CN109608382A - A kind of detection cyanide ion and hypochlorous fluorescence probe and its preparation and application - Google Patents
A kind of detection cyanide ion and hypochlorous fluorescence probe and its preparation and application Download PDFInfo
- Publication number
- CN109608382A CN109608382A CN201910072311.1A CN201910072311A CN109608382A CN 109608382 A CN109608382 A CN 109608382A CN 201910072311 A CN201910072311 A CN 201910072311A CN 109608382 A CN109608382 A CN 109608382A
- Authority
- CN
- China
- Prior art keywords
- probe
- cyanide ion
- solvent
- solution
- logical formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000523 sample Substances 0.000 title claims abstract description 147
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000001514 detection method Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims abstract description 47
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 230000004044 response Effects 0.000 claims abstract description 20
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- IOMZCWUHFGMSEJ-UHFFFAOYSA-N 4-(azaniumylamino)benzenesulfonate Chemical compound NNC1=CC=C(S(O)(=O)=O)C=C1 IOMZCWUHFGMSEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011591 potassium Substances 0.000 claims abstract description 10
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims abstract description 3
- 238000005874 Vilsmeier-Haack formylation reaction Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 70
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 43
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 40
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 39
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 18
- 239000007859 condensation product Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 12
- 150000002475 indoles Chemical class 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 11
- 229940054051 antipsychotic indole derivative Drugs 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 238000012544 monitoring process Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 239000012047 saturated solution Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000007853 buffer solution Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical group OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007995 HEPES buffer Substances 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 238000002189 fluorescence spectrum Methods 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical group OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 5
- 229940005991 chloric acid Drugs 0.000 claims description 5
- 238000004993 emission spectroscopy Methods 0.000 claims description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 238000000862 absorption spectrum Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 claims description 3
- 239000006174 pH buffer Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000003313 weakening effect Effects 0.000 claims description 3
- 238000006641 Fischer synthesis reaction Methods 0.000 claims description 2
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 claims 1
- 238000005259 measurement Methods 0.000 claims 1
- 239000006179 pH buffering agent Substances 0.000 claims 1
- IGSFZYGVWAIVHV-UHFFFAOYSA-N 1-ethyl-2,3,3-trimethyl-2h-indole Chemical compound C1=CC=C2N(CC)C(C)C(C)(C)C2=C1 IGSFZYGVWAIVHV-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 239000007787 solid Substances 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 230000002829 reductive effect Effects 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- -1 methine indoles Chemical class 0.000 description 8
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 239000002932 luster Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000004847 absorption spectroscopy Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000008520 organization Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 150000005837 radical ions Chemical class 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- VMDDSJXYVPDVLK-UHFFFAOYSA-N 2,3,4-trimethyl-1h-indole Chemical compound C1=CC(C)=C2C(C)=C(C)NC2=C1 VMDDSJXYVPDVLK-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 208000037273 Pathologic Processes Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 206010003246 arthritis Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 201000011529 cardiovascular cancer Diseases 0.000 description 1
- 230000004098 cellular respiration Effects 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 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
- 238000003384 imaging method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 231100000636 lethal dose Toxicity 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- IWPWMAJDSLSRIP-UHFFFAOYSA-N nezukone Chemical compound CC(C)C1=CC=CC(=O)C=C1 IWPWMAJDSLSRIP-UHFFFAOYSA-N 0.000 description 1
- NKCCODPFBDGPRJ-UHFFFAOYSA-N nitridocarbon(1+) Chemical compound N#[C+] NKCCODPFBDGPRJ-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000009054 pathological process Effects 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Substances [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- ADYYRXNLCZOUSU-UHFFFAOYSA-M potassium;propan-2-ol;hydroxide Chemical compound [OH-].[K+].CC(C)O ADYYRXNLCZOUSU-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000007811 spectroscopic assay Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
-
- 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"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
-
- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
- G01N2021/3155—Measuring in two spectral ranges, e.g. UV and visible
-
- 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"
- G01N2021/6443—Fluorimetric titration
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Abstract
Disclose a kind of detection cyanide ion and hypochlorous fluorescence probe and its preparation and application.Probe of the invention it be using phenylhydrazine -4- sulfonic acid and methyl isopropyl Ketone as raw material, pass through Fischer react etc. synthesis N- ethyl -2,3,3- tri-methyl indole -5- potassium sulfonate;Condensing agent for synthesizing is reacted by Vilsmeier-Haack;Condensing agent and N- ethyl -2,3,3- tri-methyl indole -5- potassium sulfonate carry out Knoevenagel Condensation and reacts then to obtain with N- phenyl -3- carbazole boric acid by Suzuki coupling reaction again.Probe of the invention is near-infrared probe, which has the characteristics that highly selective, high sensitivity and quick response to cyanide ion and hypochlorous acid.
Description
Technical field
The invention belongs to chemical analysis detection technique fields, and in particular to a kind of detection cyanide ion and hypochlorous fluorescence
Probe and its methods for making and using same.
Background technique
Cyanide plays very important effect in the industrial production, is widely used in exploitation of gold deposit, plating, resin and fibre
The fields such as dimension synthesis.However, cyanide is violent in toxicity, lethal dose 0.5-3.5mg/kg.Cyanide can pass through lung, skin
Skin, contaminated food and the intake of contaminated drinking water are internal.Cyanide ion can inhibit the cellular respiration in mammal, and
And by inhibiting central nervous system to lead to death.According to the World Health Organization (WHO), the highest cyaniding that allows in drinking water
Object concentration is 1.9 μM.Therefore, cyanide ion detection is of great significance.
Hypochlorous acid is widely used as disinfectant, antibacterial agent and bleaching agent in daily life.Meanwhile hypochlorous acid is also a kind of
Important active oxygen species (ROS), play an important role in various physiology and pathologic process.But excessive hypochlorous acid pair
Human body is harmful, will lead to a variety of diseases, such as arthritis, nerve regression disease, cardiovascular disease and cancer.Therefore, secondary
Chloric acid detection is of great significance.
So far, many detection cyanide ions and hypochlorous method are had been developed for.Including atomic absorption spectrum
Method, electrochemical methods etc..But there is such as somewhat expensives for these methods, sample preparation is complicated, and testing time length etc. lacks
Point.Organic fluorescence probe because have quickly detection, it is easy to operate and highly sensitive the advantages that and by vast researcher
Concern.In recent years, various detection cyanide ions and hypochlorous fluorescence probe come into being, these probes face it is highly selective,
The challenge of high sensitivity, quick response and good aqueous solubility.On the whole, it is directed to single cyanide ion and single hypochlorous acid at present
Probe it is relatively more, but be the absence of one kind and can while fast and efficiently detect cyanide ion and hypochlorous probe.
