CN105400507B - Preparation method and its time resolution bio-imaging application of the one kind based on thermotropic delay long-life phosphors organic material nano particle - Google Patents
Preparation method and its time resolution bio-imaging application of the one kind based on thermotropic delay long-life phosphors organic material nano particle Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of water-soluble long-life phosphors nano particle based on thermotropic delayed fluorescence (TADF) organic material and its time resolution bio-imaging applications.Its nanostructure as shown in Figure 1, CzPy represent thermotropic delayed fluorescence molecule as lead to formula (I) shown inThe pure organic TADF small molecule materials CzPy of one-step synthesis method is used first, then in fast injection CzPy/ lecithin polyethylene glycol mixed solution to deionized water, obtains the CzPy nano particles that good water solubility, luminous intensity height, fluorescence lifetime are grown.Dye marker is carried out to HELA cells and the fluorescence lifetime of this nano particle is long, cell and bio-toxicity are low, spectral signal is stablized is found to zebra fish blood vessel imaging, time-resolved fluorescence imaging is realized in terms of cell or living imaging, is had a good application prospect.
Description
Technical field
The present invention relates to synthesis with the long-life organic fluorescence molecule of thermotropic delayed fluorescence (TADF) characteristic and its water-soluble
The preparation method of property long-life nano particle and bio-imaging application.Belong to luminous organic material and nanometer bio probe and imaging
Field.
Background technology
Induced Fluorescence Microscopy as a kind of not damaged biosensor technique, cell imaging, live body, vitro tissue at
Become a kind of essential key technology as in.The core of Induced Fluorescence Microscopy, which is development, has fluorescence efficiency height, light
The good fluorescent chromophore of stability.Common fluorescent chromophore includes at present：Conventional fluorescent element, rhodamine, flower cyanines class have engine dyeing
Material, the nanocrystalline, conjugated polymer of inorganic semiconductor etc..Wherein traditional organic molecule fluorescent dye because its designability is strong, at
For the main selection of bio-sensing and clinical application.However existing organic dyestuff still faces some problems such as hydrophobicity, Yi Ju
Collect, be easy to photobleaching etc..And inorganic semiconductor is nanocrystalline, such as quantum dot, although with high brightness, high photostability it is excellent
Gesture, but itself toxicity is urgently to be resolved hurrily.In addition, general fluorescent dye in bio-imaging using easily endogenous by biosystem
The interference of background fluorescence, sensitivity and signal-to-noise ratio is relatively low, signal is easily affected by environment.Due to organism endogenous fluorescence one
As the service life be several nanoseconds or zero several nanoseconds, in this way, development with long fluorescence lifetime fluorescent chromophore, using when
Between resolution techniques evade the interference of fluorescence background in sample, to realize highly sensitive, high s/n ratio imaging.
Currently, long-life phosphors imaging is based primarily upon inorganic rare earth material, rare earth compounding and expensive, heavy metal phosphorescence hair
It penetrates, however this phosphorescence long-life signal under hypoxic condition often since it is desired that could keep.Therefore, develop air or oxygen
Under gas atmosphere with long-life phosphors, high fluorescence quantum efficiency, good water solubility fluorescence probe with important scientific research and
Market value.
In recent years, nanotechnology has become the dominant technology that science and technology advances.Organic molecule fluorescence is contaminated
Material is combined with nanotechnology, and nanometer is formed by the nano particle or small molecule dyes self aggregation that load organic molecule dyestuff
Particle is to be allowed to obtain preferably application using the nanostructure control of formation, the correlated performance that influences and improve material
The important directions of organic molecule fluorescent dye development.
Invention content
Goal of the invention：One of the object of the invention is to provide a kind of organic semiconductor fluorescent material with long-life phosphors；
The second purpose is to provide the organic molecule coating dye and is received in water-soluble DSPE-PEG2000 with forming water soluble fluorescence
The method of rice grain；The third purpose is to provide this nanometer of organic molecule dye nanoparticle in cell imaging, living imaging
The example of application.
