 diluted 100 times +500. Mu.L of NH 500 nM 3 The solution, 4.5 mL the solution of 100 times diluted by the fluorescent iron nanocluster probe prepared in the example 1 and 500 mu L of 500 nM hydrogen sulfide solution are subjected to ultraviolet-visible absorption spectrum detection, and the wavelength range is 200-600nm. As shown in fig. 10, after the preparation conditions of the fluorescent iron nanocluster probe were changed, the ultraviolet absorption peak of the fluorescent iron nanocluster probe of example 1 was significantly blue-shifted compared with the ultraviolet absorption peak of comparative example 1, indicating that the structures of the two were different. Example 1 upon addition of NH 3 After that, the absorption peak is significantly blue shifted, illustrating GSH-Fe NCs and NH of example 1 3 New complexes are formed, at the same time NH is added 3 Then the absorption at the excitation wavelength is obviously reduced, which indicates that the target object NH 3 The fluorescence emission of the fluorescent iron nanocluster probe of example 1 can be quenched by reducing the absorption efficiency of excitation light by forming a new complex, which is a typical static quenching mechanism. Absorption of GSH-Fe NCs at excitation wavelength of example 1 at addition of H 2 S has a significant rise after that, indicating object H 2 S can enhance the absorption efficiency of the fluorescent iron nanocluster probe of the embodiment 1 on excitation light and enhance the fluorescence emission of the fluorescent iron nanocluster probe.
Test example 2
This test example detects different concentrations of target detection substances ammonia and hydrogen sulfide for the fluorescent iron nanocluster probes prepared in example 1 and comparative example 1. The detection method comprises the following steps:
1) Preparing target detection objects with different concentrations: respectively preparing 2000 nM, 6000 nM and 10000 nM ammonia standard solution and hydrogen sulfide standard solution;
2) Diluting the GSH-Fe NCs original solution prepared in the example 1 or the comparative example 1 by 100 times with high-purity water to prepare GSH-Fe NCs diluent;
3) Adding 500 mu L of GSH-Fe NCs diluent in the step 2) and 4.5 mL high purity water into a 5mL centrifuge tube, mixing uniformly, stabilizing for 30 min, and testing the fluorescence intensity of the test solution as the initial fluorescence intensity F of a probe 0 ；
4) Taking 5 centrifuge tubes of 5mL, adding 500 mu L of GSH-Fe NCs diluent and 4.0 mL high purity water in the step 2) into each centrifuge tube, adding 500 mu L of target detection object standard solutions with the concentration of 2000 nM, 6000 nM and 10000 nM into different centrifuge tubes, at the moment, the detection concentration of the target detection objects in the detection systems is 200nM, 600nM and 1000nM respectively, shaking the detection systems uniformly, and detecting the fluorescence intensity F of the probes in the detection systems after the target detection object standard solutions fully act with the iron nanoclusters for 30 min;
when the target detection object is ammonia, calculating the fluorescence quenching rate of the probe of each system（F 0 -F）/F 0 And the bar charts of example 1 and comparative example 1 were obtained with the values thereof as the ordinate, and the detection results are shown in fig. 11. When the target analyte is hydrogen sulfide, the fluorescence enhancement ratio (F-F 0 ）/F 0 And the values are taken as the ordinate to obtain a bar chart of example 1 and comparative example 1, and the detection results are shown in fig. 12. The fluorescent iron nanocluster probe of example 1 of the present invention has a relationship that is significantly quenched by ammonia and enhanced by hydrogen sulfide, whereas the fluorescent iron nanocluster probe of comparative example 1 does not have this rule.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (6)
1. The application of the dual-response fluorescent iron nanocluster probe in detecting ammonia and/or hydrogen sulfide is characterized in that the preparation method of the dual-response fluorescent iron nanocluster probe comprises the following steps:
1) Adding ferrous salt aqueous solution into reduced glutathione aqueous solution, stirring to obtain reduced glutathione-Fe 2+ Precursor solution of reduced glutathione-Fe 2+ The precursor solution is in a light yellow hydrogel shape, and the molar ratio of the reduced glutathione in the reduced glutathione aqueous solution to ferrous ions in the ferrous salt aqueous solution is (3.6-4.6): 1, a step of;
2) To the reduced glutathione-Fe obtained in step 1) 2+ Adding a reducing agent into the precursor solution, stirring and reacting for 30-120min at 15-35 ℃ to obtain the double-response fluorescent iron nanocluster probe, wherein the double-response fluorescent iron nanocluster probe is reddish brown fluorescent iron nanocluster solution, and the reducing agent is NaBH (sodium silicate-alumina) 4 The molar ratio of the reducing agent to ferrous ions in the ferrous salt aqueous solution is%2-7）：1。
2. The use according to claim 1, characterized in that the mass concentration of reduced glutathione in the aqueous solution of reduced glutathione in step 1) is 10-15mg/mL.
3. Use according to claim 1 or 2, characterized in that the molar concentration of ferrous ions in the aqueous ferrous salt solution is between 0.07 and 0.15 mol/L;
and/or the ferrous salt aqueous solution is FeCl 2 An aqueous solution.
4. The use according to claim 1 or 2, wherein the aqueous ferrous salt solution is added dropwise in step 1).
5. Use according to claim 1 or 2, wherein the stirring time in step 1) is 10-20 min.
6. The use according to claim 1, wherein the water used for preparing the reduced glutathione aqueous solution is high purity water;
and/or the water used for preparing the ferrous salt aqueous solution is at least one of high-purity water and distilled water.
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