CN103613692B - A kind of single molecular fluorescence polymer micelle and the application as pH probe thereof - Google Patents
A kind of single molecular fluorescence polymer micelle and the application as pH probe thereof Download PDFInfo
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Abstract
The invention discloses and belong to a kind of single molecular fluorescence polymer micelle of fluorescent probe synthesis technical field and the application as pH probe thereof.The technical scheme is that (1) is carried analog derivative of at least four oh group and the like and carried out nucleophilic substitution with 2 bromine isobutyl acylbromides, obtain the multiple spot initiator that end group is bromine group；(2) the oil-soluble fluorescent star polymer with blocking group is obtained by Transfer Radical Polymerization (ATRP) polymerization；(3) utilize protective reaction to remove blocking group, obtain the water soluble fluorescence star polymer with pH sensitive group.Being dissolved in water by different types of water soluble fluorescence star polymer, can obtain different types of single molecular fluorescence polymer micelle solution, every kind of single molecular fluorescence polymer micelle solution can demarcate specific pH value.Single molecular fluorescence polymer micelle prepared by the present invention has good water solublity, photo and thermal stability, is the novel pH polymer probe of a class.
Description
Technical field
The invention belongs to fluorescent probe synthesis technical field, particularly to a kind of single molecular fluorescence polymer micelle and work thereof
Application for pH probe.
Background technology
In recent years, single polymer molecule micelle (Unimolecular polymeric micelle, UPM) causes people
Great interest.By the chemical design to its core and shell, the dissolubility of particle, biocompatibility, stimulating responsive etc. can
It is modified.Additionally, UPM is also used as carrier for medicine and the transport of gene.For self-assembly method, star is gathered
Compound method has exclusive advantage in terms of preparation UPM, and as nucleocapsid structure can design, size can control, it is easy to prepares in a large number
Etc. advantage.In a word, star polymer method provides more possibility for preparing functional type UPM polymer particle.
Being accurately controlled in scientific research of pH value is most important.The important physiological activity energy of chemical reaction even cell
No it is normally carried out, all closely related with pH value.Under normal physiological conditions, H in extracellular fluid+Concentration be about 40nmol/L
(pH=7.40), its amplitude of fluctuation is typically 0.1-0.2 pH unit.Acid and the too strong meeting of alkalescence causes the heart, pneumonopathy to become or neural
Class disease, even can be in peril of one's life time serious.Therefore, the accurately measurement of pH value is particularly significant to chemical biology research.
Some have the organic compound change along with pH value of ad hoc structure, and their fluorescence or extinction property become
Change, and this change can be used to indicate the change of Acidity of Aikalinity in destination media.Wherein, fluorescence spectrometry pH has sensitivity
High, mitigation pattern operation (this technology be particularly suitable for research is muddy and heterogeneous system), the geometry of analytical tool can be used
Design the features such as more flexible.
In numerous fluorescence organic compounds, and derivant has good light, heat, chemical stability, fluorescence volume
Sub-productivity (FQY) is high, and fluorescence emission peak is narrow.Due to the dyeability of its excellence, be widely used in laser dye and
Biological fluorescent labeling field.
Summary of the invention
It is an object of the invention to provide a class light, Heat stability is good, good water solubility, structure are programmable derives with class
Thing or its analog are as single molecular fluorescence polymer micelle (the Unimolecular fluorescent of fluorescent core
Polymeric micelle, UFPM) and preparation method thereof.Utilize potentiometric titration can record its pKa value, near this value
The fluorescence intensity of UFPM solution shows reversibility change, and the response time of this change was less than 1 minute.Poly-by changing
The length of right i.e. polymer chain, can regulate and control the pKa value of polymer, the most just can regulate corresponding pH measured value.
The technical scheme is that (1) carries analog derivative of at least four oh group and the like and 2-
Bromine isobutyl acylbromide carries out nucleophilic substitution, obtains the multiple spot initiator that end group is bromine group；(2) atom transferred free radical is passed through
Polymerization (ATRP) polymerization obtains the oil-soluble fluorescent star polymer with blocking group；(3) protective reaction is utilized to remove
Blocking group, obtains the water soluble fluorescence star polymer with pH sensitive group.By different types of water soluble fluorescence star
Polymer is dissolved in water, and can obtain different types of single molecular fluorescence polymer micelle solution, and every kind of unimolecule is glimmering
Photopolymer micellar solution can demarcate specific pH value.
