CN108102645A - The preparation and application of a kind of fluorescence probe for hypochlorite ion's detection - Google Patents
The preparation and application of a kind of fluorescence probe for hypochlorite ion's detection Download PDFInfo
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- CN108102645A CN108102645A CN201711320024.5A CN201711320024A CN108102645A CN 108102645 A CN108102645 A CN 108102645A CN 201711320024 A CN201711320024 A CN 201711320024A CN 108102645 A CN108102645 A CN 108102645A
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- fluorescence probe
- hypochlorite
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- 239000000523 sample Substances 0.000 title claims abstract description 71
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000001514 detection method Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003384 imaging method Methods 0.000 claims description 12
- 239000000741 silica gel Substances 0.000 claims description 12
- 229910002027 silica gel Inorganic materials 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000003480 eluent Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 230000006837 decompression Effects 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 5
- 230000000007 visual effect Effects 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical class Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical class [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- 230000005284 excitation Effects 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- HZDNNJABYXNPPV-UHFFFAOYSA-N (2-chloro-2-oxoethyl) acetate Chemical class CC(=O)OCC(Cl)=O HZDNNJABYXNPPV-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims description 2
- 150000002475 indoles Chemical class 0.000 claims description 2
- 238000005424 photoluminescence Methods 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims 2
- 150000007980 azole derivatives Chemical class 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 150000002923 oximes Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 2
- 238000011896 sensitive detection Methods 0.000 abstract 2
- 239000000975 dye Substances 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 10
- 239000005708 Sodium hypochlorite Substances 0.000 description 8
- 229960001866 silicon dioxide Drugs 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- 239000007853 buffer solution Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000004113 cell culture Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 102000003896 Myeloperoxidases Human genes 0.000 description 2
- 108090000235 Myeloperoxidases Proteins 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000003501 hydroponics Substances 0.000 description 2
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000003642 reactive oxygen metabolite Substances 0.000 description 2
- UXTFKIJKRJJXNV-UHFFFAOYSA-N 1-$l^{1}-oxidanylethanone Chemical compound CC([O])=O UXTFKIJKRJJXNV-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- MFFMQGGZCLEMCI-UHFFFAOYSA-N 2,4-dimethyl-1h-pyrrole Chemical class CC1=CNC(C)=C1 MFFMQGGZCLEMCI-UHFFFAOYSA-N 0.000 description 1
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- 201000001320 Atherosclerosis Diseases 0.000 description 1
- 0 CC(C1*)=C(*)N[C@]1C(C=NO)=C1N=C(*)C(*)C1* Chemical compound CC(C1*)=C(*)N[C@]1C(C=NO)=C1N=C(*)C(*)C1* 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229940054051 antipsychotic indole derivative Drugs 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VQLYBLABXAHUDN-UHFFFAOYSA-N bis(4-fluorophenyl)-methyl-(1,2,4-triazol-1-ylmethyl)silane;methyl n-(1h-benzimidazol-2-yl)carbamate Chemical compound C1=CC=C2NC(NC(=O)OC)=NC2=C1.C=1C=C(F)C=CC=1[Si](C=1C=CC(F)=CC=1)(C)CN1C=NC=N1 VQLYBLABXAHUDN-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010980 drying distillation Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000007124 immune defense Effects 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 238000009630 liquid culture Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 210000004493 neutrocyte Anatomy 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 201000003068 rheumatic fever Diseases 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000000451 tissue damage Effects 0.000 description 1
- 231100000827 tissue damage Toxicity 0.000 description 1
Classifications
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- 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
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—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
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- 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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms
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- General Physics & Mathematics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Optics & Photonics (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a kind of preparations and application of the fluorescence probe for hypochlorite ion's detection.The present invention, as fluorescent parent, is introduced oximido in No. 8 positions of the glimmering parent of fluorine boron and responds group as hypochlorite using the glimmering dyestuff of fluorine boron；In the presence of hypochlorite, photophysical property changes fluorescence probe.Fluorescence probe of the present invention can realize highly selective, the highly sensitive detection to hypochlorite ion, and possibility is provided to build a kind of chemical biosensor of highly selective, highly sensitive detection hypochlorite ion.
