CN105669708B - One kind is based on cumarin schiff bases copper ion complex mercaptan fluorescence probe and its preparation method and application - Google Patents
One kind is based on cumarin schiff bases copper ion complex mercaptan fluorescence probe and its preparation method and application Download PDFInfo
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- CN105669708B CN105669708B CN201610030550.7A CN201610030550A CN105669708B CN 105669708 B CN105669708 B CN 105669708B CN 201610030550 A CN201610030550 A CN 201610030550A CN 105669708 B CN105669708 B CN 105669708B
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000000523 sample Substances 0.000 title claims abstract description 30
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 13
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000002262 Schiff base Substances 0.000 title claims abstract description 12
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 title claims abstract description 11
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 150000004753 Schiff bases Chemical class 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 229940125904 compound 1 Drugs 0.000 claims abstract description 35
- 239000010949 copper Substances 0.000 claims abstract description 15
- PMWXGSWIOOVHEQ-UHFFFAOYSA-N pyridine-2,6-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=N1 PMWXGSWIOOVHEQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229940125782 compound 2 Drugs 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- 229960003180 glutathione Drugs 0.000 abstract description 31
- -1 Coumarins Schiff base Chemical class 0.000 abstract description 17
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 abstract description 14
- 239000007995 HEPES buffer Substances 0.000 abstract description 14
- 108010024636 Glutathione Proteins 0.000 abstract description 13
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- 239000002253 acid Substances 0.000 abstract description 12
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- 206010008342 Cervix carcinoma Diseases 0.000 abstract description 2
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- 201000010881 cervical cancer Diseases 0.000 abstract description 2
- 235000001671 coumarin Nutrition 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
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- 238000002371 ultraviolet--visible spectrum Methods 0.000 abstract description 2
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- 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 description 6
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- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003834 intracellular effect Effects 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-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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- 231100000277 DNA damage Toxicity 0.000 description 1
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 1
- FFFHZYDWPBMWHY-UHFFFAOYSA-N L-Homocysteine Natural products OC(=O)C(N)CCS FFFHZYDWPBMWHY-UHFFFAOYSA-N 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- 235000013878 L-cysteine Nutrition 0.000 description 1
- FFFHZYDWPBMWHY-VKHMYHEASA-N L-homocysteine Chemical compound OC(=O)[C@@H](N)CCS FFFHZYDWPBMWHY-VKHMYHEASA-N 0.000 description 1
- 108010061951 Methemoglobin Proteins 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
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- 125000002228 disulfide group Chemical group 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 231100000753 hepatic injury Toxicity 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
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- 230000037041 intracellular level Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000003068 molecular probe Substances 0.000 description 1
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- 230000004770 neurodegeneration Effects 0.000 description 1
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- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
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- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000019491 signal transduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 238000005303 weighing 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
- 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
-
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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- General Health & Medical Sciences (AREA)
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- Pathology (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention discloses one kind based on cumarin schiff bases copper ion complex mercaptan fluorescence probe and its preparation method and application, wherein with tonka-bean hydrazides and 2,6- pyridine dicarbaldehyde is a kind of Coumarins Schiff base derivatives (compound 1) of Material synthesis, compound 1 forms Coumarins-copper ion complex of schiff base structure, as (compound 1-Cu after being coordinated with copper ion2+).The probe is due to Cu2+Paramagnetism and chelation influence, make 1 fluorescent quenching of compound.After mercaptoamino acid is added, compound 1-Cu2+Fluorescence enhancement.And other non-mercaptoamino acids have little influence on.Uv-vis spectra absorbs and fluorescence spectrum shows compound 1-Cu2+In CH3The amino acid containing sulfydryl is had good selectivity in CN:HEPES (3:2, v/v) solution and sensitivity.The present invention is used successfully in human cervical cancer 1 squamous cell carcinoma, has carried out the cell imaging experiment of detection glutathione.It is expected to be used for the detection of mercaptan compound in organism.
Description
Technical field
The present invention relates to application probe technologies, and in particular to one kind is glimmering based on cumarin schiff bases copper ion complex mercaptan
Light probe and its preparation method and application.
