CN110204564A - A kind of fluorescence probe and its preparation method and application detecting cyanide ion - Google Patents
A kind of fluorescence probe and its preparation method and application detecting cyanide ion Download PDFInfo
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- CN110204564A CN110204564A CN201910464404.9A CN201910464404A CN110204564A CN 110204564 A CN110204564 A CN 110204564A CN 201910464404 A CN201910464404 A CN 201910464404A CN 110204564 A CN110204564 A CN 110204564A
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- cyanide ion
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- 239000000523 sample Substances 0.000 title claims abstract description 65
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000001514 detection method Methods 0.000 claims abstract description 17
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 4
- 238000004993 emission spectroscopy Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N methyl cyanide Natural products CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 85
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- 229910052796 boron Inorganic materials 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000012360 testing method Methods 0.000 claims description 15
- -1 4- aminomethyl phenyl Chemical group 0.000 claims description 14
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000543 intermediate Substances 0.000 claims description 10
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 10
- 150000002467 indacenes Chemical class 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- IWCBFNUUALXQBB-UHFFFAOYSA-N B(O)(O)O.B(F)(F)F Chemical compound B(O)(O)O.B(F)(F)F IWCBFNUUALXQBB-UHFFFAOYSA-N 0.000 claims 1
- 238000007689 inspection Methods 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 150000001450 anions Chemical class 0.000 abstract description 23
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 4
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract description 3
- SNZXMAHBUQXQSE-UHFFFAOYSA-N acetonitrile;benzene Chemical group CC#N.C1=CC=CC=C1 SNZXMAHBUQXQSE-UHFFFAOYSA-N 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000002189 fluorescence spectrum Methods 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000007850 fluorescent dye Substances 0.000 description 5
- 238000004448 titration Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- NKCCODPFBDGPRJ-UHFFFAOYSA-N nitridocarbon(1+) Chemical compound N#[C+] NKCCODPFBDGPRJ-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 206010002660 Anoxia Diseases 0.000 description 1
- 241000976983 Anoxia Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 102000000634 Cytochrome c oxidase subunit IV Human genes 0.000 description 1
- 108050008072 Cytochrome c oxidase subunit IV Proteins 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000007953 anoxia Effects 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 150000007980 azole derivatives Chemical class 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002024 ethyl acetate extract Substances 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
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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
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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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
- 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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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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
-
- 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
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- Engineering & Computer Science (AREA)
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- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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Abstract
The present invention relates to a kind of fluorescence probes and its preparation method and application for detecting cyanide ion, the fluorescence probe is with two pyrroles of boron fluoride (BODIPY) for fluorescence signal group, the CH group activated in benzene acetonitrile group is the cyanide ion fluorescence probe of recognition site, the probe be by 3,5- dibromo 8- phenyl boron fluoride, two pyrroles and benzene acetonitrile as obtained by nucleophilic substitution.Find that the probe can identify cyanide ion with unicity by UV absorption and the research of fluorescence emission spectrometry, while minimum detection limit is up to 148nM in 70% aqueous solution, and this identification process is not by the interference of other anion.Compared with prior art, fluorescence probe synthetic method of the invention is simple, raw material is easy to get, cost is relatively low,, high sensitivity good to the selectivity of cyanide ion has invertibity and can detect in aqueous solution, therefore have a good application prospect in the detection to cyanide ion.
Description
Technical field
The present invention relates to fluorescence probe fields, more particularly, to a kind of fluorescence probe for detecting cyanide ion and its preparation side
Method and application.
Background technique
Anion is widely present in nature and organism, is led in environmental science, clinical medicine, chemistry, biology etc.
Domain plays an important role.In numerous anion, cyanide ion has high toxicity to human body, and mechanism of poisoning is cyanogen
Radical ion can cause ferric iron to lose transmitting electronic capability, make to exhale by being complexed with the ferric ion of cytochrome oxidase
Chain interruption is inhaled, eventually leads to human body anoxia and dead.Furthermore cyanide ion is in synthetic fibers, leather and fur products, metallurgical industry and electricity
Also very important effect is played in coating technology, but a large amount of use of cyanide in the industrial production necessarily will cause organism
Harm and environment pollution.Therefore, develop good, the high sensitivity of selectivity, the method for low-cost detection cyanide ion
It is of great significance.