Summary of the invention
It is an object of the invention to provide the chemiluminescence spies that a kind of easily prepared, inexpensive, quick detection, performance are stable
Needle, and the synthetic method of the probe is provided, a kind of while highly selective and highly sensitive detection cyanogen is also developed on this basis
Radical ion and hypochlorous method.
It is characteristic of the invention that using classical nir dye --- seven methine indoles cyanines derivatives be fluorophor with
Recognition group devises the novel seven methines indoles cyanines of carbazole modification using the nucleophilicity and hypochlorous oxidisability of cyanide ion
Derivative probe Cz-Cy7, the probe can rapidly and efficiently identify cyanide ion and hypochlorous acid simultaneously.
To achieve the above object, technical solution provided by the invention is as follows:
According to the first embodiment of the present invention, the compound with logical formula (I) is provided:
According to the second embodiment of the present invention, the preparation method of above compound is provided, which is characterized in that the preparation
Method the following steps are included:
1) using phenylhydrazine -4- sulfonic acid, methyl isopropyl Ketone, bromoethane as raw material, pass through Fischer reaction and alkylated reaction
The N- ethyl -2,3 with logical formula (II) is synthesized, 3- tri-methyl indole -5- potassium sulfonate is labeled as " indole derivatives ";Reaction is such as
Under:
2) using cyclohexanone and phosphorus oxychloride as raw material, methylene chloride is solvent, and n,N-Dimethylformamide (DMF) is solvent
And reaction reagent, there is the condensing agent of following general formula (III) by the synthesis of Vilsmeier-Haack formylation reaction:
3) indole derivatives with logical formula (II) for synthesizing step 1) lead to formula (III) with having for step 2) synthesis
Condensing agent carries out Knoevenagel Condensation reaction, obtains the condensation product (M1) with following general formula (IV):
4) condensation product (M1) with logical formula (IV) for obtaining step 3) passes through with N- phenyl -3- carbazole boric acid (B)
Suzuki coupling reaction has the target-probe compound of logical formula (I) to obtain:
Preferably, in the above preparation method, step 1) is done as follows:
Acetic acid, phenylhydrazine -4- sulfonic acid and methyl isopropyl Ketone are added in the reactor, carries out back flow reaction (preferably in inertia
Back flow reaction 3-15 hours under the protection of gas);Then be added potassium hydroxide Organic Alcohol saturated solution (such as isopropanol saturation
Solution: potassium hydroxide is dissolved in saturation potassium hydroxide aqueous isopropanol made in isopropanol);Add bromoethane and second
Nitrile carries out back flow reaction (preferably back flow reaction 5-48 hours under the protection of inert gas);After being cooled to room temperature, filters, wash
It washs and (is preferably washed using ether), obtain N- ethyl -2,3 with logical formula (II), 3- after dry (preferably using vacuum drying)
Tri-methyl indole -5- potassium sulfonate is labeled as " indole derivatives ".
Preferably, the molar ratio of phenylhydrazine -4- sulfonic acid and methyl isopropyl Ketone be 1:2-5, preferably 1:3-4, it is more excellent
It is selected as 1:3.5-3.8;.
Preferably, the molar ratio of phenylhydrazine -4- sulfonic acid and bromoethane be 1:1-3, preferably 1:1.2-2.5, more preferably
1:1.5-2。
Preferably, in the above preparation method, step 1) is done as follows:
Acetic acid, phenylhydrazine -4- sulfonic acid and methyl isopropyl Ketone are added in the reactor, is returned under the protection of inert gas
It flows (such as 3-15 hours);Reaction mixture is cooling, then it is added drop-wise to poor solvent or precipitating solvent (such as acetic acid second
Ester) in, there is pink solid precipitation;Then reaction mixture is filtered, solids is washed with solvent (such as ether), is done
It is dry;Pink powder organic solvent (such as methanol or ethyl alcohol) dissolution after drying is obtained to the solution (example of compound (A)
Such as the methanol solution or ethanol solution of compound (A)), the Organic Alcohol of potassium hydroxide is then added dropwise into the solution of compound (A)
Saturated solution (such as isopropanol saturated solution: potassium hydroxide is dissolved in saturation potassium hydroxide isopropanol made in isopropanol
Solution), yellow solid, centrifuge separation is precipitated, and washed and dried with solvent (such as ether), obtains corresponding sylvite;So
Above-mentioned sylvite, organic solvent (such as acetonitrile) and bromoethane is added in another reactor afterwards, in inert gas (such as nitrogen
Gas) the lower reflux of protection (such as 10-40 hours, such as 24 hours), there is red solids to be precipitated;After being cooled to room temperature, reaction is mixed
Object is closed to be filtered, solids is washed with solvent (such as ether), and it is dry, obtain the compound of logical formula (II).
It is further preferred that step 1) is done as follows: into single port bottle, sequentially adding acetic acid, phenylhydrazine -4- sulfonic acid and first
Base nezukone, reflux (such as 3-12 hours, such as 8 hours) under inert gas (such as nitrogen) protection, solution becomes at this time
Kermesinus;After being cooled to room temperature, reaction solution is slowly dropped into ethyl acetate, there is pink solid precipitation in solution;Then it takes out
Filter, and washed repeatedly with ether, finally it is dried in vacuo;Pink powder after above-mentioned drying is dissolved with methanol, by hydroxide
Potassium, which is dissolved in isopropanol, is made saturated solution, and the isopropanol saturated solution of potassium hydroxide is then added dropwise into methanol solution, obtains
Yellow solid, centrifuge separation, and washed (such as 3-4 times) with ether, it is dried in vacuo;A single port bottle separately is taken, successively into bottle
Above-mentioned yellow solid, acetonitrile and bromoethane is added, flow back under inert gas (such as nitrogen) protection (such as 10-40 hours, such as
24 hours), there is red solid to be precipitated;It after being cooled to room temperature, filters, and washed with ether, is dried in vacuo, obtain logical formula (II)
Compound.
Preferably, in the above preparation method, wherein step 2) is done as follows:
DMF is added into reactor, phosphorus oxychloride and dichloromethane are added under cooling (such as under the cooling of 0 DEG C of ice bath)
Alkane, reaction (are preferably reacted 0.2-6 hours) at room temperature, and cyclohexanone, back flow reaction (preferably heating reflux reaction 1- is added
12 hours);After reacting cooling (after being preferably cooled to room temperature), reaction mixture is instilled in ice water, stirring (is preferably stirred
Mix 6-48 hours), it filters, it is dry (being preferably dried in vacuo), obtain the condensing agent with logical formula (III).
