CN108658881B - Fluorene fluorescent probe for detecting mercury ions and preparation and application thereof - Google Patents
Fluorene fluorescent probe for detecting mercury ions and preparation and application thereof Download PDFInfo
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- CN108658881B CN108658881B CN201810533801.2A CN201810533801A CN108658881B CN 108658881 B CN108658881 B CN 108658881B CN 201810533801 A CN201810533801 A CN 201810533801A CN 108658881 B CN108658881 B CN 108658881B
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 58
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims abstract description 51
- -1 mercury ions Chemical class 0.000 title claims abstract description 38
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- QKFJKGMPGYROCL-UHFFFAOYSA-N phenyl isothiocyanate Chemical compound S=C=NC1=CC=CC=C1 QKFJKGMPGYROCL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002220 fluorenes Chemical class 0.000 claims abstract description 12
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- WPBZMCGPFHZRHJ-UHFFFAOYSA-N 4-aminobenzohydrazide Chemical compound NNC(=O)C1=CC=C(N)C=C1 WPBZMCGPFHZRHJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 9
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940117953 phenylisothiocyanate Drugs 0.000 claims abstract description 8
- 239000001119 stannous chloride Substances 0.000 claims abstract description 8
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000523 sample Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000035484 reaction time Effects 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
- CYKLQIOPIMZZBZ-UHFFFAOYSA-N 2,7-dibromo-9,9-dioctylfluorene Chemical compound C1=C(Br)C=C2C(CCCCCCCC)(CCCCCCCC)C3=CC(Br)=CC=C3C2=C1 CYKLQIOPIMZZBZ-UHFFFAOYSA-N 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- YFZHODLXYNDBSM-UHFFFAOYSA-N 1-ethenyl-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(C=C)C=C1 YFZHODLXYNDBSM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 abstract description 29
- 238000001514 detection method Methods 0.000 abstract description 15
- 238000006862 quantum yield reaction Methods 0.000 abstract description 6
- 230000021615 conjugation Effects 0.000 abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 60
- 239000000243 solution Substances 0.000 description 29
- 239000000047 product Substances 0.000 description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000011550 stock solution Substances 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical compound C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- TVWHTOUAJSGEKT-UHFFFAOYSA-N chlorine trioxide Chemical compound [O]Cl(=O)=O TVWHTOUAJSGEKT-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- KBYOBAICCHNMNJ-UHFFFAOYSA-L diperchloryloxymercury Chemical compound [Hg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O KBYOBAICCHNMNJ-UHFFFAOYSA-L 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003068 molecular probe Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- HSAJRDKFYZAGLU-UHFFFAOYSA-M perchloryloxymercury Chemical compound [Hg+].[O-]Cl(=O)(=O)=O HSAJRDKFYZAGLU-UHFFFAOYSA-M 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/48—Two nitrogen atoms
- C07D251/50—Two nitrogen atoms with a halogen atom attached to the third ring carbon atom
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- 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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- 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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Abstract
The invention relates to a fluorenes fluorescent probe for detecting mercury ions and preparation and application thereof, wherein the structural formula of the fluorescent probe is as follows:
the preparation method comprises the following steps: dissolving p-aminobenzoyl hydrazine in a solvent, introducing nitrogen, and dropwise adding phenyl isothiocyanate for reaction to obtain a product 1; dissolving 2, 7-dinitrostyryl-9, 9' -dioctyl fluorene in a solvent, introducing nitrogen, and dropwise adding a stannous chloride solution for reaction to obtain a product 2; dissolving the product 1 in a solvent, adding an acid-binding agent, and dropwise adding a cyanuric chloride solution in a nitrogen atmosphere for reaction to obtain a product P1; and dissolving the product 2 in a solvent, dropwise adding a solution of the product P1, and adding an acid-binding agent to obtain the product. The fluorescent probe is a derivative of fluorene with a large conjugation length obtained by modifying fluorene, has high fluorescence quantum yield and fluorescence intensity, and can be used for mercury ion detection.
Description
Technical Field
The invention belongs to the field of fluorescent probe materials and preparation and application thereof, and particularly relates to a fluorenes fluorescent probe for detecting mercury ions and preparation and application thereof.
