CN105669708A - Coumarin schiff-base copper ion complex-based fluorescent probe for thiol as well as preparation method and application thereof - Google Patents
Coumarin schiff-base copper ion complex-based fluorescent probe for thiol as well as preparation method and application thereof Download PDFInfo
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- CN105669708A CN105669708A CN201610030550.7A CN201610030550A CN105669708A CN 105669708 A CN105669708 A CN 105669708A CN 201610030550 A CN201610030550 A CN 201610030550A CN 105669708 A CN105669708 A CN 105669708A
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- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 26
- 235000001671 coumarin Nutrition 0.000 title claims abstract description 19
- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 17
- 229960000956 coumarin Drugs 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002262 Schiff base Substances 0.000 title claims abstract description 5
- 150000004753 Schiff bases Chemical class 0.000 title abstract 3
- 125000003396 thiol group Chemical class [H]S* 0.000 title 1
- 238000006177 thiolation reaction Methods 0.000 title 1
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 claims abstract description 55
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
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- -1 coumarin schiff-base Chemical class 0.000 claims abstract description 17
- 238000001514 detection method Methods 0.000 claims abstract description 13
- 238000003384 imaging method Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- PMWXGSWIOOVHEQ-UHFFFAOYSA-N pyridine-2,6-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=N1 PMWXGSWIOOVHEQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 5
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- 239000002253 acid Substances 0.000 claims description 11
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 claims description 10
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- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical class [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
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- FFFHZYDWPBMWHY-VKHMYHEASA-N L-homocysteine Chemical compound OC(=O)[C@@H](N)CCS FFFHZYDWPBMWHY-VKHMYHEASA-N 0.000 description 1
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- 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
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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Abstract
The invention discloses a coumarin schiff-base copper ion complex-based fluorescent probe for thiol as well as a preparation method and an application thereof. Coumarin hydrazide and 2,6-pyridinedicarboxaldehyde are used as raw materials for synthesis of a coumarin schiff-base derivative (a compound 1), the compound 1 and copper ions are coordinated in order to form the coumarin-copper ion complex with a schiff-base structure, and the compound 1-Cu<2+> is obtained. The probe ensures fluorescence quenching of the compound 1 due to influences of paramagnetism and chelation of Cu<2+>. When thiol-containing amino acids are added, fluorescence of the compound 1-Cu<2+> is enhanced. Other amino acids which do not contain thiols do not influence the fluorescence effects. UV-visible spectrum absorption and fluorescence spectrum show that the compound 1-Cu<2+> has good selectivity and sensitivity for thiol-containing amino acids in a CH3CN:HEPES(3:2,v/v) solution. The probe was successful to be applied to SiHa cells, and was used for carrying out cell imaging experiments of glutathione. The method is hopeful to be applied to detection of thiol compounds in organisms.
Description
Technical field
The present invention relates to application probe technology, be specifically related to a kind of based on coumarin Schiff's base copper ion coordination compound mercaptan fluorescent probe and its preparation method and application.
Background technology
Sulfydryl (-SH) is the group that in cell, chemism is significantly high. There is numerous protein and non-protein sulfhydryl compound in organism, such as reduced glutathion (GSH) and cysteine (CYS) etc., they have important physiological function. And the exception of these thiol levels is relevant with numerous disease. Glutathion is the mercaptan that intracellular level is the abundantest, as bioactive sulfhydryl compound important in body, glutathion plays vital effect in normal oxidation reduction reaction, the transduction of cell signal, gene regulation etc. in maintenance organism. The more important thing is, reduced glutathion can harmful poisonous substance in purged body and metabolite, maintaining the integrity of cell membrane, reducing the attack of radical pair DNA, thus reducing damage and the sudden change of DNA. Glutathion also participates in the reduction of metahemoglobin, and promotes the absorption etc. of ferrum. The concentration (1～10mM) of glutathion inside cell is significantly larger than extracellular levels (2uM). The generation of human body numerous disease is all relevant with the shortage of glutathion, as: hepatic injury, cancer, acquired immune deficiency syndrome (AIDS), neurodegenerative diseases etc. Therefore, quick and easy, measure glutathione content in organism accurately, delicately, enjoy the great attention of people all the time.
