CN114773369A - Carborane-based fluorescent probe and preparation method and application thereof - Google Patents
Carborane-based fluorescent probe and preparation method and application thereof Download PDFInfo
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 7
- 125000006575 electron-withdrawing group Chemical group 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 40
- 239000000523 sample Substances 0.000 claims description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 17
- GJLPUBMCTFOXHD-UPHRSURJSA-N (11z)-1$l^{2},2$l^{2},3$l^{2},4$l^{2},5$l^{2},6$l^{2},7$l^{2},8$l^{2},9$l^{2},10$l^{2}-decaboracyclododec-11-ene Chemical compound [B]1[B][B][B][B][B]\C=C/[B][B][B][B]1 GJLPUBMCTFOXHD-UPHRSURJSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 16
- 238000001514 detection method Methods 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- 229940045803 cuprous chloride Drugs 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- IRSNNPCAZZDVIL-UHFFFAOYSA-N 3-bromo-n,n-diethylaniline Chemical compound CCN(CC)C1=CC=CC(Br)=C1 IRSNNPCAZZDVIL-UHFFFAOYSA-N 0.000 claims description 3
- USEXQPWLCGBYNT-UHFFFAOYSA-N 3-bromo-n,n-dimethylaniline Chemical compound CN(C)C1=CC=CC(Br)=C1 USEXQPWLCGBYNT-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 3
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- -1 dimyristyl boron fluoride Chemical compound 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 230000004044 response Effects 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 238000001035 drying 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
- 239000013078 crystal Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000004262 preparative liquid chromatography Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- DUBMREMHPDYPNH-UHFFFAOYSA-N CCCCCCCCCCCCCC[B]CCCCCCCCCCCCCC Chemical compound CCCCCCCCCCCCCC[B]CCCCCCCCCCCCCC DUBMREMHPDYPNH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004557 single molecule detection Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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Abstract
The invention discloses a carborane-based fluorescent probe, a preparation method and an application thereof, wherein the carborane-based fluorescent probe has a chemical structure shown as a formula I:
Description
Technical Field
The invention relates to the technical field of fluorescent probes, in particular to a carborane-based fluorescent probe and a preparation method and application thereof.
Background
Fluorescent probes are one of the most active research hotspots in recent years. The switch type probe is a probe with weak self-fluorescence property, and the fluorescence intensity of the switch type probe can be greatly increased after meeting a specific detection object. Compared with other probes, the probe has higher practicability because the self fluorescence interferes the detection process less. Fluorescent probes have incomparable advantages with other detection methods, which makes them widely used in environmental chemistry, clinical medicine, pharmaceutical chemistry, biochemistry and the like. Its advantages mainly include: (1) the sensitivity is high, and single molecule detection can be realized; (2) the fluorescence detection is simple, safe and low in cost; (3) non-invasive measurement, and no damage to the sample.
Proton (H)+) Is the most active chemical unit, which plays an important role in numerous chemical and biological processes. However, organic small molecule fluorescent probes capable of detecting protons are still rarely reported at present and far from other ion probes (such as Ca)2+Etc.). The reported proton fluorescent probe based on organic molecules has the following characteristics: (1) common molecular building units are aryl and vinyl, and common response groups are nitrogen-containing groups; (2) the detection mechanism of the proportional probe is mainly excited intramolecular proton transfer or intramolecular charge transfer, and the proportional probe has low response sensitivity and is not reusable; (3) there are few reports of turning off the fluorescent probe of the on type.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a carborane-based fluorescent probe, a preparation method and application thereof, and the fluorescent probe can effectively solve the problems of low response sensitivity and unrepeatable use of the existing fluorescent probe.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
a carborane-based fluorescent probe has a chemical structure shown as formula I:
wherein Donor is an electron-donating group, Acceptor is an electron-withdrawing group.
Furthermore, the Acceptor group is dimyristyl boron, the Donor group is dimethylamino benzene and diethylamino benzene, and the chemical structural formulas are shown as formulas II and III:
further, the preparation method of the compound of formula II or the compound of formula III is as follows: weighing the Compound
Adding toluene, sequentially adding n-butyl lithium solution and toluene solution of dimyristyl boron fluoride at ultralow temperature in a nitrogen protection environment, reflux extracting, suction filtering with dichloromethane after reaction, evaporating the obtained solution to dryness, and recrystallizing to obtain yellow solid compound
And pale yellow solid compound
Further, the air conditioner is characterized in that,
the preparation method comprises the following steps: adding ethylene glycol dimethyl ether into o-carborane under the protection of nitrogen, adding N-butyl lithium N-hexane solution into the o-carborane under the condition of ice-water bath, stirring for reaction, adding cuprous chloride into the o-carborane, continuously stirring for reaction, adding pyridine into the o-carborane, adding 3-bromo-N, N-dimethylaniline or 3-bromo-N, N-diethylaniline into the o-carborane, heating for reflux reaction, dropwise adding ethanol into the o-carborane for quenching after the reaction is finished, performing suction filtration on a reaction system by using a mixed solution of petroleum ether and dichloromethane, removing a solvent from the obtained solution, passing the obtained solution through a chromatographic column, and removing the solvent from the obtained solution to obtain a white solid
The carborane-based fluorescent probe is applied to proton detection.
