CN113307771A - Fluorescent dye with large Stokes shift and preparation method thereof - Google Patents
Fluorescent dye with large Stokes shift and preparation method thereof Download PDFInfo
- Publication number
- CN113307771A CN113307771A CN202110671960.0A CN202110671960A CN113307771A CN 113307771 A CN113307771 A CN 113307771A CN 202110671960 A CN202110671960 A CN 202110671960A CN 113307771 A CN113307771 A CN 113307771A
- Authority
- CN
- China
- Prior art keywords
- fluorescent dye
- stokes shift
- reaction
- raw materials
- taking
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/06—Ring systems of three rings
- C07D221/14—Aza-phenalenes, e.g. 1,8-naphthalimide
-
- 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
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/14—Styryl dyes
- C09B23/143—Styryl dyes the ethylene chain carrying a COOH or a functionally modified derivative, e.g.-CN, -COR, -COOR, -CON=, C6H5-CH=C-CN
-
- 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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- 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
-
- 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
-
- 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
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
-
- 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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a fluorescent dye with large Stokes shift and a preparation method thereof, and the fluorescent dye is prepared by synthesizing an intermediate TEM (transmission electron microscope) by taking isophorone and malononitrile as raw materials through a Knoevenagel condensation reaction; then 4-bromo-1, 8-naphthalic anhydride and N- (2-aminoethyl) morpholine are used as raw materials to synthesize an intermediate BMD; then BMD and 4-piperazine-1-benzaldehyde are used as raw materials to synthesize an intermediate NAA; and finally, synthesizing the fluorescent dye by taking the TEM and the NAA as raw materials. In the dye, naphthalimide is used as a FRET energy donor, and dicyan isophorone derivative is used as an energy acceptor, so that increase of Stokes shift is realized. The fluorescence emission spectra in various organic solvents were tested to find: the Stokes shifts are all between 173 nm and 234nm, and the fluorescence signals are obviously emitted.
Description
Technical Field
The invention belongs to the technical field of fluorescent dye preparation, and particularly relates to a fluorescent dye with large Stokes shift, and a preparation method of the fluorescent dye.
Background
Traditional organic fluorescent dyes, such as BODIPY, fluorescein, rhodamine, and the like, have been widely applied to high and new technology fields such as luminescent materials, fluorescent probes, fluorescent labels, and the like. However, these organic fluorescent dyes have disadvantages in terms of photophysical and optical properties during practical use, thereby limiting their wide use.
Stokes shift (Stokes shift) is one of the important parameters for evaluating the photophysical properties of fluorescent dyes. If the Stokes shift of the organic dye is relatively small, the fluorescence self-quenching phenomenon is easily caused in the biological imaging process, and the imaging resolution is further reduced. Therefore, the reasonable design and synthesis of the organic fluorescent dye with larger Stokes shift have important research significance.
Disclosure of Invention
The invention aims to provide a fluorescent dye with large Stokes shift, which is constructed based on Fluorescence Resonance Energy Transfer (FRET).
It is another object of the present invention to provide a method for preparing the above fluorescent dye having a large Stokes shift.
The technical scheme adopted by the invention is that the fluorescent dye with large Stokes displacement has a structural formula shown as the following formula (I):
the invention adopts another technical scheme that the preparation method of the fluorescent dye with large Stokes shift is implemented according to the following steps:
and 4, synthesizing the fluorescent dye by taking the intermediate TEM obtained in the step 1 and the intermediate NAA obtained in the step 3 as raw materials.
The present invention is also characterized in that,
in the step 1, the method specifically comprises the following steps:
dissolving isophorone, malononitrile and a catalyst in N, N-dimethylformamide, stirring for 6 hours at 120 ℃ by taking argon as a protective gas, cooling to room temperature after the reaction is finished, injecting the reaction mixed solution into ice water, separating out a brown solid, drying, and separating and purifying by using column chromatography to obtain an intermediate TEM; the catalyst is a viscous liquid formed by mixing acetic anhydride, glacial acetic acid and piperidine; the molar ratio of isophorone to malononitrile was 1: 1.
