CN110229120A - A kind of long wavelength's luminescent dye molecule and preparation method thereof - Google Patents
A kind of long wavelength's luminescent dye molecule and preparation method thereof Download PDFInfo
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- CN110229120A CN110229120A CN201910523036.0A CN201910523036A CN110229120A CN 110229120 A CN110229120 A CN 110229120A CN 201910523036 A CN201910523036 A CN 201910523036A CN 110229120 A CN110229120 A CN 110229120A
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- long wavelength
- dye molecule
- luminescent dye
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
- C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
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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
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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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
- G01N21/6428—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
- 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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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Abstract
The invention discloses a kind of long wavelength's luminescent dye molecule, the chemical formula of the fluorescent dye is C42H29NO2S and its biologic applications of synthesis and fluorescent dye.The compound synthesis is the described method includes: by 4-(1,2,2- triphenylethylene base) acetophenone is stirred at room temperature in ethanol solution, under alkaline condition with 4- benzothiazole -3- hydroxy benzaldehyde and reacts 2~16 hours, it isolates and purifies to obtain the luminescent dye molecule after reaction；The structure for the tetraphenyl ethylene that the present invention selects has biggish conjugated system, and introducing benzothiazole group using Aldol condensation reaction has good photostability, and the structure in compound with chalcone increases its conjugated degree；The compound wavelength is longer, and background interference is small, and can rapidly enter cell, issues the fluorescence compared with strong signal, permeability of cell membrane is good, and photopermeability is preferable.
Description
Technical field
The invention belongs to fluorescent dye fields, and in particular to a kind of novel organic fluorescent dye being simply readily synthesized.
Background technique
Small organic molecule fluorescent dye is widely used in bio-imaging, biomolecular labeling, environmental analysis, cell dye
Color and clinical examination diagnosis, photochemical therapy, Organic Light Emitting Diode etc. are chemistry, biology, environmental science, medicine
With important tool indispensable in investigation of materials field.
Traditional some fluorescent dyes are easy to be influenced by temperature, solution acid alkalinity and concentration etc., therefore are carrying out
During fluorescent staining, often there is more limitation, the bioanalysis and other application fields for not being able to satisfy continuous development are answered
It is required that.In order to meet bioanalysis with rapid changepl. never-ending changes and improvements using the demand to fluorescent dye, research and develop with more good
The novel fluorescent material of good property and fluorescence spectrum performance is the key that fluorescence analysis development and core.
Summary of the invention
It is an object of the present invention to provide the new organic fluorescent dyestuff being easily-synthesized, which has fluorescence under solution.
The purpose of the invention is achieved by the following technical solution:
A kind of novel fluorescence dyestuff, the dyestuff chemistry structural formula are as follows:
The specific synthetic route of the fluorescent dye 1 is as follows:
It includes the next steps:
Alkali is added into reaction flask at room temperature, adding solvent dissolves it sufficiently；By 4- (1,2,2- triphenylethylene
Base) acetophenone is added in solution among the above, 4- benzothiazole -3- hydroxy benzaldehyde is added after stirring and dissolving, room temperature is stirred
Mix 2~16h of reaction；Water is added into reaction solution, after being then extracted with dichloromethane, is spin-dried for obtaining after being dried with anhydrous sodium sulfate
Crude product obtains Yellow fluorochrome 1 with the further separating-purifying of silica gel column chromatography；
Wherein, the structural formula of all compounds is as shown in synthetic route；4- (1,2,2- triphenylethylene base) acetophenone and
The molar ratio of 4- benzothiazole -3- hydroxy benzaldehyde is 1:(0.5~4)；It is 100-200 mesh that the column, which chromatographs stationary phase used,
Silica gel；The mobile phase of column chromatography used in the separating-purifying of compound 1 is petroleum ether-methylene chloride mixed solution, and volume ratio is
(1~3): 1.The alcoholic solution is dehydrated alcohol or mass fraction is the mixed solution of 10-12%NaOH solution and dehydrated alcohol,
It is 1:4.5-6 that wherein mass fraction, which is the volume ratio of 10-12%NaOH solution and dehydrated alcohol,.