In recent years, anion fluorescent probe is since the selection identity of its method is good, detection sensitivity is high, anti-interference ability
It is strong to obtain very extensive application with easy to operate.The cardinal principle that fluorescence probe detects anion is by means of Fluorescence Spectrometer
Device, by the specific reaction occurred between observation anion and fluorescent probe molecule, so as to cause being sent out on fluorescent molecular structure
Changing realizes the quantitative and qualitative analysis to anion eventually by the change of this fluorescence signal.People have been at present
It designs, synthesized many anion fluorescent probes with potential using value, but the synthesis of most probe is complicated, cost
Height, not reproducible identification, and be difficult to realize and identify anion in aqueous solution.Therefore, it develops a kind of high sensitivity, can follow
Ring identifies anion, and the fluorescence probe that can detect cyanide ion in aqueous solution is of great significance.
Two azole derivatives of fluorine boron are a kind of outstanding fluorogens, since it has in visible light near infrared spectrum region
It is high-intensitive absorb, the advantages that high-fluorescence quantum yield, quite long excited triplet lifetimes and good chemical stability.
Therefore, anion fluorescent probe can be designed as a kind of potential fluorogen using it, at the same two pyrylium dyes of fluorine boron also by
It is widely used in the research fields such as bioprobe, fluorescent switch and light harvesting arrays, becomes current the great of chemical research person and grind
Study carefully target.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of detection cyanide ions
Fluorescence probe and its preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of fluorescence probe detecting cyanide ion, its chemical name is the fluoro- 8- benzene of the bromo- 5- aryl acetonitrile -4,4- bis- of 3-
Base -4- boron the indacene -3a, 4a- diaza-s- (BODIPY1), structural formula is as follows:
It is a kind of detect cyanide ion fluorescence probe preparation method, using pyrroles and benzaldehyde as raw material, pass through condensation, bromine
Change, oxidation, fluoroboration, then with benzene acetonitrile as obtained by nucleophilic substitution, reaction process is as follows:
Specific step of preparation process are as follows:
(1) synthesis of 5- (4- aminomethyl phenyl) dipyrrylmethanes:
In nitrogen atmosphere, by benzaldehyde, pyrroles and anhydrous CH2Cl2Mixing, is then added trifluoroacetic acid, stirs at room temperature
Reaction washs after reaction, is dry, collecting filtrate, concentration, after purification, obtaining yellow solid 5- (4- aminomethyl phenyl) two pyrroles
Cough up methane；
(2) synthesis of brominated product intermediate:
Dipyrrylmethanes are dissolved in anhydrous tetrahydro furan to the 5- (4- aminomethyl phenyl) that step (1) is prepared, and use nitrogen
Displacement, then N-bromosuccinimide is added in two batches for cooling down, after stirring, then by chloro- 5, the 6- dicyan pair of 2,3- bis-
After benzoquinones is dissolved in tetrahydrofuran, above-mentioned reaction system is added；After complete reaction, restore to room temperature, vacuum distillation is chromatographed through column
It collects afterwards and obtains brominated product intermediate；
(3) synthesis of bromo- bis- indacene fluoro- 8- phenyl -4- boron -3a, 4a- diaza-s- 4,4- 3,5- bis-:
The brominated product intermediate that step (2) is prepared is dissolved in toluene, triethylamine is added, is added three after 15min
Be fluorinated borate ether, back flow reaction, after fully reacting wash, extract, merge organic phase, drying, be concentrated, isolate and purify after obtain it is red
Bromo- bis- indacene fluoro- 8- phenyl -4- boron -3a, 4a- diaza-s- 4,4- color solid 3,5- bis-；
(4) synthesis of bromo- two indacene fluoro- 8- phenyl -4- boron -3a, 4a- diaza-s- 5- aryl acetonitrile -4,4- 3-:
Under nitrogen atmosphere, after anhydrous tetrahydro furan and sodium hydrogen are mixed, benzene acetonitrile is added, is stirred to react, 3,5- will be contained
The anhydrous tetrahydro furan of two bromo- bis- indacene fluoro- 8- phenyl -4- boron -3a, 4a- diaza-s- 4,4- is added in reaction system,
Reaction is stirred at room temperature, adjusts pH after reaction, extraction, drying, remove solvent, isolate and purify to obtain the bromo- 5- of red solid 3-
Two indacene fluoro- 8- phenyl -4- boron -3a, 4a- diaza-s- aryl acetonitrile -4,4-.
