CN101844983B - Start fluorescent polymer, initiator thereof and preparation methods for start fluorescent polymer and initiator - Google Patents

Start fluorescent polymer, initiator thereof and preparation methods for start fluorescent polymer and initiator Download PDF

Info

Publication number
CN101844983B
CN101844983B CN201010140590.XA CN201010140590A CN101844983B CN 101844983 B CN101844983 B CN 101844983B CN 201010140590 A CN201010140590 A CN 201010140590A CN 101844983 B CN101844983 B CN 101844983B
Authority
CN
China
Prior art keywords
formula
compound
compound shown
reaction
mol ratio
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.)
Active
Application number
CN201010140590.XA
Other languages
Chinese (zh)
Other versions
CN101844983A (en
Inventor
马玉国
牛志强
高凡
裴坚
梁德海
张新祥
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Peking University
Original Assignee
Peking University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Peking University filed Critical Peking University
Priority to CN201010140590.XA priority Critical patent/CN101844983B/en
Publication of CN101844983A publication Critical patent/CN101844983A/en
Application granted granted Critical
Publication of CN101844983B publication Critical patent/CN101844983B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention discloses a start fluorescent polymer, an initiator thereof and preparation methods for the start fluorescent polymer and the initiator. The general structural formula of the fluorescent polymer is shown as a formula VII. The initiator used for preparing the fluorescent polymer is shown as a formula I. When the fluorescent polymer is used for conducting DNA or protein separation, the separation speed is rapid, the separation effect is good, the capillary is not required to be modified, the reuse can be realized at one glue pouring step and the repetitiveness is good; the invention can introduce comparable different topological structures into separation medium and the impact of linear polymers on the separation result of biological macromolecules can be systematically compared; and moreover, since the fluorescent polymer has a fluorescent core, the fluorescent core can be introduced into the separation medium, the goal of observing the separation medium and the biological macromolecules is realized, the more intuitive images of the biological macromolecules during separation can be obtained and the more powerful method is provided for disclosing the separation mechanism.

Description

Star fluorescent polymer and initiator thereof and their preparation method
Technical field
The present invention relates to separation of biopolymer field, particularly relate to a kind of star fluorescent polymer for capillary electrophoresis separation medium and initiator and their preparation method.
Background technology
Capillary electrophoresis is to divide at present analysis of variance biomacromolecule one of the most effective means.With the example that is separated into of DNA, different DNA fragmentations has the identical specific charge of being close to, and in free solution (free solution), they have similar rate of migration under External Electrical Field.Therefore,, for realizing the separation of the DNA fragmentation of different lengths or structure, must in kapillary, add separating medium.The separating medium of widespread use is at present mainly noncrosslinking polymers soln, common are: linear homopolymer (comprises linear polyacrylamide, poly-(N, N-DMAA), polyoxyethylene, Polyvinylpyrolidone (PVP), Mierocrystalline cellulose and derivative thereof etc.), multipolymer and mixture etc.Under identical weight-average molecular weight, the viscosity of line polymer is very large, therefore the separating medium that non-linear polymkeric substance is used as to capillary electrophoresis also has some trials, see CONTROLLED-ARCHITECTUREPOLYMERS AND USE THEREOF AS SEPARATION MEDIA Klaerner G., et al.WO:2001009204,20020417.Yet, for line polymer and non-line polymer to separation of biopolymer effect, more do not carry out systematic research.
The concentration of polymers soln is determining the separating mechanism of biomacromolecule conventionally.With the example that is separated into of DNA, the separating mechanism of DNA in entanglement macromolecular solution comprises Ogston model, the model that crawls of various corrections, entropy barrier model etc.The separating mechanism of DNA in Dilute Polymer Solutions comprises moment entanglement coupling mechanism, collision model, " collective motion " model etc.Although the separating mechanism of DNA is numerous, the restricted application of each model, can not explain all experimental results.The mechanism that further discloses capillary electrophoresis separation DNA is extremely important: can reduce the blindness while selecting separating medium on the one hand, can better explain experimental result on the other hand.For this reason, people dye to DNA with EB, the motor behavior in sepn process at fluorescence microscopy Microscopic observation DNA molecular then, thus infer the interaction between separating medium and DNA molecular.Simultaneously, also someone attempt to after separating medium dyeing at the motor behavior of fluorescence microscopy Microscopic observation separating medium, see Method and apparatus for screeningflowable separation media for electrophoresis and related applications McWaid, T.H., etal.USA:2003196896,20031023.Can certainly fluorescence chromophore be incorporated in polymkeric substance by chemical process, see Synthesis of poly (N-isopropylacrylamide) by ATRP using a fluorescein-basedinitiator Lu Xiaoju, et al.Polymer Bulletin 2007,59,195-206.But, under fluorescent microscope, observe the trial of the motion of DNA molecular and separating medium simultaneously and not yet did.