In the step 2, the method specifically comprises the following steps:
dissolving 4-bromo-1, 8-naphthalic anhydride and N- (2-aminoethyl) morpholine in 1, 4-dioxane, and reacting at 80 ℃ for 8 hours; cooling to room temperature after the reaction is finished, injecting the reaction solution into ice water to generate a precipitate, performing suction filtration to obtain a light yellow solid, drying, separating and purifying by batch column chromatography, wherein an eluent is dichloromethane to obtain a white solid, namely the intermediate BMD; the molar ratio of 4-bromo-1, 8 naphthalic anhydride to N- (2-aminoethyl) morpholine was 1: 2.
In step 3, the method specifically comprises the following steps:
dissolving BMD, 4-piperazine-1-benzaldehyde and a catalyst in dimethyl sulfoxide, heating and stirring at 100 ℃, tracking by TLC until the reaction is finished, cooling to room temperature, adding water into the reaction solution to generate yellow solid precipitate, performing suction filtration and air drying, and performing separation and purification by using column chromatography to finally obtain a yellow green solid product, namely an intermediate NAA; the molar ratio of BMD to 4-piperazine-1-benzaldehyde was 2.5:3 and the catalyst was cesium carbonate.
In step 4, the method specifically comprises the following steps:
dissolving an intermediate TEM, an intermediate NAA and a catalyst in absolute ethyl alcohol, heating and stirring for 4 hours at 80 ℃ by taking argon as protective gas, cooling to room temperature after the reaction is finished, filtering to obtain a reddish-brown solid product, and naturally airing to obtain the fluorescent dye with large Stokes shift; the molar ratio of TEM to NAA is 2: 3; the catalyst is piperidine.
The invention has the beneficial effects that fluorescent dye molecules with larger Stokes displacement are constructed by bridging naphthalimide and dicyan isophorone by utilizing a fluorescence resonance energy transfer mechanism (FRET). The dye molecule of the invention has good strong acid resistance, is suitable for a wide pH range of neutral or even weak alkaline, and is not easily interfered by other active ions. The fluorescent dye disclosed by the invention has excellent performance and application potential of imaging systems with different viscosities.
Drawings
FIG. 1 is a fluorescence emission spectrum of fluorescent dye TB (10. mu. mol/L) in different organic solutions;
FIG. 2 is DMSO: H2pH stability test of fluorescent dye TB (10. mu. mol/L) in O (1:1, V: V) solution;
FIG. 3 is DMSO: H2Testing the performance of the fluorescent dye TB (10 mu mol/L) in the O (1:1, V: V) solution for resisting interference of other active ions;
FIG. 4 is a graph showing the change in fluorescence spectrum of fluorescent dye TB (10. mu. mol/L) at different viscosities;
FIG. 5 is a schematic diagram of the design of a fluorescent dye prepared by the method of the present invention;
FIG. 6 is a reaction scheme of a fluorescent dye prepared according to an embodiment of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a fluorescent dye with large Stokes shift, wherein a fluorescent dye molecule has a structural formula shown as the following formula (I):
the invention relates to a preparation method of a fluorescent dye with large Stokes displacement, which is implemented according to the following steps:
the method specifically comprises the following steps: dissolving isophorone, malononitrile and a catalyst in N, N-dimethylformamide, stirring for 6 hours at 120 ℃ by taking argon as a protective gas, cooling to room temperature after the reaction is finished, injecting the reaction mixed solution into ice water, separating out a brown solid, drying, and separating and purifying by using column chromatography to obtain an intermediate TEM;
the catalyst is a viscous liquid formed by mixing acetic anhydride, glacial acetic acid and piperidine; the molar ratio of isophorone to malononitrile is 1: 1;