Tetraphenyl ethylene (Tetraphenylethene, TPE) is a kind of typical, with big pi-conjugated structure organic molecule
Chromophore has been widely used in material because it has the characteristics that be readily synthesized, good convenient for modified with functional group, luminescent properties
The Related Research Domains such as chemistry, biochemistry.In addition, chalcone is α, β beta-unsaturated carbonyl compounds, generally by aromatic aldehyde and virtue
Ketone musk is obtained through cross aldol condensation.Chalcone derivative has the bioactivity such as anti-oxidant, antidepression, anticancer, antiviral,
It may be used as drug, because having big conjugated structure, have preferable optical property, be also used as nonlinear optical organic, light
The functional materials such as storage, photosensitive.It can be by converting the aryl at unsaturated bond both ends come real to the chemical modification of chalcone structure
Existing, the substitution base type changed on aromatic ring position can greatly change the fluorescence quantum efficiency of product and the wavelength of compound.
Fluorescent dye of the present invention emits close to red light district, can effectively avoid the dry of cell self-absorption and autofluorescence
It disturbs, there is red signal light to have stronger penetration power in vivo, the active site hydroxyl of the dyestuff, which can be done, to be simply modified to
Fluorescence probe can be directly used for cell imaging dyeing and the application of other field.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of fluorescent dye made from embodiment 1 or embodiment 2.
Fig. 2 is the nuclear-magnetism carbon spectrogram of fluorescent dye made from embodiment 1 or embodiment 2.
Fig. 3 is fluorescence spectra of the fluorescent dye in different solvents in embodiment 3, and the solvent includes dichloromethane
Alkane, N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, toluene.
Fig. 4 be 4 fluorescent dye of embodiment in the imaging in B-16 cell: figure A dye solution processing after, 530nm~
The cell imaging of the range fluorescent emission signals of 610nm, the superposition of the cell fluorescence imaging and light field of figure B dye solution processing.
Specific embodiment
The synthesis of dyestuff
The present invention is further illustrated below with reference to embodiment, but the scope of protection of present invention is not limited to implement
The range of example statement.
Embodiment 1: the synthesis of fluorescent dye 1
NaOH solution (the EtOH:H of configuration 10%2O, V:V=5:1), it is stirred at room temperature, dissolves sodium hydroxide sufficiently；It will
4- (1,2,2- triphenylethylene base) acetophenone (74.7mg, 0.2mmol) is added in above-mentioned 10% sodium hydroxide solution, stirring
4- benzothiazole -3- hydroxy benzaldehyde (50.8mg, 0.2mmol) is added after dissolution, continues that reaction 12h is stirred at room temperature.Reaction
After, the water of 20mL is added into reaction solution, is then extracted with dichloromethane, it is thick with being spin-dried for obtaining after anhydrous sodium sulfate drying
Product obtains yellow sterling, as dyestuff 1, yield 42.5% with silica gel column chromatography separation (petroleum ether: methylene chloride=1:1).
Embodiment 2
It weighs 0.2g sodium hydroxide to be dissolved in the ethyl alcohol of 10mL, is stirred at room temperature, dissolves sodium hydroxide sufficiently；By 4- (1,
2,2- triphenylethylene bases) acetophenone (74.9mg, 0.2mmol) is added in the ethanol solution of above-mentioned sodium hydroxide, stirring and dissolving
After add 4- benzothiazole -3- hydroxy benzaldehyde (51.2mg, 0.2mmol), room temperature reaction is stirred to react 16h.Reaction terminates
Afterwards, the water of 20mL is added into reaction solution, is then extracted with dichloromethane, is spin-dried for slightly being produced after being dried with anhydrous sodium sulfate
Product obtain yellow sterling, as dyestuff 1, yield 54.1% with silica gel column chromatography separation (petroleum ether: methylene chloride=1:1).
Embodiment 3: compound fluorescent characteristic
Fluorescent dye is accurately weighed, the fluorescence that the compound n,N-Dimethylformamide compound concentration is 500 μM contaminates
Expect mother liquor, draws 30 μ L with liquid-transfering gun and be added separately in 3mL different organic solvents (methylene chloride, N, N- dimethyl phenacyl
Amine, dimethyl sulfoxide, acetonitrile, tetrahydrofuran, toluene), its fluorescence spectrum, optical property data are tested after sufficiently shaking up at room temperature
As shown in Figure 3.The dyestuff has a good solvent mutagens and solvent compatibility.