The concrete operation step of the synthetic method of single molecular fluorescence polymer micelle of the present invention is as follows:
(1) 0.1-1g is dissolved in 20-100mL dichloromethane with the fluorescent chemicals of at least four oh group,
2-bromine isobutyl acylbromide and catalyst of triethylamine is added at 0 DEG C, with the fluorescence chemical combination of at least four oh group under nitrogen atmosphere
The hydroxyl value of thing is (1:10)-(1:20) with the mol ratio of 2-bromine isobutyl acylbromide, and the molal quantity of triethylamine is 2-bromine isobutyl acylbromide
1-1.5 times, be the most gradually warmed up to be stirred at room temperature 24-48h, wash product, then with dichloromethane as eluent, column chromatography is divided
From obtaining the ATRP initiator with multiple bromine substituents；
(2) the ATRP initiator with multiple bromine substituents obtained in step (1) and monomer are dissolved in 2-butanone,
Being subsequently adding catalyst CuBr, the bromine substituent number of ATRP initiator and the mol ratio of monomer with multiple bromine substituents are
(1:10)-(1:200), monomer concentration is 0.1-0.3g/mL；After freezing pump drainage three times, under inert gas shielding, add tertiary fourth
Base bipyridyl, with the bromine substituent number of ATRP initiator of multiple bromine substituents and CuBr, tert-butyl group bipyridyl mole
Ratio is 1:(1-1.5): (2-3)；Seal stirring, at 65-90 DEG C, then react 0.1-20h, by product through neutral alumina
Pillar, then precipitates in the mixed solvent of first alcohol and water, and vacuum drying obtains oil-soluble fluorescent star polymer；
(3) the oil-soluble fluorescent star polymer that 0.1-0.5g step (2) obtains is dissolved in 5-15mL dichloromethane, and
Adding the trifluoroacetic acid of 1-1.5 times of volume, stir 2-24h, ether sedimentation under room temperature condition, vacuum drying obtains water soluble fluorescence
Star polymer；
(4) the water soluble fluorescence star polymer that 0.01-0.05g step (3) obtains is dispersed in 1-10mL water, obtains
Single molecular fluorescence polymer micelle.
The fluorescent chemicals with at least four oh group described in step (1) is analog derivative or its analog
The compound that on naphthalene nucleus or phenyl ring, at least four hydrogen is replaced with ether-oxygen bond by the group with hydroxy functional group.
Described analog derivative or its analog are chosen in particular from both-end naphthalimide, single-ended naphthalimide, both-end acyl
Imines, single-ended acid imide, both-end terylene acid imide, single-ended terylene acid imide.
Monomer described in step (2) includes tert-butyl acrylate, acrylic acid-2-(tertiary oxygen carbonyl) ammonia ethyl ester, acrylic acid uncle
The derivant of butyl ester, acrylic acid-2-(tertiary oxygen carbonyl) derivant of ammonia ethyl ester.
The derivant of described tert-butyl acrylate, acrylic acid-2-(tertiary oxygen carbonyl) derivant of ammonia ethyl ester is acrylic acid
The tert-butyl ester and acrylic acid-2-(tertiary oxygen carbonyl) ammonia ethyl ester double bond on-hydrogen atom taken by the alkyl chain that carbon number is 1-12
Compound after instead of.
The single molecular fluorescence polymer micelle of said method synthesis is as the application of pH probe.
There is advantages that
1., by design fluorescent core molecule, " island " position of analog derivative and the like is modified, obtains
Multi-arm ATRP fluorescence initiator, has synthesized a series of in aqueous with the existence of unimolecular micelle state subsequently by ATRP method
Water soluble fluorescence star polymer.The UFPM prepared by such water soluble fluorescence star polymer can be as pH probe for essence
Really measure the pH value of sample.
2. to utilize ATRP active free radical polymerization method can prepare molecular weight distribution in a large number and rapidly single for the present invention
Star polymer, thus plant the distribution of sizes of UFPM prepared by polymer also the narrowest.