In various analysis methods, fluoroscopic examination, due to the characteristic such as imaging in it is simple, convenient, cost is low, highly sensitive and it is potential cell, has proved to be a kind of very useful detection method. At present, many organic reactions have been used for the synthesis of mercaptan fluorescent probe, as the cyclization between aldehyde and amino, Michael addition reaction, 2,4-dinitro benzenes react with the cracking reaction of mercaptan, nucleophilic substitution reaction, disulfide exchange, Cu2+Complex demetalization reaction etc.A kind of method is based on the molecular probe of chemodosimetric reaction, but this method needs longer incubation time, is generally 20 minutes to 1 hour even for more time, and practicality is relatively low. Another kind of method is to utilize Cu2+Fluorescent probe is designed with the high-affinity of-SH. This reaction mostly occurs within 1 millisecond, thus, it is expected that can be used for Clinical detection. Due to mercaptan and Cu2+Specificity affinity so that it is probe has higher sensitivity, also improves the method for probability that various fluorescent probes design simultaneously.
Coumarin is one of most popular fluorophor of fluorescence imaging probe. Due to they stronger fluorescence intensities, excellent dissolubility, efficient cell permeability and the advantage such as easily prepared so that it is become the Raw fluorescence material had a great attraction.
Summary of the invention
In order to solve the deficiencies in the prior art, the invention provides a kind of based on coumarin Schiff's base copper ion coordination compound mercaptan fluorescent probe and its preparation method and application, new fluorescent probe compounds 1-Cu2+. It is compound 2 (tonkabean hydrazides) as the compound 1 of precursor and 2,6-pyridine dicarbaldehyde are bound up. Compound 1 and Cu2+Coordination, prepares into compound 1-Cu2+. Compound 1 has stronger fluorescence, and compound 1-Cu2+Almost without fluorescence. When adding after containing mercaptoamino acid, compound 1-Cu2+Fluorescence recover, and add without after the aminoacid of sulfydryl, compound 1-Cu2+Fluorescence intensity almost without change. Therefore, compound 1-Cu2+Can be used for detecting mercaptan, for instance: such as glutathion. May apply even in cell imaging.
The technical scheme is that a kind of preparation method based on coumarin Schiff's base copper ion coordination compound mercaptan fluorescent probe, compound 2 i.e. tonkabean hydrazides and 2,6-pyridine dicarbaldehyde chemical combination prepare compound 1 i.e. Coumarins Schiff base derivatives, compound 1 and Cu2+Coordination, prepares into mercaptan fluorescent probe and compound 1-Cu2+。
Further improvement of the present invention includes:
The compound 2 (1.1mmol) of 0.3028g is dissolved in minimal amount of ethanol, adds 2, the 6-pyridine dicarbaldehyde (0.5mmol) of 0.0676g; Under nitrogen protection, it is heated to reflux 12 hours; Having Precipitation after cooling, the pure substance obtained is compound 1.
Another object of the present invention is to provide a kind of based on coumarin Schiff's base copper ion coordination compound mercaptan fluorescent probe, prepare according to above-mentioned method.
Present invention also offers a kind of application based on coumarin Schiff's base copper ion coordination compound mercaptan fluorescent probe, specifically the application in detection mercaptoamino acid.
Described application, the specifically application in detection glutathion.
Described application, the detection being particularly used in organism mercaptan compound.
Invention further provides a kind of application based on coumarin Schiff's base copper ion coordination compound mercaptan fluorescent probe, the application in living cells GSH-PX activity imaging.
Described application, the specifically application of imaging in human cervical cancer 1 squamous cell carcinoma.
The present invention tonkabean hydrazides and 2,6-pyridine dicarbaldehyde have synthesized a kind of new compound 1, as compound 1 and Cu2+After coordination, prepare mercaptan fluorescent probe, i.e. compound 1-Cu2+. Fluorescence spectrum test shows: at CH3In CN:HEPES (3:2, v/v) solution, mercaptan is had good selectivity and susceptiveness by this probe, especially to GSH. In addition, probe also has good cell membrane permeability and low cytotoxicity, can be used for GSH imaging in living cells, will be expected to the detection for GSH clinically.
Accompanying drawing explanation
Fig. 1 is at CH3In CN:HEPES (3:2, v/v) solution, along with Cu2+Addition, the ultraviolet spectra of compound 1 (10 μm of ol/L). Embed figure: at 440nm place, the UV, visible light spectra for titration of compound 1.
Fig. 2 is at CH3In CN:HEPES (3:2, v/v) solution, along with Cu2+Addition, the fluorescence spectrum of compound 1 (10 μm of ol/L). Embed figure: at 485nm place, the fluorescence titration spectrum (exciting: 440nm) of compound 1.