Further, the fluorescent probe includes a solution state, a thin film state and a crystal state.
A detection kit, the fluorescent probe.
The beneficial effects produced by the invention are as follows:
the Donor-o-carborane-Acceptor type probe material takes o-carborane as a central unit, and a dimethylamino or diethylamino modified phenyl unit is introduced to one carbon atom of the central unit, so that the structure can endow the material with a higher HOMO energy level; meanwhile, a two-meter-based boron unit is introduced to another carbon atom, the structure can reduce the LUMO energy level of the material, and the push-pull structure enables the HOMO energy level and the LUMO energy level of the material molecule to be separated spatially to a greater degree, so that the material molecule is favorable for responding to protons through the intramolecular charge transfer process, and becomes a proton fluorescent probe.
The fluorescent probe solution in the application has strong absorption capacity in an ultraviolet region and weak emission capacity in a near infrared region, which is beneficial to the sensitivity and the detection of the fluorescent probe solution formed in the later period under naked eyes and sunlight. In addition, the two molecules obtained by the method have better thermal stability and solubility in a solid state, and basically do not emit light, so that the stability, film forming property, sensitivity, naked eyes and sunlight detection of the thin film fluorescent probe formed in the later period are facilitated.
The fluorescent probe has the advantages of simple synthetic route and easiness in preparation, the structure of the probe is novel, the solubility, namely the membrance property is good, the structural integrity of the membrane probe prepared by the probe is good, and after the membrane probe is applied to a proton probe, the detection form is various, the detection sensitivity is high, and the detection speed is high.
Detailed Description
Example 1
A compound of formula II
The synthesis method comprises the following steps:
weighing o-carborane (0.432g, 3mmol) and placing the o-carborane into a Schlenk tube with tetrafluoro stopper, adding newly distilled ethylene glycol dimethyl ether (5ml) under the protection of nitrogen, adding 1.5ml N-butyl lithium and N-hexane solution (3.75mmol, 2.5M) under the condition of ice bath, stirring for one hour, then adding cuprous chloride (300mg), stirring for one hour, then adding pyridine (1.8ml), 3-bromo-N, N-dimethylaniline (0.72g, 3.6mmol), heating and refluxing for two days, adding a few drops of ethanol after the reaction is finished, quenching the reaction, and then adding petroleum ether into the reaction system: filtering a mixed solution with dichloromethane of 1:1 through silica gel of 5 cm, carrying out reduced pressure spin drying on the obtained solution on a rotary evaporator, mixing the obtained solid and the silica gel, passing through a chromatographic column, wherein a developing agent is a petroleum ether solution, and finally evaporating the obtained solution under reduced pressure to remove a solvent to obtain a white solid AOCb-1 with the weight of about 280mg and the yield of 35.5%.
NMR spectra of Compound AOCb-11H NMR(500MHz,Chloroform-d)δ＝7.15(t,J＝8.0Hz,1H),6.79(s,1H),6.76-6.66(m,2H),3.97(s,1H),2.97(s,6H)ppm.
Weighing a compound AOCb-1(280mg, 1.06mmol), putting the compound AOCb-1 into a Schlenk tube with a tetrafluoro cock, adding newly steamed toluene (5ml) into a glove box, adding a 2.5M n-butyl lithium solution (0.4ml) at-78 ℃ under the protection of nitrogen, then adding a toluene (5ml) solution of boron fluoride diminyl (285mg, 1.06mmol), refluxing for two days, after the reaction is finished, performing suction filtration on a reaction system by using dichloromethane through silica gel of 5 centimeters, performing reduced pressure spin drying on the obtained solution on a rotary evaporator, purifying by a circulating preparative liquid chromatography to obtain a crude product, and then performing recrystallization in n-hexane to obtain a yellow solid compound II, wherein the weight is about 195mg and the yield is about 36.0%.
