CN106188003A - Cu based on chinoline backbone2+and Fe3+double target spot fluorescent probes and its preparation method and application - Google Patents
Cu based on chinoline backbone2+and Fe3+double target spot fluorescent probes and its preparation method and application Download PDFInfo
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- CN106188003A CN106188003A CN201610591243.6A CN201610591243A CN106188003A CN 106188003 A CN106188003 A CN 106188003A CN 201610591243 A CN201610591243 A CN 201610591243A CN 106188003 A CN106188003 A CN 106188003A
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 28
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical group N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 17
- 238000003384 imaging method Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- JWYUFVNJZUSCSM-UHFFFAOYSA-N 2-aminobenzimidazole Chemical compound C1=CC=C2NC(N)=NC2=C1 JWYUFVNJZUSCSM-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 229910052756 noble gas Inorganic materials 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 36
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 28
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 20
- 239000010949 copper Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 229960005070 ascorbic acid Drugs 0.000 description 14
- 235000010323 ascorbic acid Nutrition 0.000 description 14
- 239000011668 ascorbic acid Substances 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 238000001514 detection method Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 238000003775 Density Functional Theory Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000003013 cytotoxicity Effects 0.000 description 4
- 231100000135 cytotoxicity Toxicity 0.000 description 4
- 230000012447 hatching Effects 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000010205 computational analysis Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- 230000003834 intracellular effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000012531 culture fluid Substances 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000010534 mechanism of action Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N methylquinoline Natural products C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- -1 quinaldine acyl chlorides Chemical class 0.000 description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000000954 titration curve Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000040710 Chela Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 108010019160 Pancreatin Proteins 0.000 description 1
- 239000012980 RPMI-1640 medium Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000005515 coenzyme Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000001215 fluorescent labelling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001900 immune effect Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000011246 intracellular protein detection Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004770 neurodegeneration Effects 0.000 description 1
- 208000015122 neurodegenerative disease Diseases 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000004768 organ dysfunction Effects 0.000 description 1
- 229940055695 pancreatin Drugs 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- 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
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
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- 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
- C09K2211/18—Metal complexes
- C09K2211/187—Metal complexes of the iron group metals, i.e. Fe, Co or Ni
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The present invention provides a kind of Cu based on chinoline backbone2+And Fe3+Double target spot fluorescent probes and its preparation method and application, this pair of target spot fluorescent probe has the structure shown in Formulas I.Double target spot fluorescent probes of the present invention are to Cu2+And Fe3+Identification there is high sensitivity and high selectivity.
Description
Technical field
The present invention relates to biological fluorescent labeling field, more particularly, to a kind of Cu based on chinoline backbone2+And Fe3+Double
Target spot fluorescent probe and its preparation method and application.
Background technology
Copper and ferrum are the metals being widely used in human being's production life, and both have significant biology as transition elements
Dependency.They participate in the growth metabolism of organism often as coenzyme or other cofactors.The Cu of excess2+And Fe3+Can draw
Play organism metabolism obstacle and other serious epidemic diseases.Cu2+And Fe3+The dysbolismus disease caused mainly includes Organ Dysfunction
Or neurodegenerative diseases.Therefore the detection for transition metal is particularly significant.
Fluoroscopic examination has high sensitivity, high selectivity, operates the advantages such as simple, quick response.Cell fluorescence imaging is made
Receive much concern for efficient detection means a kind of in biology and pharmaceutical science field.And for the fluorescent material of cell imaging, should
When there being good water solublity, high brightness, light stability and hypotoxicity.Fluorescent small molecule is due to its good biocompatibility, excellent
Photophysical Behaviors more is applied to intracellular image checking.Quinoline is a big conjugated system, can produce π easily
To the electron transition of π *, quinolyl derivant not only has stronger fluorescence, and its heterocyclic nitrogen atom can participate in coordination, i.e. same
Time have identification and fluorescent functional.In recent years based on chinoline backbone specific recognition Zn2+, Ag+, Fe3+, Cu2+Isoionic little point
Sub-fluorescent probe is by wide coverage.But, identify that the fluorescent probe of double target spot or Mutiple Targets is by less report simultaneously.Double target spots are glimmering
Light probe has efficiently, low cost, the easy advantage of operation, and therefore, design one can identify double target spot, bio-compatible simultaneously
The fluorescent probe that property is good seems and becomes more and more important.
Summary of the invention
It is an object of the invention to provide a kind of Cu based on chinoline backbone2+And Fe3+Double target spot fluorescent probes, and offer should
The preparation method of double target spot fluorescent probes and its application in cell imaging.
A first aspect of the present invention is to provide a kind of Cu based on chinoline backbone2+And Fe3+Double target spot fluorescent probes are (following
It is called for short QLBM), this pair of target spot fluorescent probe has a structure shown in Formulas I:
A second aspect of the present invention is to provide the preparation method of this pair of target spot fluorescent probe, and the method includes:
I (), in the presence of the first organic solvent, makes quinaldinic acid. react with oxalyl chloride, obtain compound shown in Formula II；
(ii) in the presence of the second organic solvent, make compound shown in Formula II react with 2-aminobenzimidazole, obtain Formulas I
Shown compound.
A third aspect of the present invention is to provide the application in cell imaging of this pair of target spot fluorescent probe.
The effect of the present invention shows:
(1) QLBM is to Cu2+And Fe3+Identification there is high sensitivity and high selectivity.
(2) reaction system of this probe is pure water phase.
(3) propose first to utilize ascorbic acid to Cu2+And Fe3+Make a distinction.
(4) mass spectrum, DFT is utilized to analyze its mechanism of action, and as Cu2+And Fe3+Double target spot probe applications are in carefully
Born of the same parents' imaging.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
By combining accompanying drawing, exemplary embodiment of the invention is described in more detail, the present invention above-mentioned and its
Its purpose, feature and advantage will be apparent from.
Fig. 1 is the hydrogen spectrum of the double target spot fluorescent probe of the present invention.
Fig. 2 is the carbon spectrum of the double target spot fluorescent probe of the present invention.
Fig. 3 is the uv absorption spectrogram of the double target spot fluorescent probe of the present invention.
Fig. 4 (a) shows Tris-HCl (50mM, the pH that the different metal ion of 200 μMs adds QLBM (20 μMs)
7.2) the fluorescent emission spectrogram after solution；Fig. 4 (b) shows and the different metal ion of 200 μMs is added QLBM's (20 μMs)
Color diagram under ultraviolet light after Tris-HCl (50mM, pH 7.2) solution.Fig. 4 (c) and Fig. 4 (d) respectively illustrates QLBM (20 μ
M) in Tris-HCl (50mM, pH 7.2) solution with Cu2+(200 μMs), Fe3+(200 μMs) and other metal ions (500 μMs)
Fluorescent emission spectrogram.Secret note represents other competition metal ions.Red bar represents and adds Cu after adding competition metal ion2+
(200 μMs) and Fe3+(200μM)。
Fig. 5 (a) shows and constantly drips Cu in Tris-HCl (50mM, the pH 7.2) solution of QLBM (20 μMs)2+Glimmering
Light emission spectrogram.Fig. 5 (b) shows and constantly drips Cu at QLBM (20 μMs) in Tris-HCl (50mM, pH 7.2) solution2+?
Fluorescent value at 508nm and Cu2+The titration curve of dropping concentration.Inner curve is QLBM fluorescent value and Cu2+The line of ion concentration
Property interval curve.Fig. 5 (c) shows and constantly drips Fe in Tris-HCl (50mM, the pH 7.2) solution of QLBM (20 μMs)3+'s
Fluorescent emission spectrogram.Fig. 5 (d) shows and constantly drips Fe at QLBM (20 μMs) in Tris-HCl (50mM, pH 7.2) solution3+
Fluorescent value at 508nm and Fe3+The titration curve of dropping concentration.Inner curve is QLBM fluorescent value and Fe3+Ion concentration
Linear zone half interval contour.
Fig. 6 (a) shows addition Fe in Tris-HCl (50mM, the pH 7.2) solution of QLBM (20 μMs)3+(200 μMs) from
After son, add again the change of the fluorescence emission spectrum figure after ascorbic acid (500 μMs).Fig. 6 (b) shows QLBM's (20 μMs)
Tris-HCl (50mM, pH 7.2) solution adds Cu2+After (200 μMs) ion, add again the fluorescence after ascorbic acid (500 μMs)
Emission spectra figure changes.Fig. 6 (c) shows and is comprising Cu2+(200 μMs) and Fe3+The Tris-HCl of the QLBM (20 μMs) of (200 μMs)
(50mM, pH 7.2) solution adds the fluorescent value of (508nm) time gradient at ascorbic acid (500 μMs) maximum emission wavelength afterwards
Change.Fig. 6 (d) shows addition Cu in Tris-HCl (50mM, the pH 7.2) solution of QLBM (20 μMs)2+(200 μMs) and Fe3 +(200 μMs) add the color change under ascorbic acid (500 μMs) ultra violet lamp afterwards.
Fig. 7 shows QLBM-CuCl2With 2 equivalent QLBM-FeCl3Mass spectral results.
Fig. 8 (a), Fig. 8 (b), Fig. 8 (c) respectively illustrate QLBM, QLBM-Cu of DFT computational analysis2+And QLBM-Fe3+'s
Optimization structure.
Fig. 9 shows the cytotoxicity of variable concentrations QLBM.
Figure 10 (a) is HeLa cell and 20 μMs of QLBM hatch the Laser Scanning Confocal Microscope imaging after 6h altogether.Figure 10 (b) is
After HeLa cell and 20 μMs of QLBM hatch 6h altogether, add 200 μMs of Cu2+Hatch the Laser Scanning Confocal Microscope imaging of 30min.Figure 10
C () is HeLa cell and after 20 μMs of QLBM hatch 6h altogether, add 200 μMs of Fe3+Hatch the Laser Scanning Confocal Microscope imaging of 30min.
Scale: 50 μm.
Detailed description of the invention
It is more fully described the present invention below with reference to accompanying drawings.
The present invention provides a kind of Cu based on chinoline backbone2+And Fe3+Double target spot fluorescent probes, this pair of target spot fluorescent probe
There is the structure shown in Formulas I:
The present invention provides the preparation method of above-mentioned pair of target spot fluorescent probe, and the method includes:
I (), in the presence of the first organic solvent, makes quinaldinic acid. react with oxalyl chloride, obtain compound shown in Formula II；
(ii) in the presence of the second organic solvent, make compound shown in Formula II react with 2-aminobenzimidazole, obtain Formulas I
Shown compound.
In accordance with the present invention it is preferred that, in step (i), quinaldinic acid. is 1:5-20 with the mol ratio of oxalyl chloride.
Described first organic solvent in step (i) can be the aprotic organic solvent that this area is conventional, preferably two
At least one in chloromethanes, toluene and normal hexane.It is further preferred that above-mentioned organic solvent is organic molten after dried
Agent.
Specifically, step (i) comprises the steps that
The oxalyl chloride being dissolved in the first organic solvent is added drop-wise in quinaldinic acid. solution, after mix homogeneously, in inertia
In the presence of gas, distillation stirring reaction.
Wherein, described quinaldinic acid. solution preferably quinaldinic acid. is dissolved in the first organic solvent the solution formed, quinoline
The concentration of which pyridine acid solution can determine as required.
Described dropping is carried out the most at low temperatures, such as condition of ice bath.
Described noble gas can be such as nitrogen.
Step (i) can also include the post-processing step of routine, such as, cool down, revolve steaming solvent etc..
According to the present invention, in step (ii), the mol ratio of compound shown in Formula II and 2-aminobenzimidazole is preferably 1:
1-2。
Described second organic solvent in step (ii) can be the aprotic organic solvent that this area is conventional, preferably two
At least one in chloromethanes, toluene and normal hexane.It is further preferred that above-mentioned organic solvent is organic molten after dried
Agent.
Preferably, step (ii) including: adds acid binding agent in reaction system.Described acid binding agent can be such as trimethylamine
Or triethylamine.
According to the present invention, the reaction condition of step (ii) preferably includes: temperature is-4 to 5 DEG C, and the time is 2-10h.
Step (ii) can also include the post-processing step of routine, such as, cool down, revolve steaming solvent, column chromatography etc..
The present invention also provides for the application in cell imaging of the above-mentioned double target spot fluorescent probes.
According to one preferred implementation of the present invention, synthesize fluorescent probe QLBM by two-step reaction design, synthesized
Journey is shown below:
Synthetic method: be dissolved in by quinaldinic acid. in dry dichloromethane, is then dissolved in dry dichloromethane by oxalyl chloride
In alkane, under condition of ice bath and magnetic agitation, oxalyl chloride solution is dripped in quinaldinic acid. solution, the most in a nitrogen environment
Distillation reaction.Subsequently, reactant liquor being cooled to room temperature, rotation is evaporated off solvent, obtains crude product quinaldine acyl chlorides (referred to as C2).
Then the product C2 obtained is joined in the dry dichloromethane mixed solution with trimethylamine with 2-aminobenzimidazole, stir
Mixing reaction, rotation is evaporated off solvent, and by silica gel column chromatography separating purification, obtains QLBM.
By following example, the present invention is further described.
Embodiment 1
Quinaldinic acid. (C1,0.38g, 2mM) is dissolved in dry dichloromethane (20mL) and joins the two-mouth bottle of 100mL
In, put into magnetic rotor.Then oxalyl chloride (2.60g, 20mM) is dissolved in the dry methylene chloride of 10mL, in condition of ice bath
Under drip in quinaldinic acid. solution, stir 30 minutes, the most in a nitrogen environment distillation stirring 5 hours.Subsequently, will reaction
Liquid is cooled to room temperature, and rotation is evaporated off solvent, obtains crude product quinaldine acyl chlorides (referred to as C2).Then by the product C2 that obtains with
2-aminobenzimidazole (0.27g, 2mM) joins the mixed solution in the dichloromethane that 30mL is dried with the trimethylamine of 0.1mL
In, stirring reaction 5 hours under the conditions of 0 DEG C, rotation is evaporated off solvent, and by silica gel column chromatography separating purification, obtains QLBM yellow
Color solid 0.42g, productivity is 73%.
Fig. 1 and Fig. 2 is respectively hydrogen spectrum and the carbon spectrum of QLBM.
Test case 1
The optical physics of 1QLBM characterizes
The absorption spectrogram of 1.1 test QLBM.Configure Tris-HCl (50mM, the pH 7.2) solution of the QLBM of 20 μMs, take 2mL
Add in quartz colorimetric utensil, use ultraviolet-visible spectrophotometer to test it and absorb spectrogram.
The fluorescent emission spectrogram of 1.2 test QLBM.Configure the QLBM solution of 20 μMs in 50mM Tris-HCl (pH 7.2),
Take 1mL to add in cuvette, spectrofluorophotometer is tested the fluorescent emission spectrogram of QLBM.Excitation wavelength is 370nm, sends out
Penetrate interval for 400-700nm.
Test case 2
The selectivity of different metal ion is studied by 2QLBM
The aqueous solution of the Tris-HCl (50mM, pH 7.2) of 2.1 configurations QLBM (20 μMs), adds in each cuvette
The solution of 1mL, is sequentially added into Na in each cuvette+, K+, Mg2+, Zn2+, Ca2+, Fe2+, Mn2+, Hg2+, Cd2+, Co2+, Al3+,
Pd2+, Cu2+, Fe3+Saline solution.Mix homogeneously after addition, in each ware, concentration of metal ions is Na+(500 μMs), K+(500 μMs), Mg2 +(500 μMs), Zn2+(500 μMs), Ca2+(500 μMs), Fe2+(500 μMs), Mn2+(500 μMs), Hg2+(500 μMs), Cd2+(500 μMs),
Co2+(500 μMs), Al3+(500 μMs), Pd2+(500 μMs) ion salt solution.
2.2 detections (excitation wavelength is 370nm) carrying out fluorescence intensity on spectrofluorophotometer.
2.3 gather and process data.
Test case 3
3Cu2+And Fe3+Titration experiments to QLBM
3.1 20 μMs of QLBM solution of configuration, solvent is 50mM Tris-HCl (pH 7.2), takes 1mL and adds in cuvette.
The CuCl of 3.2 configuration 10mM2And FeCl3Aqueous solution.
3.3 drip Cu in cuvette respectively2+, Cu2+Concentration range be 0～300 μM, on spectrofluorophotometer
Test fluorescent emission spectrogram successively.
3.4 same methods, test is added dropwise over Fe3+Fluorescent emission spectrogram.
3.5 gather and process data.
Test case 4
4 ascorbic acid are to Cu2+And Fe3+Differentiation
4.1 20 μMs of QLBM solution of configuration, solvent is 50mM Tris-HCl (pH 7.2), takes 1mL and is separately added into two ratios
In color ware.
4.2 Cu being separately added into 200 μMs2+And Fe3+Saline solution, tests fluorescent emission spectrogram.
4.3 are separately added into 500 μMs of ascorbic acid solutions then, mix homogeneously, the fluorescent emission collection of illustrative plates in record 1h, and every 10
Minute test once.
4.4 gather and process data.
Test case 5
5QLBM and Cu2+And Fe3+Mechanism of action analysis
5.1 configuration QLBM and the CuCl of two equivalents2And FeCl3Solution, carry out mass spectral analysis.
5.2 mass spectral analyses obtain QLBM and Cu2+/Fe3+In conjunction with ratio.
5.3 utilize Gauss 09 software to carry out density functional theory (DFT) computational analysis on computers.
Test case 6
6 cell culture processes
HeLa cell is positioned over 37 DEG C, and carbon dioxide content is in the incubator of 5%.Culture medium is containing 10%FBS's
RPMI-1640.Use when cell density about 90% pancreatin cell dissociation buffer to pass on, within average 2 days, pass on once.
Test case 7
7 cytotoxicity detections
Collecting logarithmic (log) phase HeLa cell, adjustment cell solution concentration is to 50000/mL, and in 96 orifice plates, every hole adds 100
μL.At 5%CO2, after the incubator overnight incubation of 37 DEG C, add the QLBM 100 μ L of variable concentrations gradient, make each gradient concentration
For (0,2 μM, 5 μMs, 10 μMs, 20 μMs, 50 μMs, 100 μMs).The multiple hole of each gradient five.After cultivating 24h, every hole adds 20 μ L's
The PBS solution (5mg/mL) of 3-(4,5-dimethylthiazole-2)-2,5-diphenyltetrazolium bromide bromide (MTT), hatches 4h altogether.Suck
Supernatant, every hole adds the DMSO of 150 μ L, puts low speed on shaking table and shakes 10 minutes, makes crystal fully dissolve.Examine at enzyme linked immunological
Survey the light absorption value measuring each hole at instrument OD 490nm.
Test case 8
8 cell imagings
8.1QLBM Yu HeLa cytosis imaging experiment.At the bottom of copolymerization Jiao's glass of HeLa passage to a diameter of 20mm
Culture dish, at 5%CO2, after the incubator of 37 DEG C cultivates 24h.Being added by QLBM in culture medium, the concentration of QLBM is 20 μMs, incubates
After educating 6h, remove culture fluid, with 1 × PBS cell six times.At Laser Scanning Confocal Microscope (Olympus FV1000-
IX81confocal laser scanning microscope) under observe.Exciting light selects mercury laser (72.0%
405nm)。
8.2 intracellular detection QLBM and Cu2+And Fe3+Cell imaging is tested.By HeLa passage to a diameter of 20mm
Culture dish at the bottom of copolymerization Jiao's glass, at 5%CO2, after the incubator of 37 DEG C cultivates 24h.QLBM is added in culture medium, the concentration of QLBM
It is 20 μMs, after hatching 6h, adds 200 μMs of Cu2+And Fe3+Culture fluid is removed, with 1 × PBS cell six after hatching 30min altogether
Secondary.See under Laser Scanning Confocal Microscope (Olympus FV1000-IX81confocal laser scanning microscope)
Survey.Exciting light selects mercury laser (72.0%405nm).
9 data and analysis
9.1QLBM uv absorption in Tris-HCl (50mM, pH 7.2) solution system and fluorescent emission spectrogram
As it is shown on figure 3, QLBM has the absorption region of 300～400nm.It it is its maximum emission wavelength at 508nm.
9.2QLBM uv absorption in Tris-HCl (50mM, pH 7.2) solution system and fluorescent emission spectrogram
As it is shown on figure 3, QLBM has the absorption region of 300～400nm.It it is its maximum emission wavelength at 508nm.
9.3QLBM studies with the selectivity of different metal ion
QLBM designs based on chinoline backbone, and the quinoline of its heterocyclic nitrogen atom can be as the chela of metal ion
Closing site, so the selectivity research carried out between QLBM and different metal ion, the present invention have chosen 14 kinds of common metal altogether
Ion (Na+, K+, Mg2+, Zn2+, Ca2+, Fe2+, Mn2+, Hg2+, Cd2+, Co2+, Al3+, Pd2+, Cu2+, Fe3+)。
As shown in Fig. 4 (a)-4 (d), after adding different metal ions, Cu2+And Fe3+The fluorescence display of QLBM is gone out
Significant cancellation, and other ions are not changed significantly.Corresponding therewith, QLBM-Cu under ultra violet lamp2+With
QLBM-Fe3+Fluorescence have a notable cancellation, and add the QLBM solution significantly color change of other ions.Other from
The QLBM solution of son is separately added into Cu then2+And Fe3+, the QLBM solution fluorescence of other ions shows obvious cancellation.With
Upper result explanation QLBM is to Cu2+And Fe3+There is special response, and under conditions of other ions exist, without interference with QLBM to Cu2 +And Fe3+Special response.
9.4Cu2+And Fe3+Titration experiments to QLBM
As shown in Fig. 5 (a)-5 (d), in Tris-HCl (50mM, the pH 7.2) solution system of QLBM (20 μMs), along with
Cu2+And Fe3+Dropping concentration be continuously increased, the fluorescent value at maximum emission wavelength (508nm) place of QLBM constantly declines, and works as Cu2+
And Fe3+Dropping concentration when reaching 200 μMs, the fluorescent value cancellation efficiency of QLBM reaches about 90%.Work as Cu2+And Fe3+Dropping dense
Spend when 0～50 μM, the maximum emission wavelength (508nm) of QLBM and Cu2+/Fe3+Dropping concentration present preferably linear.Logical
Crossing LOD=3*Sb/S and calculate its detection line, QLBM is to Cu2+Detection be limited to 1.35 × 10-7M, to Fe3+Detection be limited to 1.24
×10-7M.In Tris-HCl (50mM, the pH 7.2) solution system of QLBM (20 μMs), along with Cu2+And Fe3+Dropping concentration
Being continuously increased, the fluorescent value at maximum emission wavelength (508nm) place of QLBM constantly declines, and works as Cu2+And Fe3+Dropping concentration reach
During to 200 μMs, the fluorescent value cancellation efficiency of QLBM reaches about 90%.Work as Cu2+And Fe3+Dropping concentration when 0～50 μM,
The maximum emission wavelength (508nm) of QLBM and Cu2+/Fe3+Dropping concentration present preferably linear.Counted by LOD=3*Sb/S
Calculating its detection line, QLBM is to Cu2+Detection be limited to 1.35 × 10-7M, to Fe3+Detection be limited to 1.24 × 10-7M。
9.5 ascorbic acid (AA) are to Cu2+And Fe3+Differentiation
As shown in Fig. 6 (a)-6 (d), Cu2+And Fe3+QLBM is all demonstrated preferable quenching effects (cancellation rate～
90%), after then adding the ascorbic acid (500 μMs) of excess, QLBM-Fe3+Solution shows that obvious fluorescence is replied, and
QLBM-Cu2+Fluorescence there is no notable change.This has stronger reproducibility mainly due to ascorbic acid, it is possible to quickly by Fe3 +It is reduced to Fe2+.Showing according to Fig. 4 result, QLBM is to Fe2+Do not obvious response to.And ascorbic acid is to Cu2+Reduction need more
Harsh condition, thus QLBM-Cu2+Fluorescence there is no notable change.Solution colour under ultra violet lamp changes also with above-mentioned
Result is consistent.Ascorbic acid and Fe3+Reaction belong to redox reaction, this reaction needs the regular hour, again investigate
Ascorbic acid and Fe3+Action time, find after reaching 1h, fluorescence is returned to maximum.
9.6QLBM and Cu2+And Fe3+Study on mechanism
The mass spectral results of Fig. 7 (a)-7 (b) shows, m/z=289.1106 (value of calculation=289.1084) corresponds to [QLBM+
H]+, m/z=350.0238 (value of calculation=350.0218) corresponds to [QLBM+Cu2++ H]+, m/z=385.9989 (value of calculation=
385.9990) corresponding to [QLBM+Cu2++Cl-]+, m/z=378.0009 (value of calculation=378.0410) corresponds to [QLBM+Fe3+
+Cl-+OH-]+, m/z=396.0105 (value of calculation=396.0071) corresponds to [QLBM+Fe3++2OH-]+, m/z=413.9745
(value of calculation=413.9732) correspond to [QLBM+Fe3++2Cl-]+.Result display QLBM and Cu2+And Fe3+Combination ratio be 1:
1。
By DFT computational analysis, QLBM, QLBM and Cu2+And QLBM and Fe3+Binding site such as Fig. 8 (a), 8 (b) and figure
Shown in 8 (c).Cu2+With the N (1) in QLBM structure, N (2), Cl (3), the distance of Cl (4) atom is respectivelyWithFe3+With the N (1) in QLBM structure, N (2), Cl (3), Cl (4) atom
Distance is respectively WithIn figure, structure is QLBM,
QLBM-Cu2+Complex and QLBM-Fe3+The optimization structure of complex.
9.7 cell imaging
9.7.1 cytotoxicity
By the cytotoxicity of mtt assay research QLBM, as it is shown in figure 9, after hatching 24h when QLBM concentration reaches 20 μMs,
Cell survival rate reaches more than 90%.
9.7.2QLBM intracellular imaging
Result in Figure 10 (a)-10 (c) shows, carries out confocal microscopic image after HeLa cell is hatched altogether after 6h,
HeLa cell shows bright green fluorescence.After hatching 6h, it is separately added into 200 μMs of Cu2+Ion and 200 μMs of Fe3+Ion is laggard
Row confocal microscopic image, HeLa cell fluorescence compared with Figure 10 (a) presents obvious cancellation.Result display QLBM can act as
Intracellular image checking Cu2+And Fe3+。
Claims (10)
1. a Cu based on chinoline backbone2+And Fe3+Double target spot fluorescent probes, it is characterised in that this pair of target spot fluorescent probe tool
There is a structure shown in Formulas I:
2. the preparation method of the double target spot fluorescent probes described in claim 1, it is characterised in that the method includes:
I (), in the presence of the first organic solvent, makes quinaldinic acid. react with oxalyl chloride, obtain compound shown in Formula II；
(ii) in the presence of the second organic solvent, make compound shown in Formula II react with 2-aminobenzimidazole, obtain shown in Formulas I
Compound.
Method the most according to claim 2, wherein, in step (i), quinaldinic acid. is 1:5-with the mol ratio of oxalyl chloride
20。
Method the most according to claim 2, wherein, described first organic solvent is in dichloromethane, toluene and normal hexane
At least one.
Method the most according to claim 2, wherein, step (i) including:
The oxalyl chloride being dissolved in the first organic solvent is added drop-wise in quinaldinic acid. solution, after mix homogeneously, at noble gas
In the presence of, distillation stirring reaction.
Method the most according to claim 2, wherein, in step (ii), compound shown in Formula II and 2-aminobenzimidazole
Mol ratio be 1:1-2.
Method the most according to claim 2, wherein, described second organic solvent is in dichloromethane, toluene and normal hexane
At least one.
Method the most according to claim 2, wherein, step (ii) including: adds acid binding agent in reaction system.
Method the most according to claim 2, wherein, the reaction condition of step (ii) including: temperature is-4 to 5 DEG C, the time
For 2-10h.
10. the application in cell imaging of the double target spot fluorescent probes described in claim 1.
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| CN115772125A (en) * | 2022-11-30 | 2023-03-10 | 青海师范大学 | Benzoquinolinyl AIE fluorescent probe, preparation method and application thereof in Fe 3+ Applications in assays |
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