Preferably, in step (1): benzaldehyde, pyrroles, anhydrous CH2Cl2It is 5.00g with the ratio between the additive amount of trifluoroacetic acid:
20mL:250mL:200mg。
Preferably, in step (1): after complete reaction, being washed with saturated sodium bicarbonate solution.Organic layer anhydrous slufuric acid
Sodium is dry, collects filtrate, concentration, silica gel column chromatography purifying, petroleum ether: ethyl acetate=2:1.
Preferably, in step (2): 5- (4- aminomethyl phenyl) dipyrrylmethanes, N-bromosuccinimide and 2,3- bis- are chloro-
The ratio between additive amount of 5,6- dicyanoquinone is 2.22g:3.60g:2.27g.
Preferably, in step (2): the temperature to cool is -78 DEG C.
Preferably, in step (2): after complete reaction, reaction mixture temperature is warmed to room temperature, decompression boils off solvent,
Rapid column chromatography is carried out to crude product using methylene chloride.
Preferably, in step (3): the ratio between brominated product intermediate, toluene, triethylamine and additive amount of boron trifluoride ether
For 3.36g:100mL:9mL:10mL.
Preferably, in step (3): after fully reacting, saturation NaHCO is added in back flow reaction 2h3Washing, and use dichloromethane
Alkane extraction merges organic phase, and anhydrous magnesium sulfate is dry, concentration, silica gel column chromatography separating purification (petroleum ether: methylene chloride=2:
1)。
Preferably, in step (4): anhydrous tetrahydro furan, sodium hydrogen, benzene acetonitrile and 3, the bis- fluoro- 8- phenyl-of bromo- 4,4- bis- of 5-
The ratio between additive amount of the indacene 4- boron -3a, 4a- diaza-s- is 30mL:12mmol:4.88mmol:1.22mmol.
Preferably, in step (4): bis- fluoro- 8- phenyl -4- boron -3a, the 4a- diaza-s- of bromo- 4,4- bis- containing 3,5-, which draws, to be reached
The anhydrous tetrahydro furan of province is added by syringe.
Preferably, in step (4): saturated lemon being added after reaction and is adjusted to acidity, and is extracted with ethyl acetate three
Secondary, organic phase is dry with anhydrous sodium sulfate, and solvent, silica gel column chromatography separating purification (petroleum ether: ethyl acetate=10:1) are removed in rotation.
A kind of application of the fluorescence probe detecting cyanide ion cyanide ion in detection aqueous solution.
Preferably, when being detected using UV absorption and fluorescence emission spectrometry, fluorescence probe is dissolved in acetonitrile and water 3:7 is mixed
It closes in solution, cyanide ion is tested.
Preferably, Test paper is prepared, the specific steps are as follows:
The acetonitrile solution of fluorescence probe is added dropwise on processed filter paper, makes fluorescence probe uniform adsorption on filter paper, from
It so dries, CN is prepared-Test paper.
Fluorescence probe of the invention is using two pyrroles of boron fluoride as fluorogen, and hydrocarbon in aryl acetonitrile is recognition site,
Acetonitrile and water (V/V=3:7) have ultraviolet absorption peak at 357nm, 514nm, CN are added as under conditions of solvent-Afterwards,
Absorption peak reduces at 357nm and 514nm.And other anion are added, the ultra-violet absorption spectrum of the fluorescence probe is not bright
Aobvious variation.In fluorescence spectrum, using 388nm as excitation wavelength, the maximum emission wavelength of the fluorescence probe is 533nm, is had
CN is added in very strong green fluorescence-Afterwards, the fluorescence intensity at 533nm is substantially reduced, and other anion are added, fluorescence intensity
There is no significant change.Under ultraviolet lamp 365nm irradiation, observes and CN is added-After there is fluorescent quenching, and other anion do not have
Variation.
Compared with prior art, probe molecule synthetic route of the invention is simple, and raw material is easy to get, and sensitivity is higher, to cyanogen
Radical ion recognition capability is strong, and response speed is very fast, and minimum detection limit is up to 148nM；It is same to have simultaneously in aqueous solution detection
There is more highly selective and sensitivity；And the probe have cyclicity, invertibity, can repeated detection cyanide ion, cyanogen root from
It is had a good application prospect in the detection of son.