Technical solution：In order to overcome the deficiencies of the prior art, we select design, synthesis with thermotropic delayed fluorescence characteristic
Organic semiconductor luminescent material, and select appropriate means with water-soluble and long fluorescence lifetime, to according to there is water solubility
Well, the fluorescent microscopic imaging chromophore for the features such as fluorescence lifetime is long, fluorescence efficiency is high, fluorescence spectrum stability is good.This nanometer of material
Material is characterized in that：Organic molecule fluorescent material is combined with nanotechnology, obtained nanoparticles stable is high, the fluorescence longevity
Life length, fluorescence quantum yield is high, and the biocompatibility having had and low bio-toxicity.
The present invention provides a kind of water-soluble long-life phosphors nano particle based on thermotropic delayed fluorescence organic fluorescence materials
Composed structure, wherein nanostructure of the present invention is as shown in Fig. 1, TADF material C zPy structural formulas such as logical formula (I) institute
Show：
Wherein, star-like pattern table shows that the aggregations of CzPy molecules, the black on ball-type surface are bent in CzPy nanoparticle structures
Line represents lecithin-polyethylene glycol (DSPE-PEG2000) molecule, and water-wet side outside, provides water solubility；It merges at lipophilic end
CzPy molecule aggregates form nano luminous body core.
TADF material structures representated by CzPy lead in formula (I), and Py is Pyridine Molecules, and Cz is class carbazole molecules, wherein Ar1
It is indicated respectively with Ar2 in the aryl such as benzene, thiophene, fluorenes, carbazole, naphthalene, anthracene, substituted aryl, heterocyclic aryl and substituted heterocycle aryl
One kind, 4 Cz structures are connected by its 9 nitrogen-atoms with the 4- cyanopyridines of core.
TADF molecules representated by CzPy of the present invention, in feature structure general formula formula (I), Ar1 and Ar2 and pyrroles
And the nitro ring closure reaction that is synthesized by of ring structure is realized.Preparation method can be indicated with following reaction formulas (II).
Synthetic schemes leads in formula (II), and the group representated by Ar1 and Ar2 is respectively benzene, thiophene, fluorenes, carbazole, naphthalene, anthracene etc.
One kind in the aromatic groups such as aryl, substituted aryl, heterocyclic aryl and substituted heterocycle；X can be bromine atom or iodine atom, Y
Can be boronate, one kind of boric acid ester group or trialkyl tinbase.
TADF organic semiconducting materials synthetic method disclosed by the invention is mainly carried out in three steps, as shown in logical formula (II)：
(1), step 1) is generally Suzuki coupling reactions or Stille coupling reactions；When step 1) is Suzuki coupling reactions,
Need to use the aqueous solution of palladium-containing catalyst and inorganic base, solvent is generally toluene or tetrahydrofuran, reacts 16 under reflux
Obtain III-3 within~24 hours；When step 1) is Stille coupling reactions, need with palladium-containing catalyst in toluene or tetrahydrofuran
Back flow reaction 5~24 hours in solution obtain compound III-3 through silica gel column chromatography.Palladium catalyst can select Pd (PPh3)4
Or Pd3dba2/P(o-tol)3；The aqueous slkali used in Suzuki coupling reactions can be the potassium carbonate of 2mol/L, sodium carbonate
Or sodium bicarbonate solution.(2), step 2) is to obtain the cyclization step of Cz molecules, it is characterised in that cyclization reagent is triphenyl
Phosphine or triethoxy phosphine, solvent used are chlorobenzene, o-dichlorohenzene, and reaction temperature is 125~145 DEG C, and the reaction time is 6~12
Hour.Compound III-3 and the molar ratio of cyclization reagent, solvent are about 1mmol:2.5mmol:2mL.(3), needed for step 3)
Solvent be anhydrous and oxygen-free dimethyl sulfoxide, reaction temperature be 100 DEG C~150 DEG C, the reaction time be 12~24 hours.
