CN106518900A - Synthesis and application of BODIPY dye-based hypochlorite fluorescent probe - Google Patents
Synthesis and application of BODIPY dye-based hypochlorite fluorescent probe Download PDFInfo
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- CN106518900A CN106518900A CN201610823604.5A CN201610823604A CN106518900A CN 106518900 A CN106518900 A CN 106518900A CN 201610823604 A CN201610823604 A CN 201610823604A CN 106518900 A CN106518900 A CN 106518900A
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- hypochlorite
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- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 18
- 239000007850 fluorescent dye Substances 0.000 title abstract 5
- 239000000975 dye Substances 0.000 title abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004440 column chromatography Methods 0.000 claims abstract description 15
- 229940125782 compound 2 Drugs 0.000 claims abstract description 15
- 238000001514 detection method Methods 0.000 claims abstract description 14
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 229940125904 compound 1 Drugs 0.000 claims abstract description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 10
- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 claims abstract description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 72
- 239000000523 sample Substances 0.000 claims description 72
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 35
- 239000003208 petroleum Substances 0.000 claims description 17
- 239000003480 eluent Substances 0.000 claims description 15
- 239000012043 crude product Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 239000005457 ice water Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910019213 POCl3 Inorganic materials 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims 1
- 239000005708 Sodium hypochlorite Substances 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 5
- -1 hypochlorite ions Chemical class 0.000 abstract description 3
- 239000012264 purified product Substances 0.000 abstract 1
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract 1
- 238000004659 sterilization and disinfection Methods 0.000 abstract 1
- 239000008399 tap water Substances 0.000 abstract 1
- 235000020679 tap water Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- 150000002500 ions Chemical class 0.000 description 15
- 238000002189 fluorescence spectrum Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000645 desinfectant Substances 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 3
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000012496 blank sample Substances 0.000 description 3
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000002211 ultraviolet spectrum Methods 0.000 description 3
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 1
- MFFMQGGZCLEMCI-UHFFFAOYSA-N 2,4-dimethyl-1h-pyrrole Chemical class CC1=CNC(C)=C1 MFFMQGGZCLEMCI-UHFFFAOYSA-N 0.000 description 1
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 206010003246 arthritis Diseases 0.000 description 1
- 230000003143 atherosclerotic effect Effects 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- WHGBPBQHEFZYHO-UHFFFAOYSA-N sodium hypochlorous acid hypochlorite Chemical compound [Na+].OCl.[O-]Cl WHGBPBQHEFZYHO-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RTKIYNMVFMVABJ-UHFFFAOYSA-L thimerosal Chemical compound [Na+].CC[Hg]SC1=CC=CC=C1C([O-])=O RTKIYNMVFMVABJ-UHFFFAOYSA-L 0.000 description 1
- 229940033663 thimerosal Drugs 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
- 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
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic Table without C-Metal linkages
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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"
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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
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
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- General Health & Medical Sciences (AREA)
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention belongs to the technical fields of preparation and application of compounds, and in particular, relates to synthesis and application of a BODIPY dye-based hypochlorite fluorescent probe; a BODIPY derivative is firstly synthesized as a fluorescent probe; the synthesis comprises the steps: utilizing N,N-dimethyl formamide and phosphorus oxychloride, then adding a compound 1, dissolving in dichloroethane, carrying out a reaction, adding NaHCO3 until the solution is weakly alkaline, and after completion of the reaction, purifying through column chromatography to obtain a compound 2; then dissolving diamino maleonitrile and the compound 2 in ethanol, adding a few drops of acetic acid, carrying out a stirring reaction at room temperature, and finally obtaining the purified product. The fluorescent probe is used for detection of hypochlorite ions in tap water, Yangtze River water and sodium hypochlorite disinfection liquids; the fluorescent probe is capable of rapid identification of ClO<->, the fluorescence intensity is increased rapidly and obviously with addition of the hypochlorite and can be stable within 10 s, and thus the detection time is greatly shortened.
