CN114213385B - Fluorescein type ionic liquid, synthesis method thereof and application of fluorescein type ionic liquid in mercury ion or methyl mercury ion detection - Google Patents
Fluorescein type ionic liquid, synthesis method thereof and application of fluorescein type ionic liquid in mercury ion or methyl mercury ion detection Download PDFInfo
- Publication number
- CN114213385B CN114213385B CN202111446269.9A CN202111446269A CN114213385B CN 114213385 B CN114213385 B CN 114213385B CN 202111446269 A CN202111446269 A CN 202111446269A CN 114213385 B CN114213385 B CN 114213385B
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- fluo
- fluorescein
- type ionic
- mercury ions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 33
- 238000001514 detection method Methods 0.000 title claims abstract description 30
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 title claims abstract description 23
- DBUXSCUEGJMZAE-UHFFFAOYSA-N methylmercury(1+) Chemical compound [Hg+]C DBUXSCUEGJMZAE-UHFFFAOYSA-N 0.000 title abstract description 9
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 title abstract description 6
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- -1 mercury ions Chemical class 0.000 claims abstract description 60
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 96
- 239000000243 solution Substances 0.000 claims description 34
- 235000019441 ethanol Nutrition 0.000 claims description 28
- 230000005284 excitation Effects 0.000 claims description 24
- 239000000523 sample Substances 0.000 claims description 24
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 claims description 13
- 238000002189 fluorescence spectrum Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003957 anion exchange resin Substances 0.000 claims description 7
- 229910000370 mercury sulfate Inorganic materials 0.000 claims description 7
- 229940074994 mercuric sulfate Drugs 0.000 claims description 6
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 241001122767 Theaceae Species 0.000 claims description 4
- BABMCXWQNSQAOC-UHFFFAOYSA-M methylmercury chloride Chemical compound C[Hg]Cl BABMCXWQNSQAOC-UHFFFAOYSA-M 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000007850 fluorescent dye Substances 0.000 claims description 3
- KXDPICLMJAKLDW-UHFFFAOYSA-N CCCCCCCCCCCCCCP(CCCCCC)(CCCCCC)CCCCCC.Cl Chemical compound CCCCCCCCCCCCCCP(CCCCCC)(CCCCCC)CCCCCC.Cl KXDPICLMJAKLDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000012086 standard solution Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 235000020097 white wine Nutrition 0.000 claims 1
- 238000005342 ion exchange Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000004451 qualitative analysis Methods 0.000 abstract description 2
- 238000006862 quantum yield reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229940098773 bovine serum albumin Drugs 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 210000002381 plasma Anatomy 0.000 description 3
- 210000002700 urine Anatomy 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 238000001391 atomic fluorescence spectroscopy Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001176 liquid chromatography-inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 210000002966 serum Anatomy 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 108091006905 Human Serum Albumin Proteins 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000601 blood cell Anatomy 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003907 kidney function Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000003908 liver function Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229940008718 metallic mercury Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- G01N21/75—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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- 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"
- G01N2021/6432—Quenching
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pathology (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses a fluorescein type ionic liquid, a synthesis method thereof and application thereof in mercury ion or methyl mercury ion detection, wherein the fluorescein type ionic liquid has a chemical formula of [ Fluo ]][P 66614 ] 2 The structural formula is shown as formula (I); the invention synthesizes the ionic liquid with green fluorescence emission by a simple ion exchange method, and the method has simple synthesis steps and easily obtained raw materials; design of synthetic [ Fluo][P 66614 ] 2 The fluorescent ionic liquid has high quantum yield, good thermal stability and small environmental pollution; the invention can carry out qualitative analysis and quantitative detection on mercury ions and methyl mercury ions in the actual sample, and provides possibility for rapid detection of the mercury ions and the methyl mercury ions in the actual sample;
Description
Technical Field
The invention relates to a fluorescein type ionic liquid and a synthesis method thereof, and application thereof in fluorescence/colorimetric rapid detection of mercury ions or methyl mercury ions in an actual sample.