the method specifically comprises the following steps: dissolving 4-bromo-1, 8-naphthalic anhydride and N- (2-aminoethyl) morpholine in 1, 4-dioxane, and reacting at 80 ℃ for 8 hours; cooling to room temperature after the reaction is finished, injecting the reaction solution into ice water to generate a precipitate, performing suction filtration to obtain a light yellow solid, drying, separating and purifying by batch column chromatography, wherein an eluent is dichloromethane to obtain a white solid, namely the intermediate BMD;
the molar ratio of 4-bromo-1, 8 naphthalic anhydride to N- (2-aminoethyl) morpholine is 1: 2;
(Ⅳ)；
the method specifically comprises the following steps: dissolving BMD, 4-piperazine-1-benzaldehyde and a catalyst in dimethyl sulfoxide, heating and stirring at 100 ℃, tracking by TLC until the reaction is finished, cooling to room temperature, adding a small amount of water into the reaction solution to generate yellow solid precipitate, performing suction filtration, air drying, and separating and purifying by using column chromatography to finally obtain a yellow green solid product, namely an intermediate NAA;
the molar ratio of BMD to 4-piperazine-1-benzaldehyde is 2.5:3, and the catalyst is cesium carbonate;
the method specifically comprises the following steps: dissolving an intermediate TEM, an intermediate NAA and a catalyst in absolute ethyl alcohol, heating and stirring for 4 hours at 80 ℃ by taking argon as protective gas, cooling to room temperature after the reaction is finished, filtering to obtain a reddish-brown solid product, and naturally airing to obtain the fluorescent dye TB with large Stokes shift;
the molar ratio of TEM to NAA is 2: 3; the catalyst is piperidine.
The design principle of the fluorescent dye prepared by the method is shown in figure 5;
fluorescence Resonance Energy Transfer (FRET) is an effective mechanism to increase Stokes shift. However, the rational construction of fluorescent molecules with FRET mechanisms is harsh. Mainly comprises three aspects, respectively: 1) the two classes of fluorophores involved must be at suitable spatial distances; 2) the emission spectrum of one fluorescent molecule must partially overlap the absorption spectrum of another fluorescent molecule; 3) a suitable refractive index. Therefore, through reasonable selection, the naphthalimide and the dicyan isophorone derivative are finally bridged to obtain the fluorescent dye TB with large Stokes shift and excellent FRET effect.
Examples
The invention relates to a preparation method of a fluorescent dye with large Stokes shift, which is implemented according to the following steps, wherein the reaction formula is shown in figure 6;
the method specifically comprises the following steps: to a 250mL three-necked flask, under an argon atmosphere, were added 0.2g of acetic anhydride, 0.4mL of glacial acetic acid, and 1.8mL of piperidine, followed by 16.5mL (110mmol) of isophorone, 6.6g (110mmol) of malononitrile, and the mixture was dissolved in 55mL of N, N-dimethylformamide and stirred at 120 ℃ for 6 hours. After the reaction was completed, the reaction mixture was cooled to room temperature. Pouring the reaction mixed solution into ice water, separating out a brown solid, drying, and separating and purifying by using column chromatography, wherein an eluent is petroleum ether and dichloromethane is 1:1(v: v), so as to obtain a yellow solid;
the method specifically comprises the following steps: 2.5g (9.0mmol) of 4-bromo-1, 8-naphthalic anhydride and N- (2-aminoethyl) morpholine were dissolved in 50mL of 1, 4-dioxane and refluxed at 80 ℃ overnight, after which they were cooled to room temperature. Thereafter, the reaction solution was poured into ice water to form a precipitate, which was filtered with suction to obtain a pale yellow solid. Drying and separating and purifying by batch column chromatography, wherein an eluent is dichloromethane, and finally a white solid is obtained;
wherein the product is characterized as follows:
1H NMR(400MHz,Chloroform-d)δ8.65(d,J＝7.2Hz,1H),8.57 (d,J＝8.5Hz,1H),8.40(d,J＝7.9Hz,1H),8.04(d,J＝7.8Hz,1H), 7.85(t,J＝7.9Hz,1H),4.39-4.27(m,2H),3.67(s,4H),2.70(t,J＝6.7 Hz,2H),2.59(s,4H).