Description
Technical field
The present invention relates to it is a kind of available for hypochlorite ion detection fluorescence probe preparation and its in hypochlorite
The purposes in ion chemistry bio-sensing field.
Background technology
Reactive active oxygen is a kind of important bioactive substance being widely present in vivo.Hypochlorite
(ClO-) ion is a kind of common active oxygen species.In field of biology, hypochlorite microorganism immune defense with
And it is also played an important role in inflammation.In neutrophil leucocyte, under the catalytic action of myeloperoxidase, hydrogen peroxide
It has an effect with intracellular chlorion and generates hypochlorite ion.But the factors meeting such as disorderly expression of myeloperoxidase
Cause horizontal not normal of hypochlorite concentration in organism, this can trigger serious tissue damage and corresponding disease, such as artery
Atherosclerosis, the rheumatic arthritis even generation of tumour.Therefore, by detecting hypochlorite concentration abnormal in organism
It can predict specific disease.
The method for being usually used in hypochlorite detection at present has electrochemical methods, spectrophotometry and chemoluminescence method etc..
It is different from traditional detection method, biodiversity resources technology by using highly sensitive fluorescence probe carry out luminescent marking so as to
The in vivo hypochlorite of biology is detected.Due to fluorescence probe have highly sensitive, high-resolution and multidimensional data acquisition and
The advantages that real time imagery, biodiversity resources have become a kind of real-time, hypochlorite detection method of Noninvasive.Secondary chlorine
Acid group concentration variation in biological cell is very fast, so detecting hypochlorous fluorescence probe needs certain response speed, to reach
To the purpose detected in real time to biosystem hypochlorite.There is substantial amounts of different types of active oxygen object in organism
Kind (such as superoxide radical, hydroxyl radical free radical, hydrogen peroxide, singlet oxygen), in item existing for other interfering ions or molecule
Under part, internal hypochlorite is identified in specific manner, it is necessary to which probe molecule has preferable anti-interference.
The content of the invention
The present invention is provided a kind of with fast response time, good, high sensitivity the secondary chlorine of selectivity by Molecular Design
Sour fluorescence probe.A kind of fluorescence probe for hypochlorite ion's detection, which is characterized in that draw No. 8 positions of the glimmering parent of fluorine boron
Enter oximido, there is following general structure：
Wherein, R1And R3Respectively there is the alkyl chain or hydrogen of 1 to 6 carbon, R2To have the alkyl chain of 1 to 6 carbon, hydrogen
Or cyano；
Wherein, R4To contain the alkyl chain or hydrogen of not more than 2 carbon, R5To R8To have the alkyl chain or hydrogen of 1 to 6 carbon.