The system of water-soluble long-life phosphors nano particle disclosed by the invention based on TADF organic semiconducting materials CzPy
Preparation Method, it is characterized in that by three steps.The CzPy of 2mg is dissolved in 2mL tetrahydrofurans, is added 2mg's by step 1
DSPE-PEG2000, ultrasonic mixing is uniform, and is kept for 10 minutes, forms clear solution.Step 2 takes the solution of step 1
0.5mL is rapidly injected in the PBS or deionized water solution of the pH=7.4 of 10mL；Tetrahydrofuran is removed under nitrogen stream.Step 3,
Nano particle aqueous solution obtained by step 2 is filtered through 0.22 micrometer Millipore filtering head, and rotary evaporation removes most of solvent
Water, the remaining freeze-dried removing of water, obtains target nanoparticle powder.
CzPy nano particles disclosed by the invention and preparation method thereof, the weight of long-life phosphors molecule and DSPEG-2000
Than being 1:3~3:1；Rotary evaporation removes water.
Pure organic long-life phosphors nano particle of one kind disclosed by the invention and preparation method thereof, step 3 is obtained
Nano particle diameter is 10~50 nanometers (such as Fig. 4)；Its fluorescence lifetime measured in air reaches Microsecond grade (such as Fig. 3).
The type nano granular disclosed by the invention carries out dye marker (such as Fig. 5) to HELA cells and to zebra fish blood vessel
With good imaging effect (such as Fig. 6).
Advantageous effect：
1, the presently disclosed water-soluble long-life phosphors nanometer based on thermotropic delayed fluorescence organic semiconducting materials
Grain, makes full use of the TADF materials with crowded aroma system in the collected state with fluorescent emission more stronger than solution state；
2, using DSPE-PEG2000 as enhancing agents, by rapid precipitation method, stable, controllable preparation has size
Uniform, signal-stabilized water-soluble nanoparticles.
3, most crucial advantage, which is this nano particle, has fluorescence lifetime more better than common organic or conjugated material steady
Qualitative and longer fluorescence lifetime has all reached the level of Microsecond grade even if measuring and operating in air, this makes this
A kind of long-life nano particle of disclosure of the invention is overcome in cell imaging, live body or imaging of tissue by TIME RESOLVED TECHNIQUE
Whether there is or not with the advantage of rival in terms of background fluorescence interference.
4, the water-soluble long-life phosphors nanometer disclosed by the invention based on thermotropic delayed fluorescence organic semiconducting materials
Grain is expected to be widely used in the sensing detections such as bio-imaging, cell imaging field.
Description of the drawings
Fig. 1 is CzPy nanoparticle structures schematic diagram obtained；
Fig. 2-1 is long-life phosphors organic molecule Ultraluminescence spectrogram obtained；
Fig. 2-2 is the fluorescence contrast figure of organic molecule and its nano particle；
Fig. 3 is the fluorescence lifetime figure of organic nanometer granule；
Fig. 4 is organic nanometer granule transmission electron microscope figure；
Fig. 5 is organic nanometer granule cell imaging Laser Scanning Confocal Microscope photo；(nano particle being prepared is in cell membrane
Place is imaged as green fluorescence.)
Fig. 6 is organic nanometer granule in zebra fish blood vessel imaging Laser Scanning Confocal Microscope photo.(nano particle is in zebra fish blood
Pipe imaging has good resolution ratio, and shown in green fluorescence is imaged compared with bright part on zebra fish.)
Specific embodiment
For the clearer elaboration present invention, below by specific embodiment, the present invention will be further described, no
It is limitation of the present invention.