Background
Mercury and its compounds are extremely toxic heavy metal ion pollutants which are serious harm to the environment and human health, and the toxicity of mercury is greatly related to the existence state. The mercury mainly comprises three existing forms of metallic mercury, inorganic mercury and organic mercury, wherein Hg 2+ Is the main existing state in the water sample. Hg in water samples 2+ The mercury ions can be easily changed into methyl mercury ions with larger toxicity under the action of microorganisms or chemical reactions, are easily amplified through a food chain, are enriched in organisms, can be transported into tissues of the whole body through cell membranes by blood cell tissues after entering the human body, damage the central nervous system, influence the liver and kidney functions and cause the human body to be chronically poisoned.
The traditional detection methods for mercury ions and methyl mercury ions mainly comprise liquid chromatography-atomic fluorescence spectrometry (LC-AFS), liquid chromatography-inductively coupled plasma mass spectrometry (LC-ICP-MS), gas chromatography-atomic fluorescence spectrometry (GC-FS) and the like, and the detection methods generally have lower detection limit and higher sensitivity, but require precise and expensive large-scale instruments, depend on the operation of professionals, have longer detection time and cannot meet the requirement of detecting mercury ions and methyl mercury ions in real time. Therefore, a method for detecting methyl mercury ions with low cost, simple operation and high sensitivity needs to be established.
Ionic liquids are a compound that is liquid at or near room temperature and is composed entirely of anions and cations, also known as room temperature molten salts. As a functional material, ionic liquids have been widely used in various fields such as catalysts, solvents, electrochemistry and extraction. In recent years, fluorescent ionic liquids with strong fluorescence emission have attracted attention from many scientific researchers, and have been applied to detection of various harmful or effective components such as antioxidants, antibiotics, heavy metal ions and the like. The ionic liquid has excellent thermal stability and stable structure, and simultaneously has high adjustability and great development potential.
In order to solve the problems of long detection time, complex pretreatment and the like of mercury ions and methyl mercury ions in an actual sample, the invention synthesizes the ionic liquid [ Fluo ] with strong green fluorescence emission by a simple ion exchange method][P 66614 ] 2 The sensor can quench fluorescence after being complexed with mercury ions and methyl mercury ions, thereby providing possibility for detecting the mercury ions and the methyl mercury ions in an actual sample in real time.
Disclosure of Invention
The invention provides a fluorescein type ionic liquid and a synthesis method thereof, wherein the fluorescein type ionic liquid has high sensitivity and specificity to mercury ions and methyl mercury ions, can be used for rapidly detecting the mercury ions and the methyl mercury ions in an actual sample, and has the advantages of low detection limit, high sensitivity, obvious visual effect and simplicity in operation.
The invention emits with green fluorescenceIonic liquids [ Fluo][P 66614 ] 2 Is a fluorescent/colorimetric probe, and takes mercury ion or methyl mercury ion as an object to be detected, when the mercury ion or methyl mercury ion is combined with [ Fluo ]][P 66614 ] 2 Complexing will result in [ Fluo ]][P 66614 ] 2 The fluorescence of the fluorescent probe is obviously quenched, and then the accurate identification and quantitative detection of mercury ions or methyl mercury ions in a complex matrix are realized according to a fitted linear curve.
