CN108148575A - 一种二价铜离子荧光探针及其制备方法和应用 - Google Patents
一种二价铜离子荧光探针及其制备方法和应用 Download PDFInfo
- Publication number
- CN108148575A CN108148575A CN201810164181.XA CN201810164181A CN108148575A CN 108148575 A CN108148575 A CN 108148575A CN 201810164181 A CN201810164181 A CN 201810164181A CN 108148575 A CN108148575 A CN 108148575A
- Authority
- CN
- China
- Prior art keywords
- fluorescence probe
- compound
- cupric ion
- bivalent cupric
- ion fluorescence
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000000523 sample Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 9
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 8
- 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 4
- 239000000243 solution Substances 0.000 claims description 31
- 239000010949 copper Substances 0.000 claims description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- -1 4- tolyl aldehydes Chemical class 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- MFFMQGGZCLEMCI-UHFFFAOYSA-N 2,4-dimethyl-1h-pyrrole Chemical class CC1=CNC(C)=C1 MFFMQGGZCLEMCI-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910001431 copper ion Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 230000000536 complexating effect Effects 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 6
- 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 claims description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 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 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 150000001768 cations Chemical class 0.000 abstract description 18
- 238000001514 detection method Methods 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 4
- 238000010189 synthetic method Methods 0.000 abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 45
- 238000002189 fluorescence spectrum Methods 0.000 description 14