Synthetic route is specific as follows：
Detailed process is as follows：
(1) by compound 1 (pyrroles or indole derivatives, as shown in reaction scheme) (10mmol) and 0.7mL acetyl oxygen
Base chloroacetic chloride (6.5mmol) is dissolved in the dichloromethane of 10mL drying anaerobics, be protected from light 1 it is small when after, it is to be restored to room temperature
Add in 3.5mL N, N- diisopropyl ethyl amines (21mmol)；Reaction adds in the complexing of 2.49mL Eorontrifluoride etherates after 30 minutes
Object (19mmol), reaction 1 it is small when after stop reaction, decompression be spin-dried for solvent.With silica gel post separation, eluant, eluent proportioning for petroleum ether/
Dichloromethane=1:1, obtain solid product 2；
(2) mixing that product 2 (1mmol) and 84mg lithium hydroxides (2mmol) are dissolved in 50mL tetrahydrofurans and water is molten
(volume ratio 1 in agent:1).It is detected and reacted with TCL plates, after the reaction was complete, decompression is spin-dried for solvent.With silica gel post separation, elution
Agent proportioning is dichloromethane/ethyl acetate=2:1, obtain solid product 3；
(3) product 3 (0.2mmol) is dissolved in the dichloromethane of 20mL drying anaerobics, 127.2mg (0.3 mmol) is worn
This-Martin's oxidant is dissolved in the dichloromethane of 20mL drying anaerobics, the former is added slowly under condition of ice bath with syringe
The latter, after all adding when reaction 5 is small under the conditions of 45 DEG C.Reaction is quenched with saturated sodium thiosulfate, is extracted with saturated salt solution
It takes three times, adds in anhydrous sodium sulfate drying, vacuum distillation removes solvent.With silica gel post separation, eluant, eluent proportioning for petroleum ether/
Dichloromethane=10:1, obtain solid product 4；
(4) weigh product 4 (0.12mmol) and 16.7mg hydroxylamine hydrochlorides (0.24mmol) are added in single port bottle, add in
10mL absolute ethyl alcohols, when condensing reflux reaction 2 is small under the conditions of 80 DEG C.Decompression is spin-dried for solvent.With silica gel post separation, eluant, eluent is matched somebody with somebody
Than for petroleum ether/dichloromethane=1:1, obtain solid product 5 i.e. fluorescence probe.
The fluorescence probe can be applied to the detection of hypochlorite in biosystem, detection comprising fluoroscopic examination, cell into
Picture and and visual colorimetric determination.
When the fluorescence probe is applied to detection hypochlorite, fluorescence probe unstressed configuration itself or fluorescence are very weak, visible
Color change, visual colorimetric determination, available for qualitative detection hypochlorite occur for light area.
When the secondary fluorescence probe is applied to detection hypochlorite, excited with wavelength 495nm light, with hypochlorite
Content gradually increases, and the photoluminescence peak at 572nm gradually enhances；When detecting hypochlorous acid in cell, excitation wavelength is
515 nm, transmitting light detection range are 570-620nm.In the range of a certain concentration, fluorescence intensity is linear with hypochlorous acid concentration
Positive correlation, so as to fulfill hypochlorous concentration is quantitative determined.
Advantageous effect
The synthesis of probe is relatively easy；The quick detection to hypochlorite ion is realized, and it is selective good, resist other
Molecule interference performance is strong；The variation of solution colour can be with the naked eye observed, it has also been observed that fluorescence face under ultraviolet lamp
Color change is a kind of fluorescence probe with the sensing function that adds lustre to；Specific based on its and significant color change, the reagent
Specificity indicator existing for hypochlorite ion in display biological cell can be used as, the detection of real-time qualitative can be carried out；Pass through
TIME RESOLVED TECHNIQUE can carry out qualitative detection to hypochlorite ion in solution, cell and live body.So the present invention is a kind of
Simply, quickly, sensitive hypochlorite ion's specific detection agents, biomolecule detection field have wide application
Prospect.
Description of the drawings
Fig. 1 is the structural formula of fluorescence probe A of the present invention；
Fig. 2 is that hypochlorite ion titrates figure to the absorption of fluorescence probe A of the present invention；
Fig. 3 is fluorescence titration figure of the hypochlorite ion to fluorescence probe A of the present invention；
Fig. 4 is fluorescence titration data fitted figure of the hypochlorite ion to fluorescence probe A of the present invention；
Fig. 5 is selective fluorescence spectrums of the fluorescence probe A of the present invention to Typical reactive oxygen species；
Fig. 6 is selective histogram datas of the fluorescence probe A of the present invention to Typical reactive oxygen species；
Fig. 7 adds in the co-focusing imaging figure before and after sodium hypochlorite for fluorescence probe A of the present invention after cell culture；
Fig. 8 is that fluorescence probe A of the present invention adds in the front and rear comparison diagram under visible ray and ultraviolet light of sodium hypochlorite；
Fig. 9 adds in the fluorescence lifetime imaging figure before and after sodium hypochlorite for fluorescence probe A of the present invention after cell culture.