Background
The mercury ions have serious pollution and damage to the nature and human health, so the mercury ion detection method has very important significance for detecting the mercury ions in the environment and living tissues. Compared with the traditional analysis detection method, the fluorescence analysis method has great advantages in the aspect of detecting mercury ions, such as rapid detection, low price and simple operation, and can detect the mercury ions in animal bodies through cell and living body imaging. In recent years, a large number of fluorescent emission group, polymer, DNA enzyme, nucleic acid and functionalized nano materials are reported to be used for detecting mercury ions.
Fluorene and its derivatives are a class of fluorescent sensing materials with high fluorescent efficiency, good solubility, wide energy gap and two-photon properties. The chemical and physical properties can be improved by carrying out structural modification on the 2,7 and 9 positions. Currently, fluorene and its derivatives are used for biological imaging, small molecule and metal detection due to their high fluorescence quantum yield and two-photon properties. (The Journal of organic chemistry,2010,75,3975-3982) reports a thiophene-containing alkynyl fluorene molecular probe, which has high quantum yield and good two-photon absorption and is used for imaging COS-7 and HCT 116 cells. (Macromolecular Rapid Communications,2007,28,1905-1911) reported a water-soluble polyfluorene-thiophene PFT for the detection of oxalic acid. Before oxalic acid is added, the polymer has stronger fluorescence, and after the oxalic acid is added, the polymer is crosslinked to form compact pi-stacking copolymerization due to the dicarboxyl in the oxalic acid, so that the fluorescence of the polymer is quenched, and the detection of the oxalic acid is realized. (The Journal of Physical Chemistry B,2014,114,9313-9321) reported that using fluorene as The fluorophore designed and synthesized a two-photon fluorescent probe, which selected a macrocyclic ligand containing N, O heteroatom as The recognition group, and Zn2+After binding, fluorescence change of the probe is caused, and Zn is realized2+Two-photon detection. Chinese patent 201210088732.1 entitled spirobifluorene fluorescent probe and its preparation and use, the compound has higher fluorescence quantum yield and fluorescence intensity due to the introduction of the three-dimensional rigid structure of spirobifluorene, and has high sensitivity and good selectivity for silver ion detection, so the macroscopic detection limit can reach 10-5M。
Disclosure of Invention
The invention aims to solve the technical problem of providing a fluorene fluorescent probe for detecting mercury ions and preparation and application thereof, wherein the fluorescent probe is a derivative of fluorene with a large conjugation length obtained by modifying fluorene and has high fluorescence quantum yield and fluorescence intensity; the preparation raw materials are cheap and easy to obtain, the synthetic route is simple, the yield is high, and the method is suitable for large-scale production and has good application prospect.
The invention relates to a method for detecting mercury ion fluoreneA fluorescent-like probe, said probe having the chemical formula C62H68ClN9OS, structural formula:
the invention discloses a preparation method of a fluorene fluorescent probe for detecting mercury ions, which comprises the following steps:
(1) dissolving p-aminobenzoyl hydrazine in a solvent, stirring, introducing nitrogen, dropwise adding phenyl isothiocyanate for reaction, cooling, spin-drying and recrystallizing to obtain a product 1, wherein the molar ratio of the p-aminobenzoyl hydrazine to the phenyl isothiocyanate is 1:1-2, the concentration of the p-aminobenzoyl hydrazine in the solvent is 0.05-0.07mmol/mL, and the structural formula of the product 1 is shown in the specification
(2) Dissolving 2, 7-dinitrostyryl-9, 9 ' -dioctyl fluorene in a solvent, stirring, introducing nitrogen, dropwise adding a stannous chloride solution for reaction, cooling, extracting, drying, concentrating, and carrying out column chromatography separation to obtain a product 2, wherein the molar ratio of the 2, 7-dinitrostyryl-9, 9 ' -dioctyl fluorene to the stannous chloride is 1:15-16, the concentration of the 2, 7-dinitrostyryl-9, 9 ' -dioctyl fluorene in the solvent is 0.005-0.006mmol/mL, and the structural formula of the product 2 is shown in the specification
(3) Dissolving the product 1 obtained in the step (1) in a solvent, adding an acid-binding agent, stirring in a nitrogen atmosphere, dropwise adding a cyanuric chloride solution for reaction, filtering, spin-drying, and recrystallizing to obtain a product P1, wherein the molar ratio of the product 1, the acid-binding agent and the cyanuric chloride is 1-1.2: 2-2.5: 1-1.2, the concentration of the product 1 in the solvent is 0.1-0.2mmol/mL, and the structural formula of the product P1 is shown in the specification
(4) Dissolving the product 2 in the step (2) in a solvent, dropwise adding the solution of the product P1 in the step (3), stirring, adding an acid-binding agent, reacting, filtering, spin-drying, and performing column chromatography separation to obtain the fluorene fluorescent probe, wherein the molar ratio of the product P1 to the acid-binding agent to the product 2 is 1-2: 1-2.5: 1-2, and the concentration of the product 2 dissolved in the solvent is 0.06-0.07 mmol/mL.