Embodiment 1
The preparation of TADF molecules CzPy-T
In two-mouth bottle (100mL), by 2- bromo nitrobenzenes (2.01g, 10mmol), 2- thienyl boric acids (1.42g, 11mmol)
It is dissolved in 30mL toluene, injection 2M solution of potassium carbonate 20mL. substitutes gas three times, and under nitrogen protection, four (triphenylphosphines) are added
Palladium (150mg, 0.14mmol) is heated to 90 DEG C, reacts 16 hours.Naturally it is cooled to room temperature, dichloromethane extraction is dry, concentrates,
Column chromatography for separation obtains glassy yellow powder 1.85g, yield 81%.1H NMR(400MHz,CDCl3) δ 7.95 (d, J=1.9Hz,
1H), 7.77 (dd, J=8.1,1.9Hz, 1H), 7.56 (d, J=8.1Hz, 1H), 7.42 (d, J=1.0Hz, 1H), 7.39 (dd,
J=5.1,1.1Hz, 1H), 7.11 (d, J=1.4Hz, 1H)13C NMR(101MHz,CDCl3)δ141.03,132.68,
128.69,128.53,127.94,127.50,127.24,127.21,126.71,124.88,120.74。
2- nitros-benzene bithiophene (9.37g, 33mmol), triphenylphosphine are added in two mouthfuls of round-bottomed flasks (250mL)
(22.7g, 100mmol) and chlorobenzene (60mL), nitrogen protection are heated to 140 DEG C and are stirred to react 7 hours, be cooled to room temperature, dichloromethane
Alkane extracts, concentration, and benzene bithiophene and pyrroles powder 4.83g, yield 70.1% are obtained through column chromatography for separation.1H NMR(400MHz,
CDCl3) δ 8.21 (br, 1H), 7.60 (d, J=6.7Hz, 2H), 7.39 (d, J=5.2Hz, 1H), 7.29 (dd, J=8.4,
1.7Hz, 1H), 7.07 (d, J=5.2Hz, 1H)13C NMR(101MHz,CDCl3)δ143.37,141.83,127.73,
123.02,121.07,119.98,117.88,116.02,114.81,111.51。
Above-mentioned benzene bithiophene and pyrroles (3.08g, 18mmol), tetra- fluoro- 4- of 2,3,5,6- are added in two-mouth bottle (250mL)
Cyanopyridine (0.72g, 4mmol), potassium carbonate (6.9g, 50mmol) and dimethyl sulfoxide (100mL), under nitrogen protection, 150 DEG C are stirred
It mixes for 24 hours.Dichloromethane extracts, anhydrous sodium sulfate drying.Concentration, silica gel chromatograph post separation obtain CzPy-T, 2.56g, yield 82%
。1H NMR(400MHz,CDCl3) δ 8.25 (br, 2H), 7.78 (m, 2H), 7.59 (d, J=8.4Hz, 4H), 7.50 (d, J=
1.6Hz, 4H), 7.39 (d, J=5.2Hz, 4H), 7.29 (dd, J=8.4,1.7Hz, 2H), 7.07 (d, J=5.2Hz, 2H).13C
NMR(101MHz,CDCl3)δ146.16,142.42,143.37,141.83,133.9,133.5,128.5,127.29,
123.02,122.03,121.30,119.97,119.90,117.88,116.02,115.84,115.73,114.81。
Embodiment 2
The preparation of TADF molecules CzPy
Above-mentioned benzene bithiophene and pyrroles (6.05g, 48mmol), tetra- fluoro- 4- of 2,3,5,6- are added in two-mouth bottle (250mL)
Cyanopyridine (1.76g, 10mmol), potassium carbonate (9.6g, 70mmol) and dimethyl sulfoxide (100mL), under nitrogen protection, 150 DEG C
Stirring is for 24 hours.Dichloromethane extracts, anhydrous sodium sulfate drying.Concentration, silica gel chromatograph post separation obtain CzPy, 6.34g, yield 82%
。1H NMR(400MHz,CDCl3) δ 7.59 (d, J=8.4Hz, 1H), 7.50 (d, J=1.6Hz, 1H), 7.39 (d, J=5.2Hz,
