CN101792531A - Preparation method of fluorescent polymer with hydrophilic outer shell and hydrophobic inner core - Google Patents
Preparation method of fluorescent polymer with hydrophilic outer shell and hydrophobic inner core Download PDFInfo
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Abstract
The invention discloses a preparation method of a fluorescent polymer with a hydrophilic outer shell and a hydrophobic inner core, which mainly comprises the following steps: (1) carrying out cyclotrimerization on diacetylene monomers containing fluorescent chromophores for preparing a hyperbranched fluorescent polymer, wherein the periphery of the hyperbranched fluorescent polymer comprises non-reacted alkynyl; carrying out substitution on a hydrophilic polymer chain segment for obtaining the hydrophilic polymer chain segment which can be added or coupled, or carrying out polymerization on hydrophilic monomers for obtaining the hydrophilic polymer chain segment which can be added or coupled; and (2) correspondingly carrying out addition or coupling reaction on the hyperbranched fluorescent polymer and the hydrophilic polymer chain segment which can be added or coupled for obtaining the fluorescent polymer with the hydrophilic outer shell and the hydrophobic inner core. The preparation method belongs to the technical field of functional materials; compared with the prior art, the hydrophilicity of the fluorescent polymer is significantly improved; the defects of optical bleaching and poor stability of organic small molecular fluorescent dyes; and the detection result is accurate.
Description
Technical field
The invention belongs to technical field of function materials, be specifically related to a kind of preparation method of amphipathic fluorescent polymer.
Background technology
Fluoroscopic examination has high sensitivity, highly selective, fast-response and does not have advantages such as destructiveness, and more and more subject begins to use the fluoroscopic examination means and carries out scientific research, and some of them have obtained practical application.Especially at biomedical aspect, fluoroscopic examination has broad application prospects.Research as biological processes such as the identification of the hydrolysis of metabolic process, ATP in the detection of glucose in the blood of human body, the vital movement, DNA, clinical analysiss all needs the instrument of a kind of highly sensitive and ease for operation to realize, the fluorescent probe of being made by fluorescent material is undoubtedly one of best choice.Yet, be used for biological field, at first to solve two key issues of water-soluble and high sensitivity of fluorescent material.
At present, the organic molecule fluorescence dye is used widely in fluoroscopic examination, and it is water-soluble to improve by means such as chemically modified or embeddings.Molecular probe company (Molecular Probes, the U.S.) has released more than 4700 kind of small molecules fluorescent probe, occupies governance property status in the international market.The problem that this class probe exists is: because photobleaching, fluorescence molecule fluorescence intensity after optical radiation for some time significantly reduces even complete failure, has a strong impact on detected result.In recent years, scientists begins to attempt replacing the small molecules fluorescent probe with fluorescent polymer, attempts to solve photobleaching and light stability problem, and obtained major progress in fundamental research.Because fluorescent polymer normally contains the line polymer of big conjugation group, so itself be water-fast.Water-soluble in order to obtain, method in common is by chemically modified this base polymer to be prepared into polyelectrolyte.But strong interaction is arranged between polyelectrolyte and the biomolecules, can influence detected result.Scientist has also been developed inorganic quantum dot in recent years as fluorescent probe, this class material can effectively solve photobleaching and stability problem, but constitute luminous inorganic quantum dot and contain elements such as cadmium, tellurium, arsenic, bio-toxicity is quite big, must carry out a lot of chemically modifieds on its surface and improve its biocompatibility, complex steps.And inorganic quantum dot degradation mechanism in vivo is not clear at present, and whether wherein metal ion can discharge and be still waiting further research when existing in vivo for a long time.
Therefore, develop a kind of high-efficiency fluorescence probe material of good hydrophilic property, significant for the research in fields such as biology.
Summary of the invention
The objective of the invention is to provide a kind of preparation method of fluorescent polymer newly with hydrophilic outer shell and hydrophobic inner core.