Description
Technical field
The invention belongs to the preparation of compound and applied technical field, and in particular to a kind of secondary chlorine based on BODIPY dyestuffs
Synthesis and application of the acid with fluorescence probe.
Background technology
Hypochlorous acid（HOCl）It is a kind of internal important active oxygen of biology（ROS）, it is considered that, it is interior
The hypochlorous acid of source property is by H2O2And Cl-There is peroxidization under Catalyzed Synthesis By Peroxidase and produce, especially white thin
Intracellular.Hypochlorous acid can destroy the bacterium of invasion and pathogen, therefore significant to human immune system however, the secondary chlorine of excess
Acid can also destroy DNA and protein molecule, ultimately result in some diseases, such as angiocardiopathy, atherosclerotic, ephrosis, bone
Arthritis and cancer etc..Additionally, HOCl and its conjugate base ClO-It is common drinking water, swimming sterilizing agent and bleaching in life
Agent.Just because of the hypochlorous acid of excess is easily caused disease and can produce threat to people, so in control daily life in water body
ClO-Concentration is particularly important, and the high selectivity and highly sensitive real-time detection to secondary acid group is also therefore very meaningful, causes
Extensive concern.
In recent years, some detections ClO has been reported-Fluorescence probe, wherein most is to utilize ClO-Strong oxidizing property it is former
Reason.Some functional groups such as acyl nitroso, p methoxy phenol, mercaptan, oxime, hydroxamic acid etc. can easily by hypochlorite
Oxidation, so be commonly used for the recognition group of fluorescence probe.But at the same time, some shortcomings of these probes also come out, than
Such as with certain cytotoxicity, slow course of reaction, poor selectivity, relatively low fluorescence quantum yield, easily by other
Ion interference etc., these shortcomings also greatly limit the application in vivo of these probes.Therefore, it is badly in need of a kind of energy of design
Enough overcome the novel fluorescence probe of these shortcomings.
The content of the invention
It is an object of the invention to provide a kind of new novel B ODIPY fluorescence probe based on C=N isomerization and its preparation
Method.
Another object of the present invention is that the novel fluorescence probe is used for hypochlorite ion in actual water sample product to have
Effect identification and quantitative determination.
For achieving the above object, the technical solution used in the present invention is：
One of the object of the invention technical method is that research synthesizes a kind of BODIPY derivatives as fluorescence probe, and its molecular formula is
C24H21BF2N6, structural formula are as follows：
The preparation method of above-mentioned fluorescence probe is as follows：
（1）The synthesis of midbody compound 2.
A certain amount of DMF (DMF) is added in 250 mL round-bottomed flasks, nitrogen protection is passed through, in ice
POCl3 is added under water-bath, is stirred 10min, is removed ice bath, return to and 30 min are stirred at room temperature.Then, 316 are weighed
mg（1 mmol）Compound 1 is dissolved in dichloroethanes（ClCH2CH2Cl）In, and inject in flask, continue anti-at a certain temperature
Should.Then room temperature is cooled to, saturation NaHCO slowly poured under ice-water bath3In, add appropriate NaHCO3Until solution is weak base
Property, continue 1 h is stirred at room temperature.After the completion of question response, dichloromethane is used（3×50 mL）Extraction, merges organic phase, decompression
It is spin-dried for solvent.The crude product for obtaining is purified by column chromatography（Eluent：Petroleum ether/dichloromethane）.Orange red solid is obtained, that is, is changed
Compound 2.