3. the UFPM that prepared by the present invention carries different functional groups, due to difference and the chain length of peripheral type of polymer
Difference, show different pH sensitivity characteristics, its mechanism of action is the change of size, has uniqueness compared with other pH probes
Part.
4. the UFPM that prepared by the present invention has good photo and thermal stability, and reversible fluorescence can be occurred near pKa value strong
Degree change, can regulate its measurable pH value by regulation pKa value, have reversibility pH sensitive, repeatable utilization.
5. the present invention designs conveniently, prepares simply, and the UFPM water solublity of synthesis is excellent, stable in properties, and reaction is efficient soon
Speed, and facilitate recycling, is the novel pH polymer probe of a class.
Accompanying drawing explanation
The structural formula of Fig. 1 analog derivative and the like, alkyl chain that R=contains 2 to 12 C atomic numbeies or arrive containing 6
The fragrant hydrocarbons and their derivates of 14 C atomic numbeies.
Fig. 2 has the carboxyl polymer of pH sensitivity characteristic and amino polymer and the structural formula of the two copolymer, and R=contains
There are the alkyl chain of 2 to 12 C atomic numbeies, n=1-100.
The reacting flow chart of synthesizing water-solubility Fluorescent star-like polymer 4 in Fig. 3 embodiment 1.
The UFPM prepared by water soluble fluorescence star polymer 4 in Fig. 4 embodiment 1 state simulation figure in water.
The uv absorption of UFPM and fluorescent emission spectrogram in Fig. 5 embodiment 3.
In Fig. 6 embodiment 3, UFPM fluorogram and photoluminescence peak in different pH buffer solution change at various ph values
Trendgram.
The mechanism figure of fluorescence intensity change is there is in the UFPM in Fig. 7 embodiment 1 near pKa value.
Detailed description of the invention
Following example are used for illustrating the present invention, but are not limited to the scope of the present invention.If not specializing, embodiment
In the conventional means that is well known to those skilled in the art of technological means used, raw materials used be commercial goods.
Embodiment 1
1. by a generation eight hydroxyl both-end acid imide (8OH-PBI-G1), (400mg, 0.15mmol, be designated as compound 1, knot
Structure formula is as implied above) it is dissolved in 40mL CH2Cl2, it is transferred to 250mL there-necked flask, under nitrogen atmosphere, flask is added in ice bath, directly
To lowering the temperature and being maintained near 0 DEG C, it is initially charged triethylamine (1.64mL, 11.7mmol), the most dropwise dropping 2-bromine isobutyl acylbromide
(1.46mL, 11.7mmol)；After stirring 10min, it is gradually heating to room temperature and starts reaction；Use thin layer chromatography detection reaction interval
Degree, terminates reaction after 48h；The method washed with water removes the salt in reactant, obtains crude product；Dichloromethane is used to do drip washing
Agent, pillar layer separation obtains the ATRP initiator 436mg (being designated as compound 2, structural formula is as follows) with multiple bromine substituents, produces
Rate 76%.
2. by compound 2(17.6mg, 4.5 μm ol), catalyst CuBr(5.1mg, 36 μm ol) and the tertiary fourth of monomeric acrylic
Ester (461mg, 3.6mmol) adds in 25mL reaction tube, dissolves with 2mL 2-butanone, reaches to remove through 3 freezing pump drainage processes
The purpose of oxygen, under the protection of noble gas, adds part tert-butyl group bipyridyl (DTB-bipy), subsequently by plug seal, and warp
After crossing stirring CuBr and the complete complexation of part, reaction tube is added in 100 DEG C of oil baths and start reaction, can obtain through 10min-20h
To oil-soluble fluorescent star polymer, n value was directly proportional to the response time.Mantoquita is removed by product through neutral alumina pillar,
Precipitate 3 times in the mixed solvent of first alcohol and water afterwards, be dried under vacuum to constant weight, obtain sterling oil-soluble fluorescent star polymer
3, structural formula is as follows.
Wherein, n=1-100.