The technical scheme of the invention is as follows:
fluorescein type ionic liquid with chemical formula of [ Fluo ]][P 66614 ] 2 The structural formula is shown as formula (I):
the invention relates to a fluorescein type ionic liquid [ Fluo ]][P 66614 ] 2 The preparation method of (2) is as follows:
will [ P ] 66614 ][OH]Mixing with fluorescein in absolute ethyl alcohol, stirring at 40-80 deg.C for reaction for 8-20 hr, vacuum evaporating solvent and drying to obtain fluorescein type ionic liquid][P 66614 ] 2 (orange viscous liquid);
the structural formula of the fluorescein is shown as a formula (II):
the [ P ] 66614 ][OH]The molar ratio of the fluorescent dye to the fluorescein is 1.5-2.5: 1, a step of;
the [ P ] 66614 ][OH]The preparation method comprises the following steps:
trihexyl (tetradecyl) phosphine chloride ([ P ] 66614 ][Cl]) Adding the ethanol solution into a chromatographic column filled with strong alkaline anion exchange resin, and collecting effluent liquid 66614 ][OH]Ethanol solution (without evaporating to dryness, used directly in subsequent reactions);
the strong base anion exchange resin is 717 strong base type I anionThe sub-exchange resin is pretreated as follows before use: the anion exchange resin is filled in a packed column and washed with 1 to 2mol/L sodium hydroxide aqueous solution until the solution of acidified silver nitrate is added dropwise into the effluent liquid without generating white precipitate (proved to be Cl-free) - Existing), then washing with deionized water to ph=7.0, and finally washing with absolute ethanol, and completely washing out the deionized water in the packed column for later use.
The invention relates to a fluorescein type ionic liquid [ Fluo ]][P 66614 ] 2 Can be used as a fluorescent/colorimetric probe for rapidly detecting mercury ions or methyl mercury ions in an actual sample. The actual sample is for example: tea, white spirit, urine, human blood plasma, human serum and bovine serum albumin.
The specific application method comprises the following steps:
(1) Drawing a standard curve
Fluorescein-type ionic liquid [ Fluo ]][P 66614 ] 2 Dissolving in absolute ethanol, adding standard solution prepared from mercuric sulfate or methylmercury chloride standard substance, and scanning under excitation wavelength of 460nm and excitation and emission slit width of 10nm][P 66614 ] 2 The fluorescence emission spectrum records the position of a fluorescence emission peak and the corresponding fluorescence intensity;
by F 1 /F 0 Performing linear fitting on the ordinate and the abscissa of the concentration of the mercury sulfate to establish a standard curve of mercury ions; wherein F is 0 、F 1 Respectively adding Hg 2+ Front and back [ Fluo][P 66614 ] 2 Is a fluorescent intensity of (2);
by F 1 /F 0 Performing linear fitting on the ordinate and the concentration of the methylmercury chloride as the abscissa, and establishing a standard curve of methylmercury ions; wherein F is 0 、F 1 Respectively add CH 3 Hg + Front and back [ Fluo][P 66614 ] 2 Is a fluorescent intensity of (2);
(2) Actual sample detection
Fluorescein-type ionic liquid [ Fluo ]][P 66614 ] 2 Dissolving in absolute ethanol to give [ Fluo ]][P 66614 ] 2 The fluorescence intensity of (C) is 800 to ultra-high at 460nm excitation wavelength1200a.u.; then adding an actual sample to be detected, collecting fluorescence emission spectra under the conditions that the excitation wavelength is 460nm and the widths of the excitation slit and the emission slit are 10nm, and recording the position of a fluorescence emission peak and the corresponding fluorescence intensity; and finally, quantifying the mercury ions and methyl mercury ions in the actual sample according to the linear curve fitted in the step (1).
The fluorescence spectrum measurement conditions in the invention are that the excitation wavelength is 460nm, the widths of the excitation slit and the emission slit are 10nm, and the measurement range of the emission wavelength is 475-620 nm.
Compared with the prior art, the invention has the following beneficial effects:
(1) The ionic liquid with green fluorescence emission is synthesized by a simple ion exchange method, and the method has simple synthesis steps and easily obtained raw materials;
(2) Design of synthetic [ Fluo][P 66614 ] 2 The fluorescent ionic liquid has high quantum yield, good thermal stability and small environmental pollution;
(3) Ionic liquid [ Fluo ] prepared][P 66614 ] 2 The method has strong specificity and sensitivity to mercury ions and methyl mercury ions, and has obvious visual effect on mercury ion and methyl mercury ion detection;
(4) The invention can carry out qualitative analysis and quantitative detection on the mercury ions and the methyl mercury ions in the actual sample, and provides possibility for rapid detection of the mercury ions and the methyl mercury ions in the actual sample.