Preferably, cyclohexanone: phosphorus oxychloride: the molar ratio of DMF is 1:1-5:2-8, preferably 1:1.5-4.5:2.5-
7, more preferably 1:2-4:3-6.
Preferably, in the above preparation method, wherein step 2) is done as follows:
Organic solvent (such as DMF) is added in the reactor, slowly drips under cooling (such as under the cooling of 0 DEG C of ice bath)
Add the mixed solution of phosphorus oxychloride and methylene chloride, then (example will be reacted after mixed solution heating (such as being warmed to room temperature)
Such as 0.5-3 hours, such as 1 or 2 hour), then cyclohexanone is slowly added dropwise into mixed solution;After cyclohexanone drips, heat back
It flowing (such as 2-6 hours), mixed solution becomes orange red at this time, after reaction mixture cooling (such as being cooled to room temperature),
Mixed solution is added drop-wise in trash ice, is stirred (such as being stirred overnight), is filtered, it is dry (such as vacuum drying), obtain general formula
(III) condensing agent.
Preferably, step 2) is done as follows: DMF being added into there-necked flask, trichlorine is slowly added dropwise under 0 DEG C of ice bath
The mixed solution of oxygen phosphorus and methylene chloride;Remove ice bath, mixed solution reacts that (such as 0.5-3 hours, such as 1 or 2 is small at room temperature
When), then cyclohexanone is slowly added dropwise into mixed solution;After dripping, mixture be heated to reflux (such as be heated to 40 DEG C, such as
Reflux 2-6 hours, such as 4 hours), solution becomes orange red at this time;After reaction mixture is cooled to room temperature, mixed liquor is instilled
It in ice, overnight, filters, is dried in vacuo (such as 24 hours), obtain the condensing agent of logical formula (III).
Preferably, in the above preparation method, wherein step 3) is done as follows:
The indole derivatives with logical formula (II) of addition step 1) synthesis, having for step 2) synthesis are led in the reactor
Condensing agent, sodium acetate and the acetic anhydride of formula (III), back flow reaction (preferably back flow reaction 6-24 hours under nitrogen protection);
Cooling (being preferably cooled to room temperature), separation (preferably use and settle in ether and purify through column chromatography for separation), had
The condensation product (M1) of following general formula (IV).
Preferably, step 1) synthesis has general formula with the indole derivatives and rapid 2) synthesis for leading to formula (II)
(III) molar ratio of condensing agent is 1-10:1, preferably 2-8:1, more preferably 3-5:1.
Preferably, in the above preparation method, wherein step 3) is done as follows:
Compound N-ethyl -2,3,3- the tri-methyl indole-of the logical formula (II) obtained in step 1) is added in the reactor
Condensing agent, sodium acetate and the acetic anhydride for the logical formula (III) that 5- potassium sulfonate, step 2) obtain, flow back (example under inert gas protection
80 DEG C of reflux are such as heated to, such as are flowed back 4-20 hours, such as 12 hours), solution colour is rendered as green at this time;By reaction solution
After cooling (such as being cooled to room temperature), acetic anhydride is removed under reduced pressure, and gained residue is dissolved with solvent (such as methanol or ethyl alcohol),
Acquired solution is instilled in poor solvent or precipitating solvent (such as ether) again, is filtered, and with solvent (such as a large amount of ether)
Washing, it is dry;Gained green crude product is purified (such as using column chromatography purification), obtains consolidating for green band metallic luster
Body, i.e., the condensation product (M1) of logical formula (IV).
Preferably, into single port bottle, compound N-ethyl -2,3 of the logical formula (II) obtained in step 1) is sequentially added,
Condensing agent, sodium acetate and the acetic anhydride for the logical formula (III) that 3- tri-methyl indole -5- potassium sulfonate, step 2) obtain, in inert gas
The lower reflux of (such as nitrogen) protection (such as 80 DEG C of reflux are heated to, and it flows back 4-20 hours, such as 12 hours), solution colour is at this time
It is now green;After being cooled to room temperature, acetic anhydride is removed under reduced pressure, is dissolved with methanol, then is instilled in ether, filters, and with greatly
Measure ether washing, vacuum drying;Gained green crude product uses column chromatography purification, is with chloroform/methanol (such as 4:1, v/v)
Eluant, eluent, collects the colour band of green, and solvent evaporated finally obtains the solid of green band metallic luster, i.e., the condensation of logical formula (IV)
Product (M1).
Preferably, in the above preparation method, wherein step 4) is done as follows:
Condensation product (M1), the N- phenyl -3- carbazole boric acid of the logical formula (IV) that step 3) obtains are added into reactor
(B), palladium catalyst, potassium carbonate and solvent, (preferably 78 DEG C reflux, preferably reaction 12-48 is small under nitrogen protection for back flow reaction
When);Cooling (being preferably cooled to room temperature), removes mixed solvent and the target for purifying to obtain logical formula (I) through column chromatography for separation is visited
Needle compound.
Preferably, the condensation product (M1) of logical formula (IV) and the rubbing for N- phenyl -3- carbazole boric acid (B) of step 3) acquisition
You are than being 1:0.8-5, preferably 1:1-4, more preferably 1:1.2-3.
Preferably, the solvent is the mixed liquor of second alcohol and water, preferably, the volume ratio of ethyl alcohol and water is 2-10:
1, preferably 3-8:1, more preferably 4-6:1.
Preferably, the palladium catalyst is Pd (PPh3)4Or Pd (OAc)2Or PdCl2Or Pd (dba)2.Palladium catalyst is excellent
It is selected as Pd (PPh3)4。
Preferably, the dosage of palladium catalyst is 0.1-2%, the preferably 0.5-1.5% of condensation product M1 mass, more preferably
0.6-1.2%.
Preferably, in the above preparation method, wherein step 4) is done as follows:
Be added in the reactor the condensation product (M1) of logical formula (IV) obtained in step 3), N- phenyl -3- carbazole boric acid,
Pd(PPh3)4, potassium carbonate and ethanol/water mixed solvent (such as 5:1 ratio, v/v), protected at inert gas (such as nitrogen)
Lower reflux (such as reflux temperature is 78 DEG C, is flowed back 10-30 hours, such as 20 hours);(such as room is cooled to for reactant is cooling
Temperature) after, mixed solvent is removed under reduced pressure, is then dissolved with solvent (such as methanol), then acquired solution is instilled into poor solvent or is sunk
It forms sediment in solvent (such as ether), filters, and washed with solvent (such as ether), it is dry;Gained green crude product is purified
(such as using column chromatography purification) obtains the solid of green band metallic luster, i.e., the compound of logical formula (I).