3. take 400mg oil-soluble fluorescent star polymer 3, use 10mL CH2Cl2It is dissolved in 100mL round-bottomed flask,
Add the trifluoroacetic acid of same volume, under room temperature, stir 24h；Precipitate 3 times in a large amount of ether subsequently, be dried under vacuum to constant weight,
Obtaining 215mg water soluble fluorescence star polymer 4, structural formula is as follows.
Wherein n=1-100.
4. the water soluble fluorescence star polymer 4 that 0.01g step 3 obtains is dispersed in 1mL water, obtains single molecular fluorescence
Polymer micelle.
The synthetic route of water soluble fluorescence star polymer 4 is as it is shown on figure 3, its uv absorption and fluorescence spectrum figure such as Fig. 4
Shown in.
Embodiment 2
1. with embodiment 1 step 1；
2. by compound 2(8.8mg, 2.2 μm ol), catalyst CuBr(2.5mg, 17.6 μm ol), with monomer metering system
Acid-2-(tertiary oxygen carbonyl) ammonia ethyl ester (806mg, 3.52mmol) adds in 25mL reaction tube and is dissolved in 2-butanone, and monomer concentration is
0.1g/mL, reaches the purpose of deoxygenation through 3 freezing pump drainage processes, adds part tert-butyl group connection under the protection of noble gas
Pyridine, subsequently by rubber stopper seal, after stirring CuBr and the complete complexation of part, adds reaction tube in 65 DEG C of oil baths and starts
Reaction, reacts through 10-50min, and catalyst is removed by product through neutral alumina pillar, afterwards in the mixing of first alcohol and water
In solvent (v:v=1:1), precipitation 3 times, are dried under vacuum to constant weight, obtain oil-soluble fluorescent star polymer 3 ' (chain length n and reaction
Time is directly proportional).Its structural formula is as follows:
Wherein, n=1-100.
3. take 400mg oil-soluble fluorescent star polymer 3 ' to be dissolved in 10mL dichloromethane, and add the three of same volume
Fluoroethanoic acid, is stirred at room temperature 24h, then concentrates solution, with a large amount of ether sedimentations three times, i.e. obtains as follows water-soluble of structural formula
Property Fluorescent star-like polymer 4 '.
Wherein, n=1-100.
4. the water soluble fluorescence star polymer 4 ' that 0.02g step 3 obtains is dispersed in 5mL water, obtains unimolecule glimmering
Photopolymer micelle.
Embodiment 3
1. with embodiment 1 step 1；
2. by compound 2(17.6mg, 4.5 μm ol), catalyst CuBr(5.1mg, 36 μm ol) and the tertiary fourth of monomeric acrylic
Ester (461mg, 3.6mmol) adds in 25mL reaction tube, dissolves with 2mL 2-butanone, reaches to remove through 3 freezing pump drainage processes
The purpose of oxygen, adds part tert-butyl group bipyridyl (19.3mg, 72 μm ol) under the protection of noble gas, close with rubber stopper subsequently
Envelope, after stirring CuBr and the complete complexation of part, adds reaction tube in 100 DEG C of oil baths and starts reaction, react through 5h, produce
Catalyst is removed by thing through neutral alumina pillar, precipitation 3 times in the mixed solvent (v:v=1:1) of first alcohol and water afterwards,
It is dried under vacuum to constant weight, obtains 130mg oil-soluble fluorescent star polymer 3(n=30).
3. take the oil-soluble fluorescent star polymer 3 that 100mg step 2 obtains, use 10mL CH2Cl2It is dissolved in 100mL
In round-bottomed flask, add the trifluoroacetic acid of same volume, stir under room temperature 24 hours, precipitation 3 times in a large amount of ether subsequently, very
Sky is dried to constant weight, obtains 56mg water soluble fluorescence star polymer 4(n=30).
4. water soluble fluorescence star polymer 4(n=30 0.02g step 3 obtained) it is dispersed in 5mL water, obtain single point
Sub-fluorescent polymer micelle.