Specific embodiment
Below by specific embodiment, the present invention is further illustrated, but the present invention protection content be not limited to
Under.
Raw material used in the embodiment of the present invention is known compound, can have market to buy or the side according to the prior art
Method synthesizes to obtain.
Embodiment 1：The preparation of fluorescence probe A.
The present embodiment employs following syntheti c route：
(1) 1ml 2,4- dimethyl pyrroles (10mmol) and 0.7ml acetoxy acetyl chlorides (6.5mmol) are dissolved in
10ml drying anaerobic dichloromethane in, be protected from light 1 it is small when after, it is to be restored to room temperature add in 3.5ml N, N- diisopropyls
Ethylamine (21mmol)；Reaction 30 minutes after add in 2.49ml boron trifluoride-ether complex (19mmol), reaction 1 it is small when after
Stop reaction, decompression is spin-dried for solvent.With silica gel post separation, eluant, eluent proportioning is petroleum ether/dichloromethane=1:1, it obtains
240mg bright yellow solid product A2, yield 15%.
(2) 320mg products 2 (1mmol) and 84mg lithium hydroxides (2mmol) are dissolved in 50mL tetrahydrofurans and water
In the mixed solvent (volume ratio 1:1).It is detected and reacted with TCL plates, after the reaction was complete, decompression is spin-dried for solvent.With silicagel column point
From eluant, eluent proportioning is dichloromethane/ethyl acetate=2:1, obtain 189mg yellow solid product A3, yield 68%.
(3) 55.6mg products 3 (0.2mmol) are dissolved in the dichloromethane of 20ml drying anaerobics, by 127.2mg
(0.3mmol) Dai Si-Martin's oxidant is dissolved in the dichloromethane of 20ml drying anaerobics, with syringe by the former in ice bath item
The latter is added slowly under part, after all adding when reaction 5 is small under the conditions of 45 DEG C.Reaction is quenched with saturated sodium thiosulfate, uses
Saturated salt solution extracts three times, adds in anhydrous sodium sulfate drying, and vacuum distillation removes solvent.With silica gel post separation, eluant, eluent is matched somebody with somebody
Than for petroleum ether/dichloromethane=10:1, obtain 39.2mg yellow solid product A4, yield 71%.
(4) 33.2mg products 4 (0.12mmol) are weighed and 16.7mg hydroxylamine hydrochlorides (0.24mmol) are added to single port bottle
In, 10ml absolute ethyl alcohols are added in, when condensing reflux reaction 2 is small under the conditions of 80 DEG C.Decompression is spin-dried for solvent, with silica gel post separation, washes
De- agent proportioning is petroleum ether/dichloromethane=1:1, obtaining the i.e. fluorescence probe A of 30.7mg gold solid products A5, (structural formula is such as
Shown in Fig. 1), yield 88%.1H NMR(400MHz,CD3CN):δ9.70(s,1H),8.25(s,1H),6.17 (s,2H),
2.47(s,6H),2.17(s,6H).13C NMR(101MHz,CD3CN)δ157.67,145.25,144.01,132.57,
132.18,122.29,16.23,14.81.GC-MS molecular weight is measured as 273.
Embodiment 2：The fluorescence probe A detections to hypochlorite ion in the solution.
The solution of fluorescence probe A prepared in configuration embodiment 1, solvent are dimethyl sulfoxide (DMSO), concentration 10-3Mol/L is surveyed
With second alcohol and water (volume ratio 1 during examination:1) mixed solvent is diluted to 10-5mol/L。
At ambient temperature, liquor natrii hypochloritis's mistake is added dropwise with ultraviolet-visible absorption spectra instrument test fluorescence probe solution
It is as shown in Figure 2 to absorb spectra for titration figure for the variation of absorption intensity in journey.From fig. 2 it can be seen that in system chlorine
The increase (0-50 μM) of acid ion concentration, absorption intensity of the fluorescence probe at 510nm or so places gradually die down, and
The absorption intensity at 560nm or so places is gradually strengthened.
