CN109912634B - Aggregation-induced emission type fluorescent material and preparation method and application thereof - Google Patents
Aggregation-induced emission type fluorescent material and preparation method and application thereof Download PDFInfo
- Publication number
- CN109912634B CN109912634B CN201811533942.0A CN201811533942A CN109912634B CN 109912634 B CN109912634 B CN 109912634B CN 201811533942 A CN201811533942 A CN 201811533942A CN 109912634 B CN109912634 B CN 109912634B
- Authority
- CN
- China
- Prior art keywords
- fluorescent material
- aggregation
- induced emission
- compound
- emission fluorescent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a gathering induced luminescence type fluorescent material, a preparation method and application thereof, wherein the general structural formula of the fluorescent material is
Wherein R represents a hydrogen atom, a cyano group, a halogen, C1～C4Alkyl radical, C1～C3Alkoxy, hydroxyl or N, N-dimethyl, which is prepared by taking salicylaldehyde derivatives and para-substituted aniline as raw materials, obtaining intermediate imine through simple dehydration condensation reaction, and then reacting with boron trifluoride diethyl etherate. The fluorescent material has aggregation-induced emission characteristics, can specifically mark lipid droplets in living cells, and is an excellent lipid droplet imaging dye.
Description
Technical Field
The invention belongs to the technical field of fluorescent materials for biomedicine, and particularly relates to a fluorescent material with aggregation-induced emission property, a preparation method of the fluorescent material and application of the fluorescent material in marking lipid droplets.
Background
Fluorescent materials have great application value in the fields of photoelectric devices, environmental sensors, bioscience and the like, and have attracted great attention of scientists in recent years. Fluorescence detection not only has high sensitivity, but also overcomes a series of problems in biochemical tests that require expensive and difficult-to-handle radioactive tracing reagents. As the use of fluorescence in cellular and molecular imaging has increased, fluorescence imaging has revealed the localization and measurement of molecules within cells, and has sometimes enabled detection at the single molecule level. At present, there are many reports on lipid droplet bioimaging, and the bioimaging research attracts the interest of researchers, but the traditional fluorescent materials are easy to quench fluorescence at high concentration and have low solid quantum yield. With the development of Aggregation Induced Emission (AIE) fluorescent materials with high emission efficiency, strong light resistance, and good biocompatibility, a large number of AIE fluorescent materials are used for biological imaging.
Disclosure of Invention
The invention aims to provide a fluorescent material with aggregation-induced emission performance, and provides a preparation method and application for the fluorescent material.
In view of the above object, the structural general formula of the fluorescent material used in the present invention is as follows:
wherein R represents a hydrogen atom, a cyano group, a halogen, C1～C4Alkyl radical, C1～C3Preferably, R represents any one of a hydrogen atom, a cyano group, fluorine, a methoxy group, a hydroxyl group and N, N-dimethyl.
The preparation method of the aggregation-induced emission fluorescent material comprises the following steps:
1. taking toluene as a solvent, carrying out reflux reaction on m-anisidine, iodobenzene and potassium tert-butoxide at 120-130 ℃ under the catalytic action of catalytic amount of 1, 10-phenanthroline and cuprous iodide in an inert atmosphere until the reaction is complete, and separating and purifying the product to obtain a compound I.
2. And (3) taking dichloromethane as a solvent, reacting the compound I and boron tribromide at normal temperature to be complete, and separating and purifying a product to obtain a compound II.
3. And (3) taking N, N-dimethylformamide as a solvent, reacting the compound II with phosphorus oxychloride at 50-70 ℃ under an inert atmosphere till the reaction is complete, and separating and purifying the product to obtain a compound III.
4. Taking ethanol as a solvent, completely carrying out reflux reaction on the compound III and para-substituted aniline shown in a formula IV at 90-100 ℃, and evaporating to remove ethanol to obtain intermediate imine shown in a formula V; and then, taking dichloromethane as a solvent, carrying out a reflux reaction on the intermediate imine, boron trifluoride ethyl ether and N, N-diisopropylethylamine at 70-90 ℃ completely, and separating and purifying the product to obtain the aggregation-induced emission fluorescent material.