Nuclear magnetic resonance hydrogen spectrum of Compound 11H NMR (500MHz, Chloroform-d) δ 6.80(d, J59.6 Hz,2H),6.67-6.28(m,6H),2.81(s,6H),2.31(s,12H),2.18(s,6H) ppm; nuclear magnetic resonance carbon spectrum 13C NMR (125MHz, Chloroform-d) δ 149.24,139.32,138.82,132.13,129.21,128.31,118.36,114.18,113.35,87.54,87.02,40.00,26.72,20.72ppm.
Example 2
A compound of formula III
The synthesis method comprises the following steps:
o-carborane (0.432g, 3mmol) was weighed into a schlenk tube with tetrafluoro stopper, under nitrogen protection, freshly distilled ethylene glycol dimethyl ether (5ml) was added, under ice bath conditions, 1.5ml N-butyllithium N-hexane solution (3.75mmol, 2.5M) was added, stirred for one hour, followed by cuprous chloride (300mg) and stirred for one hour, pyridine (1.8ml), 3-bromo-N, N-diethylaniline (0.8g, 4.0mmol) were added, and heated under reflux for two days. After the reaction was completed, a few drops of ethanol were added to quench the reaction, and then the reaction system was quenched with petroleum ether: filtering the mixed solution of dichloromethane of 1:1 through silica gel of 5 cm, drying the obtained solution on a rotary evaporator under reduced pressure, mixing the obtained solid with the silica gel, and passing through a chromatographic column, wherein a developing agent is petroleum ether solution. Finally, the solvent was distilled off under reduced pressure from the resulting solution to obtain AOCb-2 as a white solid weighing about 315.5mg in 40.0% yield.
Weighing a compound AOCb-2(315.5mg, 1.19mmol) into a Schlenk tube with a tetrafluoro cock, adding newly steamed toluene (5ml) into a glove box, adding a 2.5M n-butyl lithium solution (0.4ml) into the glove box at-78 ℃ under the protection of nitrogen, then adding a toluene (5ml) solution of boron fluoride (315.5mg, 1.19mmol) into the glove box, refluxing for two days, after the reaction is finished, performing suction filtration on a reaction system by using dichloromethane through 5 cm of silica gel, performing reduced pressure spin drying on the obtained solution on a rotary evaporator, purifying by a circulating preparative liquid chromatography to obtain a crude product, and then performing recrystallization in n-hexane to obtain a light yellow solid compound III, wherein the weight is about 220mg and the yield is about 40.6%.
Nuclear magnetic resonance hydrogen spectrum of Compound 21H NMR(500MHz,Chloroform-d)δ＝7.20(d,J＝59.6Hz,2H),6.67-6.28(m,6H),3.41(d,4H),2.71(s,6H),2.40(s,12H),2.20(s,6H)ppm.
Test examples
A compound shown in a formula II and a compound shown in a formula III are respectively used as fluorescent probe materials to prepare a solution-state probe, a film-state probe and a crystal-state probe, and the fluorescent response behavior of the probes to protons is detected, wherein the specific preparation method comprises the following steps:
preparation of a solution-state fluorescent probe: dissolving a compound of formula II and a compound of formula III in n-hexane respectivelyIn hexane solution (10)-5M), then 0.5ml of solution is taken to be put in a sample bottle, and then acid titration is carried out, wherein the molar concentration of the fluorescent probe and the acid preparation can be 1:10-800, and the molar concentration ratio of 1:20 is adopted in this time.
Preparing a thin film fluorescent probe: according to the using sequence of a cleaning agent, ethanol and acetone, cleaning a quartz substrate sheet, then putting the cleaned quartz substrate sheet into an oven for drying, then respectively spreading a compound solution fluorescent probe solution shown in a formula II and a compound solution fluorescent probe solution shown in a formula III on the quartz substrate sheet, spinning by using a spin coating instrument to prepare a fluorescent probe film, and then placing the fluorescent probe film in an atmosphere of hydrochloric acid or sulfuric acid.
Preparation of a crystal state fluorescent probe: and recrystallizing the fluorescent probe in the solution fluorescent probe to obtain a yellow compound shown as a formula II and a pale yellow compound shown as a formula III.
The photophysical properties of the prepared solution-state fluorescent probe, thin-film-state fluorescent probe and crystal-state fluorescent probe were measured, respectively, and the specific results are shown in table 1.
Table 1: photophysical properties of the compound and p-H+In response to (2)
Wherein λ isabsRepresents the peak of the UV-visible absorption spectrum, λemRepresents the peak of the fluorescence emission spectrum, λabs,H +And λem,H +Showing the absorption spectrum and emission spectrum peaks in an acidic environment.