1H), 7.27-7.24 (dd, J=1.7Hz, 1H), 7.02 (d, J=5.2Hz, 1H), 4.06 (d, J=7.5Hz, 2H), 2.04 (m,
1H),1.28(m,24H),0.84-0.89(m,6H).13C NMR(101MHz,CDCl3)δ146.16,142.42,127.29,
122.03,121.30,119.97,115.84,115.73,113.02,110.56,49.79,38.37,31.88,31.78,
31.68,31.6,29.90,29.58,29.50,29.27,26.4,26.40,22.68,22.63,14.14,14.10。
Embodiment 3
The preparation of TADF molecules CzPy-Na
In two-mouth bottle (100mL), by 2- bromo nitrobenzenes (2.01g, 10mmol), 2- naphthalene boronic acids (1.86g, 11mmol) are molten
Solution injects 2M solution of potassium carbonate 20mL in 30mL tetrahydrofurans.It substitutes gas three times, under nitrogen protection, four (triphenyls is added
Phosphine) palladium (150mg, 0.14mmol), 90 DEG C are heated to, is reacted 16 hours.Naturally it is cooled to room temperature, dichloromethane extraction is dry, dense
Contracting, column chromatography for separation obtain glassy yellow powder 1.67g, yield 65%.1H NMR(400MHz,CDCl3) δ 8.05 (d, J=
1.9Hz, 1H), 8.00 (m, 3H), 7.90 (t, 2H), 7.75 (m, 1H), 7.64 (s, 1H), 7.56 (d, J=8.1Hz, 2H).13C
NMR(101MHz,CDCl3)δ141.13,136.68,134.21,133.1,132.7,130.45,128.5,128.2,128.1,
127.7,126.69,124.4。
Addition 2- nitros-benzene dinaphthalene (2.5g, 10mmol) in two mouthfuls of round-bottomed flasks (250mL), triphenylphosphine (6.3g,
It 28mmol) being heated to 140 DEG C with chlorobenzene (22mL), nitrogen protection and is stirred to react 7 hours, be cooled to room temperature, dichloromethane extracts,
Concentration obtains benzene through column chromatography for separation and joins naphthazole (Cz-Na) powder 1.65g, yield 79%.1H NMR(400MHz,CDCl3)δ
8.16 (d, 2H), 7.71 (m, J=6.7Hz, 2H), 7.65 (m, 1H), 7.51 (d, J=5.2Hz, 1H), 7.40 (m, 1H), 7.29
(dd, J=8.4,1.7Hz, 1H), 7.07 (d, J=5.2Hz, 1H).13C NMR(101MHz,CDCl3)δ135.6,135.5,
133.9,133.5,128.5,127.3,127.2,127.19,121.7,121.4,120.5,119.8,111.1,111.0。
Above-mentioned benzene connection naphthazole (2.18g, 10mmol), tetra- fluoro- 4- cyanogen of 2,3,5,6- are added in two-mouth bottle (250mL)
Yl pyridines (350mg, 2.1mmol), potassium carbonate (3.3g, 25mmol) and dimethyl sulfoxide (100mL), under nitrogen protection, 150 DEG C are stirred
It mixes for 24 hours.Dichloromethane extracts, anhydrous sodium sulfate drying.Concentration, silica gel chromatograph post separation obtain CzPy-Na, 1.84g, yield
85%.1H NMR(400MHz,CDCl3) δ 8.17 (d, J=8.4Hz, 1H), 8.18 (d, J=8.3Hz, 1H), 8.12 (d, J=
8.2Hz, 1H), 7.50~7.65 (m, 4H), 7.48 (s, 1H), 7.41 (s, 1H).13C NMR(101MHz,CDCl3)δ136.7,
136.4,136.1,136.0,135.9,135.87,135.8,135.6,134.4,134.1,133.9,133.8,132.8,
132.6,127.4,127.3,27.29,127.21,127.19,127.0,122.03,121.30,119.97,115.84,
115.73,115.02。
Embodiment 4
It is prepared by CzPy@DSPE-PEG2000 nano particles
1) CzPy of 2mg is dissolved in 2mL tetrahydrofurans, the DSPEG of 2mg is added, at room temperature, ultrasonic mixing is uniform,
And kept for 10 minutes, form light yellow-green solution.