Wherein, described DMF (DMF) addition is 6-15 mL（78-195 mmol）；
The POCl3 addition is 6-15.0 mL（64-160 mmol）；
The dichloroethanes volume of addition is 40-80 mL；
Continue reaction temperature and the time respectively 40-55 degree for reacting, 3 h-6 h at a certain temperature；
Eluting liquid proportional is：Petroleum ether/dichloromethane=（5-20）:1；
The synthetic method reference literature of the 2-in-1 intermediate compound 1 into during of the compound（M. Emrullahoğlu,
M. Üçüncü, E. Karakuş, A BODIPY aldoxime-based chemodosimeter for highly
selective and rapid detection of hypochlorous acid, Chem. Commun. 49(71)
(2013) 7836-7838.）.
（2）The synthesis of probe
A certain amount of diaminomaleonitrile and compound 2 is weighed, is dissolved in ethanol, be stirred at room temperature after adding a few drop acetic acid
Reaction certain hour.Crude product is recrystallized with ethanol, then is purified with column chromatography（Eluent：Petroleum ether/dichloromethane）, most
Product after purification is obtained afterwards.
Wherein, the addition of the diaminomaleonitrile and compound 2 is respectively 0.6-1.2 mmol, 0.7 mmol；Institute
The amount for stating etoh solvent is 10-30 mL；
The catalyst acetic acid addition is 2-20 drops；
The stirring reaction time is 0.5-5 h；
The column chromatography eluent petroleum ether/methylene chloride volume ratio is（1-5）：1.
The fluorescence probe of above-mentioned synthesis is used for running water, Yangtze River Water and sodium hypochlorite by two technical methods of the object of the invention
The detection of hypochlorite ion in thimerosal.
（1）The probe mother liquor that 1 mM is prepared with EtOH is placed in -4oIt is standby in C refrigerators；Before detection with the PBS of 0.01 M
Buffer solution（PH 7.4, containing 20% EtOH, v/v）It is diluted to the solution of final concentration of 5 M.10 mM sodium hypochlorite and other from
The storing solution of son is configured to distilled water, and these ions include F-, Cl-, NO2 -, ClO4 -, HCO3 -, H2PO4 -, SO4 2-,
S2O3 2-, CO3 2-, Fe3+, Cu2+, H2O2, ONOO-, ROO•, •OH, NO•.Variable concentrations are added in probe solution
Hypochlorite ion, measures the fluorescence spectrum of solution respectively；
（2）The ion stock liquid of certain volume is separately added into in probe solution, is made final concentration of 100 M of each ion, is surveyed respectively
Measure its fluorescence and ultraviolet spectra；
（3）PBS is replaced with the water sample in real life：Running water, Yangtze River Water and hypochlorite disinfectant's water, measure which
Fluorescence spectrum.Add the hypochlorite ion of the normal concentration of certain volume again respectively in three kinds of water samples so as to final concentration
Respectively 5 M, 10 M and 20 M.Fluorescence is measured respectively obtains fluorescence intensity level.
The invention has the advantages that：
（1）C=N keys contained in the fluorescence probe of designed synthesis in the present invention, because C=N isomerizations can make dye fluorescence
Quenching.After being aoxidized by hypochlorite, C=N bond fissions generate new C=O keys, so as to recover the green fluorescence of BODIPY itself, real
Show to ClO-The identification of Fluorescence Increasing type, effect is obvious.
（2）In the present invention, fluorescence probe can be to ClO-Quick to recognize, fluorescence intensity can have fast with the addition of hypochlorite
Speed and significantly strengthen, and can reach stable in 10 s, substantially reduce detection time.
（3）In the present invention, fluorescence probe has very strong selectivity to hypochlorite, even if including some work in other ions
In the presence of property oxonium ion, also hypochlorite can effectively be recognized.
（4）In the present invention, fluorescence probe is very high to sensitivity that hypochlorite ion detects, and the detection limit of measurement is as little as
19.8 nM, it is with the obvious advantage.
（5）In the present invention, fluorescence probe can apply to the water in real life, such as to running water, Yangtze River Water and sodium hypochlorite
Hypochlorite in disinfectant effectively recognized and detected, can not only measure the dense of sodium hypochlorite in three kinds of water samples
Degree.Also by the mark-on experimental check reliability of measuring method, recovery of standard addition is between 96.1% 103.6%, it was demonstrated that should
Probe can be applicable to the detection of environmental water sample really.