Detailed description of the invention
Fig. 1 is fluorescence probe (20 μm of olL of the invention-1) acetonitrile and water (V/V=3/7) solution in different yin are added
Ion (20 μm of olL-1) when UV absorption spectrogram；
Fig. 2 is fluorescence probe (20 μm of olL of the invention-1) acetonitrile and water (V/V=3/7) solution in different yin are added
Ion (480 μm of olL-1) when fluorescent emission spectrogram (λex=388nm)；
Fig. 3 is fluorescence probe (20 μm of olL of the invention-1) acetonitrile and water (V/V=3/7) solution in different yin are added
Ion (480 μm of olL-1) when portable ultraviolet lamp 365nm irradiation under picture；
Fig. 4 is fluorescence probe (20 μm of olL of the invention-1) acetonitrile and water (V/V=3/7) solution in different CN-
Concentration (0-480 μm of olL-1) under ultra-violet absorption spectrum；
Fig. 5 is A514nm and CN-Concentration relationship curve；
Fig. 6 is fluorescence probe (20 μm of olL of the invention-1) acetonitrile and water (V/V=3/7) solution in different CN-
Concentration (0-480 μm of olL-1) under fluorescence emission spectrum；
Fig. 7 is I533nm and CN-Concentration relationship curve；
Fig. 8 is that the fluorescence probe of the invention Reversible Cycle in acetonitrile and water (V/V=3/7) solution is tested；
Fig. 9 is that the fluorescence probe of the invention fluorescence detection limit in acetonitrile and water (V/V=3/7) solution calculates figure；
Figure 10 is fluorescence probe (20 μm of olL of the invention-1) with other anion (480 μm of olL-1) when coexisting
To CN-(480μmol·L-1) response when I/I0 variation histogram；
Figure 11 is that CN is added in fluorescence probe of the invention and fluorescence probe of the invention-The 533nm in pH value 1-14 system
Locate fluorescence intensity；
Figure 12 is that various concentration CN is added dropwise in fluorescence probe test paper of the invention-When portable ultraviolet lamp 365nm irradiate the following figure
Piece.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
The title, specification of various raw materials used in various embodiments of the present invention and the information of manufacturer are shown in Table 1.
Table 1
The model of silicagel column used in various embodiments of the present invention and manufacturer are long 45cm, diameter 45mm, Beijing
The silicagel column of Lian Hua glass apparatus Co., Ltd production.
Embodiment 1
One, the synthesis of 1 molecule of fluorescence probe BODIPY of cyanide ion is detected
The present invention detects the synthesis of the fluorescent probe molecule of cyanide ion, is to pass through contracting using pyrroles and benzaldehyde as raw material
Conjunction, bromination, oxidation, fluoroboration, then with benzene acetonitrile as obtained by nucleophilic substitution.
(1) synthesis of 5- (4- aminomethyl phenyl) dipyrrylmethanes:
By benzaldehyde (5.00g, 47.20mmol), pyrroles (20mL, 289mmol) and anhydrous CH2Cl2(250mL) is added to
In 500mL round-bottomed flask, nitrogen system is replaced as in the flask, then in mixture be added trifluoroacetic acid (200mg,
2.60mmol), 2h is stirred at room temperature in reaction.After complete reaction, it is washed with saturated sodium bicarbonate solution.Organic layer nothing
Aqueous sodium persulfate is dry, collects filtrate, concentration, silica gel column chromatography purifying, petroleum ether: ethyl acetate=2:1 obtains yellow solid
(6.81g, 65%).
Above-mentioned resulting faint yellow solid powder-product passes through nuclear magnetic resonance apparatus (Bruker AVANCE III
It 500MHz) is measured, data are as follows:
1H NMR (500MHz, DMSO), δ 7.86 (s, 2H), 7.35 (t, J=7.5Hz, 2H), 7.29 (t, J=7.0Hz,
1H), 7.24 (d, J=7.0Hz, 2H), 6.69 (d, J=1.0Hz, 2H), 6.20 (d, J=2.5Hz, 2H), 5.94 (s, 2H),
5.47(s,1H)；13C-NMR(125MHz,CDCl3),δ142.26,132.72,128.76,128.56,127.10,117.48,
108.49,107.45,44.01.
It is analyzed by the nuclear magnetic resonance modal data of above-mentioned resulting faint yellow solid powder-product, the results showed that, above-mentioned institute
The yellow solid powder-product obtained is 5- (4- aminomethyl phenyl) dipyrrylmethanes.