13C NMR(400MHz,Chloroform-d)δ163.70,133.38,132.12, 131.31,131.21,130.71,130.40,129.09,128.19,123.13,122.26,67.15, 56.20,53.93,37.45.
the method specifically comprises the following steps: a25 mL round-bottom flask was charged with 1.0g (2.5mmol) of BMD, 0.6g (3mmol) of 4-piperazine benzaldehyde and 0.82g (3mmol) of cesium carbonate in 5mL of DMSO under an argon atmosphere, and stirred with heating at 100 ℃. The reaction progress was monitored by TLC and after completion cooled to room temperature. A small amount of water was added to the reaction solution, and a yellow solid precipitated. Suction filtration, air drying, separation and purification by using column chromatography, eluent: petroleum ether: 1-dichloromethane: 1, 0.26g of a yellowish green solid product is finally obtained in a yield of 21%.
Wherein the product is characterized as follows:
1H NMR(400MHz,Chloroform-d)δ9.84(s,1H),8.64-8.43(m, 3H),7.87-7.69(m,3H),7.28(d,J＝8.1Hz,1H),7.04(d,J＝8.9Hz, 2H),4.36(t,J＝6.9Hz,2H),3.79-3.64(m,8H),3.47-3.37(m,4H), 2.70(d,J＝39.2Hz,6H).
13C NMR(400MHz,Chloroform-d)δ190.58,164.43,163.96, 155.36,154.97,132.55,131.96,131.36,130.01,127.92,126.23,123.36, 117.42,115.28,114.11,66.95,56.19,53.80,52.77,47.62,37.02.
the method specifically comprises the following steps: under an argon atmosphere, 0.10g (0.2mmol) NAA and 0.056g (2.0 mmol) TEM were dissolved in 5mL of anhydrous ethanol, followed by addition of 100. mu.L of piperidine, and the reaction was heated under reflux and reacted overnight. After the reaction is finished, the reaction product is cooled to room temperature, and is filtered to obtain a reddish brown solid product, and the product is naturally aired to finally obtain 0.034g of a solid product with the yield of 54%.
Wherein the product is characterized as follows:
1H NMR(400MHz,Chloroform-d)δ8.59(d,J＝7.3Hz,1H),8.53 (d,J＝8.0Hz,1H),8.46(d,J＝8.4Hz,1H),7.72(td,J＝8.4,7.9,2.6Hz, 1H),7.48(d,J＝8.8Hz,1H),7.28(s,1H),7.20(d,J＝8.4Hz,1H),7.06 -6.97(m,2H),6.95-6.88(m,1H),6.87-6.81(m,1H),6.79(s,1H), 4.34(d,J＝6.7Hz,2H),3.78-3.65(m,4H),3.64-3.52(m,4H),3.43(s, 4H),2.74(s,2H),2.66-2.61(m,2H),2.58(s,1H),2.52(s,1H),2.46(s, 1H),2.23(s,1H),1.25(d,J＝3.7Hz,2H),1.07(s,3H),0.97(s,3H), 0.87(s,2H).
the fluorescence emission performance of the fluorescent dye TB prepared in this example was tested, specifically as follows:
and (3) testing the fluorescence property in different organic solvents.
The excitation wavelength was 450nm and the fluorescence emission of the fluorescent dye TB (10. mu. mol/L) in different organic solvents was tested, including: methanol (MeOH), acetonitrile (MeCN), ethanol (EtOH), Ethyl Acetate (EA), dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), Dichloromethane (DCM), chloroform (CHCl)3) Acetone (Acetone), Toluene (Toluene) and Tetrahydrofuran (THF). As a result, it was found that, as shown in FIG. 1, fluorescence signal emission was significant in various organic solvents. And the two have larger Stokes displacement and are between 173 nm and 234 nm.
pH stability test of the fluorescent dye TB.