Summary of the invention
The object of this invention is to provide a kind of fluorescent polymer and initiator thereof and their preparation method.
Initiator provided by the invention, its general structure is suc as formula shown in I,
(formula I)
In described formula I general structure, R 1be selected from the total number of carbon atoms and be any one in the straight or branched alkyl of 1-20, any one in the straight or branched alkyl that preferably the total number of carbon atoms is 6-12, more preferably hexyl; R 2for pi-conjugated group, described pi-conjugated group is selected from least one in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and alkynyl oligomer, described aryl is selected from least one in phenyl, thienyl, furyl and pyridyl, the aryl oligomer that preferably repeated structural unit number is 1-5, most preferably phenyl; M be 0 or 1, p be 1,2 or 3.
Shown in described formula I, compound is preferably compound shown in formula II or formula III,
(formula II)
(formula III)
M=1 in the above-mentioned formula I general structure of preparation provided by the invention, the method for compound, comprises the steps: described in p=1
1) under the condition existing at palladium catalyst, by compound shown in formula IV, mono methoxy substituted aryl boric acid, in organic solvent, carry out Suzuki linked reaction with the aqueous solution of basic cpd, obtain compound shown in formula V;
(formula IV)
In described formula IV general structure, R 1be selected from the total number of carbon atoms and be any one in the straight or branched alkyl of 1-20;
(formula V)
In described formula V general structure, R 1be selected from the total number of carbon atoms and be any one in the straight or branched alkyl of 1-20, R 2for pi-conjugated group, m=1, p=1;
2), under the condition existing at boron tribromide, by the demethylating in organic solvent of compound shown in described formula V, obtain compound shown in formula VI;
(formula VI)
In described formula VI general structure, R 1be selected from the total number of carbon atoms and be any one in the straight or branched alkyl of 1-20, R 2for pi-conjugated group, m=1, p=1;
3) under the condition existing at triethylamine, compound shown in described formula VI is reacted in organic solvent with 2-bromine isobutyl acylbromide, obtain m=1 in described formula I general structure, compound described in p=1.
The step 1 of the method) in, in described formula IV general structure, R 1for any one in the total number of carbon atoms straight or branched alkyl that is 6-12, preferred hexyl; In described formula V general structure, R 1be selected from the total number of carbon atoms and be any one in the straight or branched alkyl of 6-12, preferred hexyl, described R 2in, described pi-conjugated group is selected from least one in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and alkynyl oligomer, described aryl is selected from least one in phenyl, thienyl, furyl and pyridyl, the aryl oligomer that preferably repeated structural unit number is 1-5, most preferably phenyl; Described formula IV compound is 5,5,10,10,15,15-six hexyl-2,7,12-tribromo, three polyindenes, described palladium catalyst is selected from least one in tetrakis triphenylphosphine palladium, two (triphenylphosphine) Palladous chloride and palladium, described mono methoxy substituted aryl boric acid is to methoxyphenylboronic acid, methoxythiophene boric acid or methoxypyridine boric acid, and preferably to methoxyphenylboronic acid, described basic cpd is sodium carbonate, salt of wormwood, sodium hydroxide or potassium hydroxide; The concentration of the aqueous solution of described basic cpd is 0.5-5mol/L, preferably 2mol/L; The mol ratio of compound shown in described formula IV, described mono methoxy substituted aryl boric acid, described basic cpd and described palladium catalyst is 1: 3-6: 10-20: 0.05-0.2, preferably 1: 4: 15: 0.1; In described Suzuki linked reaction, temperature is 0-30 ℃, and preferably 20 ℃, the time is 6-24 hour, preferably 12 hours;
Described step 2) in described formula VI general structure, R 1be selected from the total number of carbon atoms and be any one in the straight or branched alkyl of 6-12, preferably hexyl; Described R 2in, described pi-conjugated group is selected from least one in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and alkynyl oligomer, described aryl is selected from least one in phenyl, thienyl, furyl and pyridyl, the aryl oligomer that preferably repeated structural unit number is 1-5, most preferably phenyl; Shown in boron tribromide and described formula V, the mol ratio of compound is 5-20: 1, and preferably 10: 1; Temperature of reaction is 0-30 ℃, and preferably 20 ℃, the time is 6-24 hour, preferably 12 hours;
Described step 3), in, described organic solvent is at least one in methylene dichloride, chloroform, ether, toluene and tetrahydrofuran (THF); The mol ratio of compound shown in triethylamine, described formula VI and 2-bromine isobutyl acylbromide is 10-200: 1: 3-15, preferably 120: 1: 10; In described reaction, temperature is 0-30 ℃, and preferably 20 ℃, the time is 6-24 hour, preferably 12 hours.