Description of the drawings
Fig. 1 is compound 11H NMR scheme；
Fig. 2 is compound 21H NMR scheme；
Fig. 3 is probe1H NMR scheme；
Fig. 4. for probe13C NMR scheme；
Mass spectrograms of the Fig. 5 for probe；
Fig. 6 is the fluorescence spectra after probe solution adds hypochlorite；
Fig. 7 is the fluorescence intensity of probe solution with the hypochlorite concentration's variation diagram for adding；
Fig. 8 is the ultraviolet spectrogram after probe solution adds hypochlorite；
Fig. 9 is that fluorescence intensity changes over curve after probe solution adds hypochlorite；
Figure 10 adds the fluorescence after different ions, ultraviolet spectrogram for probe solution；1 in figure：Blank, 2：F-, 3： Cl-,
4 ：NO2 -, 5： ClO4 -, 6： HCO3 -, 7 ：H2PO4 -, 8： SO4 2-, 9： S2O3 2-, 10： CO3 2-, 11： Fe3+,
12： Cu2+, 13： ClO-, 14： H2O2, 15 ：ONOO-, 16： ROO•, 17： •OH, 18： NO•.；
The aqueous sodium hypochlorite solution fluorescence spectra that Figure 11 probes are used for after measuring running water, Yangtze River Water and dilution.
Specific embodiment：
For making purpose, technical scheme and the advantage of the embodiment of the present invention clearer, below in conjunction with description of the drawings to the present invention
Technical scheme in embodiment is clearly and completely described, it is clear that described embodiment is that a part of the invention is implemented
Example, rather than the embodiment of whole, based on the embodiment in the present invention, those of ordinary skill in the art are not making creativeness
The every other embodiment obtained on the premise of work, belongs to the scope of protection of the invention.
Embodiment 1：The synthesis of midbody compound 1
As shown in above-mentioned process, the dichloromethane and 0.58 mL benzoyl of 80 mLs drying are added in 250 mL round-bottomed flasks
Chlorine, logical nitrogen are protected, and 2,4- dimethyl pyrroles, 1.1 mL is slowly added dropwise, and are added dropwise 5 and are dripped trifluoroacetic acid（TFA）, mix after adding
Lucifuge stirs 10 h at room temperature to close solution.Then 1.08 g 2,3-, bis- chloro- 5,6- dicyan 1,4-benzoquinone is added in reaction
（DDQ）, continue lucifuge under room temperature and stir 1 h.Afterwards under ice bath part, 10 mL triethylamines, stirring 15 is dropwise added dropwise in reaction
After min, then it is added dropwise over 10 mL BFEEs（BF3·Et2O）, ice bath is removed, 2 h are reacted in continuation at room temperature.Reaction
After the completion of, with 100 mL saturations NaHCO3Solution is quenched reaction, distilled water（3×50 mL）Use dichloromethane after washing again（3×
50 mL）Extraction, merges organic phase, adds anhydrous MgSO4It is dried, decompression is spin-dried for solvent.The crude product for obtaining is carried by column chromatography
It is pure（Eluent：Petroleum ether/dichloromethane=15:1）, Orange red solid, i.e. compound 1 totally 515 mg is obtained, yield is 33%.
Nucleus magnetic hydrogen spectrum figure such as Fig. 1：1H NMR (400 MHz, CDCl3) δ 7.50 – 7.48 (m, 3H), 7.30 – 7.28 (m,
2H), 5.99 (s, 2H), 2.57 (s, 6H), 1.38 (s, 6H).
Embodiment 2：Synthesis based on the fluorescence probe of BODIPY dyestuffs
（1）The synthesis of compound 2.