In the step 1, the molar ratio of m-anisidine to iodobenzene, potassium tert-butoxide, 1, 10-phenanthroline and cuprous iodide is preferably 1: 4-6: 0.15-0.25.
In the step 2, the molar ratio of the compound I to the boron tribromide is preferably 1: 1.2-2.
In the step 3, the molar ratio of the compound II to the phosphorus oxychloride is preferably 1: 8-9.
In the step 4, the molar ratio of the compound III to the para-substituted aniline, the boron trifluoride diethyl etherate and the N, N-diisopropylethylamine is preferably 1: 2-3: 5-7.
The application of the aggregation-induced emission fluorescent material as a dye in marking lipid droplets is the same as the existing lipid droplet marking method in the specific use method.
The invention synthesizes a series of fluorescent materials with aggregation-induced emission based on a simple skeleton formed by N, N-diphenyl salicylaldehyde and aniline by changing a substituent group at the para position on the aniline. The fluorescent material has the emission wavelength from 550nm to 578nm, has good solubility in organic solvents, is hardly dissolved in water, can form aggregates in water phase, and has remarkable aggregation-induced emission characteristics. Further biological experiments showed that: the aggregation-induced emission material has good biocompatibility, can be used for specifically marking lipid droplets in living cells, and is an excellent lipid droplet imaging dye.
Drawings
FIG. 1 is a fluorescence emission spectrum of the fluorescent material prepared in example 1 in a mixed system of dimethyl sulfoxide and water.
FIG. 2 is a graph showing the relative fluorescence intensity of the fluorescent material prepared in example 1 in a mixed system of dimethyl sulfoxide and water.
FIG. 3 is a fluorescence emission spectrum of the fluorescent material prepared in example 2 in a mixed system of dimethyl sulfoxide and water.
FIG. 4 is a graph showing the relative fluorescence intensity of the fluorescent material prepared in example 2 in a mixed system of dimethyl sulfoxide and water.
FIG. 5 is a fluorescence emission spectrum of the fluorescent material prepared in example 3 in a mixed system of dimethyl sulfoxide and water.
FIG. 6 is a graph showing the relative fluorescence intensity of the fluorescent material prepared in example 3 in a mixed system of dimethyl sulfoxide and water.
FIG. 7 is a fluorescence emission spectrum of the fluorescent material prepared in example 4 in a mixed system of dimethyl sulfoxide and water.
FIG. 8 is a graph showing the relative fluorescence intensity of the fluorescent material prepared in example 4 in a mixed system of dimethyl sulfoxide and water.
FIG. 9 is a fluorescence emission spectrum of the fluorescent material prepared in example 5 in a mixed system of dimethyl sulfoxide and water.
FIG. 10 is a graph showing the relative fluorescence intensity of the fluorescent material prepared in example 5 in a mixed system of dimethyl sulfoxide and water.
FIG. 11 is a fluorescence emission spectrum of the fluorescent material prepared in example 6 in a mixed system of dimethyl sulfoxide and water.
FIG. 12 is a graph showing the relative fluorescence intensity of the fluorescent material prepared in example 6 in a mixed system of dimethyl sulfoxide and water.
Fig. 13 is a diagram showing a cell image of the fluorescent material prepared in example 1.
Fig. 14 is a diagram showing a cell image of the fluorescent material prepared in example 2.
Fig. 15 is a diagram of a cell image of the fluorescent material prepared in example 3.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
1. In a nitrogen atmosphere, adding 2mL (17.86mmol) of m-anisidine, 10mL (89.3mmol) of iodobenzene, 10g (89.1mmol) of potassium tert-butoxide into 30mL of toluene, adding 644mg (3.572mmol) of 1, 10-phenanthroline and 680mg (3.572mmol) of cuprous iodide, carrying out reflux reaction at 125 ℃ for 24 hours, and carrying out column chromatography (eluent is pure petroleum ether) separation and purification to obtain a compound I with the yield of 75%.