Fig. 3 is at CH3In CN:HEPES (3:2, v/v) solution, along with the addition of GSH, compound 1-Cu2+The fluorescence response of (10 μm of ol/L). Embed figure: at 485nm place, compound 1-Cu2+Fluorescence titration spectrum (exciting: 440nm).
Fig. 4 is compound 1-Cu2+The fluorescence response intensity of different aminoacids (is launched: 485nm) by (10 μm of ol/L). First hurdle represents the fluorescence intensity after adding different aminoacids; Second hurdle represents the fluorescence intensity after being simultaneously introduced GSH and non-mercaptoamino acid.
Fig. 5 a is in SiHa cell, the fluorescence imaging of compound 1.
Fig. 5 b is in SiHa cell, compound 1-Cu2+Fluorescence imaging.
Fig. 5 c is in SiHa cell, compound 1-Cu2+The fluorescence imaging of+GSH.
Fig. 5 d is in SiHa cell, the light field of compound 1.
Fig. 5 e is in SiHa cell, compound 1-Cu2+Light field.
Fig. 5 f is in SiHa cell, compound 1-Cu2+The light field of+GSH.
Fig. 6 is the hydrogen spectrum of compound 1.
Fig. 7 is the carbon spectrum of compound 1.
Fig. 8 is the mass spectrum of compound 1.
Fig. 9 is that compound 1 (10 μm of ol/L) is at CH3In CN:HEPES (3:2, v/v) solution, the ultraviolet-visible absorption spectroscopy to each metal ion species.
Figure 10 is that compound 1 (10 μm of ol/L) is at CH3In CN:HEPES (3:2, v/v) solution, the fluorescence spectrum of each metal ion species is responded.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention is elaborated.
Embodiment 1
Reagent
4-diethylamino salicylide, diethyl malonate, piperidines, 80% hydrazine hydrate, 2,6-pyridine dicarbaldehyde, the perchlorate (Cr of each metal ion species3+,Ag+,Fe3+,K+,Na+,Mg2+,Pb2+,Ca2+,Hg2+,Mn2+,Cd2+,Fe2+,Zn2+,Ni2+,Co2+,Cu2+) aqueous solution (2.0 × 10-2M), various amino acid whose aqueous solutions (2.0 × 10-2M), dehydrated alcohol, acetonitrile (chromatographically pure), dimethylformamide (analytical pure), HEPES (pH:7.35-7.45) solution etc.
Building-up process
Shown in building-up process formula 1: 7-N, N-dimethylamino-2-oxygen-2H-3-tonkabean acid esters (compound 3) and compound 2 are prior art synthesis. Compound 1 is to be synthesized by compound 2 and 2,6-pyridine dicarbaldehyde, and is undertaken characterizing (Fig. 6,7,8) by hydrogen spectrum, carbon spectrum, mass spectrum. Compound 1-Cu2+It is by compound 1 and Cu (ClO4)2·6H2Prepared by O.
Compound 1 is to Cu2+Ultravioletvisible absorption and fluorescence spectrum response
At CH3In CN:HEPES (3:2, v/v) solution, the ultraviolet-visible absorption spectroscopy of compound 1 (10 μm of ol/L) is as it is shown in figure 1, maximal ultraviolet absorption is at 440nm place. Along with Cu (ClO4)2·6H2The addition of O, the uv-vis spectra of compound 1 absorbs and weakens gradually, and obvious red shift occurs in maximum absorption band. As the Cu adding 6 times amount2+After, the ultraviolet titration of compound 1 reaches balance. At CH3In CN:HEPES (3:2, v/v) solution, compound 1 (10 μm of ol/L) is to the ultraviolet-visible absorption spectroscopy of each metal ion species as shown in Figure 9. Only Cu2+The ultravioletvisible absorption of compound 1 is had response, and other metal ions are almost without interference.
At CH3In CN:HEPES (3:2, v/v) solution, along with Cu2+Addition, the fluorescence titration spectrum of compound 1 (10 μm of ol/L) is as shown in Figure 2.Exciting with 440nm, compound 1 demonstrates very strong fluorescence emission peak at 485nm place. Along with Cu2+Addition, fluorescence intensity weakens gradually. When adding 4 times amount Cu2+After, tend to balance. Mercaptan probe (compound 1-Cu2+) it is by compound 1 and 4 times amount Cu2+In conjunction with what be prepared from. Compound 1-Cu2+Low fluorescence intensity be likely to be copper ion by PET mechanism or the result of paramagnetism Quenching mechanism quenching effect. Compound 1 is to the fluorescence response of each metal ion species as shown in Figure 10.