6 mL are added in 250 mL round-bottomed flasks（78 mmol）DMF (DMF), be passed through nitrogen
Protection, adds 15.0 mL under ice-water bath（160 mmol）POCl3, stirs 10min, removes ice bath, return to room temperature
Stir 30 min.Then, 316 mg are weighed（1 mmol）The compound 1 synthesized in embodiment 1 is dissolved in 40 mL dichloroethanes
（ClCH2CH2Cl）In, and inject in flask, continue 3 h of reaction under 40 degree.Then room temperature is cooled to, ice-water bath is slowly poured into
Under saturation NaHCO3In, add appropriate NaHCO3Until solution is alkalescent, continue 1 h is stirred at room temperature.Question response is complete
Cheng Hou, uses dichloromethane（3×50 mL）Extraction, merges organic phase, and decompression is spin-dried for solvent.The crude product for obtaining passes through column chromatography
Purification（Eluent：Petroleum ether/dichloromethane=5:1）.Orange red solid, i.e. 251 mg of compound is obtained, yield is 73.2%.
（2）The synthesis of probe
Weigh 65 mg（0.6 mmol）Diaminomaleonitrile and 247 mg（0.7 mmol）Compound obtained by embodiment 1
2, it is dissolved in 10 mL ethanol, after adding 2 to drip acetic acid, 0.5 h is stirred at room temperature.Crude product is recrystallized with ethanol, then
Purified with column chromatography（Eluent：Petroleum ether/dichloromethane=5：1）, under the conditions of the chemical combination, little product is almost obtained, and
It is difficult to isolate pure product under the eluent.
Embodiment 3：Synthesis based on the fluorescence probe of BODIPY dyestuffs
（1）The synthesis of compound 2.
15 mL are added in 250 mL round-bottomed flasks（195 mmol）DMF (DMF), be passed through nitrogen
Gas shielded, adds 6.0 mL under ice-water bath（64 mmol）POCl3, stirs 10min, removes ice bath, return to room temperature
Stir 30 min.Then, 316 mg are weighed（1 mmol）The compound 1 synthesized in embodiment 1 is dissolved in 60 mL dichloroethanes
（ClCH2CH2Cl）In, and inject in flask, continue 6 h of reaction under 55 degree.Then room temperature is cooled to, ice-water bath is slowly poured into
Under saturation NaHCO3In, add appropriate NaHCO3Until solution is alkalescent, continue 1 h is stirred at room temperature.Question response is complete
Cheng Hou, uses dichloromethane（3×50 mL）Extraction, merges organic phase, and decompression is spin-dried for solvent.The crude product for obtaining passes through column chromatography
Purification（Eluent：Petroleum ether/dichloromethane=20:1）.Orange red solid, i.e. 263 mg of compound is obtained, yield is 76.7%.
（2）The synthesis of probe
Weigh 129.3 mg（1.2 mmol）Diaminomaleonitrile and 247 mg（0.7 mmol）Change obtained by embodiment 1
Compound 2, is dissolved in 30 mL ethanol, and 5 h are stirred at room temperature after adding 5 to drip acetic acid.Crude product is recrystallized with ethanol,
Purified with column chromatography again（Eluent：Petroleum ether/dichloromethane=1：1）, finally obtain 215.6 mg of product after purification, yield
For 70.8%.
Embodiment 4：Synthesis based on the fluorescence probe of BODIPY dyestuffs
（1）The synthesis of compound 2.