(2) synthesis of bromo- bis- indacene fluoro- 8- phenyl -4- boron -3a, 4a- diaza-s- 4,4- 3,5- bis-:
In 250mL three-necked flask, 5- (4- aminomethyl phenyl) dipyrrylmethanes (2.22g, 10mmol) are dissolved in anhydrous tetrahydro
Furans, and nitrogen displacement is three times, is cooled to -78 DEG C, subsequent N-bromosuccinimide (3.60g, 20.2mmol) adds in two batches
Enter in three-necked flask, low temperature stirs 2h, then chloro- 5, the 6- dicyanoquinone (2.27g, 10mmol) of 2,3- bis- is dissolved in tetrahydrofuran
In, it is slowly added dropwise into three-necked flask.After complete reaction, reaction mixture is warmed to room temperature, decompression boils off solvent, uses
Methylene chloride carries out rapid column chromatography to crude product, collects brominated product intermediate.By above-mentioned gained brominated product intermediate
3.36g is dissolved in 100mL toluene, and Et is added3N (9mL), was added BF after 15 minutes3·Et2O (10mL), is to slowly warm up to flow back
State, flow back 2h.After fully reacting, saturation NaHCO is added3Washing, and be extracted with dichloromethane, merge organic phase, anhydrous sulphur
Sour magnesium is dry, and concentration, silica gel column chromatography separating purification (petroleum ether: methylene chloride=2:1) obtains red solid (2.4g, 56%).
Above-mentioned resulting faint yellow solid powder-product passes through nuclear magnetic resonance apparatus (Bruker AVANCE III
It 500MHz) is measured, data are as follows:
1H NMR (500MHz, DMSO), δ 7.59 (t, J=7.0Hz, 1H), 7.51 (t, J=7.5Hz, 2H), 7.47 (dd,
J=8.0,1.1Hz, 2H), 6.79 (d, J=4.0Hz, 2H), 6.53 (d, J=4.0Hz, 2H)；13C-NMR(125MHz,
CDCl3),δ143.25,135.50,132.61,132.33,131.82,130.96,130.39,128.62,122.77.
It is analyzed by the nuclear magnetic resonance modal data of above-mentioned resulting faint yellow solid powder-product, the results showed that, above-mentioned institute
The red solid product obtained is bromo- bis- indacene fluoro- 8- phenyl -4- boron -3a, 4a- diaza-s- 4,4- 3,5- bis-.
(3) fluoro- 8- phenyl -4- boron -3a, the 4a- diaza-s- indacene (BODIPY of the bromo- 5- aryl acetonitrile -4,4- two of 3-
1) synthesis:
The anhydrous tetrahydro furan of 30mL and sodium hydrogen (60%, 0.48g, 12.00mmol) are added to the three-necked flask of 100mL
In, nitrogen is replaced three times, and benzene acetonitrile (0.57g, 4.88mmol) is added in flask, 30min is stirred at room temperature, 5mL is contained
The anhydrous tetrahydro of 3, the 5- bis- fluoro- 8- phenyl -4- boron indacene -3a, 4a- diaza-s- (0.52g, 1.22mmol) of bromo- 4,4- bis-
Furans is added in flask by syringe, stirs 8h at room temperature.Saturated lemon is added after reaction and is adjusted to acidity, is used in combination
Ethyl acetate extracts three times, and organic phase is dry with anhydrous sodium sulfate, and solvent, silica gel column chromatography separating purification (petroleum ether: second are removed in rotation
Acetoacetic ester=10:1) obtain red solid (0.25g, 45%).
Above-mentioned resulting faint yellow solid powder-product passes through nuclear magnetic resonance apparatus (Bruker AVANCE III
It 500MHz) is measured, data are as follows:
1H NMR (500MHz, DMSO), δ 7.61-7.55 (m, 3H), 7.52 (s, 4H), 7.41 (t, J=7.5Hz, 2H),
7.38-7.33 (m, 1H), 6.88-6.82 (m, 2H), 6.57 (d, J=4.0Hz, 1H), 6.53 (d, J=3.5Hz, 1H), 5.93
(s,1H)；13C-NMR(125MHz,CDCl3),δ152.92,145.75,135.78,134.66,133.24,133.12,
132.66,132.44,132.01,131.09,130.41,129.34,128.73,128.64,127.82,123.02,118.81,
117.49,36.08.
It is analyzed by the nuclear magnetic resonance modal data of above-mentioned resulting faint yellow solid powder-product, the results showed that, above-mentioned institute
The red solid product obtained is bromo- two indacene fluoro- 8- phenyl -4- boron -3a, 4a- diaza-s- 5- aryl acetonitrile -4,4- 3-.