2) in the PBS solution for taking the pH=7.4 that above-mentioned solution 0.5mL is rapidly injected 10mL；Tetrahydrochysene furan is removed under nitrogen stream
It mutters.
3) nano particle aqueous solution for removing THF is filtered through 0.22 micrometer Millipore filtering head, rotates and steams under the conditions of 50 DEG C
Hair removes most of aqueous solvent, and the remaining freeze-dried removing of water obtains target nanoparticle powder.It is received through transmission electron microscope confirmation
Rice grain grain size is about 10~50nm.
Application study
1. method：The presently disclosed water-soluble long-life phosphors nanometer based on thermotropic delayed fluorescence organic material
Grain makes full use of the TADF materials with crowded aroma system in the collected state with fluorescent emission more stronger than solution state,
Simultaneously using DSPE-PEG2000 as enhancing agents, by rapid precipitation method, stable, controllable preparation with size uniformity,
Signal-stabilized water-soluble nanoparticles.Most crucial advantage, which is this nano particle, to be had than common organic or conjugated material more
Good fluorescence lifetime stability and longer fluorescence lifetime has all reached Microsecond grade even if measuring and operating in air
Level, this makes a kind of long-life nano particle disclosed by the invention in cell imaging, live body or imaging of tissue, when passing through
Between resolution techniques overcome in terms of background fluorescence interference that whether there is or not with the advantage of rival.It is disclosed by the invention to be had based on thermotropic delayed fluorescence
The water-soluble long-life phosphors nano particle of machine semi-conducting material is expected to obtain in the sensing detections such as bio-imaging, cell imaging field
To being widely applied.
2. experimental procedure：Using DSPE-PEG2000 as enhancing agents, by rapid precipitation method, stable, controllable system
The standby water-soluble long-life phosphors nano particle with size uniformity, signal-stabilized water-soluble organic semiconducting materials.Transmission
Electron microscope TEM characterizations prove that this kind of material can be self-assembled into the particle of 10nm or so by Subjective and Objective in aqueous solution；
Take prepared nano particle to be dissolved in water or PBS solution, dilute after certain multiple to HELA cells carry out dye marker and
To zebra fish blood vessel imaging, Laser Scanning Confocal Microscope characterization shows that its imaging has the effect of regular hour resolution.
Claims (7)
1. a kind of water-soluble long-life phosphors nanoparticle structure based on thermotropic delayed fluorescence organic material, TADF material Cs zPy
Structural formula is as shown in logical formula (I)：
The nanostructure is made of thermotropic delayed fluorescence organic molecule CzPy and lecithin-polyethylene glycol two parts, and lecithin-is poly-
Ethylene glycol DSPE-PEG2000 molecules, outside, CzPy molecule aggregates are merged at lipophilic end to water-wet side；
In the TADF materials that CzPy is represented in logical formula (I), Py represents Pyridine Molecules, and Cz is class carbazole molecules, wherein Ar1 and Ar2
Indicate that one kind in aryl, substituted aryl, heterocyclic aryl and substituted heterocycle aryl, Cz structures pass through its 9 nitrogen-atoms respectively
It is connected with the 4- cyanopyridines of core.
2. the water-soluble long-life phosphors nanoparticle structure described in claim 1 based on thermotropic delayed fluorescence organic material
Preparation method, it is characterized in that by three steps；
The CzPy of 2mg is dissolved in 2mL tetrahydrofurans by step 1, and the DSPE-PEG2000 of 2mg is added, and ultrasonic mixing is uniform,
And kept for 10 minutes, form clear solution；
Step 2 takes the solution 0.5mL of step 1 to be rapidly injected in the PBS or deionized water solution of the pH=7.4 of 10mL；Nitrogen
Flow down removing tetrahydrofuran；
Step 3 filters nano particle aqueous solution obtained by step 2 through 0.22 micrometer Millipore filtering head, and rotary evaporation removes
Most of aqueous solvent, the remaining freeze-dried removing of water, obtains target nanoparticle powder.