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 230000004044 response Effects 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004993 emission spectroscopy Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000011167 hydrochloric acid Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000011580 syndromic disease Diseases 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- PAPNRQCYSFBWDI-UHFFFAOYSA-N DMP Natural products CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 1
- PVWAELCWLJHNPB-CHNJZELVSA-N N/C(=C(/C#N)\N)/C#N.N/C(=C(/C#N)\N)/C#N Chemical compound N/C(=C(/C#N)\N)/C#N.N/C(=C(/C#N)\N)/C#N PVWAELCWLJHNPB-CHNJZELVSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical compound [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000009870 specific binding Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- 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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
本发明提供了一种二价铜离子荧光探针及其制备方法和应用,其是以氟化硼二吡咯为荧光信号基团,二氨基马来腈为识别位点的Cu2+荧光探针;本发明荧光探针可以单一性识别Cu2+,最低检测限可达27nM,并且这一识别过程不受其它阳离子的干扰。此外,此荧光探针合成方法简单,成本低,在Cu2+的检测中具有很好的应用前景。
Description
技术领域
本发明属于利用小分子探针检测阳离子领域,尤其涉及一种二价铜离子荧光探针及其制备方法和应用。
背景技术
Cu2+是人体内除铁离子和锌离子之后第三丰富的过渡金属离子,人体内正常的代谢离不开适量的Cu2+,但是过量的Cu2+会导致代谢不正常,进而诱发各种生理疾病,例如威尔逊(Wilson)综合征,门克斯(Menkes)综合征和阿兹尔海默氏症等。目前,在建筑工业、机械制造业和医疗等领域中,铜材料的过度使用和不当的后处理会导致Cu2+成为重金属污染物之一。因此,监测水相中Cu2+的含量成为人们关注的热点问题。
目前,检测Cu2+的方法有很多种,例如:电化学法,原子吸收光谱法,纳米传感器法和荧光光谱法。其中荧光光谱法由于具有选择性好,灵敏度高,响应快,操作简单等优点得到广泛应用。荧光探针检测离子的基本原理主要是待测离子与探针发生特异性结合(络合、化学反应),导致探针结构发生一定的变化,从而出现荧光信号改变,通过前后荧光光谱的变化实现对待测离子的检测。通过这个原理化学家们设计了很多Cu2+的荧光探针。由于Cu2+具有很强的顺磁性,对荧光具有极其的淬灭性,因此大部分已经报道的Cu2+探针都是荧光淬灭性,这种识别方式很容易受到环境和仪器的影响,灵敏度一般都不高。此外,还有一些检测Cu2+的荧光探针响应时间长,选择性差,只能在有机溶剂中检测,不能应用水相中Cu2+检测。因此开发具有高灵敏度和高选择性的荧光增强型Cu2+小分子探针具有重要意义。
发明内容
针对现有技术中的上述问题,本发明的主要目的在于提供一种二价铜离子荧光探针,能够特异性识别二价铜离子,且不受其它阳离子的干扰。
为了达到上述目的,本发明采用如下技术方案:一种二价铜离子荧光探针,包括如下结构式:
本发明的另一目的在于提供上述二价铜离子荧光探针的制备方法,包括如下步骤:
以2,4-二甲基吡咯和4-甲基苯甲醛为原料,通过缩合,氧化,络合得到化合物IV,然后所述化合物IV通过维尔斯迈尔-哈克反应得到5-醛基BODIPY,所述5-醛基BODIPY与二氨基马来腈通过缩合反应得到所述铜离子荧光探针。
作为进一步的优选,所述化合物IV包括如下结构式:
作为进一步的优选,所述以2,4-二甲基吡咯和4-甲基苯甲醛为原料,通过缩合得到含有如下结构式的化合物II:
作为进一步的优选,所述通过氧化得到含有如下结构式的化合物III:
作为进一步的优选,所述络合得到化合物IV,包括如下步骤:
将所述化合物III,三乙胺,三氟化硼乙醚和CH2Cl2,在室温下搅拌,反应结束后,水洗,干燥,过滤,浓缩,柱层析分离提纯得到橙红色固体,即为化合物IV。
作为进一步的优选,所述化合物IV通过维尔斯迈尔-哈克反应得到5-醛基BODIPY,包括如下步骤:
在氮气体系和冰浴下加入DMF和POCl3,搅拌,撤掉冰浴,室温搅拌,加入溶解在1,2-二氯乙烷中的化合物IV,加热至50℃,搅拌,冷却至室温后,冰浴条件下将反应体系缓慢倒入碳酸氢钠溶液中,室温搅拌,二氯甲烷萃取,合并有机相,干燥,过滤,浓缩,柱层析分离提纯得到橙红色固体5-醛基BODIPY。
作为进一步的优选,所述5-醛基BODIPY与二氨基马来腈通过缩合反应得到所述铜离子荧光探针,包括如下步骤:
将5-醛基BODIPY溶解在乙醇和水的混合溶液中,滴加浓盐酸,然后缓慢滴加二氨基马来氰的乙醇溶液,搅拌,反应结束后,浓缩,柱层析分离提纯得红色固体化合物,为所述铜离子荧光探针。
本发明的另一目的还在于提供上述二价铜离子荧光探针的应用,所述荧光探针用于检测水溶液中的Cu2+。
作为进一步的优选,所述水溶液中Cu2+的浓度≥27nM。
本发明的有益效果是:本发明提供了一种以氟化硼二吡咯(BODIPY)为荧光信号基团,二氨基马来腈(Diaminomaleonitrile)为识别位点的Cu2+荧光探针;本发明通过紫外吸收和荧光发射光谱法研究荧光探针在乙腈溶液中对Cu2+、Mn2+、Co2+、Ni2+、Zn2+、Cd2+、Ba2+、Ca2 +、Ag+、Fe3+、K+、Na+、Mg2+十三种阳离子的识别效果,发现该荧光探针可以单一性识别Cu2+,最低检测限可达27nM,并且这一识别过程不受其它阳离子的干扰。此外,此荧光探针合成方法简单,成本低,在Cu2+的检测中具有很好的应用前景。
附图说明
图1为本发明实施例BD(8μmol·L-1)的乙腈溶液中加入不同阳离子(40μmol·L-1)时的紫外吸收谱图;
图2为本发明实施例BD(8μmol·L-1)的乙腈溶液中加入不同阳离子(40μmol·L-1)时颜色变化示意图;
图3为本发明实施例BD(8μmol·L-1)的乙腈溶液中加入不同阳离子(40μmol·L-1)时的荧光发射谱图(lex=500nm);
图4为本发明实施例BD(8μmol·L-1)的乙腈溶液中加入不同阳离子(40μmol·L-1)时在手提紫外灯365nm照射下图片;
图5为本发明实施例BD(8μmol·L-1)的乙腈溶液中在不同Cu2+浓度(0—64μmol·L-1)下荧光发射光谱,插图:I522nm与Cu2+浓度关系曲线;
图6为I522nm与Cu2+浓度(0—8μmol·L-1)线性曲线图;
图7为本发明实施例BD(8μmol·L-1)在与其它阳离子(40μmol·L-1)共存时对Cu2+(40μmol·L-1)响应时I522nm的变化柱状图;
图8为本发明实施例BD(8μmol·L-1)的乙腈溶液中对Cu2+(16μmol·L-1)响应时间;
图9为本发明实施例化合物VI的紫外吸收光谱图;
图10为本发明实施例化合物VI的荧光发射光谱图(激发波长为480nm);
图11为本发明实施例BD检测Cu2+机理示意图。
具体实施方式
本发明通过提供一种二价铜离子荧光探针及其制备方法和应用,解决了现有监测水相中Cu2+含量的方法的缺陷。
为了解决上述缺陷,本发明实施例的主要思路是:
本发明实施例二价铜离子荧光探针,包括如下结构式:
上述荧光探针的化学名称为1,3,5,7-四甲基-6-(((2-氨基-1,2-二氰乙烯基)亚氨基)甲基)-8-苯基-氟化硼二吡咯,标记为BD。
本发明实施例二价铜离子荧光探针的制备方法,包括如下步骤:
以2,4-二甲基吡咯和4-甲基苯甲醛为原料,通过缩合,氧化,络合得到化合物IV,然后所述化合物IV通过维尔斯迈尔-哈克反应得到5-醛基BODIPY,所述5-醛基BODIPY与二氨基马来腈通过缩合反应得到所述铜离子荧光探针。
本发明实施例中所用的材料、试剂、仪器等,如无特殊说明,均可从商业途径得到,且材料、试剂、反应名称、仪器名称等均为本领域常规术语。
以下针对上述内容进行进一步地详细说明,但本发明的范围并不局限于以下实施例。在不脱离本发明的发明内容的前提下,对其进行本领域常规技术知识和手段上的变更均属于本发明的保护范围。
实施例1
本发明实施例二价铜离子荧光探针的制备方法,包括如下步骤:
以2,4-二甲基吡咯和4-甲基苯甲醛为原料,通过缩合,氧化,络合得到化合物IV,然后所述化合物IV通过维尔斯迈尔-哈克反应得到5-醛基BODIPY,所述5-醛基BODIPY与二氨基马来腈通过缩合反应得到所述铜离子荧光探针,名称为1,3,5,7-四甲基-6-(((2-氨基-1,2-二氰乙烯基)亚氨基)甲基)-8-苯基-氟化硼二吡咯,标记为BD。具体合成路线如下所示:
(1)化合物II的合成:
在250mL干燥的两口瓶中加入苯甲醛(3mL,30mmol)和2,4-二甲基吡咯(77mL,0.75mol),将瓶内的气体置换成N2,加入三氟乙酸(3mmol),室温搅拌1h,旋转蒸发掉多余的2,4-二甲基吡咯,将剩余的物质用乙醇进行重结晶,得到棕色固体化合物II(5.08g,21.9mmol),收率为73%。
(2)化合物III的合成:
500mL单口瓶中,加入化合物II(5.08g,21.9mmol),DDQ(4.98g,21.9mmol)和CH2Cl2(300mL),室温搅拌2h,反应结束后,浓缩,硅胶柱层析分离提纯(石油醚:二氯甲烷=2:1)得黄色固体(2.6g,9.4mmol),收率为43%。
(3)化合物IV的合成:
250mL的单口瓶中,加入化合物III(2.6g,9.4mmol),三乙胺(2.9mL,20.7mmol),三氟化硼乙醚(5.1mL,40.4mmol)和CH2Cl2(150mL),室温搅拌4h,反应结束后,水洗(3×100mL),无水硫酸镁干燥,过滤,浓缩,硅胶柱层析分离提纯(石油醚:乙酸乙酯:三乙胺=20:1:0.2)得橙红色固体(2.34g,7.2mmol),收率为77%。1H NMR(400MHz,CDCl3)δ7.48-7.46(m,3H),7.28-7.26(m,2H),5.97(s,1H),2.55(s,6H),1.37(s,6H).13C NMR(100MHz,CDCl3)δ155.41,143.14,141.73,134.98,131.42,129.12,128.93,127.93,121.18,14.57,14.32。
(4)化合物V的合成(5-醛基BODIPY):
将250mL干燥的两口瓶置换成氮气体系,冰浴下加入DMF(13.5mL)和POCl3(13.5mL),搅拌5min,撤掉冰浴,室温搅拌30min,加入溶解在1,2-二氯乙烷(130mL)中的化合物IV(362mg,1.12mmol),加热至50℃,搅拌2h,冷却至室温后,冰浴条件下将反应体系缓慢倒入碳酸氢钠溶液中(34.7g碳酸氢钠溶解在445ml的蒸馏水中),室温搅拌30min,二氯甲烷萃取(3×100mL),合并有机相,无所硫酸镁干燥,过滤,浓缩,硅胶柱层析分离提纯(CH2Cl2)得橙红色固体(0.39g,1.1mmol),收率为98%。1H NMR(400MHz,CDCl3)δ10.01(s,1H),7.54-7.52(m,3H),7.30-7.26(m,2H),6.15(s,1H),2.83(s,3H),2.62(s,3H),1.65(s,3H),1.42(s,3H).13C NMR(100MHz,CDCl3)δ185.91,161.63,156.51,147.29,143.56,142.92,134.16,134.07,129.78,129.55,129.48,127.70,126.32,123.99,77.34,77.23,77.03,76.71,15.09,14.83,13.02,11.55。
(5)化合物I的合成(荧光探针):
250ml的单口瓶中,将化合物V(0.3g,0.85mmol)溶解在乙醇(40mL)和水(9mL)的混合溶液中,滴加3滴浓盐酸,然后缓慢滴加二氨基马来氰(0.1g,0.935mmol)的乙醇溶液(30mL),搅拌1h,反应结束后,浓缩,硅胶柱层析分离提纯(CH2Cl2)得红色固体化合物I(0.26g,0.595mmol),收率为70%。1H NMR(400MHz,DMSO)δ8.21(s,1H),7.58(m,3H),7.51-7.26(m,4H),6.35(s,1H),2.73(s,3H),2.51(s,3H),1.56(s,3H),1.36(s,3H);13C NMR(101MHz,DMSO)δ159.65,155.74,150.25,146.07,143.21,141.17,134.14,132.92,130.19,130.02,129.89,128.28,125.45,125.00,123.91,115.10,114.11,105.27,55.38,15.04,14.76,14.41,12.67。
为了验证铜离子荧光探针的检测效果,进行下述系列试验,得到氰根离子的荧光探针对阴离子的识别性能结果:
1、Cu2+的荧光探针的选择性研究
将BD溶于分析纯乙腈中配制10-3mol·L-1的储备液;分别配制Cu2+、Mn2+、Co2+、Ni2+、Zn2+、Cd2+、Ba2+、Ca2+、Ag+、Fe3+、K+、Na+、Mg2+的水溶液10-2mol·L-1。在比色皿中加入20μL的BD储备液,2480μL乙腈溶液,检测紫外吸收光谱和荧光发射光谱,分别加入10μL的离子储备液,此时BD的浓度为8×10-6mol·L-1,阴离子的浓度为受体的5倍,检测紫外吸收光谱和荧光发射光谱(λex=480nm),观察荧光探针BD对各种阳离子的响应。
结果表明,BD在乙腈作为溶剂的条件下,在340nm,373nm,413nm和530nm处分别有吸收峰,加入Cu2+后,340nm,373nm,413nm和530nm处的吸收峰消失,在500nm处出现新的吸收峰。而加入其它阳离子,BD的紫外吸收光谱没有明显变化(图1)。同时,BD溶液中加入Cu2+水溶液后,颜色从紫红色变为淡黄色,而其它阳离子的加入并无明显变化(图2),这说明BD可以用于裸视检测Cu2+。在荧光光谱中,以480nm作为激发波长,BD荧光强度非常弱,加入Cu2+后,在522nm出现很强的荧光发射光谱,加入其它阳离子除Fe3+可以引起荧光微弱增强外,基本没有任何变化(图3)。在紫外灯365nm照射下,加入Cu2+后出现黄绿色荧光,而其它阳离子没有明显变化(图4),说明该荧光探针可以专一性的检测Cu2+。
2、Cu2+的荧光探针滴定实验
将BD溶于无水乙腈中配制10-3mol·L-1的储备液,在水溶液中配制Cu2+储备液,浓度为10-2mol·L-1.检测时在在比色皿中加入20μL的BD储备液,2480μL乙腈溶液(最终浓度8μmol·L-1),加入Cu2+储备液0.2μL,摇晃均匀后分别检测其荧光发射光谱(激发波长480nm),重复此操作,直至加入8.0当量的氰根离子溶液.
结果表明,BD的荧光发射光谱受Cu2+浓度的影响(图5),随着Cu2+逐渐加入,BD在522nm处的荧光强度逐渐增强,直至加入20μmol·L-1Cu2+时达到平衡。当Cu2+的浓度为0—8μmol·L-1时,I522nm与Cu2+的浓度表现出比较好的线性关系,拟合得到的线性方程为y=2.4×107x+3.38(R2=0.9913),因此BD可以通过荧光法定量检测Cu2+的浓度(图6)。
3、BD荧光探针对Cu2+最低限的测定
当Cu2+的浓度为0—8μmol·L-1时,I522nm与Cu2+的浓度表现出比较好的线性关系,拟合得到的线性方程为y=2.4×107x+3.38(R2=0.9913),依据″检测限=3σ/k″可计算BD对Cu2+的检测限,其中σ为标准平均偏差,k为线性拟合直线的斜率.通过对BD(8μmol·L-1)分别进行15次荧光检测,将得到的测量结果计算标准偏差σ为0.21805,k为2.4×107.通过公式计算可以得出,BD对Cu2+的检测限为27nM,远低于世界卫生组织对饮用水中的Cu2+的最大规定值20μmol·L-1。因此,BD可用于实际水样中Cu2+的测定.
4、抗干扰能力检测
比色皿中分别加入配制好的BD储备液20μL,乙腈2480μL,使其最终浓度8μmol·L-1,检测荧光发射光谱(激发波长480nm),然后加入阳离子储备液(例如钾离子)20μL(Cu2+除外),充分摇匀,检测荧光发射光谱,最后加入10μL的Cu2+,摇匀,再次检测荧光发射光谱,其它每个阳离子重复上述操作。
实验表明,在与其他阳离子共存的情况下,Cu2+依然可以使BD在522nm处的荧光强度明显增强(图7),因此BD对Cu2+检测具有很好的抗干扰能力,其他阳离子不会对检测结果带来任何干扰。
5、BD对Cu2+响应时间
比色皿中分别加入配制好的BD储备液20μL,乙腈2480μL,使其最终浓度8μmol·L-1,检测荧光发射光谱,加入Cu2+水溶液(16μmol·L-1),检测荧光发射光谱,振荡,每60s检测一次荧光发射光谱。
如图8所示的结果表明,BD对Cu2+响应时间快,5min后荧光强度不变,达到平衡,因此BD可作为快速检测Cu2+的荧光传感器。
6、BD用于检测Cu2+的机理
取60mg BD溶于45mL乙腈中,加入高氯酸铜(100mg),室温搅拌10min,反应结束后,将溶液冻干,硅胶柱层析分离提纯得橘红色固体化合物VI。测试化合物VI的紫外和荧光发射光谱,核磁氢谱,核磁碳谱,质谱。
如图9和图10所示,化合物VI的紫外和荧光光谱与BD加入Cu2+后谱图是一致的,这说明化合物VI的生成是BD与Cu2+发生反应产生光谱变化的主要原因。通过对化合物VI的氢谱,碳谱和质谱分析可以确定其结构为1,3,5,7-四甲基-8-苯基-6-羧基氟化硼二吡咯,因此可以推断BD用于检测Cu2+的机理主要Cu2+使BD水解得到1,3,5,7-四甲基-8苯基-6-醛基氟化硼二吡咯,随后醛基被氧化成羧基得到化合物VI(图11)。
上述本申请实施例中的技术方案,至少具有如下的技术效果或优点:
本发明实施例提供了一种以氟化硼二吡咯(BODIPY)为荧光信号基团,二氨基马来腈(Diaminomaleonitrile)为识别位点的Cu2+荧光探针;本发明通过紫外吸收和荧光发射光谱法研究荧光探针在乙腈溶液中对Cu2+、Mn2+、Co2+、Ni2+、Zn2+、Cd2+、Ba2+、Ca2+、Ag+、Fe3+、K+、Na+、Mg2+十三种阳离子的识别效果,发现该荧光探针可以单一性识别Cu2+,最低检测限可达27nM,并且这一识别过程不受其它阳离子的干扰。此外,此荧光探针合成方法简单,成本低,在Cu2+的检测中具有很好的应用前景。
以上内容已经用一般性说明及具体的实施结果对本发明做了详尽的描述,但在本发明基础上,可以对之做一些修改或改进,这对本领域技术人员是显而易见的。因此,在不偏离本发明精神的基础上所作的修改或改进,均属于本发明要求保护的范围。
Claims (10)
1.一种二价铜离子荧光探针,其特征在于:包括如下结构式:
2.如权利要求1所述二价铜离子荧光探针的制备方法,其特征在于:包括如下步骤:
以2,4-二甲基吡咯和4-甲基苯甲醛为原料,通过缩合,氧化,络合得到化合物IV,然后所述化合物IV通过维尔斯迈尔-哈克反应得到5-醛基BODIPY,所述5-醛基BODIPY与二氨基马来腈通过缩合反应得到所述铜离子荧光探针。
3.根据权利要求2所述二价铜离子荧光探针的制备方法,其特征在于:所述化合物IV包括如下结构式:
4.根据权利要求2所述二价铜离子荧光探针的制备方法,其特征在于:所述以2,4-二甲基吡咯和4-甲基苯甲醛为原料,通过缩合得到含有如下结构式的化合物II:
5.根据权利要求2所述二价铜离子荧光探针的制备方法,其特征在于:所述通过氧化得到含有如下结构式的化合物III:
6.根据权利要求5所述二价铜离子荧光探针的制备方法,其特征在于:所述络合得到化合物IV,包括如下步骤:
将所述化合物III,三乙胺,三氟化硼乙醚和CH2Cl2,在室温下搅拌,反应结束后,水洗,干燥,过滤,浓缩,柱层析分离提纯得到橙红色固体,即为化合物IV。
7.根据权利要求2所述二价铜离子荧光探针的制备方法,其特征在于:所述化合物IV通过维尔斯迈尔-哈克反应得到5-醛基BODIPY,包括如下步骤:
在氮气体系和冰浴下加入DMF和POCl3,搅拌,撤掉冰浴,室温搅拌,加入溶解在1,2-二氯乙烷中的化合物IV,加热至50℃,搅拌,冷却至室温后,冰浴条件下将反应体系缓慢倒入碳酸氢钠溶液中,室温搅拌,二氯甲烷萃取,合并有机相,干燥,过滤,浓缩,柱层析分离提纯得到橙红色固体5-醛基BODIPY。
8.根据权利要求2所述二价铜离子荧光探针的制备方法,其特征在于:所述5-醛基BODIPY与二氨基马来腈通过缩合反应得到所述铜离子荧光探针,包括如下步骤:
将5-醛基BODIPY溶解在乙醇和水的混合溶液中,滴加浓盐酸,然后缓慢滴加二氨基马来氰的乙醇溶液,搅拌,反应结束后,浓缩,柱层析分离提纯得红色固体化合物,为所述铜离子荧光探针。
9.如权利要求1所述二价铜离子荧光探针的应用,其特征在于:所述荧光探针用于检测水溶液中的Cu2+。
10.根据权利要求9所述二价铜离子荧光探针的应用,其特征在于:所述水溶液中Cu2+的浓度≥27nM。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810164181.XA CN108148575A (zh) | 2018-02-27 | 2018-02-27 | 一种二价铜离子荧光探针及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810164181.XA CN108148575A (zh) | 2018-02-27 | 2018-02-27 | 一种二价铜离子荧光探针及其制备方法和应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108148575A true CN108148575A (zh) | 2018-06-12 |
Family
ID=62456078
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810164181.XA Pending CN108148575A (zh) | 2018-02-27 | 2018-02-27 | 一种二价铜离子荧光探针及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108148575A (zh) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108864162A (zh) * | 2018-06-21 | 2018-11-23 | 杭州师范大学 | 含2,2’-二吡啶胺的bodipy基荧光探针及其合成方法与应用 |
CN109320535A (zh) * | 2018-09-29 | 2019-02-12 | 江汉大学 | 一种检测Cu2+的比率型荧光探针、其制备方法及应用 |
CN111925383A (zh) * | 2019-07-30 | 2020-11-13 | 晋中学院 | 基于BODIPY的Cu2+荧光探针及其制法和用途 |
CN113943316A (zh) * | 2021-10-13 | 2022-01-18 | 山西农业大学 | 一种于极端pH条件下检测铜离子的荧光探针、制备方法及其应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102533255A (zh) * | 2011-12-29 | 2012-07-04 | 复旦大学 | 一种用于Cu2+检测的荧光探针分子及其制备方法与应用 |
CN106518900A (zh) * | 2016-09-14 | 2017-03-22 | 江苏大学 | 基于bodipy染料的次氯酸根荧光探针的合成及应用 |
CN107602519A (zh) * | 2017-09-15 | 2018-01-19 | 江苏大学 | 基于香豆素染料比率型双功能荧光探针及其合成与应用 |
-
2018
- 2018-02-27 CN CN201810164181.XA patent/CN108148575A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102533255A (zh) * | 2011-12-29 | 2012-07-04 | 复旦大学 | 一种用于Cu2+检测的荧光探针分子及其制备方法与应用 |
CN106518900A (zh) * | 2016-09-14 | 2017-03-22 | 江苏大学 | 基于bodipy染料的次氯酸根荧光探针的合成及应用 |
CN107602519A (zh) * | 2017-09-15 | 2018-01-19 | 江苏大学 | 基于香豆素染料比率型双功能荧光探针及其合成与应用 |
Non-Patent Citations (1)
Title |
---|
单丹丹,: "BODIPY类衍生物的合成及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108864162A (zh) * | 2018-06-21 | 2018-11-23 | 杭州师范大学 | 含2,2’-二吡啶胺的bodipy基荧光探针及其合成方法与应用 |
CN108864162B (zh) * | 2018-06-21 | 2020-11-20 | 杭州师范大学 | 含2,2’-二吡啶胺的bodipy基荧光探针及其合成方法与应用 |
CN109320535A (zh) * | 2018-09-29 | 2019-02-12 | 江汉大学 | 一种检测Cu2+的比率型荧光探针、其制备方法及应用 |
CN109320535B (zh) * | 2018-09-29 | 2021-04-13 | 江汉大学 | 一种检测Cu2+的比率型荧光探针、其制备方法及应用 |
CN111925383A (zh) * | 2019-07-30 | 2020-11-13 | 晋中学院 | 基于BODIPY的Cu2+荧光探针及其制法和用途 |
CN113943316A (zh) * | 2021-10-13 | 2022-01-18 | 山西农业大学 | 一种于极端pH条件下检测铜离子的荧光探针、制备方法及其应用 |
CN113943316B (zh) * | 2021-10-13 | 2023-04-21 | 山西农业大学 | 一种于极端pH条件下检测铜离子的荧光探针、制备方法及其应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108148575A (zh) | 一种二价铜离子荧光探针及其制备方法和应用 | |
Nayab et al. | A dual responsive colorimetric and fluorescent reversible turn-on chemosensor for iron (Fe3+): Computational and spectroscopic investigations | |
Khanmohammadi et al. | Naked-eye detection of inorganic fluoride in aqueous media using a new azo-azomethine colorimetric receptor enhanced by electron withdrawing groups | |
Tang et al. | A novel fluorescent probe based on biphenyl and rhodamine for multi-metal ion recognition and its application | |
Bao et al. | A sensitive and selective probe for visual detection of Cu2+ based on 1, 8-naphthalimidederivative | |
Yuan et al. | Highly sensitive and selective turn-on fluorescent probes for Cu 2+ based on rhodamine B | |
CN111825629B (zh) | 一种苯并噁唑类荧光探针及制备方法及应用 | |
Dai et al. | A highly selective fluorescent sensor for mercury ion (II) based on azathia‐crown ether possessing a dansyl moiety | |
CN107082785A (zh) | 一种检测氰根离子的荧光探针及其合成合应用方法 | |
Fang et al. | A highly sensitive fluorescent probe with different responses to Cu2+ and Zn2+ | |
Dong et al. | A new naphthopyran-based chemodosimeter with aggregation-induced emission: Selective dual-channel detection of cyanide ion in aqueous medium and test strips | |
Liu et al. | A novel pyrene-based fluorescent probe for Al3+ detection | |
Zhang et al. | Colorimetric and near infrared fluorescent detection of cyanide by a new phenanthroimidazole–indolium conjugated probe | |
Rani et al. | Pyrene–antipyrine based highly selective and sensitive turn-on fluorescent sensor for Th (IV) | |
Chen et al. | Enhanced fluorescence of terbium with thiabendazole and application in determining trace amounts of terbium and thiabendazole | |
Musikavanhu et al. | Turn-off detection of Cr (III) with chelation enhanced fluorescence quenching effect by a naphthyl hydrazone Shiff base chemosensor | |
CN108178766A (zh) | 一种可识别铁离子和磷酸二氢根离子的荧光探针分子及其制备方法和应用 | |
Yang et al. | Colorimetric and Highly Selective Fluorescence" Turn‐on" Detection of Cr3+ by Using a Simple Schiff Base Sensor | |
Pan et al. | AIE fluorescent probe based on tetraphenylethylene and morpholine-thiourea structures for detection of HClO | |
Niu et al. | A simple ratiometric and colorimetric chemosensor for the selective detection of fluoride in DMSO buffered solution | |
Panchal et al. | Sensing of Ce (III) using di-naphthoylated oxacalix [4] arene via realistic simulations and experimental studies | |
CN106008435B (zh) | 一种用于Au3+检测的荧光增强型荧光探针及其制备方法 | |
CN113234071B (zh) | 三苯胺基甲基吡啶盐及合成方法以及对cn-的识别和生物成像应用 | |
CN105319194B (zh) | 一种采用聚集诱导发光型荧光传感分子连续检测I‑和Hg2+的方法 | |
Sun et al. | A naphthalene based chemosensor for dual channel recognition of Al3+ and relay recognition of Fe3+ in water-bearing system and bioimaging in zebrafish |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180612 |
|
RJ01 | Rejection of invention patent application after publication |