The solvent in the step (1) is absolute ethyl alcohol; the reaction is as follows: heating to 50-80 ℃ and reacting for 6-12 h.
The mass fraction of the p-aminobenzoyl hydrazine in the step (1) is 98-99%; the mass fraction of phenyl isothiocyanate is 98-99%.
In the steps (1) and (3), absolute ethyl alcohol is used for recrystallization.
The preparation method of the 2, 7-dinitrostyryl-9, 9' -dioctyl fluorene in the step (2) comprises the following steps: under the atmosphere of nitrogen, mixing 2, 7-dibromo-9, 9' -dioctyl fluorene, palladium acetate and triphenyl phosphorus in a molar ratio of 20-25:0.2-0.25:1, adding DMF (dimethyl formamide), triethylamine and p-nitrostyrene in a volume ratio of 10:5:0.76, reacting for 48 hours at 95-105 ℃, distilling under reduced pressure, extracting, and drying to obtain the catalyst.
The solvent in the step (2) is absolute ethyl alcohol; the extraction is carried out by using dichloromethane; the solvent of the stannous chloride solution is concentrated hydrochloric acid with the mass concentration of 30-37%.
The reaction in the step (2) is as follows: heating to 78-80 ℃ and reacting for 8-11 h; and adjusting the pH value to 7-8 by using 1mol/L sodium hydroxide solution before extraction.
The mass fraction of the sodium hydroxide is 80-99%.
The column chromatography separation in the step (2) is performed by using petroleum ether and ethyl acetate in a volume ratio of 8: 1.
And in the step (2), the anhydrous sodium sulfate with the mass fraction of 80-99% is used for drying.
In the step (3), the solvent of the cyanuric chloride solution and the solvent of the cyanuric chloride solution are both anhydrous THF; the reaction temperature is 0-5 ℃, and the reaction time is 5-7 h.
In the step (3), the mass fraction of cyanuric chloride is 98-99%.
The solvent in the step (4) is anhydrous THF; stirring for 1-2 h; the reaction temperature is 65-80 ℃, and the reaction time is 12-24 h.
The column chromatography separation in the step (4) is performed by using petroleum ether and ethyl acetate in a volume ratio of 6: 1.
The fluorene fluorescent probe for detecting mercury ions is used for detecting mercury ions in a solution.
The fluorene fluorescent probe P2 has strong self-fluorescence, is dissolved in DMSO solution and mixed with mercury ions, the fluorescence is quenched, under the condition of the mercury ions, the fluorescence signal at 467nm is obviously weakened after the fluorescence is excited under 393nm light, and the concentration of the mercury ions can be detected by recording the fluorescence intensity. The fluorescence intensity of the fluorescent probe has a good linear relation with the mercury ion concentration, the linear range of the quantitative detection of the mercury ion concentration is 0.5-50 mu M, and the detection limit is 89 nM.
The invention takes cheap and easily obtained 2, 7-dibromofluorene, cyanuric chloride, phenyl isothiocyanate and P-aminobenzoyl hydrazine as raw materials to obtain a target product P2 through coupling reaction, reduction reaction, nucleophilic addition and other reactions.
The preparation route of the fluorescent probe of the invention is as follows:
the fluorescent probe contains a thiourea amide group, wherein the thiourea amide group contains a C-N bond and a C-S bond, and the C-S bond has a recognition effect on mercury ions. The mechanism is as follows: the complexation of the probe P2 and mercury ions is based on a Photoinduced Electron Transfer (PET) mechanism, the probe P2 takes fluorene as a recognition group, a triazine ring as a connecting group, and a fluorene two-photon derivative as a fluorophore. The addition of mercury ions destroys the original pi-p-pi conjugated system, blocks the PET process and quenches fluorescence.