Embodiment 4:
Dyestuff is dissolved in DMF, 500 μM of fluorescent dye solution is configured to, is trained at 37 DEG C with the dyestuff that concentration is 5 μM
Support mouse B-16 melanoma cells 20 minutes, by laser confocal scanning microscope, using 405nm as excitation wavelength,
The range reception fluorescent emission signals of 530nm~610nm, observe has stronger signal in cell, illustrates that the probe is available
In cell imaging.
Claims (5)
1. a kind of long wavelength's luminescent dye molecule, it is characterised in that: the chemical formula of the fluorescent dye is C42H29NO2S, structural formula
It is as follows:
2. the synthetic method of long wavelength's luminescent dye molecule according to claim 1, which is characterized in that the method includes
Following steps:
The synthesis of fluorescent dye: being added alkali into reaction flask at room temperature, and adding solvent dissolves it sufficiently, then thereto
4- (1,2,2- triphenylethylene base) acetophenone is added, stirring makes it that 4- benzothiazole -3- hydroxy benzaldehyde be added after completely dissolution,
It is stirred to react 2~16h, mixture is gradually poured into water after reaction, is extracted with methylene chloride, organic phase is through washing
Wash, dry, after rotary evaporation concentration by the fluorescent dye of the isolated yellow of silica gel column chromatography, reaction equation is as follows
3. the synthetic method of long wavelength's luminescent dye molecule according to claim 2, which is characterized in that 4- (1,2,2- tri-
Styryl) molar ratio of acetophenone and 4- benzothiazole -3- hydroxy benzaldehyde is 1:0.5~4.
4. the synthetic method of long wavelength's luminescent dye molecule according to claim 2, which is characterized in that the temperature is 0
~80 DEG C；The alkali is sodium hydroxide, potassium hydroxide, potassium carbonate, any one in piperidines；The alcoholic solution is dehydrated alcohol
Or mass fraction is the mixed solution of 10-12%NaOH solution and dehydrated alcohol, wherein mass fraction is 10-12%NaOH solution
Volume ratio with dehydrated alcohol is 1:4.5-6.
5. application of the long wavelength's luminescent dye molecule according to claim 1 on cell imaging.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111289336A (en) * | 2019-12-13 | 2020-06-16 | 山东源科生物科技股份有限公司 | Fungus fluorescent staining solution and preparation method thereof |
| CN114394984A (en) * | 2021-11-08 | 2022-04-26 | 三峡大学 | Aggregation-induced light-emitting and mechanochromic dye compound and preparation method thereof |
| CN114702500A (en) * | 2022-04-14 | 2022-07-05 | 三峡大学 | Fluorescent material with pressure-induced color change property and application thereof in anti-counterfeiting |
| CN117682979A (en) * | 2024-02-04 | 2024-03-12 | 有研工程技术研究院有限公司 | Acid-induced color compound, and preparation method and application thereof |
-
2019
- 2019-06-17 CN CN201910523036.0A patent/CN110229120B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| MOHAMED RAOUI等: "Highly Fluorescent Extended 2-(2’-hydroxyphenyl)benzazole Dyes:Synthesis，Optical Properties and First-principle Calculation", 《CHEMICAL COMMUNICATION》 * |
| SHAHIDA UMAR等: "A Tetraphenylethene-Naphthyridine-based AIEgen TPEN with Dual Mechanochromic and Chemosensing Properties", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111289336A (en) * | 2019-12-13 | 2020-06-16 | 山东源科生物科技股份有限公司 | Fungus fluorescent staining solution and preparation method thereof |
| CN114394984A (en) * | 2021-11-08 | 2022-04-26 | 三峡大学 | Aggregation-induced light-emitting and mechanochromic dye compound and preparation method thereof |
| CN114702500A (en) * | 2022-04-14 | 2022-07-05 | 三峡大学 | Fluorescent material with pressure-induced color change property and application thereof in anti-counterfeiting |
| CN117682979A (en) * | 2024-02-04 | 2024-03-12 | 有研工程技术研究院有限公司 | Acid-induced color compound, and preparation method and application thereof |
| CN117682979B (en) * | 2024-02-04 | 2024-05-31 | 有研工程技术研究院有限公司 | Acid-induced color compound, and preparation method and application thereof |
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