For achieving the above object, the technical solution used in the present invention is: this preparation method with fluorescent polymer of hydrophilic outer shell and hydrophobic inner core mainly may further comprise the steps:
(1) two alkynes monomers that will contain fluorescence chromophore make hyperbranched fluorescent polymer by cyclotrimerization, the unreacted alkynyl of outer shroud of this hyperbranched fluorescent polymer;
But but the hydrophilic polymer segment of band simple function group is obtained the hydrophilic polymer segment of addition or coupling by substitution reaction, but or but hydrophilic monomer carried out the hydrophilic polymer segment that polyreaction obtains addition or coupling;
(2) but but the hydrophilic polymer segment of described hyperbranched fluorescent polymer and addition or coupling is correspondingly obtained the fluorescent polymer of hydrophilic outer shell and hydrophobic inner core by addition or coupled reaction, its hydrophobic inner core is a hyperbranched polymer.Wherein, but the hydrophilic polymer segment of addition combine with hyperbranched fluorescent polymer by addition reaction, but the hydrophilic polymer segment of coupling combines with hyperbranched fluorescent polymer by coupled reaction.
Further, the present invention is in step (1), and the hydrophilic polymer segment of described band simple function group is the polyoxyethylene glycol of band simple function group.
Further, the present invention is in step (1), and described hydrophilic monomer is a N-isopropylacrylamide.
Further, step of the present invention (2) but described in addition reaction be 1 between the hydrophilic polymer segmental azido-of peripheral unreacted alkynyl of hyperbranched fluorescent polymer and addition, the 3-Dipolar Cycloaddition.
Further, the present invention is in described addition reaction, and reaction solvent is toluene and N, the mixing solutions of N '-dimethyl formamide, and temperature of reaction is 80-100 ℃.
Further, step of the present invention (2) but described in addition reaction be addition reaction between the hydrophilic polymer segmental sulfydryl of peripheral unreacted alkynyl of hyperbranched fluorescent polymer and addition.
Further, step of the present invention (2) but described in coupled reaction be coupled reaction between the hydrophilic polymer segmental iodobenzene group of peripheral unreacted alkynyl of hyperbranched fluorescent polymer and coupling.
Further, the present invention is a catalyzer with the secondary amine in the described cyclotrimerization of step (1).
The beneficial effect that the present invention compared with prior art has is:
1. this polymkeric substance has the shell that hydrophilic segment constitutes, and has protected the fluorescence chromophore of kernel on the one hand; The more important thing is that polyoxyethylene glycol and PNIPAM are typical water-soluble polymers, and be proved to be and have excellent biological compatibility and low bio-toxicity, can overcome the big shortcoming of inorganic semiconductor quanta point biological toxicity.Hydrophilic terminated is in conjunction with whole polymkeric substance wetting ability is significantly improved.
2. this polymkeric substance has the kernel that hyperbranched fluorescent polymer constitutes, dissaving structure can add lustre to a large amount of fluorescence and reunite collection in little space, can effectively improve fluorescence intensity, reduce photobleaching, thereby overcome the problem of the photobleaching and the poor stability of small molecules organic fluorescent dye.
3. this water-soluble of fluorescent polymer with hydrophilic outer shell and hydrophobic inner core is provided by hydrophilic segment, therefore, during used as fluorescent probe, can not resemble the fluorescent material such as polyelectrolyte and produce strong interaction between the biomolecules and influence detected result, guarantee the accuracy that detects.
Embodiment
The invention discloses a kind of method for preparing the fluorescent polymer of possess hydrophilic property shell, hydrophobic cores structure.Its preparation method may further comprise the steps: two alkynes monomers that (1) will contain fluorescence chromophore make hyperbranched fluorescent polymer by cyclotrimerization, the unreacted alkynyl of outer shroud of this hyperbranched fluorescent polymer; But but the hydrophilic polymer segment of band simple function group is obtained the hydrophilic polymer segment of addition or coupling by substitution reaction, but or but hydrophilic monomer carried out the hydrophilic polymer segment that polyreaction obtains addition or coupling; (2) but but the hydrophilic polymer segment of described hyperbranched fluorescent polymer and addition or coupling is correspondingly obtained the fluorescent polymer of hydrophilic outer shell and hydrophobic inner core by addition or coupled reaction.