Background technique
Sulfydryl (- SH) is the very high group of chemical activity in cell.There are many protein and nonproteins in organism
Sulfhydryl compound, such as reduced glutathione (GSH) and cysteine (CYS), they have important physiological function.And this
The exception of a little thiol levels is related with many diseases.Glutathione is the most abundant mercaptan of intracellular level, as weight in body
The bioactive sulfhydryl compound wanted, glutathione maintain organism in normal oxidation reduction reaction, cell signal transduction,
Gene regulation etc. plays vital effect.Importantly, reduced glutathione can be removed and intracorporal have
Evil poisonous substance and metabolite, maintains the integrality of cell membrane, reduces attack of the free radical to DNA, thus reduce DNA damage and
Mutation.Glutathione also participates in the reduction of ferrihemoglobin, and promotes the absorption etc. of iron.Glutathion inside cell it is dense
Degree (1~10mM) is significantly larger than extracellular levels (2uM).The generation of many diseases of human body is all related with the shortage of glutathione,
Such as: hepatic injury, cancer, AIDS, neurodegenerative disease.Therefore, quick and easy, accurate, delicately measure organism in
Glutathione content, always by the great attention of people.
In various analysis methods, fluorescence detection due to it is simple, conveniently, at low cost, high sensitivity and it is potential thin
The characteristics such as imaging intracellular have proved to be a kind of very useful detection method.Currently, many organic reactions have been used for mercaptan
The synthesis of fluorescence probe, as cyclization, Michael addition reaction, 2,4- dinitrobenzene and the mercaptan between aldehyde and amino are split
Solve reaction, nucleophilic substitution reaction, disulfide exchange reaction, Cu2+Complex compound demetalization reaction etc..A kind of method is to be based on
The molecular probe of chemodosimetric reaction, but the longer incubation time of this method needs, usually 20 minutes to 1
Hour even longer time, practicability are lower.Another method is to utilize Cu2+Fluorescence 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 it is affine
Power makes its probe have higher sensitivity, while also improving a possibility that the method is for the design of various fluorescence probes.
Cumarin is one of most popular fluorophor of fluorescence imaging probe.Due to their stronger fluorescence intensities,
Excellent dissolubility, efficient cell permeability and it is easily prepared the advantages that, become the Raw fluorescence to have a great attraction
Material.
Summary of the invention
In order to solve the deficiencies in the prior art, the present invention provides one kind to be based on cumarin schiff bases copper ion complex sulphur
Alcohol fluorescence probe and its preparation method and application, new fluorescent probe compounds 1-Cu2+.Compound 1 as precursor is chemical combination
Object 2 (tonka-bean hydrazides) and 2,6- pyridine dicarbaldehyde is bound up.Compound 1 and Cu2+Coordination, is prepared into compound 1-Cu2+.Change
Closing object 1 has stronger fluorescence, and compound 1-Cu2+Almost without fluorescence.When addition after containing mercaptoamino acid, compound 1-Cu2+
Fluorescence restore, and be added without sulfydryl amino acid after, compound 1-Cu2+Fluorescence intensity it is almost unchanged.Therefore, change
Close object 1-Cu2+It can be used for detecting mercaptan, such as: such as glutathione.It may apply even in cell imaging.
The technical scheme is that a kind of preparation based on cumarin schiff bases copper ion complex mercaptan fluorescence probe
Method, compound 2 are tonka-bean hydrazides and 2, and it is Coumarins Schiff base derivatives that compound 1, which is made, in 6- pyridine dicarbaldehyde chemical combination,
Compound 1 and Cu2+Coordination, is prepared into mercaptan fluorescence probe i.e. compound 1-Cu2+。
Further improvement of the present invention includes:
The compound 2 (1.1mmol) of 0.3028g is dissolved in minimal amount of ethyl alcohol, 2, the 6- pyridine two of 0.0676g is added
Formaldehyde (0.5mmol)；Under nitrogen protection, it is heated to reflux 12 hours；There is Precipitation after cooling, obtained pure substance is chemical combination
Object 1.
Another object of the present invention is to provide one kind to be based on cumarin schiff bases copper ion complex mercaptan fluorescence probe,
It is made according to above-mentioned method.
The present invention also provides a kind of applications based on cumarin schiff bases copper ion complex mercaptan fluorescence probe, specifically
It is the application in detection mercaptoamino acid.
The application, the specifically application in detection glutathione.
The application is particularly used for the detection of mercaptan compound in organism.
Invention further provides a kind of application based on cumarin schiff bases copper ion complex mercaptan fluorescence probe,
Application in the imaging of living cells GSH-PX activity.
The application, the application being specifically imaged in human cervical cancer 1 squamous cell carcinoma.