Probe (compound 1-Cu2+) fluorescence spectrum of mercaptan is responded
Along with the addition of mercaptan such as glutathion, due to the demetalization of mercaptan, mercaptan probe (compound 1-Cu2+) release compound 1, fluorescence recovers gradually, as shown in Figure 3. At CH3In CN:HEPES (3:2, v/v) solution, along with the addition of glutathion, compound 1-Cu2+Fluorescence intensity be gradually increased, after adding 2 times amount GSH, tend to balance. Therefore compound 1-Cu2+On fluorescence response, can be used for detecting mercaptan.
In order to explore compound 1-Cu further2+Mercaptan is had high selectivity, has carried out compound 1-Cu2+(10μmol/L,CH3CN:HEPES=3:2, v/v) with other amino acid whose fluorescence spectrum experiments being likely to affect fluorescence intensity. As shown in Figure 4. Mercaptan probe (compound 1-Cu2+) self fluorescence intensity is very weak, when the mercaptoamino acid being separately added into 2 times amount, such as L-homocysteine, Cys and GSH, fluorescence intensity is remarkably reinforced, and wherein GSH Fluorescence Increasing is the most obvious. As comparison, when being separately added into the non-mercaptoamino acid of 2 times amount, fluorescence intensity does not have significant change. But, after adding non-mercaptoamino acid, continuously adding the GSH of same equimultiple, fluorescence intensity is remarkably reinforced. Show compound 1-Cu2+Mercaptan is spectrally had special response, and this specific response of mercaptan is not competed amino acid whose interference by other. More than experiment proves compound 1-Cu2+Mercaptoamino acid is had good selectivity.
Probe (compound 1-Cu2+) fluorescence imaging to glutathion
It is extremely important that cell is carried out detection by living cells imaging by fluorescent probe. Intrauterine device bleeding achieves compound 1-Cu2+Fluorescence imaging experiments to GSH. Before fluorescence imaging, SiHa cell is cultivated 12 hours in 12 well culture plates. Then, compound 1 (3 μMs) and cell are hatched 60 minutes at 37 DEG C, rinse twice with PBS. Observing (blue-light excited) under NikonEclipseTE2000-S inverted fluorescence microscope, compound 1 demonstrates green fluorescence (Fig. 5 a) in obvious cell at SiHa cell. This shows, compound 1 has cell permeability. When compound 1 adds 4 times amount Cu2+After, green fluorescence cancellation (Fig. 5 b). But, after adding 3 times amount GSH, intensity of cellular fluorescence recovers (Fig. 5 c) gradually. In whole experimentation (about 1～2 hour), cells survival is in good condition, has visualization, it does not have significantly Side effect. Fluorescence imaging experiments shows mercaptan fluorescent probe (compound 1-Cu2+) can be used for the detection of GSH in living cells.
Fig. 5 is in SiHa cell, compound 1 (a), compound 1-Cu2+(b), compound 1-Cu2+The fluorescence imaging of+GSH (c) and they corresponding light fields (d-f).
Embodiment 2
Building-up process
The synthesis of compound 3 (7-N, N-dimethylamino-2-oxygen-2H-3-tonkabean acid esters)
4-diethylamino salicylide (7.72g, 0.04mol), diethyl malonate (12.8g, 12.16mL, 0.08mol) and piperidines (4mL) are mixed in dehydrated alcohol (120mL).Mixed liquor refluxes 6 hours under agitation. Being cooled to room temperature, rotation is steamed and is no longer steamed to alcohol solvent, obtains a small amount of oily liquids and is compound 3.
The synthesis of compound 2 (tonkabean hydrazides)
The compound 3 (7-N, N-dimethylamino-2-oxygen-2H-3-tonkabean acid esters, 15mmol) weighing 4.3400g is dissolved in 40 milliliters of ethanol, adds 80% hydrazine hydrate (density=1.032g/ml, 60mmol) of 3.6381 milliliters. After being stirred at room temperature 12 minutes, frozen water cools down 15 minutes. Gained precipitation sucking filtration, obtains product Compound 2 (tonkabean hydrazides).