Embodiment 4
1. with embodiment 1 step 1；
2. by compound 2(37.6mg, 9.6 μm ol), catalyst CuBr(11mg, 76.8 μm ol), the tertiary fourth of monomeric acrylic
Ester (492mg, 3.84mmol) adds in 25mL reaction tube, dissolves with 2mL 2-butanone, reaches to remove through 3 freezing pump drainage processes
The purpose of oxygen, adds part DTB-bipy(20.6mg, 76.8 μm ol under the protection of noble gas), close with rubber stopper subsequently
Envelope, after stirring CuBr and the complete complexation of part, adds reaction tube in 100 DEG C of oil baths and starts reaction.Anti-through 10min
Should, catalyst is removed by product through neutral alumina pillar, afterwards precipitation in the mixed solvent (v:v=1:1) of first alcohol and water
3 times, it is dried under vacuum to constant weight, obtains 42mg oil-soluble fluorescent star polymer 3(chain length n=1).
3. take the oil-soluble fluorescent star polymer 3 that 40mg step 2 obtains, use 10mL CH2Cl2It is dissolved in 100mL
In round-bottomed flask, add the trifluoroacetic acid of same volume, stir 24 hours under room temperature.Precipitation 3 times in a large amount of ether subsequently, very
Sky is dried to constant weight, obtains 35mg water soluble fluorescence star polymer 4(n=1).
4. water soluble fluorescence star polymer 4(n=1 0.01g step 3 obtained) it is dispersed in 5mL water, obtain single point
Sub-fluorescent polymer micelle.
Embodiment 5
1. with embodiment 1 step 1；
2. by compound 2(9.4mg, 2.4 μm ol), catalyst CuBr(2.8mg, 19.2 μm ol), the tertiary fourth of monomeric acrylic
Ester (492mg, 3.84mmol) adds in 25mL reaction tube, dissolves with 2mL 2-butanone, reaches to remove through 3 freezing pump drainage processes
The purpose of oxygen, adds part DTB-bipy(10.3mg, 38.4 μm ol under the protection of noble gas), close with rubber stopper subsequently
Envelope, after stirring CuBr and the complete complexation of part, adds reaction tube in 100 DEG C of oil baths and starts reaction.Anti-through 250min
Should, catalyst is removed by product through neutral alumina pillar, afterwards precipitation in the mixed solvent (v:v=1:1) of first alcohol and water
3 times, it is dried under vacuum to constant weight, obtains 240mg oil-soluble fluorescent star polymer 3(chain length n=100).
3. take the oil-soluble fluorescent star polymer 3 that 200mg step 2 obtains, use 10mL CH2Cl2It is dissolved in 100mL
In round-bottomed flask, add the trifluoroacetic acid of same volume, stir 2 hours under room temperature.Precipitation 3 times in a large amount of ether subsequently, very
Sky is dried to constant weight, obtains 110mg water soluble fluorescence star polymer (n=100).
4. the water soluble fluorescence star polymer (n=100) 0.05g step 3 obtained is dispersed in 5mL water, obtains single point
Sub-fluorescent polymer micelle.
Embodiment 6
1. with embodiment 1 step 1；
2. by compound 2(8.8mg, 2.2 μm ol) catalyst CuBr(2.5mg, 17.6 μm ol), with monomer metering system
Acid-2-(tertiary oxygen carbonyl) ammonia ethyl ester (806mg, 3.52mmol) adds in 25mL reaction tube and is dissolved in butanone, and monomer concentration is
0.1g/mL, reaches the purpose of deoxygenation through 3 freezing pump drainage processes, adds part DTB-bipy under the protection of noble gas
(9.4mg, 35.2 μm ol), subsequently by rubber stopper seal, after stirring CuBr and the complete complexation of part, add 65 by reaction tube
DEG C oil bath starts reaction.Reacting through 50min, catalyst is removed by product through neutral alumina pillar, afterwards at methanol
With precipitation 3 times in the mixed solvent (v:v=1:1) of water, it is dried under vacuum to constant weight, obtains 400mg oil-soluble fluorescent star polymer
3 ' (n=100).
3. the oil-soluble fluorescent star polymer 3 ' (400mg) step 2 obtained is dissolved in 10mL dichloromethane, and adds
The trifluoroacetic acid of same volume, is stirred at room temperature 2h, then concentrates solution, with 50mL ether sedimentation three times, i.e. obtains water solublity glimmering
Light star polymer 4 ' (n=100).