12.0 mL are added in 250 mL round-bottomed flasks（156 mmol）DMF (DMF), is passed through nitrogen
Protection, adds 12.0 mL under ice-water bath（128.0 mmol）POCl3, stirs 10min, removes ice bath, return to room
Temperature 30 min of stirring.Then, 316 mg are weighed（1 mmol）The compound 1 synthesized in embodiment 1 is dissolved in 80 mL's
（Dichloroethanes）ClCH2CH2In Cl, and inject in flask, continue reaction 4h under 50 degree.Then room temperature is cooled to, slowly
Saturation NaHCO poured under ice-water bath3In, add appropriate NaHCO3Until solution is alkalescent, continue to be stirred at room temperature 1
h.After the completion of question response, dichloromethane is used（3×50 mL）Extraction, merges organic phase, and decompression is spin-dried for solvent.The crude product for obtaining
Purified by column chromatography（Eluent：Petroleum ether/dichloromethane=10:1）.Orange red solid, i.e. compound 2 totally 286 mg is obtained,
Yield is 83.3 %.Nucleus magnetic hydrogen spectrum figure Fig. 2；
（2）Weigh 97 mg（0.9 mmol）Diaminomaleonitrile and 247 mg（0.7 mmol）Change obtained by embodiment 1
Compound 2, is dissolved in 20 mL ethanol, and 2 h are stirred at room temperature after adding 5 to drip acetic acid.Crude product is recrystallized with ethanol,
Purified with column chromatography again（Eluent：Petroleum ether/dichloromethane=2：1）, 250 mg of product after purification is finally obtained, yield is
82.1%.Its nuclear-magnetism figure and mass spectrogram are as follows：1H NMR (400 MHz, CDCl3) δ 8.43 (s, 1H), 7.57 – 7.54
(m, 3H), 7.32 -7.31 (m, 2H), 6.12 (s, 1H), 4.84 (s, 2H), 2.84 (s, 3H), 2.64
(s, 3H), 1.61 (s, 3H), 1.44 (s, 3H). 13C NMR (101 MHz, DMF) δ: 159.82, 155.84,
150.64, 146.31, 143.42, 141.38, 134.52, 133.23, 130.46, 129.82, 129.74,
128.43, 125.50, 125.06, 123.71, 114.98, 113.74, 106.08, 14.45, 14.34, 13.92,
12.19. MS: 443.62 [M+H] +.
Compound 21H NMR figure such as Fig. 2；Probe1H NMR figure such as Fig. 3；Probe13C NMR figure such as Fig. 4；The mass spectrum of probe
Figure such as Fig. 5.
Embodiment 5：Probe adds spectral quality research after hypochlorite ion
（1）The probe mother liquor synthesized in the embodiment 4 for preparing 1 mM with EtOH is placed in -4oIt is standby in C refrigerators；Use before detection
Buffer solution is diluted to the solution of final concentration of 5 M.The storing solution of 10 mM hypochlorites is configured to distilled water.
（2）The hypochlorite ion of variable concentrations is added in probe solution so as to final concentration of 0-100 M, survey respectively
The fluorescence spectrum of amount solution.ClO as shown in Figure 6-Addition cause system fluorescence intensity to have one in 506 nm transmitted wave strong points
Obvious peak value, and with the increase of ion concentration, peak value illustrates ClO also like increasing as anticipation-Concentration really can
Affect the fluorescence intensity of probe solution.Work as ClO-When concentration reaches 10 times of 1 concentration of probe, fluorescence intensity nearly reaches maximum
No longer strengthen.As shown in fig. 7, hypochlorite concentration is in the range of 0-40 M, system is in line in 506 nm transmitted wave strong points fluorescence
Property strengthen, therefore can thus fluorescence intensity and sodium hypochlorite concentration be linearly：Fluorescence intensity=20.91 [ClO-] +
52.52, linear coefficient R2 =0.9979, the detection to hypochlorite is limited to 19.8 nM.
（3）The ultraviolet spectra of measurement solution.Fig. 8 is uv absorption spectra, it is found that probe has one most at 532 nm
Strong absworption peak.With the increase of hypochlorite concentration, the absorption peak at 532 nm gradually weakens until disappear, and while also companion
As the absorption at 494 nm of wavelength strengthens rapidly.This blue-shifted phenomenon also result in solution colour from pink colour to orange change
Change, while also illustrate that probe generates a kind of new material with sodium hypochlorite reaction.