In above-mentioned preparation method, when step 1) R of compound described in Chinese style IV 1for hexyl, and described mono methoxy substituted aryl boric acid is during to methoxyphenylboronic acid, obtains compound described in formula II.
M=1 in preparation formula I provided by the invention, compound described in p=2, comprises the steps:
1) under the condition existing at palladium catalyst, the aqueous solution of compound shown in formula IV, dimethoxy substituted aryl boric acid and basic cpd is carried out to Suzuki linked reaction in organic solvent, obtain compound shown in formula V;
(formula IV)
In described formula IV general structure, R 1be selected from the total number of carbon atoms and be any one in the straight or branched alkyl of 1-20;
(formula V)
In described formula V general structure, R 1be selected from the total number of carbon atoms and be any one in the straight or branched alkyl of 1-20, R 2for pi-conjugated group, m=1, p=2;
2), under the condition existing at boron tribromide, by the demethylating in organic solvent of compound shown in described formula V, obtain compound shown in formula VI;
(formula VI)
In described formula VI general structure, R 1be selected from the total number of carbon atoms and be any one in the straight or branched alkyl of 1-20, R 2for pi-conjugated group, m=1, p=2;
3) under the condition existing at triethylamine, compound shown in described formula VI is reacted in organic solvent with 2-bromine isobutyl acylbromide, obtain m=1 in formula I, compound described in p=2.
The step 1 of the method) in, in described formula IV general structure, R 1for any one in the total number of carbon atoms straight or branched alkyl that is 6-12, preferred hexyl; In described formula V general structure, R 1be selected from the total number of carbon atoms and be any one in the straight or branched alkyl of 6-12, preferred hexyl, described R 2in, described pi-conjugated group is selected from least one in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and alkynyl oligomer, described aryl is selected from least one in phenyl, thienyl, furyl and pyridyl, the aryl oligomer that preferably repeated structural unit number is 1-5, most preferably phenyl; Described formula IV compound is 5,5,10,10,15,15-six hexyls 1,7,12-tribromo, three polyindenes, described palladium catalyst is selected from least one in tetrakis triphenylphosphine palladium, two (triphenylphosphine) Palladous chloride and palladium, described dimethoxy substituted aryl boric acid is 3,4-dimethoxy phenylo boric acid, dimethoxy-thiophene boric acid, a kind of in dimethoxy-pyridine boric acid, preferably 3,4-dimethoxy phenylo boric acid, described basic cpd is sodium carbonate, salt of wormwood, sodium hydroxide or potassium hydroxide; The concentration of the aqueous solution of described basic cpd is 0.5-5mol/L, preferably 2mol/L; The mol ratio of compound shown in described formula IV, described dimethoxy substituted aryl boric acid, described basic cpd and described palladium catalyst is 1: 3-6: 10-20: 0.05-0.2, preferably 1: 4: 15: 0.1; In described Suzuki linked reaction, temperature is 0-30 ℃, and preferably 20 ℃, the time is 6-24 hour, preferably 12 hours;
Described step 2) in described formula VI general structure, R 1be selected from the total number of carbon atoms and be any one in the straight or branched alkyl of 6-12, preferably hexyl; Described R 2in, described pi-conjugated group is selected from least one in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and alkynyl oligomer, described aryl is selected from least one in phenyl, thienyl, furyl and pyridyl, the aryl oligomer that preferably repeated structural unit number is 1-5, most preferably phenyl; Shown in boron tribromide and described formula V, the mol ratio of compound is 10-30: 1, and preferably 20: 1; Temperature of reaction is 0-30 ℃, and preferably 20 ℃, the time is 6-24 hour, preferably 12 hours;
Described step 3), in, described organic solvent is at least one in methylene dichloride, chloroform, ether, toluene and tetrahydrofuran (THF); The mol ratio of compound shown in triethylamine, described formula VI and 2-bromine isobutyl acylbromide is 20-300: 1: 6-30, preferably 240: 1: 20; In described reaction, temperature is 0-30 ℃, and preferably 20 ℃, the time is 6-24 hour, preferably 12 hours.