Two, recognition performance of the fluorescence probe BODIPY 1 to anion of cyanide ion is detected
1, the selection Journal of Sex Research of the fluorescence probe of cyanide ion
BODIPY 1 is configured to the acetonitrile solution of 20 μm of olL-1；CN is prepared respectively-,F-,Cl-,Br-,I-,AcO-,
H2PO4 -,HSO4 -,ClO4 -,BF4 -,NO3 -,SCN-,S2 -5000 μm of olL-1Acetonitrile solution measures 5000 μm of ol of 0.4mL
L-1Probe solution is settled to 100mL with acetonitrile and water mixed solution (V/V=3/7), is classified as 14 groups (every group of 5mL), first
Group is blank assay, and the various anion solutions of 24 equivalents are separately added into other each groups, pass through ultra-violet absorption spectrum and fluorescence
Emission spectrum (λex=388nm), observe response of the fluorescence probe BODIPY 1 to various anion.
The result shows that BODIPY 1 is under conditions of acetonitrile and water (V/V=3:7) are used as solvent, in 514nm and 357nm
There is absorption peak at place respectively, and CN is added-Afterwards, the absorption peak at 514nm and 357nm declines, and other anion are added,
The ultra-violet absorption spectrum of BODIPY 1 does not have significant change (Fig. 1).In fluorescence spectrum, using 388nm as excitation wavelength,
The maximum emission wavelength of BODIPY 1 is 533nm, has strong fluorescence, and CN is added-Afterwards, the fluorescence intensity at 533nm occurs bright
It is aobvious to weaken, and other anion are added, the launch wavelength of BODIPY 1 does not have significant change (Fig. 2), irradiates in ultraviolet lamp 365nm
Under, CN is added-After there is green fluorescence, and other anion do not change (Fig. 3).Illustrate that the fluorescence probe can be with specificity
Detect cyanide ion.
2, the fluorescence probe titration experiments of cyanide ion
BODIPY 1 is dissolved in acetonitrile and is configured to 5000 μm of olL-1Stock solution, CN is prepared in acetonitrile-Stock solution,
Concentration is 50000 μm of olL-1.Measure 5000 μm of olL of 100 μ L-1Probe be dissolved in the volumetric flask of 25mL, be added
After 17.5mL water, the spy that 25mL is made into 20 μM of 25mL of water and acetonitrile (V/V=3:7) mixed solvent is settled to acetonitrile solution
Needle solution.Titration experiments: the probe solution of 20 μM of 25mL of water and acetonitrile (V/V=3:7) mixed solvent is poured into 100mL's
In wide mouthed Erlenmeyer bottle, 0.2 μ L, 50000 μm of olL are added dropwise every time-1The CN of (2.0 equivalent)-Solution detects respectively after rocking uniformly
Its ultra-violet absorption spectrum and fluorescence emission spectrum repeat this operation, until the cyanide ion solution of 24.0 equivalents is added.
The result shows that the ultra-violet absorption spectrum of BODIPY 1 is influenced (Fig. 4-5) by cyanide ion concentration, with cyanogen root from
Son is gradually added into, and absorption peak of the BODIPY 1 at 514nm and 357nm gradually decreases, until 480 μm of olL are added-1CN-
When reach balance.Then its fluorescence emission spectrum (Fig. 6-7) is surveyed, the fluorescence intensity of BODIPY 1 is very strong at 533nm, with cyanogen
The addition of radical ion, fluorescence intensity gradually weaken, and are finally reached and are quenched, until 480 μm of olL are added-1CN-When reach flat
Weighing apparatus.
3, the Reversible Cycle experiment of 1 fluorescence probe of BODIPY
After having surveyed the fluorescence titration of cyanide ion, continue that TFA measurement H is added dropwise+(TFA) titration spectrogram, TFA to be added dropwise
After saturation, then the CN of saturation equivalent is added dropwise-, four groups of experiments are repeated in, the variation of its fluorescence intensity at 533nm is measured,
And the variation using ultraviolet lamp 365nm observation fluorescence color.
It is as shown in Figure 8 the experimental results showed that, probe BODIPY 1 realizes 4 times reversible and reusable.Furthermore
Fluorescence becomes colorless fluorescence from green fluorescence, is then return to the realization repeatedly of green fluorescence, shows that the sensitive of BODIPY 1 can
Inverse property.