Advantageous effects
(1) The fluorescent probe is a derivative of fluorene with a large conjugation length obtained by modifying fluorene, has high fluorescence quantum yield and fluorescence intensity, and can be used for mercury ion detection;
(2) the invention has the advantages of cheap and easily obtained raw materials, simple synthetic route and high yield, and is suitable for large-scale production; has better application prospect.
Drawings
FIG. 1 shows fluorescence excitation and emission spectra of fluorescent probe P2 in example 2 after DMSO solution (10 μ M) was added to mercury ion solution (10 μ M).
FIG. 2 is a graph showing the fluorescence response of DMSO solutions of fluorescent probes P2 (concentration: 10. mu.M) in example 2 to the selective detection of different metal ions (inset: fluorescence selectivity under a portable UV lamp at 365 nm).
FIG. 3 is a fluorescence spectrum response time spectrum of example 2 for mercury ions in DMSO solution of fluorescent probe P2 (concentration of 10. mu.M).
FIG. 4 is a graph showing the relationship between the fluorescence emission spectrum of the fluorescent probe P2 and the concentration of mercury ions in example 3 (the inset shows the change of the linear curve of the fluorescence intensity of the probe added with mercury ions of different concentrations).
FIG. 5 is a Job-Plot of the complexing ratio of fluorescent probe P2 to mercury ions in DMSO solution (concentration 10. mu.M) in example 4.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) Adding 0.45g (3mmol) of p-aminobenzoyl hydrazine into a 100mL three-neck flask, then adding 50mL of absolute ethyl alcohol into the three-neck flask, stirring to fully dissolve the absolute ethyl alcohol, slowly dropwise adding 0.43g (3.2mmol) of phenyl isothiocyanate under the nitrogen atmosphere, heating to 80 ℃, reacting for 12 hours, then cooling to room temperature, carrying out rotary evaporation to remove excessive solvent, and recrystallizing the absolute ethyl alcohol to obtain a light yellow solid, namely the product 1, wherein the yield is 80%. FTIR (KBr): v 3356cm-1,3219cm-1(-NH2),2551cm-1(C＝S).1H NMR(600MHz,DMSO,298K,δ/ppm):δ＝7.36(m,4H,ArH),7.45(m,1H,ArH),7.35(m,2H,ArH),6.94(m,2H,ArH),5.29(m,2H,-NH2)。
(2) 1.09g (2.5mmol) of 2, 7-dibromo-9, 9' -dioctylfluorene, 5.6mg (2.5 × 10)-2mmol) of palladium acetate and 26.25mg (0.1mmol) of triphenylphosphine under nitrogen protection are added with 10mL of DMF, 5mL of triethylamine and 0.76mL (5.75mmol) of p-nitroanisole, reacted at 100 ℃ for 48h, distilled under reduced pressure, extracted, dried, the organic layer is dried over anhydrous sodium sulfate overnight, filtered, and the filtrate is concentrated. Subjecting the crude product to column chromatography (Al)2O3(ii) a Ethyl acetate/petroleum ether 1:50) to give a white solid, and recrystallizing with n-hexane to give the pure product in 54% yield. FTIR (KBr): nu 2952 (CH)3),2923(CH2),1592,1514,1340(NO2),819(Ar)。1H NMR(400MHz,CDCl3,298K,δ/ppm):8.25(d,4H,ArH)；7.70(m,6H,Ar H)；7.55(t,2H,ArH),7.38(d,2H,ArH),7.23(d,4H,CH),2.02(s,4H,CH2),1.13(m,20H,CH2),0.81(t,6H,CH3)；0.68(s,4H,CH2)。