2. Dissolving 2g (7.27mmol) of the compound I in 10mL of dry dichloromethane, adding 5mL of dichloromethane solution containing 1.03mL (10.9mmol) of boron tribromide in an ice bath, connecting the dichloromethane solution with a condenser tube, connecting the drying tube with the condenser tube, naturally heating to the normal temperature, stirring for reacting for 24 hours, adding water for quenching after the reaction is finished, removing dichloromethane, extracting with ethyl acetate and water, and performing column chromatography (eluent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 125: 1) to obtain the compound II, wherein the yield is 68%.
3. Under the protection of nitrogen, 7.81mL of N, N-dimethylformamide solution containing 3.96mL (42.5mmol) of phosphorus oxychloride is stirred at room temperature for about 30min to turn pink; dissolving 1.3g (5mmol) of a compound II in 10mL of N, N-dimethylformamide, dropwise adding the obtained pink solution under the conditions of nitrogen atmosphere and stirring, reacting at 60 ℃ for 24 hours after dropwise adding, adding ice water to quench after the reaction is finished, adjusting the pH value to be about 5-6 by using a sodium hydroxide aqueous solution with the mass fraction of 40%, extracting by using ethyl acetate and water, and performing column chromatography (eluent is a mixed solution of petroleum ether and ethyl acetate with the volume ratio of 100: 1) to obtain a compound III, wherein the yield is 41.6%.
4. Adding 81mg (0.28mmol) of the compound III and 79mg (0.71mmol) of para-fluoroaniline (formula IV-1) into 10mL of ethanol, carrying out reflux reaction at 95 ℃ for 0.5 h, and distilling off the ethanol to obtain an intermediate imine shown as a formula V-1; 10mL of dichloromethane is added into the obtained intermediate imine, 210mL (1.68mmol) of boron trifluoride diethyl ether and 280mL (1.68mmol) of N, N-diisopropylethylamine are added into the intermediate imine, the mixture is refluxed and reacted for 1.5 hours at the temperature of 80 ℃, and column chromatography is carried out (eluent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 100: 1) to obtain the fluorescent material shown as VI-1, and the yield of the fluorescent material is 83%.
The structural characterization data of the obtained fluorescent material are:1H NMR(300MHz,CDCl3)δ8.08(s,1H),7.46(dd,J＝8.7,4.7Hz,2H),7.37(t,J＝7.6Hz,4H),7.26-7.14(m,7H),7.09(t,J＝8.5Hz,2H),6.56-6.37(m,2H).
example 2
The same procedure used in example 1 was repeated except for replacing p-fluoroaniline in example 1 with an equimolar amount of p-methoxyaniline (formula IV-2) in step 4 of this example to give a fluorescent material represented by VI-2 in a yield of 35%.
The structural characterization data of the obtained fluorescent material are:1H NMR(300MHz,DMSO)δ8.78(s,1H),7.67-7.17(m,13H),7.05(d,J＝8.7Hz,2H),6.41(d,J＝7.4Hz,1H),6.05(s,1H),3.80(s,3H).
example 3
The same procedure used in example 1 was repeated except for replacing the p-fluoroaniline used in example 1 by an equimolar amount of p-cyanoaniline (formula IV-2) in step 4 of this example to give a fluorescent material represented by VI-3 in a yield of 32%.
The structural characterization data of the obtained fluorescent material are:1H NMR(300MHz,CDCl3)δ8.13(s,1H),7.75(d,J＝8.7Hz,2H),7.64(d,J＝8.5Hz,2H),7.41(t,J＝7.6Hz,4H),7.29(d,J＝7.4Hz,2H),7.23(dd,J＝11.0,3.7Hz,5H),6.51(dd,J＝8.9,2.2Hz,1H),6.42(d,J＝1.9Hz,1H).
example 4
In step 4 of this example, para-fluoroaniline in example 1 was replaced with equimolar aniline (formula IV-4), and the mixture of petroleum ether, ethyl acetate and dichloromethane in a volume ratio of 40:1:1 was used as an eluent, and the other steps were the same as in example 1, whereby a fluorescent material represented by VI-4 was obtained with a yield of 52%.