The fluorescent polymer that the present invention obtains has nuclear-shell two portions: kernel is made of the hyperbranched polymer that contains fluorescence chromophore, and shell is made of the hydrophilic polymers segment.
Further specify the present invention below in conjunction with specific embodiment.
Embodiment 1:
Step 1): on the one hand, in the 100mL flask, add 36mL N, N '-dimethyl formamide (DMF).Under 0 ℃ ice bath, the 46mL phosphorus oxychloride is dropwise added flask and constantly stirring.After treating that the phosphorus oxychloride adding finishes, take by weighing the 4.9g triphenylamine and add, remove ice bath, and be warming up to 95 ℃.After the back flow reaction 4 hours, extraction treatment, column chromatography gets intermediate product 1 after separating purification.Add 1.2g intermediate product 1 at two mouthfuls of flasks of exsiccant 250mL, guarantee the anhydrous and oxygen-free condition, add the tetrahydrofuran solution that 40mL dewaters.Under the ice bath, dropwise add the tetrahydrofuran solution of the ethynyl magnesium bromide of 20mL 0.5M.Reaction is at room temperature spent the night, and uses the saturated aqueous ammonium chloride termination reaction.Reaction solution concentrates organic phase after extraction.Concentrated solution is dissolved in the 100mL dichloromethane solution, adds 7.08g 85% activatory Manganse Dioxide.Reaction is spent the night under the room temperature, after the filtering and concentrating, separates purification with column chromatography, finally obtains containing two alkynes monomers of triphenylamine chromophore.
The monomeric structural formula of two alkynes that contains triphenylamine chromophore is as the formula (1):
The two alkynes monomers that 140mg contained triphenylamine chromophore add in the polymerizing pipes, behind the vacuum nitrogen filling gas 3 times, add the 3.5mL dioxane as solvent, and the piperidines that adds 0.45mL again is as catalyzer.Reacted 24 hours down at 100 ℃.This reaction is a cyclotrimerization.After question response finishes, precipitate dropwise adding in a large amount of methyl alcohol after the reaction solution dilution.Left standstill 24 hours, filtration drying obtains containing the hyperbranched fluorescent polymer of hydrophobicity of triphenylamine chromophore to constant weight, represents with " hb-TPA ".By formula (2) as seen, the unreacted alkynyl of outer shroud of hb-TPA.Reaction formula is as the formula (2):
On the other hand, adding in 250mL twoport flask the 7g molecular weight is the polyoxyethylene glycol (PEG of 350 band monohydroxy
350-OH), add the 20mL tetrahydrofuran (THF) and the 20mL 0.5g/mL NaOH aqueous solution again, fully stir and the ice bath cooling.The 2g Tosyl chloride is dissolved in the 60mL tetrahydrofuran (THF), dropwise joins in the flask.After dropwising, remove ice bath, make temperature of reaction rise to room temperature.Behind the question response 18 hours, the reaction solution extraction is concentrated, separate purification, obtain the single sulfonic polyoxyethylene glycol (PEG of band with column chromatography
350-OTs).In 100mL single port flask, add 3.5g PEG
350-OTs, 0.78g NaN
3With 15mL dimethyl sulfoxide (DMSO) (DMSO), reaction is 24 hours under the room temperature.After reaction finishes, add 30mL water termination reaction.With the reaction solution extracted with diethyl ether, organic phase is through anhydrous MgSO
4Dry after-filtration concentrates, and obtains carrying out the polyoxyethylene glycol (PEG of the band list azido-of addition reaction
350-N
3).