In DMSO, H2The stability of the fluorescent dyes in O (5:5, V: V) solution was tested in different pH (2-11) ranges, as shown in FIG. 2. The following are found: the fluorescent dye emits obvious fluorescent signals in a strong acid solvent, and has good and easily observed fluorescent signals in a neutral and weak alkaline pH range (2-9). Therefore, the fluorescent dye has wide pH application range.
And (3) testing the anti-active ion interference performance of the fluorescent dye TB.
In DMSO, H2In O (5:5, V: V) solution, fluorescence spectra of fluorescent dye TB (10. mu. mol/L) added with different kinds of interfering ions were tested, which included: 200. mu. mol/L, 1) H2O2；2)TBHP；3)NO2 -；4)Met；5)Hcy；6)GSH；7)HSO3 2-； 8)SO3 2-；9)HOCl；10)HS-. As shown in FIG. 3, the fluorescence spectrum did not change significantly at the excitation wavelength of 450nm, except for the three thiol analytes. The results show that the fluorescent dye TB can still maintain the excellent fluorescence property in the presence of various other interference ions. In addition, the method can be used for producing a composite materialWhen the viscosity of the solvent system is increased, such as glycerol (Gly), the fluorescence intensity value is obviously increased, and the application potential of imaging different viscosity systems is shown.
The fluorescent dye TB is used for testing the fluorescent effect in systems with different viscosities.
In the glycerol (Gly) and the water solution, the viscosity of the system is adjusted by changing the ratio of the glycerol (Gly) and the water solution. As shown in fig. 4, the fluorescence intensity value also shows a significant increase trend in the course of increasing the proportion of Gly to 100%, i.e., the viscosity of the system is gradually increased. Further proves the application potential of the fluorescent dye in imaging systems with different viscosities. The reason for this may be due to the presence of an easily rotatable double bond in the dye molecule. First, when the viscosity of the system is low, the rotation and vibration of the double bond will cause a part of the charge distribution to be uneven, resulting in quenching of the fluorescence signal. When the viscosity of the system is increased, the molecules are in a rigid plane, and finally, a brighter fluorescence signal is displayed.
The fluorescent dye provided by the invention is constructed on the basis of Fluorescence Resonance Energy Transfer (FRET) and has large Stokes shift. In the dye, naphthalimide is used as a FRET energy donor, and dicyan isophorone derivative is used as an energy acceptor, so that increase of Stokes shift is realized. The fluorescence emission spectra in various organic solvents were tested to find: the Stokes shifts are all between 173 nm and 234nm, and the fluorescence signals are obviously emitted.
Claims (6)
1. A fluorescent dye having a large Stokes shift, wherein the fluorescent dye molecule has a structural formula shown in formula (i):
2. a method for preparing a fluorescent dye with a large Stokes shift as defined in claim 1, which is carried out in particular according to the following steps:
step 1, synthesizing an intermediate TEM by taking isophorone and malononitrile as raw materials through a Knoevenagel condensation reaction;
step 2, synthesizing an intermediate BMD by taking 4-bromo-1, 8 naphthalic anhydride and N- (2-aminoethyl) morpholine as raw materials;
step 3, synthesizing an intermediate NAA by taking the intermediate BMD obtained in the step 2 and 4-piperazine-1-benzaldehyde as raw materials;
and 4, synthesizing the fluorescent dye by taking the intermediate TEM obtained in the step 1 and the intermediate NAA obtained in the step 3 as raw materials.