Preferably, step 4) is done as follows: into single port bottle, sequentially adding the logical formula (IV) of step 3) acquisition
Condensation product (M1), N- phenyl -3- carbazole boric acid, Pd (PPh3)4, potassium carbonate and ethanol/water mixed solvent (such as 5:1, v/v),
Reflux (such as reflux temperature is 78 DEG C, is flowed back 10-30 hours, such as 20 hours) under inert gas (such as nitrogen) protection;It will
After reactant cooling (such as being cooled to room temperature), mixed solvent is removed under reduced pressure, is then dissolved with methanol, then acquired solution is instilled
It in ether, filters, and washed with ether, is dried in vacuo;Gained green crude product uses column chromatography purification, with ethyl acetate/
Methanol (such as 5:1, v/v) is eluant, eluent, collects dirty-green colour band, and solvent evaporated finally obtains consolidating for green band metallic luster
Body, i.e., the compound of logical formula (I).
Preferably, having the compound of logical formula (I) to have following characteristics prepared by the present invention:1H NMR(400MHz,
DMSO-d6) δ (ppm): 8.31-8.29 (d, J=8Hz, 2H), 8.20-8.19 (d, J=4.0Hz, 2H), 7.79 (s, 1H),
7.77-7.62 (t, 2H), 7.744-7.741 (d, J=1.2Hz, 1H), 7.57-7.54 (t, 2H), 7.51-7.50 (d, J=
4.0Hz, 4H), 7.497-7.495 (d, J=0.8Hz, 1H), 7.48-7.47 (d, J=4Hz, 1H), 7.29-7.28 (t, 1H),
7.264-7.260 (d, J=1.6Hz, 1H), 7.21 (s, 1H), 7.23 (s, 1H), 6.24-6.21 (d, J=12Hz, CH),
4.13-4.10(m,4H),2.75-2.74(t,4H),2.02-1.99(t,2H),1.25-1.15(t,6H),1.07-0.97(s,
12H).13C NMR(100MHz,DMSO-d6)δ(ppm):171.34,163.03,148.09,145.36,142.16,141.36,
140.42,137.24,132.08,130.93,128.50,128.07,127.4,127.2,126.55,123.41,122.81,
122.29,121.27,120.86,120.23,110.16.100.43,48.63,27.28,24.81,21.43,
12.42.MALDI-TOF MS(C52H51BrN3O6S2)m/z:calcd.958.01,found:878.93[Cz-Cy7-Br]+。
According to the third embodiment the present invention, the compound of above-mentioned logical formula (I) is provided or by above-mentioned preparation method institute
Purposes of the compound of preparation as detection cyanide ion and/or hypochlorous fluorescence probe.
Qualitative detection and/or quantitative determination are carried out to cyanide ion and/or hypochlorous acid using the compound as probe.
Preferably, probe is 0.09 μM to the Monitoring lower-cut of cyanide ion concentration.
Preferably, probe is 0.014 μM to the Monitoring lower-cut of hypochlorous acid concentration.
It is preferred that probe dissolves in a solvent, to cyanide ion when being detected using UV absorption and fluorescence emission spectrometry
And/or hypochlorous acid is detected.
Preferably, probe is dissolved in the first solvent, when detection cyanide ion using UV absorption and fluorescent emission
Spectroscopic methodology detection cyanide ion.Preferably, the mixed solution that first solvent is water and DMF volume ratio is 3:7, first is molten
Agent is more preferably the water for being added with pH buffer and DMF volume ratio is the mixed solution of 3:7.The pH buffer is slow for HEPES
Rush solution.The pH of first solvent is 9-11.
Preferably, probe is dissolved in the second solvent, when detection hypochlorous acid using UV absorption and fluorescence emission
Spectrometry detects hypochlorous acid.Preferably, the second solvent PBS buffer solution.Second solvent is more preferably the PBS containing acetonitrile
Buffer solution, the volume content of acetonitrile are 40-60%.The pH of second solvent is 3-5.
Preferably, probe carries out colorimetric judgement to cyanide ion and/or hypochlorous detection under the conditions of daylight naked eye,
Probe is either measured to cyanide ion and hypochlorous response by UV absorption and fluorescence emission spectrum.
Preferably, cyanide ion is added in the solution containing probe, solution colour becomes glassy yellow by blackish green, glimmering
Light weakens.Hypochlorous acid is added in the solution containing probe, solution colour becomes khaki, fluorescent weakening by blackish green.
It is preferred that probe to the detection of cyanide ion there is no when fluorescence response, cyanide ion and probe in solution to be detected
Molar ratio be 12:1.
It is preferred that probe acts on cyanide ion, there is no times when ultraviolet response to be no more than 5 minutes.
It is preferred that probe to hypochlorous detection there is no when fluorescence response, hypochlorous acid and probe rubs in solution to be detected
You are than being 10:1
It is preferred that probe acts on hypochlorous acid, there is no times when ultraviolet response to be no more than 1 minute.
The above-mentioned synthesis process of the compound of the present invention (I) is as shown below:
In the present invention, it is based on seven methine indoles cyanines derivatives that cyanide ion and hypochlorous acid, which detect difunctional fluorescence probe,
Compound (I), be labeled as fluorescence probe Cz-Cy7.
Another object of the present invention be to provide it is a kind of using the above method obtain fluorescence probe detection cyanide ion and time
The application method of chloric acid, the probe both obtained using the above method carry out qualitative and quantitative determination to cyanide ion and hypochlorous acid.
Preferably, when being detected using UV absorption and fluorescence emission spectrometry, ingredient is the fluorescence probe of compound (I)
It is dissolved in water and DMF (volume ratio 3:7) mixed solution, cyanide ion is detected.
Preferably, in the probe solution be added cyanide ion after solution colour rapidly gone to by original green it is bright orange
Color, color change can also with the naked eye understand under fluorescent light to be differentiated.
Application of the fluorescence probe prepared by the present invention in cyanide ion detection.Probe is dissolved in water/DMF (volume
Than being preferably added to HEPES buffer solution, pH=10 for 3:7) in the mixed solvent, preferably 5 μM of probe solution, cyanogen is then added
Radical ion measures probe to the response of cyanide ion or the variation of directly observation solution colour by ultra-violet absorption spectrum.Cyanogen
The addition of radical ion makes probe solution color become glassy yellow by blackish green, and absorption intensity reduces at 771nm.