The present invention tonka-bean hydrazides and 2,6- pyridine dicarbaldehyde has synthesized a kind of new compound 1, as compound 1 and Cu2+
After coordination, mercaptan fluorescence probe, i.e. compound 1-Cu are prepared2+.Fluorescence spectrum test shows: in CH3CN:HEPES(3:2,v/
V) in solution, which has good selectivity and sensitivity to mercaptan, especially to GSH.In addition to this, probe also has
Good cell membrane permeability and low cytotoxicity can be used in living cells GSH and be imaged, and will be expected to be used for clinically GSH's
Detection.
Detailed description of the invention
Fig. 1 is in CH3In CN:HEPES (3:2, v/v) solution, with Cu2+Addition, the purple of compound 1 (10 μm of ol/L)
External spectrum.Insertion figure: at 440nm, the UV, visible light spectra for titration of compound 1.
Fig. 2 is in CH3In CN:HEPES (3:2, v/v) solution, with Cu2+Addition, compound 1 (10 μm of ol/L) it is glimmering
Light spectrum.Insertion figure: at 485nm, the fluorescence titration spectrum (excitation: 440nm) of compound 1.
Fig. 3 is in CH3In CN:HEPES (3:2, v/v) solution, with the addition of GSH, compound 1-Cu2+(10μmol/L)
Fluorescence response.Insertion figure: at 485nm, compound 1-Cu2+Fluorescence titration spectrum (excitation: 440nm).
Fig. 4 is compound 1-Cu2+The fluorescence response intensity (transmitting: 485nm) of (10 μm of ol/L) to different aminoacids.First
Column represents the fluorescence intensity after different aminoacids are added；The fluorescence that second column is represented while being added after GSH and non-mercaptoamino acid
Intensity.
Fig. 5 a is the fluorescence imaging of compound 1 in SiHa cell.
Fig. 5 b is the compound 1-Cu in SiHa cell2+Fluorescence imaging.
Fig. 5 c is the compound 1-Cu in SiHa cell2+The fluorescence imaging of+GSH.
Fig. 5 d is the light field of compound 1 in SiHa cell.
Fig. 5 e is the compound 1-Cu in SiHa cell2+Light field.
Fig. 5 f is the compound 1-Cu in SiHa cell2+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 compound 1 (10 μm of ol/L) in CH3In CN:HEPES (3:2, v/v) solution, to the purple of each metal ion species
Outer visible absorption spectra.
Figure 10 is compound 1 (10 μm of ol/L) in CH3In CN:HEPES (3:2, v/v) solution, to each metal ion species
Fluorescence spectrum response.
Specific embodiment
It elaborates with reference to the accompanying drawing to the present invention.
Embodiment 1
Reagent
4- diethylamino salicylide, diethyl malonate, piperidines, 80% hydrazine hydrate, 2,6- pyridine dicarbaldehydes, various gold
Belong to the perchlorate (Cr of ion3+,Ag+,Fe3+,K+,Na+,Mg2+,Pb2+,Ca2+,Hg2+,Mn2+,Cd2+,Fe2+,Zn2+,Ni2+,Co2 +,Cu2+) aqueous solution (2.0 × 10-2M), the aqueous solution (2.0 × 10 of various amino acid-2M), dehydrated alcohol, acetonitrile (chromatography
It is pure), dimethylformamide (analysis is pure), HEPES (pH:7.35-7.45) solution etc..
Synthesis process
Shown in synthesis process formula 1: 7-N, N- dimethylamino -2- oxygen -2H-3- tonka-bean acid esters (compound 3) and compound 2
It is that the prior art synthesizes.Compound 1 is by compound 2 and 2, and 6- pyridine dicarbaldehyde synthesizes, and passes through hydrogen spectrum, carbon spectrum, mass spectrum
Characterized (Fig. 6,7,8).Compound 1-Cu2+It is by compound 1 and Cu (ClO4)2·6H2O preparation.
Compound 1 is to Cu2+Ultravioletvisible absorption and fluorescence spectrum response
In CH3In CN:HEPES (3:2, v/v) solution, ultraviolet-visible absorption spectroscopy such as Fig. 1 of compound 1 (10 μm of ol/L)
Shown, maximal ultraviolet absorption is at 440nm.With Cu (ClO4)2·6H2The uv-vis spectra of the addition of O, compound 1 absorbs
Gradually weaken, and apparent red shift occurs in maximum absorption band.As the Cu that 6 times of amounts are added2+Afterwards, the ultraviolet titration of compound 1 reaches
Balance.In CH3In CN:HEPES (3:2, v/v) solution, compound 1 (10 μm of ol/L) inhales the UV, visible light of each metal ion species
It is as shown in Figure 9 to receive spectrum.Only Cu2+There is response to the ultravioletvisible absorption of compound 1, other metal ions are almost noiseless.