4. the water soluble fluorescence star polymer 4 ' (n=100) 0.05g step 3 obtained is dispersed in 5mL water, obtains list
Molecular fluorescence polymer micelle.
Embodiment 7
1. the compound 1 ' (442mg, 0.32mmol, structural formula is as implied above) with four hydroxyls is dissolved in 40mL
CH2Cl2, it is transferred to 250mL there-necked flask, logical nitrogen 15min, gets rid of air, is added in ice bath by flask, until lowering the temperature and protecting
Hold near 0 DEG C, be initially charged triethylamine (1.80mL, 12.8mmol), the most dropwise dropping 2-bromine isobutyl acylbromide (1.60mL,
12.8mmol).After stirring 10min, it is gradually heating to room temperature and starts reaction.Use the thin layer chromatography detection extent of reaction, after 48h
Terminate reaction.The method washed with water removes the salt in reactant, obtains crude product.Dichloromethane is used to do eluent, post color
Spectrum isolated is with the ATRP initiator 430mg (being designated as compound 2 ', structural formula is as follows) of multiple bromine substituents, productivity 75%.
2. by compound 2 ' (18.8mg, 9.6 μm ol), catalyst CuBr(5.5mg, 38.4 μm ol) and monomeric acrylic uncle
Butyl ester (492mg, 3.84mmol) adds in 25mL reaction tube, dissolves with 2mL 2-butanone, reaches through 3 freezing pump drainage processes
The purpose of deoxygenation, adds part DTB-bipy(20.6mg, 76.8 μm ol under the protection of noble gas), close with rubber stopper subsequently
Envelope, after stirring CuBr and the complete complexation of part, adds reaction tube in 90 DEG C of oil baths and starts reaction.React through 5h, produce
Catalyst is removed by thing through neutral alumina pillar, precipitation 3 times in the mixed solvent (v:v=1:1) of first alcohol and water afterwards,
It is dried under vacuum to constant weight, obtains 145mg oil-soluble fluorescent star polymer 3 " (n=30), its structural formula is as follows:
3. take the 100mg oil-soluble fluorescent star polymer 3 that step 2 obtains ", use 10mL CH2Cl2It is dissolved in
In 100mL round-bottomed flask, add the trifluoroacetic acid of same volume, stir 24 hours under room temperature.3 are precipitated subsequently in a large amount of ether
Secondary, be dried under vacuum to constant weight, obtain 56mg water soluble fluorescence star polymer 4 " (n=30), its structural formula is as follows:
4. the water soluble fluorescence star polymer 4 0.02g step 3 obtained " (n=30) be dispersed in 4mL water, obtains list
Molecular fluorescence polymer micelle.
Application Example 1
The pKa value of the UFPM solution obtained by embodiment 3 is 6.3, and being added by 0.2mLUFPM solution needs to regulate pH value
In 10mL solution, take 20 μ L every time and be diluted to 2mL and measure its fluorescence spectrum, when its fluorescence intensity reduces suddenly, show solution
PH value reached near 6.3.
Application Example 2
The pKa value of the UFPM solution that embodiment 6 obtains is 8.0, and being added by 0.2mLUFPM solution needs to regulate pH value
In 10mL solution, take 20 μ L every time and be diluted to 2mL and measure its fluorescence spectrum, when its fluorescence intensity reduces suddenly, show solution
PH value reached near 8.0.
Although, the present invention is described in detail the most with a general description of the specific embodiments, but
On the basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the scope of protection of present invention.