Step 2): take by weighing 34mg hb-TPA and PEG
350-N
3130mg adds DMF and each 0.5mL of toluene as solvent in polymerizing pipe, 90 ℃ were reacted 5 hours down, make unreacted alkynyl of outer shroud and the PEG of hb-TPA
350-N
3Azido-between carry out 1, the 3-Dipolar Cycloaddition.After reaction finished, reaction solution dilution back was precipitated in a large amount of normal hexanes, leaves standstill 24 hours, and filtration drying obtains amphiphilic hyper-branched fluorescent polymer to constant weight, i.e. the fluorescent polymer of hydrophilic outer shell and hydrophobic inner core.Reaction formula is as the formula (3):
Static contact angle test shows: not with PEG
350The contact angle of bonded hb-TPA is 118.2 °, and the contact angle of the fluorescent polymer of the hydrophilic outer shell and hydrophobic inner core that present embodiment obtains is 81.4 °, and the reduction of contact angle value shows that wetting ability improves.
Embodiment 2:
Step 1): the method by embodiment 1 prepares hb-TPA.
And with the molecular weight among the embodiment 1 polyoxyethylene glycol (the PEG of 350 band monohydroxy
350-OH) to change molecular weight into be 1900 polyoxyethylene glycol (PEG
1900-OH), other preparation conditions are identical with embodiment 1, and the preparation molecular weight is the polyoxyethylene glycol (PEG of 1900 band list nitrine end group
1900-N
3).
Step 2): take by weighing 40mg hb-TPA and 800mg PEG
1900-N
3In polymerizing pipe, add DMF and each 1mL of toluene as solvent, 100 ℃ were reacted 4 hours down, make unreacted alkynyl of outer shroud and the PEG of hb-TPA
1900-N
3Azido-between carry out 1, the 3-Dipolar Cycloaddition.After reaction finished, reaction solution dilution back was precipitated in a large amount of normal hexanes, leaves standstill 24 hours, and filtration drying obtains amphiphilic hyper-branched fluorescent polymer to constant weight, i.e. the fluorescent polymer of hydrophilic outer shell and hydrophobic inner core.
Static contact angle test shows: not with PEG
1900The contact angle of bonded hb-TPA is 118.2 °, and the contact angle of the fluorescent polymer of the hydrophilic outer shell and hydrophobic inner core that present embodiment obtains is 58.5 °, and wetting ability is significantly improved.Compare with traditional fluorescent material, have good wetting ability.
Embodiment 3:
Step 1): at first, 3.17g 4-bromine benzophenone is joined in two mouthfuls of flasks of 250mL of thorough drying, add the new tetrahydrofuran (THF) that steams of 60mL under the anhydrous and oxygen-free condition.With acetone/liquid nitrogen mixed solution is ice bath, and temperature dropwise adds the n-Butyl Lithium hexane solution of 10mL 1.6M about-78 ℃.Temperature of reaction system was remained on about-78 ℃ two hours, and dropwise added the DMF that 2.4mL removed water subsequently.After adding finishes, get back to room temperature, reacted 24 hours.Reaction solution obtains intermediate product 1 through extraction after the column chromatography for separation.Add 1.2g intermediate product 1 at two mouthfuls of flasks of exsiccant 250mL, under the anhydrous and oxygen-free environment, add the new tetrahydrofuran solution that steams of 40mL.Under the ice bath, dropwise add the ethynyl magnesium bromide tetrahydrofuran solution of 15mL 0.5M.Reaction is at room temperature spent the night, and uses the saturated aqueous ammonium chloride termination reaction, and reaction solution concentrates behind dichloromethane extraction.Concentrated solution is dissolved in the 100mL acetone, and the Jones reagent that adds the preparation of the chromium sesquioxide solution and the vitriol oil is with its oxidation.After reacting completely, with Virahol neutralization, after reaction solution is concentrated, column chromatography separates purification, finally obtains containing two alkynes monomers of tetraphenyl ethene chromophore.