（4）The hypochlorite ion of variable concentrations is added in probe solution, makes hypochlorite final concentration be respectively 0,15
M, 25 M, 50 M, 75 M, 100 M, respectively after the addition 0,10s, 30s, 50 s, 70 s, 90 s, 120 s, 150
S, 180s, 300 s, 420 s, 600 s time measurements simultaneously record fluorescence intensity level.It is as a result as shown in Figure 9, it is possible to find, probe is molten
Liquid fluorescence intensity after hypochlorite is added rapidly strengthens, and in 10 s reaches stable maximum.Therefore, probe is to secondary chlorine
Acid group has the response being exceedingly fast.
Embodiment 6：Selection Journal of Sex Research of the probe to hypochlorite
The probe mother liquor synthesized in the embodiment 4 for preparing 1 mM with EtOH is placed in -4oIt is standby in C refrigerators.Concentration be 10 mM its
The storing solution of his ion, including F-, Cl-, NO2 -, ClO4 -, HCO3 -, H2PO4 -, SO4 2-, S2O3 2-, CO3 2-, Fe3+,
Cu2+, H2O2, ONOO-, ROO•, •OH, NO• , ClO-Ion and blank sample are all configured to distilled water.With 0.01 M's
PBS（PH 7.4, containing 20% EtOH, v/v）The solution of final concentration of 5 M is diluted to, and is separately added into certain volume
Ion stock liquid, make final concentration of 100 M of each ion, measure its fluorescence and ultraviolet spectra respectively, as a result as shown in Figure 10.
Can be obtained by Figure 10 a, after adding hypochlorite（No. 13）, the fluorescence of solution is remarkably reinforced, and sends green fluorescence；And other ions are then
Almost as blank sample, almost unstressed configuration.Figure 10 b understand that the addition of hypochlorite causes solution to have significantly in 532 nm
Absworption peak, and the addition of other ions is almost as blank sample, only adds in 494 nm have an absworption peak, and illustration time
The solution of chlorine vinegar root（No. 13）For orange, and other ions are then aubergine.These results show that probe has very to hypochlorite
Good selectivity, can effectively identify hypochlorite in numerous common ions and some Typical reactive oxygen groups.
Embodiment 7：The detection of probe hypochlorite in environmental water sample
（1）Yangtze River Water is collected along the river from long, filters out impurity with filter paper；Hypochlorite disinfectant's water is bought back from the market, with distillation
10000 times of water dilution is standby；Running water is collected from laboratory directly to use.
（2）Volume ratio is configured to for 4 with three kinds of water samples and ethanol respectively:1 mixed solution.Use distilled water compound concentration
For 10 mM sodium hypochlorite titers.The probe mother liquor synthesized in the embodiment 4 for preparing 1 mM with EtOH is placed in -4oIn C refrigerators
It is standby.Probe solutions being diluted with three kinds of mixed solutions respectively and arriving final concentration of 5 M, to obtain fluorescence strong for measurement fluorescence spectrum respectively
Angle value, as shown in figure 11.And running water, length are obtained according to the linear relationship of fluorescence intensity and sodium hypochlorite concentration in embodiment 5
ClO in river and hypochlorite disinfectant's water-Concentration is respectively 2.34 M, 0.06 M and 119.4 mmol.
（3）Add the hypochlorite ion of the normal concentration of certain volume again respectively in three kinds of water samples so as to dense eventually
Degree is respectively 5 M, 10 M and 20 M.Fluorescence is measured respectively obtains fluorescence intensity level.Again by Standardization curve for fluorescence intensity
Method has obtained the ClO after mark-on in sample solution-The value and the standard value contrast for adding are obtained the recovery of mark-on ion by concentration
Rate.In running water, the sodium hypochlorite rate of recovery of three kinds of spiked levels is 103.6%, 98.1% and 101.5%；In Yangtze River Water, three kinds add
The sodium hypochlorite rate of recovery of mark concentration is 99.8%, 96.1% and 101.2%；Three kinds of mark-ons in hypochlorite disinfectant's water after dilution
The sodium hypochlorite rate of recovery of concentration is 99.2%, 102.9% and 99.15%.Knot that can be obtained by the measuring method by the rate of recovery
Fruit accuracy rate is higher, and the probe can be used for the identification of sodium hypochlorite in actual water sample product and Concentration Testing.