3. the preparation method of the TADF molecules representated by CzPy described in claim 1, which is characterized in that in the formula (I) of general formula,
Ar1 and Ar2 is synthesized by the realization of nitro ring closure reaction with pyrrolo- ring structure, and preparation method can be with following reaction formulas
(II) it indicates；
Wherein synthetic schemes leads in formula (II), and the group representated by Ar1 and Ar2 is respectively aryl described in claim 1, substitution
One kind in aryl, heterocyclic aryl and substituted heterocycle aromatic group；X is bromine atom or iodine atom, and Y can be boronate, boron
One kind of perester radical or trialkyl tinbase.
4. the preparation method of the TADF molecules representated by CzPy according to claim 3, which is characterized in that
(1) step 1) is Suzuki coupling reactions or Stille coupling reactions；When step 1) is Suzuki coupling reactions, need
The aqueous solution of palladium-containing catalyst and inorganic base is used, solvent is toluene or tetrahydrofuran, and it is small to react 16~24 under reflux
When obtain III-3；When step 1) is Stille coupling reactions, need with palladium-containing catalyst in toluene or tetrahydrofuran solution
Back flow reaction 5~24 hours obtains compound III-3 through silica gel column chromatography；
(2) step 2) obtains the cyclization preparation method of Cz molecules, it is characterised in that cyclization reagent is triphenylphosphine or triethoxy
Phosphine, solvent used are chlorobenzene, o-dichlorohenzene, and reaction temperature is 125~145 DEG C, and the reaction time is 6~12 hours；
(3) solvent needed for step 3) is the dimethyl sulfoxide of anhydrous and oxygen-free, and reaction temperature is 100 DEG C~150 DEG C, and the reaction time is
12~20 hours.
5. the water-soluble long-life phosphors nanoparticle structure based on thermotropic delayed fluorescence organic material described in claim 2
Preparation method, it is characterised in that the weight ratio of the TADF and DSPE-PEG2000 is 1:3~3:1；Rotary evaporation removes water temperature
Degree is 50~60 DEG C.
6. the water-soluble long-life phosphors nanoparticle structure described in claim 1 based on thermotropic delayed fluorescence organic material,
It is characterized in that, nano particle diameter is 10~50 nanometers.
7. the preparation method of the TADF molecules representated by the CzPy described in claim 4, which is characterized in that obtained nanometer
The fluorescence lifetime that grain measures in air reaches Microsecond grade.
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| CN108586318B (en) * | 2018-01-16 | 2020-09-18 | 东南大学 | Solution-processable thermally-activated delayed fluorescent material and preparation method thereof |
| CN108329252A (en) * | 2018-01-16 | 2018-07-27 | 东南大学 | A kind of aggregation inducing hot activation delayed fluorescence material and its organic electroluminescence device |
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| CN110093152B (en) * | 2019-05-29 | 2022-02-11 | 南京邮电大学 | Long-life fluorescent nano probe and preparation method and application thereof |
| CN111234809B (en) * | 2020-03-17 | 2023-08-08 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Universal preparation method of water-soluble organic long-afterglow nano aqueous solution |
| CN114105868B (en) * | 2020-09-01 | 2024-03-29 | 江苏三月科技股份有限公司 | Organic compound with 4-cyanopyridine as core and organic electroluminescent device comprising same |
| CN112852410A (en) * | 2021-01-11 | 2021-05-28 | 广州大学 | Electrochemiluminescence active particles and preparation method and application thereof |
| CN113185477A (en) * | 2021-04-15 | 2021-07-30 | 西安交通大学 | Organic light-emitting nanocrystalline material and preparation method thereof |
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