3. The method for preparing a fluorescent dye with large Stokes shift according to claim 2, wherein in the step 1, the steps are specifically as follows:
dissolving isophorone, malononitrile and a catalyst in N, N-dimethylformamide, stirring for 6 hours at 120 ℃ by taking argon as a protective gas, cooling to room temperature after the reaction is finished, injecting the reaction mixed solution into ice water, separating out a brown solid, drying, and separating and purifying by using column chromatography to obtain an intermediate TEM; the catalyst is a viscous liquid formed by mixing acetic anhydride, glacial acetic acid and piperidine; the molar ratio of isophorone to malononitrile was 1: 1.
4. The method for preparing a fluorescent dye with large Stokes shift according to claim 2, wherein in the step 2, the steps are specifically as follows:
dissolving 4-bromo-1, 8-naphthalic anhydride and N- (2-aminoethyl) morpholine in 1, 4-dioxane, and reacting at 80 ℃ for 8 hours; cooling to room temperature after the reaction is finished, injecting the reaction solution into ice water to generate a precipitate, performing suction filtration to obtain a light yellow solid, drying, separating and purifying by batch column chromatography, wherein an eluent is dichloromethane to obtain a white solid, namely the intermediate BMD; the molar ratio of 4-bromo-1, 8 naphthalic anhydride to N- (2-aminoethyl) morpholine was 1: 2.
5. The method for preparing a fluorescent dye with large Stokes shift according to claim 2, wherein in the step 3, specifically:
dissolving BMD, 4-piperazine-1-benzaldehyde and a catalyst in dimethyl sulfoxide, heating and stirring at 100 ℃, tracking by TLC until the reaction is finished, cooling to room temperature, adding water into the reaction solution to generate yellow solid precipitate, performing suction filtration and air drying, and performing separation and purification by using column chromatography to finally obtain a yellow green solid product, namely an intermediate NAA; the molar ratio of BMD to 4-piperazine-1-benzaldehyde was 2.5:3 and the catalyst was cesium carbonate.
6. The method for preparing a fluorescent dye with large Stokes shift according to claim 2, wherein in the step 4, the steps are specifically as follows:
dissolving an intermediate TEM, an intermediate NAA and a catalyst in absolute ethyl alcohol, heating and stirring for 4 hours at 80 ℃ by taking argon as protective gas, cooling to room temperature after the reaction is finished, filtering to obtain a reddish-brown solid product, and naturally airing to obtain the fluorescent dye with large Stokes shift; the molar ratio of TEM to NAA is 2: 3; the catalyst is piperidine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110671960.0A CN113307771B (en) | 2021-06-17 | 2021-06-17 | Fluorescent dye with large Stokes displacement and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110671960.0A CN113307771B (en) | 2021-06-17 | 2021-06-17 | Fluorescent dye with large Stokes displacement and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113307771A true CN113307771A (en) | 2021-08-27 |
| CN113307771B CN113307771B (en) | 2023-06-09 |
Family
ID=77379195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110671960.0A Active CN113307771B (en) | 2021-06-17 | 2021-06-17 | Fluorescent dye with large Stokes displacement and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113307771B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5279967A (en) * | 1992-01-24 | 1994-01-18 | Nalco Chemical Company | Fluorescent labeling of hydrocarbons for source identification |
| GB2533166A (en) * | 2014-12-12 | 2016-06-15 | Univ Malta | Sensor molecule |
| CN108129459A (en) * | 2018-01-10 | 2018-06-08 | 济南大学 | A kind of novel fluorescence probe and its application for being used to detect sulfur dioxide |
| CN108250220A (en) * | 2018-02-06 | 2018-07-06 | 广西师范学院 | Phenothiazines coumarine dye and synthetic method with big Stokes displacements |
| CN111334078A (en) * | 2018-12-18 | 2020-06-26 | 中国科学院大连化学物理研究所 | 405nm excited high-brightness and high-stability fluorescent dye and synthetic method thereof |