Preferably, which is studied to the quantitative detection performance of cyanide ion using fluorescent spectrometry, acquisition probe adds
Enter fluorescent emission intensity of the cyanide ion fore-and-aft architecture at 806nm;Experiment shows when to be added to probe molten for cyanide ion solution
In liquid after 5 minutes, fluorescence intensity no longer extends with further variation with the time, illustrate the probe 5 minutes it
The response to cyanide ion inside can be completed.Meanwhile fluorescence intensity increases with cyanide ion concentration and is reduced, when probe and cyanogen root
When the concentration of ion is 1:12, fluorescent emission intensity of the system at 806nm reaches minimum, illustrates that probe and cyanide ion act on
Completely, the variation of fluorescence probe intensity and cyanide ion concentration are linear, and Monitoring lower-cut is respectively 0.09 μM, much low
In 1.9 μM of the safty of drinking water standard that the World Health Organization determines.
Preferably, other ten kinds of common anion of experimental selection detect probe, the results showed that probe
Detection have not significant impact, illustrate the probe to cyanide ion detection have very excellent selectivity.
Fluorescence probe prepared by the present invention is applied in hypochlorous acid detection.Probe is dissolved in the buffering of the PBS containing acetonitrile
In solution (pH=4 contains 50% acetonitrile), then the probe solution that preferred concentration is 5 μM is added hypochlorous acid, passes through UV absorption
Spectroscopic assay probe observes the variation of solution colour to hypochlorous response or directly.Hypochlorous addition makes probe solution face
Color becomes khaki by blackish green, and absorption intensity reduces at 762nm.
Preferably, which is studied to hypochlorous quantitative detection performance using fluorescent spectrometry, acquisition probe is added
Fluorescent emission intensity of the hypochlorous acid fore-and-aft architecture at 795nm;Experiment shows to be added to 1 in probe solution as hypochlorite solution
After minute, fluorescence intensity no longer extends with further variation with the time, illustrates the probe within 1 minute
It completes to hypochlorous response.Meanwhile fluorescence intensity increases with hypochlorous acid concentration and is reduced, when probe and hypochlorous concentration are
When 1:10, fluorescent emission intensity of the system at 795nm reaches minimum, illustrates probe and hypochlorous acid effect completely, fluorescence probe
The variation of intensity and hypochlorous acid concentration are linear, and Monitoring lower-cut is respectively 0.014 μM.
Fluorescence probe prepared by the present invention has highly selective, other common active oxygen species to hypochlorous acid detection
(ONOO-,HO·,H2O2, TBHP and O2) detection of probe is had not significant impact.
Fluorescence probe prepared by the present invention can be used for cyanide ion and hypochlorous acid detection in the solid state, such as consolidate probe
It is scheduled on filter paper, when cyanide ion and hypochlorous acid is added dropwise, color identical with solution state can be observed visually under natural light
Variation.
In the present invention, hypochlorous acid and hypochlorite ion are general.
Beneficial effects of the present invention are as follows:
1, the fluorescence probe (compound for having general formula (1)) based on seven methine indoles cyanines derivatives that the present invention synthesizes
Cyanide ion and hypochlorous acid can be detected simultaneously;
2, the present invention provides a kind of novel near-infrared probe, cyanide ion and time chlorine can be carried out in the presence of water
Acid detection is expected to be applied to cyanide ion and hypochlorous fluorescent tracing and imaging in living biological cell;
3, probe of the invention has faster response speed, and cyanide ion detection can be completed in 5 minutes;Hypochlorous acid
Detection can be completed in 1 minute, can be applied to cyanide ion and hypochlorous field quick detection and monitoring;
4, the fluorescence probe based on seven methine indoles cyanines derivatives that the present invention synthesizes has the characteristics that naked eyes identify;
5, probe of the invention reaches 0.09 μM to the Monitoring lower-cut of cyanide ion concentration, is more than many other types of cyanogen
Radical ion probe, far below cyanide ion concentration in the safty of drinking water of World Health Organization's license;To hypochlorous Monitoring lower-cut
Reach 0.014 μM, far below the hypochlorous acid probe based on indoles cyanines derivative reported at present;
6, probe of the invention has excellent selectivity and competitiveness, and when detecting cyanide ion and hypochlorous acid, other are normal
The anion and active oxygen species seen do not generate interference.
Detailed description of the invention
Fig. 1 is the general structure of compound prepared by the present invention.
Fig. 2 is the synthetic route chart for having the compound of logical formula (I) prepared by the present invention.
Fig. 3 is probe to the ultraviolet-visible absorption spectroscopy response of cyanide ion, linear relationship curve and its under natural light
Photo.
Fig. 4 is probe to the fluorescence spectrum response of cyanide ion, linear relationship curve.
Fig. 5 is kinetics relation curve of the probe to cyanide ion.
Fig. 6 detects cyanide ion for probe highly selective.
Fig. 7 be probe hypochlorous ultraviolet-visible absorption spectroscopy is responded, linear relationship curve and its under natural light
Photo.
Fig. 8 be probe hypochlorous fluorescence spectrum is responded, linear relationship curve.
Fig. 9 is probe to hypochlorous kinetics relation curve.
Figure 10 detects hypochlorous acid for probe highly selective.
Figure 11 is the test paper (filter paper) based on probe to cyanide ion and hypochlorous portable inspectiont photo.
Specific embodiment
The present invention is described in further detail technical solution by following examples, but the present invention is not restricted to these implement
Example.
Embodiment 1: the synthesis of target-probe Cz-Cy7
(1) synthesis (compound (II)) of N- ethyl -2,3,3- tri-methyl indole -5- potassium sulfonate
Into 50mL single port bottle, it is different to sequentially add 10mL acetic acid, phenylhydrazine -4- sulfonic acid (2.000g, 0.010mol) and methyl
Propyl ketone 4.00mL (0.037mol) flows back 8 hours under nitrogen protection, and solution becomes kermesinus at this time.After being cooled to room temperature,
Reaction solution is slowly dropped into ethyl acetate, there is pink solid precipitation in solution;It filters, and is washed repeatedly with ether, vacuum
It is dry;Pink powder after above-mentioned drying is dissolved with proper amount of methanol, 0.561g potassium hydroxide is dissolved in isopropanol and is made
Then the isopropanol saturated solution of potassium hydroxide is added dropwise into methanol solution, obtains yellow solid for saturated solution, be centrifuged, be used in combination
Ether washs 3-4 times, vacuum drying.A 50mL single port bottle separately is taken, above-mentioned yellow solid, 20mL acetonitrile are sequentially added into bottle
It with bromoethane 1.49mL (0.020mol), flows back 24 hours under nitrogen protection, there is red solid to be precipitated.It is cooled to room temperature
Afterwards, it filters, and is washed (3 × 10mL) with ether, vacuum drying obtains compound (II).