Drawings
FIG. 1 shows the reaction of the present invention in [ Fluo][P 66614 ] 2 Fluorescence emission spectra of ethanol solutions with different concentrations (1 nmol,3nmol,5nmol,7nmol,10nmol,15nmol,20nmol,25nmol,30nmol,35nmol,40 nmol) of mercury sulfate were added to the ethanol solutions.
FIG. 2 shows the invention in terms of F 0 /F 1 On the ordinate, the mercury sulfate concentration (1-15 nM) is a linear curve fitted on the abscissa.
FIG. 3 shows the reaction of the present invention in [ Fluo][P 66614 ] 2 Adding different concentrations (0, 100nmol,10nmol,1nmol,0.1nmol,0.01 nmol) of mercuric sulfate in ethanol solutionVisual photographs taken under irradiation of ultraviolet lamps.
FIG. 4 shows the reaction of the present invention in [ Fluo][P 66614 ] 2 Adding mercuric sulfate ethanol solution (30 mu mol), methylmercury ion ethanol solution (30 mu mol) and F of other common metal ions into the ethanol solution of the mercuric sulfate 0 And F is equal to 1 Is a ratio graph of (2).
FIG. 5 shows the results of the present invention in the actual samples (white spirit, tea, human plasma, human serum, bovine serum albumin, urine) for the labeled recovery.
FIG. 6 shows the present invention in [ Fluo][P 66614 ] 2 To the ethanol solution of different concentrations (0, 1. Mu. Mol, 3. Mu. Mol, 5. Mu. Mol, 7. Mu. Mol, 10. Mu. Mol, 30. Mu. Mol, 50. Mu. Mol, 70. Mu. Mol) of methyl mercury ions.
FIG. 7 shows the invention in F 0 /F 1 The methyl mercury ion concentration (0.1-5. Mu.M) is plotted on the ordinate as a linear curve fitted on the abscissa.
FIG. 8 shows the present invention in [ Fluo ]][P 66614 ] 2 To the ethanol solution of methyl mercury ions of different concentrations (0,0.1. Mu. Mol, 1. Mu. Mol, 10. Mu. Mol) were added, and a visual photograph was taken under irradiation of an ultraviolet lamp.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to illustrate the present invention further, but are not to be construed as limiting its scope, as claimed.
The chemicals and solvents used in the examples were all analytically pure, the strongly basic anion exchange resin was 717 strongly basic type I anion exchange resin, available from ala Ding Huaxue inc.
The fluorescence spectrum measurement conditions are that the excitation wavelength is 460nm, the emission wavelength is 475-620 nm, and the excitation and emission slit widths are 10nm.
Example 1
The specific synthesis method of the fluorescent ionic liquid comprises the following steps:
(1)[P 66614 ][Cl]is subjected to dechlorination treatment:
will [ P ] 66614 ][Cl]Slowly adding the ethanol solution into a chromatographic column filled with strong alkaline anion exchange resin, and collecting effluent liquid [ P ] 66614 ][OH]Is a solution of (a) in ethanol.
(2) Fluorescent ionic liquid [ Fluo][P 66614 ] 2 Is prepared from
Weigh 2mol fluorescein and 4mol [ P ] 66614 ][OH]Is placed in a 250ml round bottom flask, 50ml of absolute ethanol is added, and the mixture is reacted for 12 hours in an oil bath at 60 ℃ while being heated and stirred. Removing solvent from the product solution after reaction by rotary evaporator, heating in 60 deg.C oil bath, and introducing nitrogen gas (about 30 min) while heating to obtain orange yellow viscous liquid. And (5) sealing and preserving at room temperature.