The structural characterization data of the obtained fluorescent material are:1H NMR(300MHz,CDCl3)δ8.14(s,1H),7.58-7.32(m,9H),7.22(dt,J＝8.9,3.1Hz,7H),6.55-6.43(m,2H).
example 5
In step 4 of this example, p-fluoroaniline in example 1 was replaced with N, N-dimethyl-p-phenylenediamine (formula IV-5) in equimolar amounts, and the mixture of petroleum ether and ethyl acetate in a volume ratio of 20:1 was used as an eluent, and the other steps were the same as in example 1, whereby a fluorescent material shown in VI-5 was obtained with a yield of 47%.
The structural characterization data of the obtained fluorescent material are:1H NMR(300MHz,CDCl3)δ8.09(s,1H),7.45-7.29(m,6H),7.25-7.14(m,7H),6.71(d,J＝9.1Hz,2H),6.55-6.45(m,2H),2.99(s,6H).
example 6
In step 4 of this example, para-fluoroaniline in example 1 was replaced with an equimolar amount of para-hydroxyaniline (formula IV-6), and a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 10:1 was used as an eluent, and the other steps were the same as in example 1, whereby a fluorescent material represented by VI-6 was obtained at a yield of 60%.
The structural characterization data of the obtained fluorescent material are:1H NMR(300MHz,CDCl3)δ8.08(s,1H),7.37(dd,J＝12.6,5.2Hz,6H),7.21(dd,J＝11.3,4.9Hz,7H),6.86(t,J＝9.4Hz,2H),6.55-6.43(m,2H),5.30(s,1H).
the inventors have carried out an aggregation-induced emission performance test on the fluorescent materials prepared in the above examples 1 to 6, and the specific test method is as follows: preparing aqueous solution of dimethyl sulfoxide with water content of 0%, 10%, 30%, 50%, 70%, 90%, 95%, 99%, adding fluorescent material into the obtained solution to obtain a solution with concentration of 1 × 10-5And (3) testing the aggregation-induced emission property of the fluorescent material by using a Hitachi F-7000 fluorescence spectrophotometer in the mol/L fluorescent material solution, wherein the result is shown in the figure 1-12. As can be seen from the figure, the fluorescent materials obtained in the embodiments 1 to 6 of the invention all have aggregation-induced emission properties.
Example 7
Application of fluorescent material prepared in embodiments 1-6 as dye in marking lipid droplets
The assay was performed using Hela cells, which were grown in the logarithmic phase, were trypsinized with Hella cells, centrifuged for 5 minutes, the supernatant was removed, 1.0mL of fresh DMEM incomplete high-sugar medium was added to prepare a single cell suspension, and the number of cells was counted at 1X 1042.0mL of DMEM incomplete high-sugar culture solution was inoculated on a 35mm dish, cultured for 48 hours, and cell morphology was observed for a certain period of time. When the cells can be used for cell imaging, the floating cells are washed away by PBS buffer solution, and 20 mu mol/L of the prepared PBS solution of the fluorescent material prepared in the example 1-3 is respectively added at 37 DEG CAfter incubation for 30 minutes in the cell incubator, the PBS medium was carefully removed and washed twice with PBS solution, and then cell imaging was performed under an olympus fluorescence confocal microscope.
As can be seen from FIGS. 13 to 15, the fluorescent materials prepared in examples 1 to 3 were labeled with lipid droplets in cells.
Claims (8)
1. A kind of aggregation-induced emission fluorescent material is characterized in that the structural general formula of the fluorescent material is as follows:
wherein R represents a hydrogen atom, a cyano group, a halogen, C1～C4Alkyl radical, C1～C3Any one of alkoxy, hydroxyl and N, N-dimethyl.
2. The aggregation-induced emission fluorescent material according to claim 1, wherein: and R represents any one of a hydrogen atom, a cyano group, fluorine, a methoxy group, a hydroxyl group and N, N-dimethyl.