The monomeric structural formula of two alkynes that contains tetraphenyl ethene chromophore is as the formula (4):
The two alkynes monomers that 200mg contained tetraphenyl ethene chromophore add in the polymerizing pipes, behind the vacuum nitrogen filling gas 3 times, add the 3.5mL dioxane as solvent, and the piperidines that adds 0.45mL again is as catalyzer.Reacted 24 hours down at 100 ℃.This reaction is a cyclotrimerization.After question response finishes, precipitate dropwise adding in a large amount of methyl alcohol after the reaction solution dilution.Left standstill 24 hours, filtration drying obtains containing the hyperbranched fluorescent polymer of hydrophobicity of tetraphenyl ethene chromophore to constant weight, with " hb-TPE " expression, the unreacted alkynyl of outer shroud of same hb-TPE.
Secondly, with the molecular weight among the embodiment 1 be the polyoxyethylene glycol (PEG of 350 band monohydroxy
350-OH) to change molecular weight into be 6000 polyoxyethylene glycol (PEG
6000-OH), other preparation conditions are identical with embodiment 1, and the preparation molecular weight is the polyoxyethylene glycol (PEG of 6000 band list nitrine end group
6000-N
3).
Step 2): take by weighing 40mg hb-TPE and 1g PEG
6000-N
3In polymerizing pipe, add DMF and each 1mL of toluene as solvent, 80 ℃ were reacted 7 hours down, make unreacted alkynyl of outer shroud and the PEG of hb-TPA
6000-N
3Azido-between carry out 1, the 3-Dipolar Cycloaddition.After reaction finished, reaction solution dilution back was precipitated in a large amount of normal hexanes, leaves standstill 24 hours, and filtration drying obtains amphiphilic hyper-branched fluorescent polymer to constant weight, i.e. the fluorescent polymer of hydrophilic outer shell and hydrophobic inner core.
Static contact angle test shows: not with PEG
6000The contact angle of bonded hb-TPE is 124.4 °, and the contact angle of the fluorescent polymer of the hydrophilic outer shell and hydrophobic inner core that present embodiment obtains is 45.7 °, and wetting ability improves greatly, and hydrophilicity is very good.
Embodiment 4:
Step 1): the method by embodiment 3 prepares hb-TPE.
In addition, add the N-isopropylacrylamide monomer in the 20mL polymerizing pipe, under the anhydrous and oxygen-free condition, the DMF that adding dewaters is as solvent, and cumyl dithiobenzoic acid ester is as RAFT reagent, and Diisopropyl azodicarboxylate is as initiator.Wherein, RAFT reagent and monomeric mol ratio are 1: 135, and the mol ratio of RAFT reagent and initiator is 5: 1.Polyreaction was carried out under 70 ℃ 18 hours.After reaction finishes, reaction solution dilution back is precipitated in a large amount of ether, left standstill 24 hours, filtration drying obtains PNIPAM (PNIPAM) polymkeric substance to constant weight.With the hydrolysis in sodium borohydride solution of this polymkeric substance, purifying by dialysis method to obtain the PNIPAM (PNIPAM-SH) of an edge tail band sulfydryl, can further carry out addition reaction with triple bond.By the gel chromatography analysis, the molecular weight of PNIPAM-SH about 10,000.
Step 2): take by weighing 30mg hb-TPE and 800mg PNIPAM-SH in polymerizing pipe, add 2.5mL DMF under the anhydrous and oxygen-free condition as solvent, add the 0.5g diphenylamine as catalyzer, reaction is 24 hours under the room temperature, makes between the sulfydryl of the unreacted alkynyl of outer shroud of hb-TPE and PNIPAM-SH to carry out addition reaction.After reaction finished, reaction solution dilution back was precipitated in a large amount of normal hexanes, leaves standstill 24 hours, and filtration drying obtains amphiphilic hyper-branched fluorescent polymer to constant weight, i.e. the fluorescent polymer of hydrophilic outer shell and hydrophobic inner core.