(3) 0.685g (1mmol) of 2, 7-dinitrostyryl-9, 9' -dioctylfluorene was put into a 250mL three-necked flask, 180mL of absolute ethanol was added into the three-necked flask, and the mixture was magnetically stirred for 20min to be sufficiently dissolved. After a strong nitrogen flow is introduced for 10min, a solution of dissolving 3g of stannous chloride in 30mL of concentrated hydrochloric acid is added by a constant pressure dropping funnel, the temperature is raised to 78 ℃, and the reaction is carried out for 10 h. Adding crushed ice into the reaction solution, cooling, adjusting the pH value to 7-8 by using 1mol/L sodium hydroxide solution, extracting by using dichloromethane, collecting an organic phase, adding anhydrous sodium sulfate, drying, concentrating, and performing silica gel column chromatography (V)Petroleum ether：VEthyl acetate1) gave the product 2 as a tan solid powder in 85% yield. FTIR (KBr): v 3356cm-1,3219cm-1(-NH2),2927cm-1,2853cm-1(-CH2,-CH3).1H NMR(600MHz,DMSO,298K,δ/ppm):δ＝8.25(d,4H,ArH),7.66(m,6H,ArH),7.53(t,2H,ArH),7.35(d,2H,ArH),7.23(d,4H,CH),5.29(m,4H,-NH2),2.01(m,4H,CH2),1.09(m,20H,CH2),0.71(m,6H,CH3),0.52(m,4H,CH2)。
(4) 0.28g (1.0mmol) of product 1, 0.28g (2.0mmol) of K2CO3Dissolving in 10mL of tetrahydrofuran, heating to 0-5 ℃ in an ice-water bath, dissolving 0.18g (1.0mmol) of 99% cyanuric chloride in 10mL of tetrahydrofuran, slowly dripping into a three-neck flask, stirring for 1h, stirring the mixed solution at 0-5 ℃, reacting for 6h, filtering, spin-drying, and recrystallizing with absolute ethyl alcohol to obtain the product P1 with the yield of 70%. FTIR (KBr): v 3356cm-1,3219cm-1(-NH2),2551cm-1(C ═ S),851 (triazine ring).1H NMR(600MHz,DMSO,298K,δ/ppm):δ＝11.29(m,4H,-NH),7.36(m,2H,ArH),7.45(m,1H,ArH),7.35(m,2H,ArH),6.94(m,2H,ArH),6.57(m,2H,ArH)。
(5) 1.25g (2.0mmol) of product 2 are dissolved in 30mL of THF to give a solution of product 2, 0.87g (2.0mmol) of product P1 are dissolved in 15mL of tetrahydrofuran, poured into a constant-pressure dropping funnel and slowly added dropwise to the solution of product 2, after stirring for 1h at 65 ℃ the temperature is controlled, 0.165g of NaHCO are added3The solution was added dropwise to prevent the system from becoming acidic. After 24 hours of reaction, the reaction mixture was poured into a single-neck flask, the solvent was removed by rotary evaporation, and the mixture was separated by silica gel column chromatography (V)Petroleum ether：VEthyl acetate1) to obtain orange yellow solid powder, namely fluorene fluorescent probe P2, and drying the solid powder in a vacuum oven at 35 ℃ to constant weight, wherein the yield is 35%. mp: 237-. FTIR (KBr) v 3290cm-1(-NH-),2924cm-1,2857cm-1(-CH3,-CH2),1702cm-1(C＝O),1158cm-1,1409cm-1,1106cm-1(triazine).1H NMR(600MHz,DMSO,298K,δ/ppm):δ＝7.91(m,4H,ArH),7.75(m,6H,ArH),7.61(m,4H,ArH),7.43(m,1H,ArH),7.30～7.10(m,8H,ArH),7.23(d,4H,CH),10.57(m,-NH-,5H),3.82(m,-NH2,2H),2.02(m,4H,CH2),1.37(m,20H,CH2),1.02(m,6H,CH3),0.68(m,4H,CH2).13C NMR (600MHz, DMSO,298K, δ/ppm): δ ═ 14.1,22.6,23.8,29.2,30.0,31.8,40.5,55.1,102.55,123.66,124.75,129.14,129.85,134.57,150.21,153.14,159.32,163.67,168.06,169.52,170.23 elemental analysis (C)62H68ClN9OS) theoretical value C, 72.81%; h, 6.70%; n, 12.33%. experimental values: c, 69.19%; h, 6.33%; n,11.98 percent.
Example 2
The method for testing mercury ions by using the fluorene fluorescent probe in the embodiment 1 comprises the following specific steps:
step 1, dissolving the fluorescent probe P2 synthesized in example 1 in a solvent DMSO, and fixing the volume in a 100mL volumetric flask by using the solvent DMSO to obtain a concentration of 1.0 × 10-3M probe stock solution;
step 3, 0mL, 0.1mL, 0.2mL, 0.3mL, 0.4mL, 0.5mL, 0.6mL, 0.7mL, 0.8mL, 0.9mL, 1mL of 1.0 × 10-5And (3) adding 1mL of the probe stock solution obtained in the step (1) into the mercury ion standard solution of M, fixing the volume in a 10mL volumetric flask by using a solvent DMSO, standing for 5min, detecting the fluorescence intensity under 467nm excitation wavelength by using a fluorescence spectrometry, and determining that the fluorescence intensity and the mercury ion concentration present a good linear relation.