At ambient temperature, fluorescence is strong during liquor natrii hypochloritis being added dropwise with fluophotometer test fluorescence probe solution
The variation of degree, fluorescence titration figure and titration data fitted figure difference are as shown in Figure 3 and Figure 4.It can be seen in figure 3 that with
The increase (0-50 μM) of hypochlorite ion's concentration, absorption intensity of the fluorescence probe at 572nm or so places are gradual in system
Enhancing.Using sodium hypochlorite concentration as abscissa, map by ordinate of fluorescence intensity, Fig. 4 is obtained, with NaClO concentrations
Increase, fluorescence intensity dramatically increases.As seen from the figure in 0-30 μM of concentration range, fluorescence intensity and NaClO concentration are linear
Positive correlation.
Embodiment 3：Responses of the fluorescence probe A to other active oxygen species
Be respectively configured containing hydrogen peroxide, nitric oxide, singlet oxygen (1O2), superoxide anion (O2 ·-), peroxide from
By base (ROO) and the solution of hydroxy radical (OH), concentration is 5 X 10-5Mol/L adds in 10-5The probe solution of mol/L,
Reaction detects the fluorescence emission spectrum variation of solution after 30 minutes, the results are shown in Figure 5.According to the glimmering of different activities oxygen species
Luminous intensity is mapped, as shown in Figure 6.Seen by Fig. 5 and Fig. 6 it can be found that fluorescence probe have to a variety of competition molecules it is stronger anti-dry
Immunity has little to no effect fluorescence of the fluorescence probe at 572nm, and the addition of liquor natrii hypochloritis makes fluorescence probe exist
Fluorescence at 572nm significantly increases.
Embodiment 4：Applications of the fluorescence probe A in cell imaging
The solution of fluorescence probe A prepared in configuration embodiment 1, solvent are dimethyl sulfoxide (DMSO), concentration 10-3Mol/L,
In cell imaging experiment the mother liquor is taken to be diluted in PBS buffer solutions, concentration 10-5mol/L。
Cultured HeLa cells are washed three times with PBS buffer solutions, it is then molten with the above-mentioned fluorescence probe prepared
After liquid culture 15 minutes, add in aqueous sodium hypochlorite solution and continue culture 15 minutes.Reference group is then only with the fluorescence probe solution
Culture 15 minutes.Light field is imaged and fluorescence imaging is observed with Laser Scanning Confocal Microscope.Laser Scanning Confocal Microscope excitation wavelength is 515nm,
Collection waveband channels are 530-630nm regions.Fig. 7 adds in sodium hypochlorite for fluorescence probe of the present invention after cell culture
Co-focusing imaging figure before and after solution.Wherein, Fig. 7 A, Fig. 7 B, Fig. 7 C be add in fluorescence probe culture after HeLa cells into
As figure, wherein Fig. 7 A are to collect the images that waveband channels are 530-630nm, and Fig. 7 B are photograph via bright field, and Fig. 7 C are superimposed field
Photo.Fig. 7 D, Fig. 7 E, Fig. 7 F are the HeLa cell imaging figures added in after liquor natrii hypochloritis's culture, and wherein Fig. 7 D are collection ripple
Duan Tongdao is the images of 530-630nm, and Fig. 7 E are photograph via bright field, and Fig. 7 F are superimposed field photo.From figure 7 it can be seen that only
It is weaker in 530-630nm channel fluorescence signals with the aquicultural HeLa cells of the fluorescence probe；And add in sodium hypochlorite
After solution, there is very strong fluorescence signal in the passage.Light field observation is it can be seen that good cellular morphology, it was demonstrated that entire
Cytoactive is good in experimentation.