(2) synthesis (compound (III)) of condensing agent
DMF 10mL (0.130mol) is added into 100mL there-necked flask, 10mL is slowly added dropwise under 0 DEG C of ice bath
The mixed solution of (0.107mol) phosphorus oxychloride and 5mL methylene chloride.Ice bath is removed, is reacted 1 hour at room temperature, then to mixing
3.5mL (0.034mol) cyclohexanone is slowly added dropwise in solution.After dripping, it is heated to reflux 4 hours, solution becomes orange red at this time
Color.After reacting and being cooled to room temperature, mixed liquor is instilled in ice, overnight, is filtered, vacuum drying obtains compound (III).
(3) compound (IV), the i.e. synthesis of condensation product M1
Into 25mL single port bottle, N- ethyl -2,3 is sequentially added, 3- tri-methyl indole -5- potassium sulfonate (0.843g,
2.2mmol), condensing agent (step 2 gained compound (III), 0.188g, 1.1mmol), sodium acetate (0.180g, 2.2mmol) and
10mL acetic anhydride flows back 12 hours under nitrogen protection, and solution colour is rendered as green at this time.After being cooled to room temperature, decompression is removed
Acetic anhydride is removed, is dissolved with a small amount of methanol, then instilled in ether, is filtered, and washed with a large amount of ether, is dried in vacuo;Gained
Green crude product uses column chromatography purification, with chloroform/methanol (4:1, v/v) for eluant, eluent, collects the colour band of green, is evaporated molten
Agent finally obtains solid (M1) 0.664g of green band metallic luster, yield 64.4%.
(4) synthesis (compound (I)) of target product Cz-Cy7
Into 100mL single port bottle, condensation product M1 (1.220g, 2.00mmol) (step 3 gained compound is sequentially added
(IV)), N- phenyl -3- carbazole boric acid (1.040g, 3.60mmol), Pd (PPh3)4(0.230g, 0.20mmol), potassium carbonate
0.280g, 2.00mmol) and 50mL ethanol/water (5:1, v/v), it flows back 20 hours under nitrogen protection.After being cooled to room temperature, subtract
Pressure removes mixed solvent, is then dissolved with a small amount of methanol, then instilled in ether, filters, and washed with ether, and vacuum is dry
It is dry.Gained green crude product uses column chromatography purification, with ethyl acetate/methanol (5:1, v/v) for eluant, eluent, collects dirty-green
Colour band, solvent evaporated finally obtain the solid 1.197g of green band metallic luster.
Probe characterization:1H NMR (400MHz, DMSO-d6) δ (ppm): 8.31-8.29 (d, J=8Hz, 2H), 8.20-
8.19 (d, J=4.0Hz, 2H), 7.79 (s, 1H), 7.77-7.62 (t, 2H), 7.744-7.741 (d, J=1.2Hz, 1H),
7.57-7.54 (t, 2H), 7.51-7.50 (d, J=4.0Hz, 4H), 7.497-7.495 (d, J=0.8Hz, 1H), 7.48-7.47
(d, J=4Hz, 1H), 7.29-7.28 (t, 1H), 7.264-7.260 (d, J=1.6Hz, 1H), 7.21 (s, 1H), 7.23 (s,
1H), 6.24-6.21 (d, J=12Hz), 4.13-4.10 (m, 4H), 2.75-2.74 (t, 4H), 2.02-1.99 (t, 2H),
1.25-1.15(t,6H),1.07-0.97(s,12H).13CNMR(100MHz,DMSO-d6)δ(ppm):171.34,163.03,
148.09,145.36,142.16,141.36,140.42,137.24,132.08,130.93,128.50,128.07,127.4,
127.2,126.55,123.41,122.81,122.29,121.27,120.86,120.23,110.16.100.43,48.63,
27.28,24.81,21.43,12.42.MALDI-TOF MS(C52H51BrN3O6S2)m/z:calcd.958.01,found:
878.93[Cz-Cy7-Br]+。
Embodiment 2: titration experiments of the cyanide ion to probe
In the in the mixed solvent of water and DMF (volume ratio 3:7 is preferably added to HEPES buffer solution, pH=10), prepare
The probe solution that concentration is 5 μM.Then respectively be added dropwise various concentration cyanide ion (0 μM, 5 μM, 10 μM, 15 μM, 20 μM, 25 μ
M, 30 μM, 35 μM, 40 μM, 45 μM, 50 μM, 55 μM, 60 μM), after 5min, passes through ultraviolet-visible absorption spectroscopy and fluorescence spectrum is surveyed
Try the absorption and fluorescent emission response of mixed system.
From the figure 3, it may be seen that absorption peak strength of the probe at 771nm increases with cyanide ion concentration and is reduced, solution colour
Become glassy yellow from blackish green.
As shown in Figure 4, emission peak intensity of the probe at 806nm increases with cyanide ion concentration and is reduced, probe and 12
Equivalent cyanide ion fully reacting, emission peak intensity and cyanide ion concentration are linear, illustrate that this probe can be examined quantitatively
Survey cyanide ion.
Embodiment 3: probe tests the kinetics of cyanide ion
At room temperature, (water/DMF, volume ratio 3:7 are preferably added to HEPES buffering to the probe solution that compound concentration is 5 μM
Solution, pH=10), cyanide ion then is added with micro syringe and records ultraviolet suction of the different time sample at 771nm
Receive intensity.
As shown in Figure 5, as the time increases, absorption intensity of the probe at 771nm is reduced, after five minutes, system it is ultraviolet
Absorption intensity no longer extends at any time and is further change in, and illustrates that the probe can be completed within 5 minutes to cyanide ion
Detection.
Embodiment 4: the selectivity test of probe in detecting cyanide ion
At room temperature, probe solution (water/DMF, volume ratio 3:7, HEPES buffer solution, pH that compound concentration is 5 μM
=10) and various anion solutions (Na2CO3, KSCN, Na2SO4, KF, NaCl, NaBr, KI, NaNO2, NaHCO3, NaOAc), it will
Various anion and cyanide ion are separately added into probe solution, shake up placement after five minutes, probe is measured in Fluorescence Spectrometer
Fluorescent emission intensity.
It will be appreciated from fig. 6 that common anion does not significantly interfere with probe in detecting, illustrate that probe detects tool to cyanide ion
There is good selectivity.