In CH3In CN:HEPES (3:2, v/v) solution, with Cu2+Addition, compound 1 (10 μm of ol/L) fluorescence drop
It is as shown in Figure 2 to determine spectrum.It is excited with 440nm, compound 1 shows very strong fluorescence emission peak at 485nm.With Cu2+'s
It is added, fluorescence intensity gradually weakens.As 4 times of amount Cu of addition2+Afterwards, it tends to balance.Mercaptan probe (compound 1-Cu2+) it is by changing
It closes object 1 and 4 times and measures Cu2+In conjunction with what is be prepared.Compound 1-Cu2+Low fluorescence intensity be likely to be copper ion by PET machine
The result of system or paramagnetism Quenching mechanism quenching effect.Compound 1 is as shown in Figure 10 to the fluorescence response of each metal ion species.
Probe (compound 1-Cu2+) fluorescence spectrum of mercaptan is responded
With the addition of mercaptan such as glutathione, due to the demetalization of mercaptan, mercaptan probe (compound 1-Cu2+) release
Compound 1 is put, fluorescence is gradually recovered, as shown in Figure 3.In CH3In CN:HEPES (3:2, v/v) solution, with glutathione
It is added, compound 1-Cu2+Fluorescence intensity gradually increase, after 2 times of amount GSH are added, tend to balance.Therefore compound 1-Cu2+
On fluorescence response, it can be used for detecting mercaptan.
In order to further explore compound 1-Cu2+To mercaptan have it is highly selective, carried out compound 1-Cu2+(10μ
mol/L,CH3CN:HEPES=3:2, v/v) fluorescence spectrum experiments with other possible amino acid for influencing fluorescence intensities.Such as Fig. 4
It is shown.Mercaptan probe (compound 1-Cu2+) itself fluorescence intensity it is very weak, when be separately added into 2 times amount mercaptoamino acids, such as L-
Homocysteine, L-cysteine and GSH, fluorescence intensity are remarkably reinforced, and wherein GSH fluorescence enhancement is the most obvious.As control,
When being separately added into the non-mercaptoamino acid of 2 times of amounts, fluorescence intensity does not have significant change.However, non-mercaptoamino acid is added
Afterwards, the GSH of same equimultiple is continuously added, fluorescence intensity is remarkably reinforced.Show compound 1-Cu2+There spectrally have to mercaptan to be special
Response, and this specific response of mercaptan not by it is other competition amino acid interference.Above experiments have shown that compound 1-Cu2+
There is selectivity well to mercaptoamino acid.
Probe (compound 1-Cu2+) to the fluorescence imaging of glutathione
Fluorescence probe detect to cell extremely important by living cells imaging.It is realized in Intrauterine device bleeding
Compound 1-Cu2+To the fluorescence imaging experiments of GSH.Before fluorescence imaging, SiHa cell is cultivated 12 hours in 12 well culture plates.
Then, compound 1 (3 μM) and cell are incubated for 60 minutes at 37 DEG C, twice with PBS rinsing.In Nikon
(blue light excitation) is observed under EclipseTE2000-S inverted fluorescence microscope, compound 1 shows apparent thin in SiHa cell
Green fluorescence (Fig. 5 a) intracellular.This shows that compound 1 has cell permeability.As 4 times of amount Cu of addition in compound 12+Afterwards, green
Fluorescent quenching (Fig. 5 b).However, intensity of cellular fluorescence is gradually recovered (Fig. 5 c) after 3 times of amount GSH are added.Entirely testing
In process (about 1~2 hour), cells survival is in good condition, has visualization, without apparent Side effect.Fluorescence at
As experiment shows mercaptan fluorescence probe (compound 1-Cu2+) it can be used for the detection of GSH in living cells.
Fig. 5 is compound 1 (a), compound 1-Cu in SiHa cell2+(b), compound 1-Cu2+The fluorescence of+GSH (c)
Imaging and their corresponding light fields (d-f).