Cell imaging experiment shows that the fluorescence probe A can be very good penetration cell film, as hypochlorous acid in living cells
The detection of radical ion.
Embodiment 5：Fluorescence probe A colorimetric method qualitative detection hypochlorite ions by visual observation
The solution of fluorescence probe prepared in configuration embodiment 1, solvent are dimethyl sulfoxide (DMSO), concentration 10-3Mol/L is used
Second alcohol and water (volume ratio 1：1) mixed solvent is diluted to 10-5Mol/L adds into the cuvette equipped with 2mL probe solutions
Enter 5 X 10-5Mol/L liquor natrii hypochloritises, as a comparison, color exists poor the cuvette of the probe solution containing 1mL between the two
It is different, optical colorimetry qualitative detection hypochlorite ion.Fig. 8 A are the situation that shines under 365nm ultraviolet lamps, and Fig. 8 B are under natural light
Color regime.
Embodiment 6：Applications of the fluorescence probe A in the imaging of cell fluorescence service life
The solution of fluorescence probe A prepared in configuration embodiment 1, solvent are dimethyl sulfoxide (DMSO), concentration 10-3Mol/L,
In cell imaging experiment the mother liquor is taken to be diluted in PBS buffer solutions, concentration 10-5mol/L。
Six groups of HeLa cells are cultivated in 96 orifice plates, are washed three times with PBS buffer solutions, then with it is above-mentioned prepare it is described glimmering
After light probe hydroponics 15 minutes, add in various concentration aqueous sodium hypochlorite solution and continue culture 15 minutes.Reference group is then only used
The fluorescence probe hydroponics 15 minutes.For fluorescence lifetime imaging effect as shown in figure 9, A figures are reference group, B is secondary into F figures
Density of sodium chlorate is respectively 2 X 10-6mol/L、6ⅹ10-6mol/L、10-5mol/L、2ⅹ10-5Mol/L and 3 X 10-5 mol/L。
As seen from the figure, apparent fluorescence lifetime changes after various concentration liquor natrii hypochloritis is added in.
Claims (7)
1. a kind of fluorescence probe for hypochlorite ion's detection, which is characterized in that No. 8 positions of the glimmering parent of fluorine boron introduce oxime
Base has following general structure：
Wherein, R1And R3Respectively there is the alkyl chain or hydrogen of 1 to 6 carbon, R2To have the alkyl chain of 1 to 6 carbon, hydrogen or cyanogen
Base；
Wherein, R4To contain the alkyl chain or hydrogen of not more than 2 carbon, R5To R8To have the alkyl chain or hydrogen of 1 to 6 carbon.
2. the preparation method of fluorescence probe as described in claim 1, which is characterized in that synthetic route is as follows：
3. the preparation method of fluorescence probe as claimed in claim 2, which is characterized in that specific as follows：
(1) 1 indoles of 10mmol compounds or azole derivatives and 0.7mL acetoxy acetyl chlorides 6.5mmol are dissolved in 10mL
In the dichloromethane of dry anaerobic, be protected from light 1 it is small when after, it is to be restored to add in 3.5mL N, N- diisopropyl ethyl amines to room temperature
21mmol；Reaction 30 minutes after add in 2.49mL boron trifluoride-ether complex 19mmol, reaction 1 it is small when after stop reaction, subtract
Pressure is spin-dried for solvent；With silica gel post separation, eluant, eluent proportioning is petroleum ether/dichloromethane=1:1, obtain solid product 2；
(2) 1mmol products 2 and 84mg lithium hydroxides 2mmol are dissolved in the in the mixed solvent of 50mL tetrahydrofurans and water, volume
Than for 1:1；It is detected and reacted with TCL plates, after the reaction was complete, decompression is spin-dried for solvent；With silica gel post separation, eluant, eluent proportioning is dichloro
Methane/ethyl acetate=2:1, obtain solid product 3；
(3) product 3 is dissolved in the dichloromethane of 20mL drying anaerobics by 0.2mmol, by 127.2mg, that is, 0.3mmol Dai Si-Martin
Oxidant is dissolved in the dichloromethane of 20mL drying anaerobics, under condition of ice bath the former is added slowly to the latter with syringe, entirely
Portion add after under the conditions of 45 DEG C reaction 5 it is small when；Reaction is quenched with saturated sodium thiosulfate, with saturated salt solution extraction three times,
Anhydrous sodium sulfate drying is added in, vacuum distillation removes solvent；With silica gel post separation, eluant, eluent proportioning is petroleum ether/dichloromethane
=10:1, obtain solid product 4；
(4) 0.12mmol products 4 are weighed and 16.7mg hydroxylamine hydrochlorides 0.24mmol is added in single port bottle, add in the anhydrous second of 10mL
Alcohol, when condensing reflux reaction 2 is small under the conditions of 80 DEG C；Decompression is spin-dried for solvent；With silica gel post separation, eluant, eluent proportioning for petroleum ether/
Dichloromethane=1:1, obtain solid product 5 i.e. fluorescence probe.