Example 2
A fluorescence/colorimetric detection method for rapidly detecting mercury ions in an actual sample, comprising the following specific steps:
(1) Detection of mercury ions by fluorescence/colorimetric probes:
configuration [ Fluo][P 66614 ] 2 The concentration is 1 multiplied by 10 -3 The ethanol solution of mol/L is used as stock solution, and the stock solution is diluted 100 times before fluorescence test. 200 μl of [ Fluo ] was taken][P 66614 ] 2 The fluorescence emission spectra of the solutions were collected in quartz microcuvettes after which ethanol solutions of different concentrations (1 nmol,3nmol,5nmol,7nmol,10nmol,15nmol,20nmol,25nmol,30nmol,35nmol,40 nmol) of mercury sulfate were added. The excitation wavelength was 460nm and the excitation and emission slit widths were 10nm. The highest fluorescence intensity was recorded. And quantitatively detecting mercury ions according to the fitted linear curve. As shown in fig. 2, the linear correlation coefficient R 2 =0.996, detection limit of 0.4nmol, linear range of 1 to 15nmol.
The ethanol solutions with different concentrations (0, 100nmol,10nmol,1nmol,0.1nmol,0.01 nmol) of mercury ions were added under UV camera, as shown in FIG. 3, and the minimum possible visual detection of 0.1nmol of mercury ions was achieved.
(2) Common metal ion and anion pair [ Fluo][P 66614 ] 2 Detection of interference of mercury ions
200 μl of 1×10 -5 mol/L [ Fluo ]][P 66614 ] 2 Ethanol solution and 300. Mu.l 1X 10 -7 Ethanol solution of mol/L mercuric sulfate or 100. Mu.l 1X 10 -5 mol/L of other metal ions (AgNO 3 ,Zn(Ac) 2 ,MgCl 2 ,KCl,BaCl 2 ,NiCl 2 ,ZnCl 2 ,Pb(NO 3 ) 2 ,CdCl 2 ,Ni(NO 3 ) 2 ,Zn(NO 3 ) 2 ,CaCl 2 ,Co(NO 3 ) 3 ,ZnSO 4 ,Cu(NO 3 ) 2 ,CuSO 4 ,MnCl 2 ,Al(NO 3 ) 3 ,CuCl 2 ,Mn(Ac) 4 ,FeCl 2 ,FeSO 4 ,Fe(NO 3 ) 3 ,FeCl 3 ,Cr(NO 3 ) 3 ,NaCl,Na 3 PO 4 ,Na 2 S,K 2 CO 3 ) And (2) ethanol solution, using absolute ethanol to fix the volume to 1ml, and collecting fluorescence emission spectra under the conditions that the excitation wavelength is 460nm and the widths of excitation and emission slits are 10nm. Before and after adding different metal ions [ Fluo ]][P 66614 ] 2 Ratio of fluorescence intensity of solution (F 0 /F 1 ) The species of metal ions are plotted on the ordinate as a bar graph on the abscissa, as shown in fig. 4.
(3) Detection of mercury ions in actual samples
0.05g of tea leaves and a certain amount of mercury sulfate are soaked in 5ml of ethanol for 10min, and the supernatant is taken. 200 μl of 1×10 is added -5 mol/L [ Fluo ]][P 66614 ] 2 The ethanol solution collects fluorescence emission spectra under the conditions that the excitation wavelength is 460nm and the widths of the excitation slit and the emission slit are 10nm.
Similarly, a certain amount of mercury sulfate was added to white spirit, urine, human serum (0.01 g in 10ml of absolute ethanol solution), human plasma (100. Mu.l in 9.9ml of absolute ethanol), bovine serum albumin (0.01 g in 10ml of absolute ethanol solution), and the actual sample was analyzed for mercury ions by the addition-labeling recovery method, as shown in FIG. 5.