As shown in FIG. 1, the probe molecule P2 itself has a strong fluorescence emission peak at 467nm in DMSO solution.
Fluorene fluorescent probe P2 for Hg in example 12+The selective experiment comprises the following specific steps: dissolving fluorene fluorescent probe P2 in DMSO solvent to obtain 10 μ M fluorescent probe solution, and mixing with Al (NO)3)3、FeCl3、Pb(NO3)2、MnCl2、BaCl2、MgSO4、Zn(NO3)2、Cr(NO3)3、SnCl2、Ni(NO3)2、Hg(ClO3)2、CdCl2、CoCl2、CaCl2、CuSO4Dissolving in DMF solventTo prepare 10 μ M of Al3+、Fe3+、Pb2+、Mn2+、Ba2+、Mg2+、Zn2+、Cr3+、Sn2+、Ni2+、Hg2+、Cd2+、Co2+、Ca2+、Cu2+And (3) mixing 1mL of 10-mu M fluorescent probe solution with 1mL of the metal ion solution, metering the volume to 10mL, and detecting the fluorescence intensity with the emission wavelength of 467nm (shown in figure 2) under the condition that the excitation wavelength is 393nm, wherein the results show that: fluorescent probe to Hg in DMSO solution2+Has better specific selectivity.
Hg2+The time response experiment of the P2 fluorescent probe comprises the following specific steps: the fluorescence intensity of the fluorescent probe in DMSO solution (with the concentration of 10 μ M) is measured at 467nm excitation wavelength for the mercury ion solution added with 10 μ M, as shown in figure 3, when the time reaches 2min, the fluorescence intensity reaches the minimum value and tends to be stable, which indicates that the fluorescent probe is applied to heavy metal Hg2+The ions have a faster time response.
Example 3
Making Hg2+The titration experiment of the fluorene fluorescent probe P2 in example 1 comprises the following specific steps: the fluorene fluorescent probe P2 was dissolved in DMSO to prepare a 10. mu.M fluorescent probe solution, and the concentration of the probe was fixed (10:)-5M), 0 to 5.0equiv. Hg is added2+The fluorescence emission spectrum of the fluorescent probe P2 is detected in relation to the concentration of mercury ions (as shown in FIG. 4), and the result shows that the fluorescence intensity is stronger at the maximum absorption wavelength of 467nm when the probe is excited at 393nm in a DMSO solution, but the fluorescence intensity is stronger along with Hg2+The fluorescence intensity of the emission peak at 467nm gradually decreases when the concentration increases, when Hg is added2+The adding amount reaches 5 × 10-7After M, the fluorescence intensity began to decrease, and when the ion addition amount reached 5 × 10-5After M, the fluorescence intensity reached a minimum and stabilized. Hg is a mercury vapor2+The concentration of the fluorescent probe is 0.5-50 mu M, the fluorescent probe has a good linear relation with the fluorescence intensity of the probe P2, and the detection limit is 89 nM.
Example 4
Immobilization of fluorescent probes, Hg in DMSO solvent2+The total concentration of (a) is 50. mu.M, by changingChanging the concentration ratio of the fluorescent probe and the mercury ion (the mass ratio of the fluorescent probe to the mercury ion is 10:0, 9:1, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8, 1:9 and 0:10 in sequence to obtain the difference value of the fluorescence intensity at 467nm and the fluorescence intensity of the fluorescent probe under the concentration, and drawing 5 the ratio of the mercury ion to the total concentration2+The vertical coordinate can reach the maximum value when the proportion is 0.5, and the fluorescent probe and Hg can be determined2+Mainly forms a stable complex in a 1:1 mode.