4, measurement of 1 fluorescence probe of BODIPY to cyanide ion minimum detection limit
Work as CN-Concentration be 0-480 μm of olL-1When F-F0/FMax-F0With cyanide ion concentration lg [CN-] show preferably
Linear relationship, the linear equation being fitted be y=39086+0.8713*x (R2=0.9784), according to " detection limit=3 σ/
K " can calculate BODIPY 1 to CN-Detection be limited to 148nM, far below the World Health Organization to the cyanide ion in drinking water
1.9 μm of olL of maximum prescribed value-1.Therefore, BODIPY 1 can be used for the measurement of cyanide ion in actual water sample.(Fig. 9)
5, anti-interference ability detects
The probe solution of 20 μM of 25mL of water and acetonitrile (V/V=3:7) mixed solvent is poured into the examination of 14 15mL respectively
Guan Zhong, every 5mL, the first flag blank control are separately added into 48 μ L50000 μm olL in Xiang Qiyu test tube-1Difference yin from
Son (CN-,F-,Cl-,Br-,I-,AcO-,H2PO4 -,HSO4 -,ClO4-,BF4 -,NO3 -,SCN-,S2 -) sufficiently shake up, carry out ultraviolet suction
Spectrum and fluorescence emission spectrum detection are received, 48 μ L, 50000 μm of olL are finally added into every test tube-1Cyanide ion, shake
It is even, detect its ultra-violet absorption spectrum and fluorescence emission spectrum respectively again.
Experiment shows in the case where coexisting with other anion, CN-Still it can make BODIPY 1 at 514nm
Ultraviolet absorption peak reduces, and can make fluorescence intensity obvious quenching (Figure 10) of the BODIPY 1 at 533nm, therefore BODIPY
1 couple of CN-Detection has good anti-interference ability, and other anion will not bring any interference to testing result.
6, BODIPY 1 is in different pH value systems to CN-Detectability
In 15 test tubes, it is separately added into 20 μ L, 5000 μm of olL-1Probe solution, add the acetonitrile of 1.5mL, so
It is separately added into the aqueous solution 3.5mL that PH is 1 to 14 afterwards, vibrates 30s, detects fluorescence emission spectrum respectively.Then 48 μ L are added
50000μmol·L-1Cyanide ion, measure its fluorescence emission spectrum again.
It is as shown in figure 11 the experimental results showed that, pH is within the scope of 1-12, and fluorescence intensity of the BODIPY 1 at 533nm is very
By force, kept stable, and CN is added-It is afterwards within the scope of 2-12 in pH, there is obvious quenching in fluorescence, it will thus be seen that
BODIPY 1 can efficiently identify CN within the scope of pH value 2-12-。
Three, the CN of BODIPY 1-Test paper and application
Test paper preparation: filter paper is cut into long 2cm, the strip of wide 1cm is soaked in the acetonitrile solution of the probe BODIPY 1 of 1nm
In, it takes out and dries after staying overnight.0,0.2,0.5,1.0,5.0mM CN of a drop (about 0.1mL) is added dropwise on 5 test paper respectively-
Acetonitrile solution, after drying, observed under daylight and at ultraviolet lamp 365nm its fluorescence color variation.
As shown in figure 12, naked eyes are observed that test paper color gradually becomes aubergine by colourless, and in ultraviolet lamp 365nm
Under irradiation, BODIPY 1 has very strong green fluorescence, as addition CN-Afterwards, it can be seen that green fluorescence weakens, and eventually becomes
There is no fluorescence.Illustrate that BODIPY 1 can detect CN by test paper-。
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of fluorescence probe for detecting cyanide ion, which is characterized in that its chemical name is the bromo- 5- aryl acetonitriles -4,4- of 3-
Two indacene fluoro- 8- phenyl -4- boron -3a, 4a- diaza-s-, structural formula are as follows:
2. a kind of preparation method of fluorescence probe for detecting cyanide ion according to claim 1, which is characterized in that specific
Steps are as follows:
(1) synthesis of 5- (4- aminomethyl phenyl) dipyrrylmethanes:
In nitrogen atmosphere, by benzaldehyde, pyrroles and anhydrous CH2Cl2Mixing, is then added trifluoroacetic acid, and stirring is anti-at room temperature
It answers, washs after reaction, is dry, collecting filtrate, concentration, after purification, obtaining yellow solid 5- (4- aminomethyl phenyl) two pyrroles
Methane；
(2) synthesis of brominated product intermediate:
5- (4- aminomethyl phenyl) dipyrrylmethanes that step (1) is prepared are dissolved in anhydrous tetrahydro furan, and are replaced with nitrogen,