4. the application of fluorescence probe as described in claim 1, which is characterized in that the fluorescence probe is applied in biosystem
The detection of hypochlorite, detection include fluoroscopic examination, cell imaging and and visual colorimetric determination；
When the fluorescence probe is applied to detection hypochlorite, fluorescence probe unstressed configuration itself or fluorescence are very weak, in visible region
Generation color change, visual colorimetric determination, for qualitative detection hypochlorite.
5. the application of fluorescence probe as described in claim 1, which is characterized in that when fluorescence probe is applied to detection hypochlorite
When, it is excited with wavelength 495nm light, with gradually increasing for hypochlorite content, the photoluminescence peak at 572nm is gradual
Enhancing；When detecting hypochlorous acid in cell, excitation wavelength 515nm, transmitting light detection range is 570-620nm；In a certain concentration
In the range of, fluorescence intensity and the linear positive correlation of hypochlorous acid concentration, so as to fulfill hypochlorous concentration is quantitative determined.
6. the application of fluorescence probe as described in claim 1, which is characterized in that the probe is based on time-resolved fluorescence technology
Detect the hypochlorite ion in solution.
7. the application of fluorescence probe as described in claim 1, which is characterized in that the probe is based on fluorescence lifetime imaging technology
Detect the hypochlorite ion in cell and live body.
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| WO2019218594A1 (en) * | 2018-05-17 | 2019-11-21 | 南京邮电大学 | Water-soluble phosphorescent nanoparticle for detecting hypochlorous acid using ratio method and preparation method and application thereof |
| CN110627756A (en) * | 2019-10-10 | 2019-12-31 | 中国科学院新疆理化技术研究所 | Colorimetric-fluorescent probe for detecting hypochlorite, preparation method and application thereof |
| CN114702534A (en) * | 2022-04-12 | 2022-07-05 | 复旦大学 | Hypochlorous acid trigger activation type near-infrared fluorescent probe and preparation method and application thereof |
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| WO2019218594A1 (en) * | 2018-05-17 | 2019-11-21 | 南京邮电大学 | Water-soluble phosphorescent nanoparticle for detecting hypochlorous acid using ratio method and preparation method and application thereof |
| CN110627756A (en) * | 2019-10-10 | 2019-12-31 | 中国科学院新疆理化技术研究所 | Colorimetric-fluorescent probe for detecting hypochlorite, preparation method and application thereof |
| CN114702534A (en) * | 2022-04-12 | 2022-07-05 | 复旦大学 | Hypochlorous acid trigger activation type near-infrared fluorescent probe and preparation method and application thereof |
| CN114702534B (en) * | 2022-04-12 | 2023-10-03 | 复旦大学 | Hypochlorous acid trigger activation type near infrared fluorescent probe and preparation method and application thereof |
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