Example 3
A fluorescence/colorimetric detection method for rapidly detecting methyl mercury ions, which comprises the following specific steps:
(1) Detection of methyl mercury ions by fluorescent/colorimetric probes:
configuration [ Fluo][P 66614 ] 2 The concentration is 1 multiplied by 10 -3 The ethanol solution of mol/L is used as stock solution, and the stock solution is diluted 100 times before fluorescence test. 200 μl of [ Fluo ] was taken][P 66614 ] 2 In a quartz microcuvette, ethanol solutions of different concentrations (0, 1. Mu. Mol, 3. Mu. Mol, 5. Mu. Mol, 7. Mu. Mol, 10. Mu. Mol, 30. Mu. Mol, 50. Mu. Mol, 70. Mu. Mol) of methyl mercury ions were then added and the fluorescence emission spectra of the solutions were collected (FIG. 6). The excitation wavelength was 460nm and the excitation and emission slit widths were 10nm. The highest fluorescence intensity was recorded. And quantitatively detecting the methylmercury ions according to the fitted linear curve. As shown in fig. 7, the linear correlation coefficient R 2 The detection limit was 60nmol, and the linear range was 0.1 μmol to 5 μmol, = 0.9913.
The ethanol solutions to which different concentrations (0,0.1. Mu. Mol, 1. Mu. Mol, 10. Mu. Mol) of methylmercury ions were added were observed under an ultraviolet camera, as shown in FIG. 8, and a minimum of 0.1. Mu. Mol methylmercury ions were visually detected.
(2) Common metal ion and anion pair [ Fluo][P 66614 ] 2 Detection of interference of methylmercury ions
200 μl of 1×10 -5 mol/L [ Fluo ]][P 66614 ] 2 Ethanol solution and 100. Mu.l 1X 10 -6 Ethanol solution of mol/L methyl mercury ion or 100 μl of 1×10 -5 mol/L of other metal ions (AgNO 3 ,Zn(Ac) 2 ,MgCl 2 ,KCl,BaCl 2 ,NiCl 2 ,ZnCl 2 ,Pb(NO 3 ) 2 ,CdCl 2 ,Ni(NO 3 ) 2 ,Zn(NO 3 ) 2 ,CaCl 2 ,Co(NO 3 ) 3 ,ZnSO 4 ,Cu(NO 3 ) 2 ,CuSO 4 ,MnCl 2 ,Al(NO 3 ) 3 ,CuCl 2 ,Mn(Ac) 4 ,FeCl 2 ,FeSO 4 ,Fe(NO 3 ) 3 ,FeCl 3 ,Cr(NO 3 ) 3 ,NaCl,Na 3 PO 4 ,Na 2 S,K 2 CO 3 ) And (2) ethanol solution, using absolute ethanol to fix the volume to 1ml, and collecting fluorescence emission spectra under the conditions that the excitation wavelength is 460nm and the widths of excitation and emission slits are 10nm. Before and after adding different metal ions [ Fluo ]][P 66614 ] 2 Ratio of fluorescence intensity of solution (F 0 /F 1 ) The species of metal ions are plotted on the ordinate as a bar graph on the abscissa, as shown in fig. 4.
Claims (4)
1. The application of fluorescein type ionic liquid as a fluorescence/colorimetric probe in detection of mercury ions or methyl mercury ions in an actual sample; the actual sample is tea or white wine;
the chemical formula of the fluorescein type ionic liquid is [ Fluo ]][P 66614 ] 2 The structural formula is shown as formula (I):
2. use according to claim 1, wherein the fluorescein-type ionic liquid [ Fluo ]][P 66614 ] 2 The preparation method of (2) comprises the following steps:
will [ P ] 66614 ][OH]Mixing with fluorescein in absolute ethyl alcohol, stirring at 40-80 deg.C for reaction for 8-20 hr, vacuum evaporating solvent and drying to obtain fluorescein type ionic liquid][P 66614 ] 2 ;
The structural formula of the fluorescein is shown as a formula (II):
the [ P ] 66614 ][OH]The molar ratio of the fluorescent dye to the fluorescein is 1.5-2.5: 1.