The static contact angle test shows: the contact angle with PNIPAM bonded hb-TPE is not 124.4 °, and the contact angle of the fluorescent polymer of the hydrophilic outer shell and hydrophobic inner core that present embodiment obtains is 33.6 °, and wetting ability improves greatly.
Embodiment 5:
Step 1): the method by embodiment 1 prepares hb-TPA.
In addition, take by weighing the polyoxyethylene glycol (PEG that the 6g molecular weight is 3000 band monohydroxy
3000-OH) join in the flask of 250mL with the 600mg 4-Iodobenzoic acid, add 450mg N again, N '-dicyclohexyl carbodiimide (DCC) is as condensing agent, 147mg 4-Dimethylamino pyridine (DMAP) is as catalyzer, the 500mg p-methyl benzene sulfonic chloride is as dewatering agent, tetrahydrofuran (THF) with new steaming is a solvent, and reaction is 10 hours under the room temperature.After reaction finishes, filter, filtrate is dissolved in the tetrahydrofuran (THF) after concentrating once more, purifies by dialysis method, obtains having the polyoxyethylene glycol hydrophilic segment (PEG of Bian iodine group
3000-Ph-I), can further carry out coupled reaction with triple bond.
Step 2): take by weighing 40mg hb-TPA and 600mg PEG
3000-Ph-I adds in the round-bottomed flask of 250mL, add the 100mL triethylamine under the anhydrous and oxygen-free condition as solvent, add 20mg two triphenylphosphine palladium chlorides, 16mg cuprous iodide and 10mg triphenylphosphine are as catalyzer, 30 ℃ were reacted 10 hours down, make unreacted alkynyl of outer shroud and the PEG of hb-TPA
3000Carry out coupled reaction between the Bian phenyl group of-Ph-I.After reaction finished, reaction solution dilution back was precipitated in ether, leaves standstill 24 hours, filters the polymkeric substance that obtains and purifies by dialysis method, obtains amphiphilic hyper-branched fluorescent polymer, i.e. the fluorescent polymer of hydrophilic outer shell and hydrophobic inner core.
Static contact angle test shows: not with PEG
3000The contact angle of bonded hb-TPA is 118.2 °, and the contact angle of the fluorescent polymer of the hydrophilic outer shell and hydrophobic inner core that present embodiment obtains is 52.3 °, and wetting ability improves.
Claims (8)
1. preparation method with fluorescent polymer of hydrophilic outer shell and hydrophobic inner core is characterized in that may further comprise the steps:
(1) two alkynes monomers that will contain fluorescence chromophore make hyperbranched fluorescent polymer by cyclotrimerization, the unreacted alkynyl of outer shroud of this hyperbranched fluorescent polymer;
But but the hydrophilic polymer segment of band simple function group is obtained the hydrophilic polymer segment of addition or coupling by substitution reaction, but or but hydrophilic monomer carried out the hydrophilic polymer segment that polyreaction obtains addition or coupling;
(2) but but the hydrophilic polymer segment of described hyperbranched fluorescent polymer and addition or coupling is correspondingly obtained the fluorescent polymer of hydrophilic outer shell and hydrophobic inner core by addition or coupled reaction.
2. the preparation method with fluorescent polymer of hydrophilic outer shell and hydrophobic inner core according to claim 1 is characterized in that: in step (1), the hydrophilic polymer segment of described band simple function group is the polyoxyethylene glycol of band simple function group.
3. the preparation method with fluorescent polymer of hydrophilic outer shell and hydrophobic inner core according to claim 1 is characterized in that: in step (1), described hydrophilic monomer is a N-isopropylacrylamide.
4. the preparation method with fluorescent polymer of hydrophilic outer shell and hydrophobic inner core according to claim 1, it is characterized in that: step (2) but described in addition reaction be 1 between the hydrophilic polymer segmental azido-of peripheral unreacted alkynyl of hyperbranched fluorescent polymer and addition, the 3-Dipolar Cycloaddition.