Claims (10)
1. a kind of fluorescence probe BODIPY derivatives, its molecular formula is C24H21BF2N6, and structural formula is as follows：
。
2. the preparation method of fluorescence probe as claimed in claim 1, it is characterised in that carry out in accordance with the following steps：
（1）The synthesis of midbody compound 2
3 add a certain amount of DMF (DMF) in round-bottomed flask, are passed through nitrogen protection, under ice-water bath again
POCl3, stirring is added to remove ice bath, return to and be stirred at room temperature；Then, Weigh Compound 1 is dissolved in dichloroethanes
（ClCH2CH2Cl）In, and inject in flask, continue reaction at a certain temperature；Then room temperature is cooled to, ice-water bath is slowly poured into
Under saturation NaHCO3In, add appropriate NaHCO3Until solution is alkalescent, continue to be stirred at room temperature；Question response is completed
Afterwards, extracted with dichloromethane, merge organic phase, decompression is spin-dried for solvent；The crude product for obtaining is purified by column chromatography（Eluent：
Petroleum ether/dichloromethane）；Obtain Orange red solid, i.e. compound 2；
（2）The synthesis of probe
A certain amount of diaminomaleonitrile and compound 2 is weighed, is dissolved in ethanol, be stirred at room temperature after adding a few drop acetic acid
Reaction certain hour；Crude product is recrystallized with ethanol, then is purified with column chromatography（Eluent：Petroleum ether/dichloromethane）, most
Product after purification is obtained afterwards.
3. the preparation method of fluorescence probe according to claim 2, it is characterised in that step（1）In
N,N-dimethylformamide (DMF) addition is 6-15 mL；
The POCl3 addition is 6-15.0 mL.
4. the preparation method of fluorescence probe according to claim 2, it is characterised in that step（1）In
The dichloroethanes volume of the addition is 40-80 mL.
5. the preparation method of fluorescence probe according to claim 2, it is characterised in that step（1）Described in
The condition reacted at a certain temperature is 40-55 DEG C of 3 h-6 h of reaction.
6. the preparation method of fluorescence probe according to claim 2, it is characterised in that step（1）Described in
Crude product is petroleum ether and dichloromethane by the eluent that column chromatography is purified；Petroleum ether and methylene chloride volume ratio are
5-20:1。
7. the preparation method of fluorescence probe according to claim 2, it is characterised in that step（2）Described in
The usage ratio of the diaminomaleonitrile and compound 2 is 0.6-1.2 mmol, 0.7 mmol；The etoh solvent
Amount be 10-30 mL；
The catalyst acetic acid addition is 2-20 drops.
8. the preparation method of fluorescence probe according to claim 2, it is characterised in that step（2）In
The stirring reaction time is 0.5-5 h；
The column chromatography eluent is petroleum ether and dichloromethane；Petroleum ether and methylene chloride volume ratio are 1-5：1.
9. the fluorescence probe described in claim 1-7 any one claim is used for the application of the detection of hypochlorite ion.
10. the application described in claim 8 is for the hypochlorite ion in running water, Yangtze River Water and javelle water
Detection.
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| CN113527346A (en) * | 2021-07-12 | 2021-10-22 | 河南大学 | Fluorescent probe based on specific response of BODIPY dye to hypochlorous acid, preparation and application |
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| YUN WANG ET AL.，: ""A fast-responsive fluorescent probe based on BODIPY dye for sensitive detection of hypochlorite and its application in real water samples"", 《TALANTA》 * |
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