3. the use according to claim 2, whereinIn that the [ P ] 66614 ][OH]The preparation method comprises the following steps:
adding ethanol solution of trihexyl (tetradecyl) phosphine chloride into chromatographic column with strong alkaline anion exchange resin, and collecting effluent to obtain [ P ] 66614 ][OH]Is a solution of (a) in ethanol.
4. The application according to claim 1, wherein the method of application is:
(1) Drawing a standard curve
Fluorescein-type ionic liquid [ Fluo ]][P 66614 ] 2 Dissolving in absolute ethanol, adding standard solution prepared from mercuric sulfate or methylmercury chloride standard substance, and scanning under excitation wavelength of 460nm and excitation and emission slit width of 10nm][P 66614 ] 2 The fluorescence emission spectrum records the position of a fluorescence emission peak and the corresponding fluorescence intensity;
by F 1 /F 0 Performing linear fitting on the ordinate and the abscissa of the concentration of the mercury sulfate to establish a standard curve of mercury ions; wherein F is 0 、F 1 Respectively adding Hg 2+ Front and back [ Fluo][P 66614 ] 2 Is a fluorescent intensity of (2);
by F 1 /F 0 Performing linear fitting on the ordinate and the concentration of the methylmercury chloride as the abscissa, and establishing a standard curve of methylmercury ions; wherein F is 0 、F 1 Respectively add CH 3 Hg + Front and back [ Fluo][P 66614 ] 2 Is a fluorescent intensity of (2);
(2) Actual sample detection
Fluorescein-type ionic liquid [ Fluo ]][P 66614 ] 2 Dissolving in absolute ethanol to give [ Fluo ]][P 66614 ] 2 The fluorescence intensity of (2) is 800-1200 a.u. at 460nm excitation wavelength; then adding an actual sample to be detected, collecting fluorescence emission spectra under the conditions that the excitation wavelength is 460nm and the widths of the excitation slit and the emission slit are 10nm, and recording the position of a fluorescence emission peak and the corresponding fluorescence intensity; finally, according to the linear curve fitted in the step (1), the mercury ions and methyl mercury ions in the actual sample are determinedAmount of the components.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111446269.9A CN114213385B (en) | 2021-11-30 | 2021-11-30 | Fluorescein type ionic liquid, synthesis method thereof and application of fluorescein type ionic liquid in mercury ion or methyl mercury ion detection |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111446269.9A CN114213385B (en) | 2021-11-30 | 2021-11-30 | Fluorescein type ionic liquid, synthesis method thereof and application of fluorescein type ionic liquid in mercury ion or methyl mercury ion detection |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114213385A CN114213385A (en) | 2022-03-22 |
CN114213385B true CN114213385B (en) | 2023-07-11 |
Family
ID=80699091
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111446269.9A Active CN114213385B (en) | 2021-11-30 | 2021-11-30 | Fluorescein type ionic liquid, synthesis method thereof and application of fluorescein type ionic liquid in mercury ion or methyl mercury ion detection |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114213385B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115745940B (en) * | 2022-10-24 | 2023-12-05 | 浙江工业大学 | Sulfonyl fluorescein ionic liquid probe and synthesis method and application thereof |
CN115541551B (en) * | 2022-10-24 | 2024-01-16 | 浙江工业大学 | Rapid on-site detection of paraquat by using anion functionalized ion probe |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8920673B2 (en) * | 2010-12-02 | 2014-12-30 | Los Alamos National Security, Llc | Phosphonium-based ionic liquids and uses |
CN106220640B (en) * | 2016-06-29 | 2018-06-01 | 河南师范大学 | A kind of mercury ion fluorescence probe and its preparation method and application |