Embodiment 5: titration experiments of the hypochlorous acid to probe
The probe solution that (pH=4 contains 50% acetonitrile), compound concentration was 5 μM in PBS buffer solution.Then it is added dropwise respectively
The hypochlorous acid (0 μM, 5 μM, 10 μM, 15 μM, 20 μM, 25 μM, 30 μM, 35 μM, 40 μM, 45 μM, 50 μM) of various concentration, 1 minute
Afterwards, the absorption of mixed system is tested by ultraviolet-visible absorption spectroscopy and fluorescence spectrum and fluorescent emission responds.
As shown in Figure 7, absorption peak strength of the probe at 762nm with hypochlorous acid concentration increase and reduce, solution colour by
It is blackish green to become khaki.
As shown in Figure 8, emission peak intensity of the probe at 795nm increases with hypochlorous acid concentration and is reduced, and probe is worked as with 10
Hypochlorous acid fully reacting is measured, emission peak intensity is linear with hypochlorous acid concentration, illustrates that this probe can be with quantitative detection time chlorine
Acid.
Embodiment 6: probe tests hypochlorous kinetics
At room temperature, the probe solution (in PBS buffer solution, pH=4 contains 50% acetonitrile) that compound concentration is 5 μM, then
Hypochlorous acid is added with micro syringe and records UV absorption intensity of the different time sample at 762nm.
As shown in Figure 9, as the time increases, absorption peak strength of the probe at 762nm is reduced, after 1 minute, the purple of system
Outer absorption intensity no longer extends at any time and is further change in, and illustrates that the probe can be completed within 1 minute to hypochlorous
Detection.
Embodiment 7: the hypochlorous selectivity test of probe in detecting
At room temperature, compound concentration be 5 μM probe solution (in PBS buffer solution, pH=4, contain 50% acetonitrile) and respectively
Kind active oxygen species (HO, H2O2,ONOO-,·O2, TBHP), it is molten that various active oxygen species and hypochlorous acid are separately added into probe
In liquid, after shaking up placement 1 minute, the fluorescent emission intensity of probe is measured in Fluorescence Spectrometer.
As shown in Figure 10, common active oxygen species do not significantly interfere with probe in detecting hypochlorous acid, illustrate probe to secondary
Chloric acid detection has selectivity well.
Embodiment 8: portable probe (probe is fixed on filter paper) is applied in cyanide ion and hypochlorous acid detection
Certain density probe solution is prepared, the filter paper cut is immersed after probe sufficiently adsorbs, room temperature is true
Sky is dry.
It is subsequent:
(1) cyanide ion and the hypochlorite solution of various concentration is added dropwise respectively on filter paper, uses number after room temperature in vacuo is dry
Code camera shooting (see attached drawing 11a).Wherein: the concentration of cyanide ion is followed successively by 3eq, 6eq, 9eq, 12eq from left to right;Secondary chlorine
The concentration of acid ion is followed successively by 2.5eq, 5eq, 7.5eq, 10eq from left to right.
(2) several representative anion (AcO are added dropwise respectively on filter paper-,SO4 2-,CO3 2-,HCO3 -,NO2 -) and
Active oxygen (HO, H2O2,ONOO-,TBHP,·O2), (see attached drawing 11b) is shot with digital camera after room temperature in vacuo is dry.Its
In: that detects cyanide ion is successively added dropwise AcO from left to right-、SO4 2-、CO3 2-、HCO3 -、NO2 -;Detect it is hypochlorous from left to right
HO, H is successively added dropwise2O2、ONOO-、TBHP,·O2。
As shown in Figure 11, on portable test paper, probe generation and identical color change in solution, i.e., with cyanide ion
Concentration increases, and test paper gradually becomes glassy yellow by blackish green;As hypochlorous acid concentration increases, test paper gradually becomes soil by blackish green
Yellow;Other interfering ions and active specy do not interfere probe to cyanide ion and hypochlorous detection.Illustrate design of the present invention
The probe of synthesis can be used to portable, quick, efficient detection cyanide ion and hypochlorous acid.
Claims (10)
1. the compound with logical formula (I):
2. the preparation method of compound according to claim 1, which is characterized in that the preparation method the following steps are included:
1) it using phenylhydrazine -4- sulfonic acid, methyl isopropyl Ketone, bromoethane as raw material, is synthesized by Fischer reaction and alkylated reaction
N- ethyl -2,3 with logical formula (II), 3- tri-methyl indole -5- potassium sulfonate are labeled as " indole derivatives ";It reacts as follows:
2) using cyclohexanone and phosphorus oxychloride as raw material, methylene chloride is solvent, and n,N-Dimethylformamide (DMF) is for solvent and instead
Reagent is answered, there is the condensing agent of following general formula (III) by the synthesis of Vilsmeier-Haack formylation reaction:
3) by the indole derivatives with logical formula (II) of step 1) synthesis and the condensation with logical formula (III) of step 2) synthesis
Agent carries out Knoevenagel Condensation reaction, obtains the condensation product (M1) with following general formula (IV):
4) condensation product (M1) and N- phenyl -3- carbazole boric acid (B) for the logical formula (IV) for obtaining step 3) pass through Suzuki idol
Connection reaction has the target-probe compound for leading to formula (I) to obtain:
3. according to the method described in claim 2, wherein step 1) is done as follows:
Acetic acid, phenylhydrazine -4- sulfonic acid and methyl isopropyl Ketone are added in the reactor, carries out back flow reaction (preferably in inert gas
Protection under back flow reaction 3-15 hours);Then be added potassium hydroxide Organic Alcohol saturated solution (such as isopropanol saturation it is molten
Liquid: potassium hydroxide is dissolved in saturation potassium hydroxide aqueous isopropanol made in isopropanol);Bromoethane and acetonitrile are added,
It carries out back flow reaction (preferably back flow reaction 5-48 hours under the protection of inert gas);It after being cooled to room temperature, filters, washing
(preferably being washed using ether) obtains N- ethyl -2,3 with logical formula (II), 3- tri- after dry (preferably using vacuum drying)
Methyl indol -5- potassium sulfonate is labeled as " indole derivatives ";
Preferably, the molar ratio of phenylhydrazine -4- sulfonic acid and methyl isopropyl Ketone is 1:2-5, preferably 1:3-4, more preferably 1:
3.5-3.8;The molar ratio of phenylhydrazine -4- sulfonic acid and bromoethane is 1:1-3, preferably 1:1.2-2.5, more preferably 1:1.5-2.