5. the preparation method with fluorescent polymer of hydrophilic outer shell and hydrophobic inner core according to claim 4, it is characterized in that: in described addition reaction, reaction solvent is toluene and N, the mixing solutions of N '-dimethyl formamide, and temperature of reaction is 80-100 ℃.
6. the preparation method with fluorescent polymer of hydrophilic outer shell and hydrophobic inner core according to claim 1 is characterized in that: step (2) but described in addition reaction be addition reaction between the hydrophilic polymer segmental sulfydryl of peripheral unreacted alkynyl of hyperbranched fluorescent polymer and addition.
7. the preparation method with fluorescent polymer of hydrophilic outer shell and hydrophobic inner core according to claim 1 is characterized in that: step (2) but described in coupled reaction be coupled reaction between the hydrophilic polymer segmental iodobenzene group of peripheral unreacted alkynyl of hyperbranched fluorescent polymer and coupling.
8. the preparation method with fluorescent polymer of hydrophilic outer shell and hydrophobic inner core according to claim 1 is characterized in that: in the described cyclotrimerization of step (1), be catalyzer with the secondary amine.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262626A (en) * | 2014-09-03 | 2015-01-07 | 浙江大学 | Method for synthesizing multi-hydroxyl fluorescent polymer |
| CN104448061A (en) * | 2014-11-20 | 2015-03-25 | 四川大学 | Simple method for connecting acrylate copolymer with fluorescent functional groups |
| CN106008920A (en) * | 2016-06-26 | 2016-10-12 | 苏州吉人高新材料股份有限公司 | Modified epoxy resin with fluorescent characteristic and preparation method thereof |
| WO2023226264A1 (en) * | 2022-05-25 | 2023-11-30 | 苏州大学 | Hyperbranched polyphenyl and preparation method therefor and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602942A (en) * | 2009-07-22 | 2009-12-16 | 天津理工大学 | A kind of organic molecular probe material and preparation method thereof with nucleocapsid structure |
-
2010
- 2010-03-24 CN CN2010101311349A patent/CN101792531B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602942A (en) * | 2009-07-22 | 2009-12-16 | 天津理工大学 | A kind of organic molecular probe material and preparation method thereof with nucleocapsid structure |
Non-Patent Citations (2)
| Title |
|---|
| 《Chem. Commun.》 20091231 Li Tang. et al A fluorescent thermometer operating in aggregation-induced emission mechanism: probing thermal transitions of PNIPAM in water 第4974-4976页 权利要求第1-8项 , 2 * |
| 《Macromolecules》 20071231 Anjun Qin. et al Click Polymerization: Facile Synthesis of Functional Poly(aroyltriazole)s by Metal-Free, Regioselective 1,3-Dipolar Polycycloaddition 第2308-2317页 权利要求第1-8项 第40卷, 第7期 2 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262626A (en) * | 2014-09-03 | 2015-01-07 | 浙江大学 | Method for synthesizing multi-hydroxyl fluorescent polymer |
| CN104262626B (en) * | 2014-09-03 | 2016-08-24 | 浙江大学 | A kind of method of synthesis of polyhydroxy fluorescent polymer |
| CN104448061A (en) * | 2014-11-20 | 2015-03-25 | 四川大学 | Simple method for connecting acrylate copolymer with fluorescent functional groups |
| CN106008920A (en) * | 2016-06-26 | 2016-10-12 | 苏州吉人高新材料股份有限公司 | Modified epoxy resin with fluorescent characteristic and preparation method thereof |
| CN106008920B (en) * | 2016-06-26 | 2018-07-13 | 苏州吉人高新材料股份有限公司 | A kind of modified epoxy and preparation method thereof with fluorescent characteristic |
| WO2023226264A1 (en) * | 2022-05-25 | 2023-11-30 | 苏州大学 | Hyperbranched polyphenyl and preparation method therefor and application thereof |
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