3. A method for preparing the aggregation-induced emission fluorescent material according to claim 1, wherein:
(1) taking toluene as a solvent, carrying out reflux reaction on m-anisidine, iodobenzene and potassium tert-butoxide at 120-130 ℃ to be complete under the catalytic action of catalytic amount of 1, 10-phenanthroline and cuprous iodide in an inert atmosphere, and separating and purifying a product to obtain a compound I;
(2) taking dichloromethane as a solvent, reacting the compound I with boron tribromide at normal temperature to be complete, and separating and purifying a product to obtain a compound II;
(3) taking N, N-dimethylformamide as a solvent, reacting the compound II with phosphorus oxychloride at 50-70 ℃ under an inert atmosphere till the reaction is complete, and separating and purifying a product to obtain a compound III;
(4) taking ethanol as a solvent, completely carrying out reflux reaction on the compound III and para-substituted aniline shown in a formula IV at 90-100 ℃, and evaporating to remove ethanol to obtain intermediate imine shown in a formula V; then, taking dichloromethane as a solvent, carrying out a reflux reaction on the intermediate imine, boron trifluoride ethyl ether and N, N-diisopropylethylamine at 70-90 ℃ completely, and separating and purifying a product to obtain an aggregation-induced emission fluorescent material;
in the formula V, R represents a hydrogen atom, a cyano group, a halogen, C1～C4Alkyl radical, C1～C3Any one of alkoxy, hydroxyl and N, N-dimethyl.
4. The method for producing an aggregation-induced emission fluorescent material according to claim 3, wherein: in the step (1), the molar ratio of m-anisidine to iodobenzene, potassium tert-butoxide, 1, 10-phenanthroline and cuprous iodide is 1: 4-6: 0.15-0.25.
5. The method for producing an aggregation-induced emission fluorescent material according to claim 3, wherein: in the step (2), the molar ratio of the compound I to boron tribromide is 1: 1.2-2.
6. The method for producing an aggregation-induced emission fluorescent material according to claim 3, wherein: in the step (3), the molar ratio of the compound II to the phosphorus oxychloride is 1: 8-9.
7. The method for producing an aggregation-induced emission fluorescent material according to claim 3, wherein: in the step (4), the molar ratio of the compound III to the para-substituted aniline, the boron trifluoride diethyl etherate and the N, N-diisopropylethylamine is 1: 2-3: 5-7.
8. Use of the aggregation-induced emission fluorescent material according to claim 1 as a dye for labeling lipid droplets for non-disease diagnostic and therapeutic purposes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811533942.0A CN109912634B (en) | 2018-12-14 | 2018-12-14 | Aggregation-induced emission type fluorescent material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811533942.0A CN109912634B (en) | 2018-12-14 | 2018-12-14 | Aggregation-induced emission type fluorescent material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109912634A CN109912634A (en) | 2019-06-21 |
| CN109912634B true CN109912634B (en) | 2021-02-26 |
Family
ID=66959856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811533942.0A Expired - Fee Related CN109912634B (en) | 2018-12-14 | 2018-12-14 | Aggregation-induced emission type fluorescent material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109912634B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113030056B (en) * | 2021-03-29 | 2023-04-18 | 郑州大学 | Method for detecting heavy water content by using aggregation-induced emission molecules |
| CN115286563A (en) * | 2022-02-14 | 2022-11-04 | 浙江科技学院 | Schiff base fluorescent viscosity probe with aggregation-induced emission property |
| CN114605456B (en) * | 2022-03-29 | 2023-06-02 | 山东大学深圳研究院 | Donor-acceptor naphthalene salicylaldehyde imine boron difluoride compound and application thereof in lipid drop super-resolution imaging |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106478706A (en) * | 2016-10-12 | 2017-03-08 | 郑州大学 | Replace Two-photon fluorescent dye and its synthetic method of two pyrroles of fluorine boron and hexichol amido fluorenes based on phenyl |
| CN107501170A (en) * | 2017-08-17 | 2017-12-22 | 陕西师范大学 | A kind of adjustable aggregation-induced emission type fluorescent material of spectrum and its preparation method and application |