Then N-bromosuccinimide is added in two batches for cooling down, after stirring, then by chloro- 5, the 6- dicyanoquinone of 2,3- bis-
After being dissolved in tetrahydrofuran, above-mentioned reaction system is added；After complete reaction, restore to room temperature, vacuum distillation is received after column chromatographs
Collection obtains brominated product intermediate；
(3) synthesis of bromo- bis- indacene fluoro- 8- phenyl -4- boron -3a, 4a- diaza-s- 4,4- 3,5- bis-:
The brominated product intermediate that step (2) is prepared is dissolved in toluene, triethylamine is added, is added after 15min borontrifluoride
Borate ether, back flow reaction, wash, extract after fully reacting, merge organic phase, drying, be concentrated, isolate and purify after obtain it is red solid
Bromo- bis- indacene fluoro- 8- phenyl -4- boron -3a, 4a- diaza-s- 4,4- body 3,5- bis-；
(4) synthesis of bromo- two indacene fluoro- 8- phenyl -4- boron -3a, 4a- diaza-s- 5- aryl acetonitrile -4,4- 3-:
Under nitrogen atmosphere, after anhydrous tetrahydro furan and sodium hydrogen are mixed, benzene acetonitrile is added, is stirred to react, it is bromo- that 3,5- bis- will be contained
The anhydrous tetrahydro furan of 4,4- bis- indacene fluoro- 8- phenyl -4- boron -3a, 4a- diaza-s- is added in reaction system, and room temperature is stirred
Reaction is mixed, pH is adjusted after reaction, extraction, drying, removes solvent, isolate and purify to obtain the bromo- 5- aryl second of red solid 3-
Two indacene fluoro- 8- phenyl -4- boron -3a, 4a- diaza-s- nitrile -4,4-.
3. a kind of preparation method of fluorescence probe for detecting cyanide ion according to claim 2, which is characterized in that step
(1) in: benzaldehyde, pyrroles, anhydrous CH2Cl2It is 5.00g:20mL:250mL:200mg with the ratio between the additive amount of trifluoroacetic acid.
4. a kind of preparation method of fluorescence probe for detecting cyanide ion according to claim 2, which is characterized in that step
(2) in: 5- (4- aminomethyl phenyl) dipyrrylmethanes, N-bromosuccinimide and the chloro- 5,6- dicyanoquinone of 2,3- bis- add
The ratio between dosage is 2.22g:3.60g:2.27g.
5. a kind of preparation method of fluorescence probe for detecting cyanide ion according to claim 2, which is characterized in that step
(2) in: the temperature to cool is -78 DEG C.
6. a kind of preparation method of fluorescence probe for detecting cyanide ion according to claim 2, which is characterized in that step
(3) in: the ratio between brominated product intermediate, toluene, triethylamine and additive amount of boron trifluoride ether are 3.36g:100mL:9mL:
10mL。
7. a kind of preparation method of fluorescence probe for detecting cyanide ion according to claim 2, which is characterized in that step
(4) in: anhydrous tetrahydro furan, bis- fluoro- 8- phenyl -4- boron -3a, the 4a- diaza-s- of bromo- 4,4- bis- of sodium hydrogen, benzene acetonitrile and 3,5-
The ratio between additive amount of indacene is 30mL:12mmol:4.88mmol:1.22mmol.
8. a kind of fluorescence probe for detecting cyanide ion according to claim 1 cyanide ion in detection aqueous solution is answered
With.
9. a kind of application of fluorescence probe for detecting cyanide ion according to claim 8, which is characterized in that using ultraviolet
When absorbing with the detection of fluorescence emission spectrometry, fluorescence probe is dissolved in acetonitrile and water 3:7 mixed solution, is carried out to cyanide ion
Test.
10. a kind of application of fluorescence probe for detecting cyanide ion according to claim 8, which is characterized in that preparation inspection
Test paper, the specific steps are as follows:
The acetonitrile solution of fluorescence probe is added dropwise on processed filter paper, makes fluorescence probe uniform adsorption on filter paper, dries in the air naturally
It is dry, CN is prepared-Test paper.
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| CN111233909A (en) * | 2020-03-03 | 2020-06-05 | 山西大学 | Reagent for detecting cyanide ions and synthetic method and application thereof |
| CN111269251A (en) * | 2020-03-10 | 2020-06-12 | 中国科学技术大学 | Fluorescent probe and test paper of nerve agent simulant and preparation method thereof |
| CN111548789A (en) * | 2020-06-11 | 2020-08-18 | 苏州海发智能技术有限公司 | Composite sensing membrane for detecting hydrogen based on fluorescence method and application method thereof |
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