CN108456514B (en) * | 2018-05-29 | 2020-11-13 | 东华大学 | Fluorescein fluorescent probe for detecting mercury ions and preparation method and application thereof |
-
2021
- 2021-11-30 CN CN202111446269.9A patent/CN114213385B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN114213385A (en) | 2022-03-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Wu et al. | A specific turn-on fluorescent sensing for ultrasensitive and selective detection of phosphate in environmental samples based on antenna effect-improved FRET by surfactant | |
CN114213385B (en) | Fluorescein type ionic liquid, synthesis method thereof and application of fluorescein type ionic liquid in mercury ion or methyl mercury ion detection | |
Bağ et al. | Determination of Cu, Zn, Fe, Ni and Cd by flame atomic absorption spectrophotometry after preconcentration by Escherichia coli immobilized on sepiolite | |
Wu et al. | A selective fluorescent sensor for Hg2+ based on covalently immobilized naphthalimide derivative | |
Tabrizi | Development of a cloud point extraction-spectrofluorimetric method for trace copper (II) determination in water samples and parenteral solutions | |
JP2011158425A (en) | Visual fluorescence analysis device, and analysis method for trace heavy metal using the same | |
Ibrahim et al. | Sensitive and selective colorimetric nitrite ion assay using silver nanoparticles easily synthesized and stabilized by AHNDMS and functionalized with PABA | |
Tabaraki et al. | Green and simple turn off/on fluorescence sensor for mercury (II), cysteine and histidine | |
Yun et al. | A novel benzophenone-based colorimetric chemosensor for detecting Cu^ 2+ Cu 2+ and F^-F | |
Li et al. | A robust gold nanocluster-peroxyoxalate chemiluminescence system for highly sensitive detection of cyanide in environmental water | |
Dey | A simple strategy for the visual detection and discrimination of Hg 2+ and CH 3 Hg+ species using fluorescent nanoaggregates | |
Bagheri et al. | Combining gold nanoparticle-based headspace single-drop microextraction and a paper-based colorimetric assay for selenium determination | |
CN113788788B (en) | Fluorescent ionic liquid and synthesis method and application thereof | |
Ren et al. | Fabrication of silver nanoclusters with enhanced fluorescence triggered by ethanol solvent: a selective fluorescent probe for Cr 3+ detection | |
Shahat et al. | Spectrophotometric and fluorometric methods for the determination of Fe (III) ions in water and pharmaceutical samples | |
Aatif et al. | Pyridinecarbohydrazide-based fluorescent chemosensor for In3+ ions and its applications in water samples, live cells, and zebrafish imaging | |
Zhao et al. | A FRET-based ratiometric fluorescent probe for Hg2+ detection in aqueous solution and bioimaging in multiple samples | |
Kim et al. | Spectrofluorimetric determination of copper (II) by its static quenching effect on the fluorescence of 4, 5-dihydroxy-1, 3-benzenedisulfonic acid | |
CN114854405A (en) | Multi-emission fluorescent carbon dot and preparation method and application thereof | |
Saçmacı et al. | Selective extraction, separation and speciation of iron in different samples using 4-acetyl-5-methyl-1-phenyl-1H-pyrazole-3-carboxylic acid | |
CN108640867B (en) | Fluorescent probe compound containing cyano-carbazolyl Schiff base as well as preparation method and application thereof | |
CN109928912B (en) | Fluorescent probe for identifying mercury ions and preparation and identification methods thereof | |
Fu et al. | Detection of malachite green residue in aquaculture water by using a rare earth fluorescence probe | |
CN109053711B (en) | Probe compound for mercury ion detection and preparation method and application thereof | |
Zhang et al. | Morphological analysis of chromium in carbon quantum dots pairs Co-doped with zirconium and nitrogen and their applications in imaging of living cells |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |