CN107365326A - It is a kind of to be used to detect fluorescence probe of fluorine ion and preparation method thereof in living cells - Google Patents
It is a kind of to be used to detect fluorescence probe of fluorine ion and preparation method thereof in living cells Download PDFInfo
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- CN107365326A CN107365326A CN201710606941.3A CN201710606941A CN107365326A CN 107365326 A CN107365326 A CN 107365326A CN 201710606941 A CN201710606941 A CN 201710606941A CN 107365326 A CN107365326 A CN 107365326A
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 55
- 239000000523 sample Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 230000004044 response Effects 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 20
- 238000001514 detection method Methods 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- PXBFMLJZNCDSMP-UHFFFAOYSA-N 2-Aminobenzamide Chemical class NC(=O)C1=CC=CC=C1N PXBFMLJZNCDSMP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical compound CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 230000005281 excited state Effects 0.000 abstract description 3
- 125000000037 tert-butyldiphenylsilyl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1[Si]([H])([*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 230000000903 blocking effect Effects 0.000 abstract description 2
- 238000004440 column chromatography Methods 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 230000006698 induction Effects 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 21
- 238000003384 imaging method Methods 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000000799 fluorescence microscopy Methods 0.000 description 3
- 238000001727 in vivo Methods 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 229910018557 Si O Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 208000004042 dental fluorosis Diseases 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- -1 fluorine ions Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000035479 physiological effects, processes and functions Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 206010016818 Fluorosis Diseases 0.000 description 1
- 229920002683 Glycosaminoglycan Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- GCSVCUMDOQKEMT-UHFFFAOYSA-N butan-1-amine;hydrofluoride Chemical compound [H+].[F-].CCCCN GCSVCUMDOQKEMT-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000003501 co-culture Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 150000001893 coumarin derivatives Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- BVBRZOLXXOIMQG-UHFFFAOYSA-N fluoroborane Chemical compound FB BVBRZOLXXOIMQG-UHFFFAOYSA-N 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000001575 pathological effect Effects 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 108010048734 sclerotin Proteins 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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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
- G01N21/6486—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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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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
- C09K2211/10—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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biomedical Technology (AREA)
- Materials Engineering (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analysing Biological Materials (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
It is used to detect fluorescence probe of fluorine ion and preparation method thereof in living cells the invention discloses a kind of.The fluorescence probe has the structure shown in Formulas I; the probe itself is almost without any fluorescence; but under fluorine ion induction; Si O keys are broken, and take off TBDPS blocking groups, generate phenolic hydroxyl group; discharge HPQ; excited state intramolecular proton transfer effect thus occurs, produces the phenomenon that fluorescence greatly strengthens, so as to realize that " turn on " detect the strategy of fluorine ion to fluorescence.When fluorine ion is in low concentration 20uM, under ultra violet lamp, the phenomenon of fluorescence probe enhancing can be observed visually;The probe has good bio-compatibility, energy permeation cell film, with reference to laser confocal microscope, it may be observed that it produces response to the horizontal fluorine ion of micromole's level in living cells.In addition, synthetic method of the present invention is simple, post processing is easy, without being purified through column chromatography, the final product with regard to higher yields can be obtained.
Description
Technical field
It is used to detect fluorescence probe of fluorine ion and preparation method thereof in living cells the present invention relates to a kind of, belongs to fluorescence spy
Pin field.
Background technology
All played an important role in the various physiology courses of anion in vivo.Especially fluorine ion, it is even more
Indispensable a kind of micro ion in human life activity.Effect of the fluorine ion to human body is a double-edged sword:When appropriate
It is a kind of required micro ion, but it is excessive when it has toxic action again.Such as:Appropriate fluoride is dredged available for sclerotin
The treatment of loose disease and the health care of tooth;However, excessive fluorine ion is then easily caused, den tal fluorosis, fluorosis of bone, IQ reduce, enzyme loses
It is living, or even cause kidney, stomach and intestine and immune system equivalent damage.In addition, fluoride can also cause collagen and mucopolysaccharide to be metabolized
Change etc..Although the chemical constitution for fluorine ion is it has become clear that many on fluorine ion in organism
The problem of dynamic equilibrium and physiological action, does not understand still.At present, in organism the trace detection of fluorine ion and correlation physiology,
New method is developed in pathological study all an urgent demands, to monitor the dynamic change of fluorine ion in organism.Meanwhile to intracellular fluorine
Ion is monitored in real time, is also beneficial to study accumulation, metabolism and the conversion of fluorine ion in vivo.Fluorescence probe in recent years
Related research work is just being carried out like a raging fire, and it provides a kind of quick, easy and intuitively analysis method to people.Such as
If " visualization " of fluorine ion can be realized in living cells, there will be very extensive application prospect.Therefore, exploitation is a kind of high
Selectivity, in high-sensitivity detection living cells the fluorescence probe of fluorine ion become there is an urgent need to.
In the fluorescence probe for several detection fluorine ions being reported, a part is using in pyrroles or urea group
N-H and fluorine ion form the mechanism of hydrogen bond action to realize the identification to fluorine ion, but in this case, formed
The power of hydrogen bond and its influence that solvent effect is highly prone to the selectively acting of fluorine ion;For another part probe,
The strong affinity between fluoro- boron, fluoro- silicon is based primarily upon to realize the identification to fluorine ion.Such as:Tae-Hyun Kim etc. are reported
A series of probe of coumarin derivatives alternatively property identification fluorine ion;They, which design, has synthesized a series of semi-conductive polymerics
Thing, using the amplification of semi-conducting polymer with reach improve detection sensitivity purpose.It is well known that polymer
Cell membrane penetration is poor, significantly limit the fluorescence imaging of fluorine ion in living cells.Untill the present, organism can be suitably used for
The Small-molecule probe of interior fluorine ion detection and imaging is also rarely reported always.
(the 3H)-quinazolinones (HPQ) of 2- (2 '-hydroxy phenyl) -4 are a kind of probes with a variety of outstanding photoluminescent properties.
Such as:With larger stoke displacements, the Accurate Analysis available for determinand;It is prone to excited state intramolecular proton transfer
Effect, fluorescence " turn-on " strategy is realized, background signal is low, can reduce and repeatedly be washed in spectrofluorimetry and cell imaging
The step of washing probe, it enormously simplify detecting step;With the effect for focusing on induced luminescence, more conducively determinand in cell imaging
Precise positioning;Simultaneously also there is two-photon fluorescence property, presented in cell imaging and living imaging penetration power it is extremely strong, damage
Hinder small advantage.In consideration of it, how to utilize the advantage of HPQ fluorescent parent rings, the fluorescence imaging of fluorine ion in living cells is realized, into
The problem of thinking deeply for us.
The content of the invention
The primary and foremost purpose of the present invention is to provide a kind of fluorescence probe for being used to detect fluorine ion in living cells.
The secondary objective of the present invention is the preparation method for providing above-mentioned fluorescence probe.
The secondary objective of the present invention is to provide application of the above-mentioned fluorescence probe in fluorine ion detection field.
Technical scheme provided by the invention is specific as follows:
A kind of fluorescence probe for being used to detect fluorine ion in living cells, has the structure shown in Formulas I:
(abbreviation HPQF).
A kind of method for preparing above-mentioned fluorescence probe, comprises the following steps:By compound a and 2- aminobenzamides together
It is dissolved in methanol, is stirred 10 minutes prior to 0 DEG C, reheat backflow 30 minutes;Then para toluene sulfonamide is added, continues backflow 1
Hour;After question response liquid is cooled to room temperature, DDQ is added, is stirred overnight, filtered, gained filter residue is above-mentioned glimmering
Light probe;Described compound a is
Preferably, the mole dosage of compound a, 2- aminobenzamides, para toluene sulfonamide and DDQ
For 1:1:0.1:1.
Application of the above-mentioned fluorescence probe in fluorine ion detection field.
The purposes of fluorine ion in above-mentioned fluorescence probe detection living cells.
The present invention principle be:The present invention, with reference to the structure of HPQ parent rings, synthesizes target by the method for organic synthesis
Compound HPQF;Now, HPQF is broken Si-O keys, takes off TBDPS almost without any fluorescence, but under fluorine ion induction
Blocking group, phenolic hydroxyl group is generated, discharge HPQ, therefore excited state intramolecular proton transfer effect occurs, produced fluorescence and greatly increase
Strong phenomenon, so as to realize the strategy of fluorescence " turn-on " detection fluorine ion.
The present invention has advantages below and beneficial effect:
1. the present invention has synthesized the fluorescence probe HPQF for detecting fluorine ion in living cells first, synthetic method is simple,
Post processing is easy, without being purified through column chromatography, the final product with regard to higher yields can be obtained.
2. present invention firstly discovers that the mechanism that HPQF responds to fluorine ion, is broken by Si-O keys, TBDPS guarantors are sloughed
Shield, generate the compound HPQ of Fluorescence Increasing.
3. the present invention realizes the Visual retrieval of fluorine ion.When fluorine ion is in low concentration 20uM (0.38mg/L),
Under ultra violet lamp, the phenomenon of Fluorescence Increasing can be observed visually (see Fig. 2).According to National Industrial wastewater discharge standard, fluorine
Ion concentration should be less than 10mg/L;For drinking water, fluorinion concentration requirement is in below 1mg/L.Therefore, the detection of the compound
Lower limit can fully meet industrial wastewater and the exceeded testing conditions of fluoride ion in drinking water.
4. the present invention realizes the fluorescence imaging (see Fig. 3) of fluorine ion in living cells, with reference to HPQ itself two-photon
Matter, by for cell or in vivo the fluorescence monitoring of fluorine ion provides new thinking.
Brief description of the drawings
Fig. 1 is the principle of luminosity schematic diagram that compound HPQF detects fluorine ion.
Fig. 2 is the fluorescent spectrum curve that compound HPQF responds to fluorine ion;Wherein ,-F-Represent fluoride-free solution ,+F-
Represent solution of the fluorinion concentration as 20uM.
Fig. 3 is the cell imaging figure that compound HPQF detects fluorine ion in living cells;Wherein, Fig. 3 (A) represents blank control
Group, Fig. 3 (B) represent experimental group.
Embodiment
Technical scheme is further described with instantiation below.
Embodiment 1:Compound HPQF synthesis
Compound a (550.6mg) and 2- aminobenzamides (177.3mg) are together dissolved in 40mL methanol, prior to 0 DEG C
Lower stirring 10 minutes, then flow back 30 minutes;Then para toluene sulfonamide (20mg) is added, continues backflow 1 hour;Question response liquid is cold
But to after room temperature, DDQ (270.8mg) being added, is stirred overnight, filtered, gained filter residue is compound HPQF,
Yield 70%.
1H NMR(300MHz,CDCl3)δ(ppm):10.96 (s, 1H), 8.53 (d, J=6.99Hz, 1H), 8.29 (d, J=
7.86Hz, 1H), 7.77~7.70 (m, 6H), 7.48~7.35 (m, 8H), 7.20~7.13 (m, 3H), 7.07 (d, J=
8.31Hz, 1H), 6.81 (d, J=8.37Hz, 2H), 5.19 (s, 2H), 1.11 (s, 9H)13C NMR(75MHz,CDCl3)δ
(ppm):161.69,157.05,156.05,150.88,149.43,135.60,134.45,133.08,132.73,131.58,
130.03,128.92,127.90,127.65,126.48,126.47,122.14,121.36,120.54,120.34,113.91,
71.55,26.57.ESI-HRMSC37H34N2O3Si[M+Na]+Theoretical values:605.22309, actual numerical value:605.22552
Both are consistent substantially.
Embodiment 2:Compound HPQF vitro detection fluorine ions
Compound HPQF is dissolved in DMSO, solution (20-200uM) 1uL of various concentrations is configured to, then adds by four
The fluoride solution (0-2000uM) for the various concentrations that butyl ammonium fluoride (TABF) is formulated, after waiting 0-10 minutes, set
Excitation wavelength 405nm, collect the fluorescence signal intensity at wavelength 470-530nm.When fluorinion concentration is in 20uM, can just observe
To obvious fluorescence " turn-on " effect.
Embodiment 3:Fluorine ion in compound HPQF detection living cells
First by HepG2 passage culture 2-10 hours, if experimental group adds fluoride solution and co-cultures 1-6 hours, if
Blank control group and the contrast solution co-cultivation 1-6 hours for being not added with fluorine ion;Then washed repeatedly with a large amount of PBS solutions
HepG2 cells are multiple, fully wash away extracellular free fluorine ion;Add compound HPQF (20-200uM) and be incubated 0.5- altogether
3 hours, pass through the fluorescence intensity of two groups of cells of confocal laser scanning microscope.Experimental result is as shown in figure 3, and blank control
Group is compared, and experimental group visual field fluorescence intensity is remarkably reinforced, and is shown that compound HPQF has good cell membrane penetration, can be applied
In the dynamic monitoring of fluorinion concentration in living cells.
Claims (5)
1. a kind of fluorescence probe for being used to detect fluorine ion in living cells, it is characterised in that there is the structure shown in Formulas I:
A kind of 2. method for preparing the fluorescence probe described in claim 1, it is characterised in that comprise the following steps:By compound a
Together it is dissolved in 2- aminobenzamides in methanol, is stirred 10 minutes prior to 0 DEG C, reheat backflow 30 minutes;Then addition pair
Toluenesulfonamide, continue backflow 1 hour;After question response liquid is cooled to room temperature, DDQ is added, is stirred overnight, takes out
Filter, gained filter residue is the fluorescence probe described in claim 1;Described compound a is
3. according to the method for claim 2, it is characterised in that:Compound a, 2- aminobenzamides, para toluene sulfonamide
Mole dosage with DDQ is 1:1:0.1:1.
4. fluorescence probe described in claim 1 is in the application of fluorine ion detection field.
5. the purposes of fluorine ion in the fluorescence probe detection living cells described in claim 1.
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Cited By (2)
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CN108623624A (en) * | 2018-06-12 | 2018-10-09 | 兰州大学 | A method of differentiating toothpaste with fluoride with probe S-F bore holes |
CN110373181A (en) * | 2019-07-09 | 2019-10-25 | 济南大学 | A kind of fluorescence probe detecting fluorine ion |
Citations (3)
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CN108623624A (en) * | 2018-06-12 | 2018-10-09 | 兰州大学 | A method of differentiating toothpaste with fluoride with probe S-F bore holes |
CN110373181A (en) * | 2019-07-09 | 2019-10-25 | 济南大学 | A kind of fluorescence probe detecting fluorine ion |
CN110373181B (en) * | 2019-07-09 | 2021-05-04 | 济南大学 | Fluorescent probe for detecting fluorine ions |
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