4. according to the method in claim 2 or 3, wherein step 2) is done as follows:
DMF is added into reactor, phosphorus oxychloride and methylene chloride are added under cooling (such as under the cooling of 0 DEG C of ice bath),
Reaction (is preferably reacted 0.2-6 hours) at room temperature, and cyclohexanone, back flow reaction (preferably heating reflux reaction 1-12 is added
Hour);After reacting cooling (after being preferably cooled to room temperature), reaction mixture is instilled in ice water, stirring (is preferably stirred
6-48 hours), it filters, it is dry (being preferably dried in vacuo), obtain the condensing agent with logical formula (III);
Preferably, cyclohexanone: phosphorus oxychloride: the molar ratio of DMF be 1:1-5:2-8, preferably 1:1.5-4.5:2.5-7, more
Preferably 1:2-4:3-6.
5. wherein step 3) is done as follows according to method described in Claims 2 or 3 or 4:
What the indole derivatives with logical formula (II) of addition step 1) synthesis, step 2) synthesized in the reactor has general formula
(III) condensing agent, sodium acetate and acetic anhydride, back flow reaction (preferably back flow reaction 6-24 hours under nitrogen protection);It is cold
But (be preferably cooled to room temperature), separation (preferably using in ether settle and purified through column chromatography for separation), obtain have with
The condensation product (M1) of logical formula (IV) down;
Preferably, step 1) synthesis leads to formula (III) with the indole derivatives for leading to formula (II) and having for step 2) synthesis
Condensing agent molar ratio be 1-10:1, preferably 2-8:1, more preferably 3-5:1..
6. the method according to any one of claim 2-5, wherein step 4) is done as follows:
Condensation product (M1), the N- phenyl -3- carbazole boric acid (B), palladium of the logical formula (IV) that step 3) obtains are added into reactor
Catalyst, potassium carbonate and solvent, back flow reaction (are preferably reacted 12-48 hours) under nitrogen protection;It is cooling (preferably cooling
To room temperature), it removes mixed solvent and purifies to obtain the target-probe compound of logical formula (I) through column chromatography for separation;
Preferably, the condensation product (M1) for the logical formula (IV) that step 3) obtains and the molar ratio of N- phenyl -3- carbazole boric acid (B)
For 1:0.8-5, preferably 1:1-4, more preferably 1:1.2-3;Affiliated solvent is the mixed liquor of second alcohol and water, preferably, second
The volume ratio of alcohol and water is 2-10:1, preferably 3-8:1, more preferably 4-6:1;The palladium catalyst is Pd (PPh3)4Or Pd
(OAc)2Or PdCl2Or Pd (dba)2, palladium catalyst is preferably Pd (PPh3)4, the dosage of palladium catalyst is condensation product M1 mass
0.1-2%, preferably 0.5-1.5%, more preferable 0.6-1.2%.
7. the method according to any one of claim 2-6, it is characterised in that: the prepared chemical combination with logical formula (I)
Object has following characteristics:1H NMR(400MHz,DMSO-d6) δ (ppm): 8.31-8.29 (d, J=8Hz, 2H), 8.20-8.19
(d, J=4.0Hz, 2H), 7.79 (s, 1H), 7.77-7.62 (t, 2H), 7.744-7.741 (d, J=1.2Hz, 1H), 7.57-
7.54 (t, 2H), 7.51-7.50 (d, J=4.0Hz, 4H), 7.497-7.495 (d, J=0.8Hz, 1H), 7.48-7.47 (d, J
=4Hz, 1H), 7.29-7.28 (t, 1H), 7.264-7.260 (d, J=1.6Hz, 1H), 7.21 (s, 1H), 7.23 (s, 1H),
6.24-6.21 (d, J=12Hz, CH), 4.13-4.10 (m, 4H), 2.75-2.74 (t, 4H), 2.02-1.99 (t, 2H), 1.25-
1.15(t,6H),1.07-0.97(s,12H).13C NMR(100MHz,DMSO-d6)δ(ppm):171.34,163.03,
148.09,145.36,142.16,141.36,140.42,137.24,132.08,130.93,128.50,128.07,127.4,
127.2,126.55,123.41,122.81,122.29,121.27,120.86,120.23,110.16.100.43,48.63,
27.28,24.81,21.43,12.42.MALDI-TOF MS(C52H51BrN3O6S2)m/z:calcd.958.01,found:
878.93[Cz-Cy7-Br]+。
8. the compound of logical formula (I) or the compound of the preparation of the method as described in any one of claim 2-7 are as detection
The purposes of cyanide ion and/or hypochlorous fluorescence probe, wherein using the compound as probe to cyanide ion and/or secondary
Chloric acid carries out qualitative detection and/or quantitative determination;Preferably, probe is 0.09 μM to the Monitoring lower-cut of cyanide ion concentration,
Probe is 0.014 μM to the Monitoring lower-cut of hypochlorous acid concentration.
9. purposes according to claim 8, which is characterized in that probe is dissolved in the first solvent, using UV absorption
Cyanide ion is detected with fluorescence emission spectrometry;Preferably, the mixing that first solvent is water and DMF volume ratio is 3:7
Solution, the first solvent is more preferably the water for being added with pH buffer and DMF volume ratio is the mixed solution of 3:7;The pH buffering
Agent is HEPES buffer solution, and the pH of the first solvent is 9-11;And/or
Probe is dissolved in the second solvent, hypochlorous acid is detected using UV absorption and fluorescence emission spectrometry;Preferably, institute
Stating the second solvent is PBS buffer solution;Second solvent is more preferably the PBS buffer solution containing acetonitrile, the volume content of acetonitrile
For 40-60%, the pH of the second solvent is 3-5;And/or
Probe carries out colorimetric judgement to cyanide ion and/or hypochlorous detection under the conditions of daylight naked eye, or passes through purple
Outer absorption and fluorescence emission spectrum measurement probe are to cyanide ion and hypochlorous response;Preferably, containing the molten of probe
Cyanide ion is added in liquid, solution colour becomes glassy yellow, fluorescent weakening by blackish green;It is added in the solution containing probe secondary
Chloric acid, solution colour become khaki, fluorescent weakening by blackish green.
10. purposes according to claim 9, which is characterized in that there is no fluorescence responses for detection of the probe to cyanide ion
When, the molar ratio of cyanide ion and probe is 12:1 in solution to be detected, and there is no ultraviolet responses to cyanide ion effect for probe
When time be no more than 5 minutes;And/or
Probe is to hypochlorous detection there is no when fluorescence response, and the molar ratio of hypochlorous acid and probe is 10 in solution to be detected:
1, there is no times when ultraviolet response no more than 1 minute to hypochlorous acid effect for probe.
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