| US20210154330A1 (en) * | 2019-11-26 | 2021-05-27 | Texas Tech University System | Hnqo1-activatable fluorescent probe for imaging cancer cells in-vitro and in-vivo |
-
2021
- 2021-06-17 CN CN202110671960.0A patent/CN113307771B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5279967A (en) * | 1992-01-24 | 1994-01-18 | Nalco Chemical Company | Fluorescent labeling of hydrocarbons for source identification |
| GB2533166A (en) * | 2014-12-12 | 2016-06-15 | Univ Malta | Sensor molecule |
| CN108129459A (en) * | 2018-01-10 | 2018-06-08 | 济南大学 | A kind of novel fluorescence probe and its application for being used to detect sulfur dioxide |
| CN108250220A (en) * | 2018-02-06 | 2018-07-06 | 广西师范学院 | Phenothiazines coumarine dye and synthetic method with big Stokes displacements |
| CN111334078A (en) * | 2018-12-18 | 2020-06-26 | 中国科学院大连化学物理研究所 | 405nm excited high-brightness and high-stability fluorescent dye and synthetic method thereof |
| US20210154330A1 (en) * | 2019-11-26 | 2021-05-27 | Texas Tech University System | Hnqo1-activatable fluorescent probe for imaging cancer cells in-vitro and in-vivo |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113307771B (en) | 2023-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111995580B (en) | Fluorescent dye with tetraphenyl ethylene imidazole ring structure and application thereof | |
| CN109867611B (en) | Water-soluble two-photon hydrogen sulfide fluorescent probe for detecting red wine and hydrogen sulfide in vivo and preparation method and application thereof | |
| CN105462576A (en) | Near infrared BODIPY fluorescence dye and preparation method thereof | |
| CN113999254B (en) | Diazosulfide imidazole fluorescent dye and synthetic method thereof | |
| CN113307759B (en) | Cyanine near-infrared fluorescent probe and preparation method and application thereof | |
| CN111349091B (en) | Fluorescent dye and preparation method and application thereof | |
| CN111333610A (en) | Rhodamine fluorophors containing sulfoxide bridging, and synthetic method and application thereof | |
| CN108864056A (en) | Near infrared fluorescent compound and its preparation method and application with AIE performance | |
| CN111849196B (en) | Near-infrared two-region dye and synthetic method thereof | |
| CN111793371B (en) | 3, 5-asymmetrically modified BODIPY near-infrared fluorescent dye and preparation method thereof | |
| CN113307771B (en) | Fluorescent dye with large Stokes displacement and preparation method thereof | |
| CN114853656B (en) | Carbazole derivative with AEE characteristic, preparation method and application | |
| CN113402655B (en) | Polymer universal fluorescence platform for FRET fluorescent probe donor and application thereof | |
| CN113603722B (en) | Polar fluorescent probe and preparation method and application thereof | |
| CN114805297A (en) | Large-Stokes-shift near-infrared emission dye and preparation method and application thereof | |
| CN114409587A (en) | Method for producing AIE molecules, AIE molecules and use thereof | |
| CN110041226B (en) | Compound with AIE characteristics and preparation method and application thereof | |
| CN111334080B (en) | Carbonic anhydrase fluorescent probe with high brightness and high light stability | |
| CN113880760A (en) | Preparation method of lysosome targeted two-photon hydrogen sulfide fluorescent probe | |
| CN112341483A (en) | Synthesis method and application of 7-hydroxy-substituted hybrid coumarin hybrid dye | |
| CN112812088A (en) | Near-infrared luminescent triphenylamine derivative fluorescent molecule and preparation method and application thereof | |
| CN112341453A (en) | Fluorescent probe based on coumarin and preparation method and application thereof | |
| CN110357867B (en) | Glutathione ratio fluorescence sensor based on disulfide bond and preparation and application thereof | |
| CN116217576B (en) | Near infrared emission fluorescent molecule based on purine skeleton, and preparation method and application thereof | |
| CN115073487B (en) | Rhodamine derivative and preparation 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 |