The synthesis of compound 1
The compound 2 (tonkabean hydrazides, 1.1mmol) of 0.3028g is dissolved in minimal amount of ethanol, adds 2, the 6-pyridine dicarbaldehyde (0.5mmol) of 0.0676g. Under nitrogen protection, it is heated to reflux 12 hours. Precipitation is had, thin-layer chromatographic analysis inspection purity after cooling. The pure substance obtained is compound 1.
In a word, a kind of new compound 1 has been synthesized by tonkabean hydrazides and 2,6-pyridine dicarbaldehyde, as compound 1 and Cu2+After coordination, prepare mercaptan fluorescent probe, i.e. compound 1-Cu2+. Fluorescence spectrum test shows: at CH3In CN:HEPES (3:2, v/v) solution, mercaptan is had good selectivity and susceptiveness by this probe, especially to GSH. In addition, probe also has good cell membrane permeability and low cytotoxicity, can be used for GSH imaging in living cells, will be expected to the detection for GSH clinically.
The ultimate principle of the present invention and principal character and advantages of the present invention have more than been shown and described. Skilled person will appreciate that of the industry; the present invention is not restricted to the described embodiments; described in above-described embodiment and description is that principles of the invention is described; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements both fall within the claimed scope of the invention. Claimed scope is defined by appending claims and equivalent thereof.
Claims (8)
1. the preparation method based on coumarin Schiff's base copper ion coordination compound mercaptan fluorescent probe, it is characterised in that compound 2 i.e. tonkabean hydrazides and 2,6-pyridine dicarbaldehyde chemical combination prepare compound 1 i.e. Coumarins Schiff base derivatives, compound 1 and Cu2+Coordination, prepares into mercaptan fluorescent probe and compound 1-Cu2+。
2. a kind of preparation method based on coumarin Schiff's base copper ion coordination compound mercaptan fluorescent probe according to claim 1, it is characterized in that, the compound 2 (1.1mmol) of 0.3028g is dissolved in minimal amount of ethanol, add 2, the 6-pyridine dicarbaldehyde (0.5mmol) of 0.0676g; Under nitrogen protection, it is heated to reflux 12 hours; Having Precipitation after cooling, the pure substance obtained is compound 1.
3. one kind based on coumarin Schiff's base copper ion coordination compound mercaptan fluorescent probe, it is characterised in that prepare in accordance with the method for claim 1.
4. the application based on coumarin Schiff's base copper ion coordination compound mercaptan fluorescent probe, it is characterised in that the application in detection mercaptoamino acid.
5. application according to claim 4, it is characterised in that the application in detection glutathion.
6. application according to claim 4, it is characterised in that for the detection of mercaptan compound in organism.
7. the application based on coumarin Schiff's base copper ion coordination compound mercaptan fluorescent probe, it is characterised in that the application in living cells GSH-PX activity imaging.
8. application according to claim 7, it is characterised in that the application of imaging in human cervical cancer 1 squamous cell carcinoma.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948287A (en) * | 2006-11-09 | 2007-04-18 | 上海大学 | Acetyl-2,6-dimethyl pyridine-3,5-diethyl ketone hydrazone and its synthesis method |
| CN104774607A (en) * | 2015-04-24 | 2015-07-15 | 济南大学 | Fluorescent probe for specially identifying bivalent copper ions in water phase and application thereof |
| CN104961647A (en) * | 2015-06-26 | 2015-10-07 | 西北师范大学 | Fluorescent recognition cupper ion (CU2+) sensor molecules and composition and application thereof |
-
2016
- 2016-01-18 CN CN201610030550.7A patent/CN105669708B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1948287A (en) * | 2006-11-09 | 2007-04-18 | 上海大学 | Acetyl-2,6-dimethyl pyridine-3,5-diethyl ketone hydrazone and its synthesis method |
| CN104774607A (en) * | 2015-04-24 | 2015-07-15 | 济南大学 | Fluorescent probe for specially identifying bivalent copper ions in water phase and application thereof |
| CN104961647A (en) * | 2015-06-26 | 2015-10-07 | 西北师范大学 | Fluorescent recognition cupper ion (CU2+) sensor molecules and composition and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 赵秀文等: "基于香豆酰肼的高选择性的铜离子荧光探针", 《发光学报》 * |
| 齐德强等: "香豆素席夫碱的合成及光谱性质研究", 《广州化工》 * |
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