Claims (10)
1. The fluorescent probe for detecting mercury ions and fluorenes is characterized in that the structural formula of the probe is as follows:
2. a preparation method of a fluorene fluorescent probe for detecting mercury ions comprises the following steps:
(1) dissolving p-aminobenzoyl hydrazine in a solvent, stirring, introducing nitrogen, dropwise adding phenyl isothiocyanate for reaction, cooling, spin-drying and recrystallizing to obtain a product 1, wherein the molar ratio of the p-aminobenzoyl hydrazine to the phenyl isothiocyanate is 1:1-2, the concentration of the p-aminobenzoyl hydrazine in the solvent is 0.05-0.07mmol/mL, and the structural formula of the product 1 is shown in the specification
(2) Dissolving 2, 7-dinitrostyryl-9, 9 ' -dioctyl fluorene in a solvent, stirring, introducing nitrogen, dropwise adding a stannous chloride solution for reaction, cooling, extracting, drying, concentrating, and carrying out column chromatography separation to obtain a product 2, wherein the molar ratio of the 2, 7-dinitrostyryl-9, 9 ' -dioctyl fluorene to the stannous chloride is 1:15-16, the concentration of the 2, 7-dinitrostyryl-9, 9 ' -dioctyl fluorene in the solvent is 0.005-0.006mmol/mL, and the structural formula of the product 2 is shown in the specification
(3) Dissolving the product 1 obtained in the step (1) in a solvent, adding an acid-binding agent, stirring in a nitrogen atmosphere, dropwise adding a cyanuric chloride solution for reaction, filtering, spin-drying, and recrystallizing to obtain a product P1, wherein the molar ratio of the product 1, the acid-binding agent and the cyanuric chloride is 1-1.2: 2-2.5: 1-1.2, the concentration of the product 1 in the solvent is 0.1-0.2mmol/mL, and the structural formula of the product P1 is shown in the specification
(4) Dissolving the product 2 in the step (2) in a solvent, dropwise adding the solution of the product P1 in the step (3), stirring, adding an acid-binding agent, reacting, filtering, spin-drying, and performing column chromatography separation to obtain the fluorene fluorescent probe, wherein the molar ratio of the product P1 to the acid-binding agent to the product 2 is 1-2: 1-2.5: 1-2, and the concentration of the product 2 dissolved in the solvent is 0.06-0.07 mmol/mL.
3. The method for preparing the fluorescent probe for detecting mercury ions and fluorenes according to claim 2, wherein the solvent in the step (1) is absolute ethyl alcohol; the reaction is as follows: heating to 50-80 ℃ and reacting for 6-12 h.
4. The method for preparing the fluorescent probe for detecting the mercury ions and the fluorenes according to claim 2, wherein absolute ethyl alcohol is used for the recrystallization in the steps (1) and (3).
5. The method for preparing the fluorene fluorescent probe for detecting mercury ions according to claim 2, wherein the method for preparing 2, 7-dinitrostyryl-9, 9' -dioctyl fluorene in the step (2) comprises the following steps: under the atmosphere of nitrogen, mixing 2, 7-dibromo-9, 9' -dioctyl fluorene, palladium acetate and triphenyl phosphorus in a molar ratio of 20-25:0.2-0.25:1, adding DMF (dimethyl formamide), triethylamine and p-nitrostyrene in a volume ratio of 10:5:0.76, reacting for 48 hours at 95-105 ℃, distilling under reduced pressure, extracting, and drying to obtain the catalyst.
6. The method for preparing the fluorescent probe for detecting mercury ions and fluorenes according to claim 2, wherein the solvent in the step (2) is absolute ethyl alcohol; the extraction is carried out by using dichloromethane; the solvent for the stannous chloride solution is concentrated hydrochloric acid.
7. The preparation method of the fluorescent probe for detecting mercury ions and fluorenes according to claim 2, wherein the reaction in the step (2) is as follows: heating to 78-80 ℃ and reacting for 8-11 h; and adjusting the pH value to 7-8 by using 1mol/L sodium hydroxide solution before extraction.
8. The method for preparing the fluorescent probe for detecting mercury ions and fluorenes according to claim 2, wherein the solvent in the step (3) and the solvent in the cyanuric chloride solution are both anhydrous THF; the reaction temperature is 0-5 ℃, and the reaction time is 5-7 h.
9. The method for preparing the fluorescent probe for detecting mercury ions and fluorenes according to claim 2, wherein the solvent in the step (4) is anhydrous THF; stirring for 1-2 h; the reaction temperature is 65-80 ℃, and the reaction time is 12-24 h.
10. The application of the fluorescent probe for detecting mercury ions in the fluorene as claimed in claim 1, wherein the fluorescent probe is used for detecting mercury ions in a solution.
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| CN106117230A (en) * | 2016-06-29 | 2016-11-16 | 河南师范大学 | Replace rhodamine B amide groups Thiourea fluorescent probe compounds and its preparation method and application |
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