Embodiment 2
Synthesis process
The synthesis of compound 3 (7-N, N- dimethylamino -2- oxygen -2H-3- tonka-bean acid esters)
4- diethylamino salicylide (7.72g, 0.04mol), diethyl malonate (12.8g, 12.16mL, 0.08mol)
It is mixed in dehydrated alcohol (120mL) with piperidines (4mL).Mixed liquor flows back 6 hours under agitation.It is cooled to room temperature, is revolved
Steaming is no longer steamed to alcohol solvent, and obtaining a small amount of oily liquids is compound 3.
The synthesis of compound 2 (tonka-bean hydrazides)
The compound 3 (7-N, N- dimethylamino -2- oxygen -2H-3- tonka-bean acid esters, 15mmol) for weighing 4.3400g is dissolved in
In 40 milliliters of ethyl alcohol, 3.6381 milliliters of 80% hydrazine hydrate (density=1.032g/ml, 60mmol) is added.It is stirred at room temperature 12 points
Zhong Hou, it is 15 minutes cooling in ice water.Gained precipitating filters to get product Compound 2 (tonka-bean hydrazides).
The synthesis of compound 1
The compound 2 (tonka-bean hydrazides, 1.1mmol) of 0.3028g is dissolved in minimal amount of ethyl alcohol, is added 0.0676g's
2,6- pyridine dicarbaldehyde (0.5mmol).Under nitrogen protection, it is heated to reflux 12 hours.There are Precipitation, thin-layer chromatography point after cooling
Purity is examined in analysis.Obtained pure substance is compound 1.
In short, 6- pyridine dicarbaldehyde has synthesized a kind of new compound 1, as compound 1 and Cu with tonka-bean hydrazides and 22+Match
Behind position, mercaptan fluorescence probe, i.e. compound 1-Cu are prepared2+.Fluorescence spectrum test shows: in CH3CN:HEPES(3:2,v/v)
In solution, which has good selectivity and sensitivity to mercaptan, especially to GSH.In addition to this, probe also has good
Good cell membrane permeability and low cytotoxicity can be used for GSH in living cells and be imaged, will be expected to be used for the inspection of clinically GSH
It surveys.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (1)
1. a kind of preparation method based on cumarin schiff bases copper ion complex mercaptan fluorescence probe, it is characterised in that: chemical combination
Compound 1, compound 1 and Cu is made in object 2 and 2,6- pyridine dicarbaldehyde chemical combination2+Coordination, is prepared into mercaptan fluorescence probe, i.e. N, N,
N- three-fold coordination 1-Cu2+；Reaction equation are as follows:
Wherein, 1 concrete operations of compound are that the compound 2 of 1.1mmol is dissolved in minimal amount of ethyl alcohol, is added 0.5mmol's
2,6 pyridine dicarbaldehydes；Under nitrogen protection, it is heated to reflux 12 hours；There is Precipitation after cooling, obtained pure substance is chemical combination
Object 1.
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| CN107417681B (en) * | 2017-06-15 | 2020-01-17 | 安徽大学 | Fluorescent probe compound containing coumarin-thiadiazole Schiff base and preparation method and application thereof |
| CN108299414B (en) * | 2018-01-25 | 2019-12-06 | 南京工业大学 | Two-photon fluorescent probe for selectively detecting iron (III) complex of biological mercaptan |
| CN108484583B (en) * | 2018-03-30 | 2021-03-02 | 湖南师范大学 | Colorimetric method for detecting Cu in water2+And Ni2+Synthesis and application of probe |
| CN109111471B (en) * | 2018-10-15 | 2020-07-07 | 南京农业大学 | Coumarin copper complex and preparation method and application thereof |
| CN110746411A (en) * | 2019-11-15 | 2020-02-04 | 辽宁科技大学 | Fluorescent probe and preparation method thereof, fluorescent probe test paper and application thereof |
| CN111157505B (en) * | 2020-01-17 | 2022-10-21 | 天津师范大学 | Method for detecting sulfur-containing pollutant thioglycollic acid in solution |
| CN111253386A (en) * | 2020-02-14 | 2020-06-09 | 中北大学 | Naked eye recognition Cu2+Fluorescent probe and preparation method and application thereof |
| CN112480110B (en) * | 2020-12-02 | 2021-10-26 | 广东省测试分析研究所（中国广州分析测试中心） | Multi-response azacyclo-formaldehyde fluorescent probe molecule and preparation method and application thereof |
| CN112920175B (en) * | 2020-12-17 | 2022-05-31 | 吉林大学 | Coumarin-based palladium ion fluorescent probe compound and preparation method thereof |
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