Claims (3)
1. the synthetic method of a pH probe, it is characterised in that described pH probe is single molecular fluorescence polymer micelle, its tool
Body synthesis step is as follows:
(1) 0.1-1g is dissolved in 20-100mL dichloromethane with the fluorescent chemicals of at least four oh group, nitrogen
2-bromine isobutyl acylbromide and catalyst of triethylamine is added at 0 DEG C, with the fluorescent chemicals of at least four oh group under atmosphere
Hydroxyl value is (1:10)-(1:20) with the mol ratio of 2-bromine isobutyl acylbromide, and the molal quantity of triethylamine is the 1-of 2-bromine isobutyl acylbromide
1.5 times, the most gradually it is warmed up to be stirred at room temperature 24-48h, washes product, then with dichloromethane as eluent, pillar layer separation obtains
To the ATRP initiator with multiple bromine substituents；
(2) the ATRP initiator with multiple bromine substituents obtained in step (1) and monomer are dissolved in 2-butanone, then
Add catalyst CuBr, with the bromine substituent number of ATRP initiator and the mol ratio of monomer of multiple bromine substituents be (1:
10)-(1:200), monomer concentration is 0.1-0.3g/mL；After freezing pump drainage three times, under inert gas shielding, add tert-butyl group connection
Pyridine, the bromine substituent number of ATRP initiator and the mol ratio of CuBr, tert-butyl group bipyridyl with multiple bromine substituents are
1:(1-1.5):(2-3)；Seal stirring, at 65-90 DEG C, then react 0.1-20h, by product through neutral alumina pillar,
Then precipitating in the mixed solvent of first alcohol and water, vacuum drying obtains oil-soluble fluorescent star polymer；
(3) the oil-soluble fluorescent star polymer that 0.1-0.5g step (2) obtains is dissolved in 5-15mL dichloromethane, and adds
The trifluoroacetic acid of 1-1.5 times of volume, stirs 2-24h, ether sedimentation under room temperature condition, vacuum drying obtains water soluble fluorescence star
Polymer；
(4) the water soluble fluorescence star polymer that 0.01-0.05g step (3) obtains is dispersed in 1-10mL water, obtains single point
Sub-fluorescent polymer micelle；
The fluorescent chemicals with at least four oh group described in step (1) be the naphthalene nucleus of analog derivative or phenyl ring up to
The compound that rare four hydrogen are replaced with ether-oxygen bond by the group with hydroxy functional group；
Monomer described in step (2) includes tert-butyl acrylate, acrylic acid-2-(tertiary oxygen carbonyl) ammonia ethyl ester, tert-butyl acrylate
Derivant, the derivant of acrylic acid-2-(tertiary oxygen carbonyl) ammonia ethyl ester.
Synthetic method the most according to claim 1, it is characterised in that described analog derivative is chosen in particular from both-end naphthoyl
Imines, single-ended naphthalimide, both-end acid imide, single-ended acid imide, both-end terylene acid imide, single-ended Rhizoma Kaempferiae embedding two
Benzoylimino.
Synthetic method the most according to claim 1, it is characterised in that the derivant of described tert-butyl acrylate, propylene
The derivant of acid-2-(tertiary oxygen carbonyl) ammonia ethyl ester is tert-butyl acrylate and the double bond of acrylic acid-2-(tertiary oxygen carbonyl) ammonia ethyl ester
On-hydrogen atom replaced by alkyl chain that carbon number is 1-12 after compound.
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| US11441036B2 (en) * | 2016-10-06 | 2022-09-13 | Basf Se | 2-phenylphenoxy-substituted perylene bisimide compounds and their use |
| CN107141448B (en) * | 2017-03-01 | 2019-04-05 | 苏州大学 | A kind of fluorescence conjugated macromolecule of polycarboxylic acid sodium salt group, preparation method and application |
| CN107033267B (en) * | 2017-03-15 | 2020-04-28 | 北京化工大学 | Preparation of a series of water-soluble polymers based on Lerinyl compounds and application of water-soluble polymers as photothermal reagents in biomedicine |
| CN106939058B (en) * | 2017-04-11 | 2019-03-15 | 中国科学院化学研究所 | A kind of branch point fluorescent marker star-type polymer and preparation method thereof |
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| CN102504105A (en) * | 2011-11-21 | 2012-06-20 | 湖北大学 | Water-soluble naphthalene imide fluorescent polymer as well as synthesis method and purpose thereof |
| CN103172776A (en) * | 2013-04-08 | 2013-06-26 | 中国农业大学 | Fluorescent star-like polymer as well as preparation method and application thereof |
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| CN102504105A (en) * | 2011-11-21 | 2012-06-20 | 湖北大学 | Water-soluble naphthalene imide fluorescent polymer as well as synthesis method and purpose thereof |
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