As can be seen from the data in Table 1, the compounds of formula II and III in the invention can be used as fluorescent probe materials to detect protons in a solution state, a film state and a crystal state, the fluorescence intensity of the fluorescent probe materials is obviously enhanced under an acidic condition, the detection sensitivity is high, the color change is obvious under sunlight, the fluorescent probe materials can be observed by naked eyes, and the detection speed is high, simple and convenient.
The response groups of the solution-state probe, the film-state probe and the crystal-state probe to protons are amino groups, and the fluorescence of the solution-state probe, the film-state probe and the crystal-state probe is extremely weak (< 5%). The solution-state probe is changed from colorless transparency to white precipitate to be separated out under the acidic condition, and the fluorescence is obviously enhanced (> 30%). The thin film probe changes from yellow to white under acidic conditions, and the fluorescence is obviously enhanced (> 40%). The crystal probe of the fluorescent probe is changed from yellow to white (> 50%) under an acidic condition, and the fluorescence is obviously enhanced. After the alkali solvent is added into the solution-state probe, the film-state probe and the crystal-state probe, the change process is carried out reversely, and the whole process is proved to be reversible and repeatable.
Claims (7)
1. A carborane-based fluorescent probe is characterized in that the chemical structure of the carborane-based fluorescent probe is shown as formula I:
wherein Donor is an electron-donating group, Acceptor is an electron-withdrawing group.
2. The carborane-based fluorescent probe of claim 1, wherein the Acceptor group is dimimellium boron and the Donor group is dimethylaminobenzene or diethylaminobenzene having the chemical formula II or III:
3. the method of claim 2, wherein the compound of formula ii or the compound of formula iii is prepared by the following method: weighing the Compounds
Adding toluene, and sequentially adding toluene at ultralow temperature in a nitrogen protection environmentAdding n-butyllithium solution and toluene solution of dimyristyl boron fluoride, reflux extracting, suction filtering with dichloromethane after reaction, evaporating the obtained solution to dryness, and recrystallizing to obtain yellow solid compound
And light yellow solid compound
4. The method of making a carborane-based fluorogenic probe of claim 3, wherein said carborane-based fluorogenic probe is selected from the group consisting of a carbonate, a
The preparation method comprises the following steps: adding ethylene glycol dimethyl ether into o-carborane under the protection of nitrogen, adding N-butyl lithium N-hexane solution into the o-carborane under the condition of ice-water bath, stirring for reaction, adding cuprous chloride into the o-carborane, continuously stirring for reaction, adding pyridine into the o-carborane, adding 3-bromo-N, N-dimethylaniline or 3-bromo-N, N-diethylaniline into the o-carborane, heating for reflux reaction, dropwise adding ethanol into the o-carborane for quenching after the reaction is finished, performing suction filtration on a reaction system by using a mixed solution of petroleum ether and dichloromethane, removing a solvent from the obtained solution, passing the obtained solution through a chromatographic column, and removing the solvent from the obtained solution to obtain a white solid
5. Use of a carborane-based fluorescent probe as defined in claim 1 or claim 2 for proton detection.
6. The use according to claim 5, wherein the fluorescent probe comprises a solution state, a thin film state, and a crystalline state.
7. A detection kit comprising the fluorescent probe according to any one of claims 1 to 2.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3136813A (en) * | 1961-09-21 | 1964-06-09 | United States Borax Chem | Boron-carborane bonded compounds |
| JP2005343858A (en) * | 2004-06-07 | 2005-12-15 | Mebiopharm Co Ltd | Boron ion cluster lipid and liposome using the same |
| WO2008145733A2 (en) * | 2007-06-01 | 2008-12-04 | Universität Leipzig | Novel chemical compounds, production thereof, and use thereof |
| CN107353302A (en) * | 2017-07-03 | 2017-11-17 | 南京邮电大学 | A kind of carborane derivative material based on carbazole and preparation method and application |
-
2022
- 2022-05-13 CN CN202210522442.7A patent/CN114773369B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3136813A (en) * | 1961-09-21 | 1964-06-09 | United States Borax Chem | Boron-carborane bonded compounds |
| JP2005343858A (en) * | 2004-06-07 | 2005-12-15 | Mebiopharm Co Ltd | Boron ion cluster lipid and liposome using the same |
| WO2008145733A2 (en) * | 2007-06-01 | 2008-12-04 | Universität Leipzig | Novel chemical compounds, production thereof, and use thereof |
| CN107353302A (en) * | 2017-07-03 | 2017-11-17 | 南京邮电大学 | A kind of carborane derivative material based on carbazole and preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| JAN KAHLERT,ET AL.: "Syntheses and reductions of C-dimesitylboryl- 1,2-dicarba-closo-dodecaboranes", 《DALTON TRANS.》, vol. 44, pages 9766 - 9781 * |
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