| CN108069908A (en) * | 2016-11-15 | 2018-05-25 | 香港科技大学 | Fluorescence probe and its application |
-
2018
- 2018-12-14 CN CN201811533942.0A patent/CN109912634B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106478706A (en) * | 2016-10-12 | 2017-03-08 | 郑州大学 | Replace Two-photon fluorescent dye and its synthetic method of two pyrroles of fluorine boron and hexichol amido fluorenes based on phenyl |
| CN108069908A (en) * | 2016-11-15 | 2018-05-25 | 香港科技大学 | Fluorescence probe and its application |
| CN107501170A (en) * | 2017-08-17 | 2017-12-22 | 陕西师范大学 | A kind of adjustable aggregation-induced emission type fluorescent material of spectrum and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| "Boronic acid derived salicylidenehydrazone complexes for wash-free fluorescence imaging of cellular organelles";B. Zhang et al.,;《Dyes and Pigments》;20171016;第149卷;第356-362页 * |
| "Nonconjugated Fluorescent Molecular Cages of Trinuclear Fluoroborate Complexes with Salicylaldehyde-Based Schiff Base Ligands";Xiaohong Zhang et al.,;《ACS Omega》;20180813;第3卷(第8期);第8992-9002页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109912634A (en) | 2019-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109912634B (en) | Aggregation-induced emission type fluorescent material and preparation method and application thereof | |
| CN107603269B (en) | Fluorescent dye based on naphthalimide, preparation method and application thereof | |
| CN107200709B (en) | Fluorescent compound with aggregation-induced emission property and application thereof in cell fluorescence imaging field | |
| CN107501170B (en) | A kind of adjustable aggregation-induced emission type fluorescent material of spectrum and its preparation method and application | |
| CN104710816B (en) | Large Stokes shift and near infrared fluorescence emitting new rhodamine fluorescent dye and synthetic method thereof | |
| CN104710815B (en) | Novel rhodafluor fluorescent dye with characteristics of large stokes shift and near-infrared fluorescence emitting, and synthesis method thereof | |
| CN104910139B (en) | The heteroaryl of mitochondria fluorescent dye 3 substitutes the preparation and application of 2H indazole analog derivatives | |
| CN110003173B (en) | Carbazole-based two-photon polar fluorescent probe and preparation method and application thereof | |
| CN108219780B (en) | Near-infrared fluorescent probe and preparation method and application thereof | |
| CN105733563A (en) | Coumarin-based two-photon lysosome polar probe, and preparation method and application thereof | |
| CN110283586B (en) | Near-infrared fluorescent dye and preparation method thereof | |
| CN110183478B (en) | Synthesis and application of cyanine, coumarin and dicarbonyl boron fluoride hybrid fluorescent dye | |
| CN110031436B (en) | Organic silicon fluorescent probe for detecting lipid drops | |
| CN104650610A (en) | Asymmetric near-infrared BODIPY fluorescent dye as well as preparation method and application thereof | |
| CN108484479B (en) | Carbazolyl two-photon fluorescent probe and preparation method and application thereof | |
| CN107759504B (en) | Dual-phase organic fluorescent material with strong fluorescence in solid and liquid states and preparation method thereof | |
| CN110003103A (en) | A kind of two area side's acid quinoline dye of near-infrared and preparation method thereof | |
| CN1255409C (en) | Fluorescent compounds | |
| CN113651818B (en) | Condensed heteroaromatic ring organic luminescent material and preparation method and application thereof | |
| CN111349067B (en) | Aggregation-induced emission type fluorescent material and preparation method thereof | |
| CN110143977A (en) | A kind of miscellaneous boron difluoride complex compound fluorochrome of cumarin and its application | |
| CN112225721B (en) | Acid-responsive near-infrared lysosome organic small-molecule fluorescent probe and preparation method and application thereof | |
| WO2021227865A1 (en) | Preparation method and application of a series of hemicyanine fluorescent markers having high optical stability | |
| CN111961072B (en) | Lysosome-targeted infrared two-window emission fluorescent dye and preparation method and application thereof | |
| US10029996B2 (en) | Class of cyano-substituted asymmetric cyanine dyes, synthesizing method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210226 Termination date: 20211214 |