In above-mentioned preparation method, when step 1) R of compound described in Chinese style IV 1for hexyl, and described dimethoxy substituted aryl boric acid is while being 3,4-dimethoxy phenylo boric acid, obtains compound described in formula III.
Fluorescent polymer provided by the invention, its general structure is suc as formula shown in VII,
(formula VII)
In described formula VII general structure, R 1be selected from the total number of carbon atoms and be any one in the straight or branched alkyl of 1-20, any one in the straight or branched alkyl that preferably the total number of carbon atoms is 6-12, more preferably hexyl; R 2for pi-conjugated group, described pi-conjugated group is selected from least one in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and alkynyl oligomer, described aryl is selected from least one in phenyl, thienyl, furyl and pyridyl, the aryl oligomer that preferably repeated structural unit number is 1-5, most preferably phenyl; R 3for water-soluble polymers chain, described water-soluble polymers chain is selected from polyacrylamide, poly-N, at least one in N-DMAA, polyoxyethylene, Polyvinylpyrolidone (PVP), Mierocrystalline cellulose, cellulose nitrate, cellulose ethanoate, methylcellulose gum and carboxymethyl cellulose, preferably poly-N,N-DMAA; M is 0 or 1; P is 1,2 or 3; The number-average molecular weight of fluorescent polymer shown in described formula VII is 10,000-10,000,000, preferably 500, and 000-2,000,000, molecular weight dispersity is 1.5-5, preferably 2.5.
Shown in described formula VII, fluorescent polymer is preferably polymkeric substance shown in formula VIII,
(formula VIII)
Shown in described formula VIII in polymkeric substance, m is 0 or 1, the n integer that is 100-10000, and p is 1,2 or 3;
Fluorescent polymer shown in described formula VII is fluorescent polymer shown in formula IX and formula X more preferably,
(formula IX)
In described formula IX general structure, the integer that n is 100-10000;
(formula X)
In described formula X general structure, the integer that n is 100-10000.
M=1 in general structure described in preparation formula VII provided by the invention, the method for polymkeric substance, comprises the steps: take that cuprous bromide is as catalyzer described in p=1, with N, N, N ', N, " five methyl diethylentriamine is part to ' N, and with m=1 in formula I general structure, compound is initiator described in p=1; cause N; N-DMAA carries out atom transition free radical polymerization reaction, reacts the complete m=1 in general structure that obtains described in formula VII, polymkeric substance described in p=1.
In the method, described cuprous bromide, N, N, N ', N, ' N " m=1 in five methyl diethylentriamine, formula I general structure; described in p=2, the mol ratio of compound and N,N-DMAA is 3-4: 3-4: 1: 100-10000, preferably 3: 3: 1: 3000; In described atom transition free radical polymerization reaction, temperature is 100-150 ℃, and preferably 120 ℃, the time is 1-7 days, preferably 4 days.
M=1 in general structure described in preparation formula VII provided by the invention, the method for polymkeric substance, comprises the steps: take that cuprous bromide is as catalyzer described in p=2, with N, N, N ', N, " five methyl diethylentriamine is part to ' N, and with m=1 in formula I general structure, compound is initiator described in p=1; cause N; N-DMAA carries out atom transition free radical polymerization reaction, reacts the complete m=1 in general structure that obtains described in formula VII, polymkeric substance described in p=2.
In the method, described cuprous bromide, N, N, N, N, N " m=1 in five methyl diethylentriamine, formula I general structure, the mol ratio of compound and N,N-DMAA is 6-8: 6-8 described in p=2: 1: 100-10000, preferably 6: 6: 1: 3000; In described atom transition free radical polymerization reaction, temperature is 100-150 ℃, and preferably 120 ℃, the time is 1-7 days, preferably 4 days.
Shown in the formula VII general structure that the invention described above provides, the application of fluorescent polymer separating medium in as capillary electrophoresis separation DNA or protein, also belongs to protection scope of the present invention.
Utilize fluorescent polymer provided by the invention to carry out DNA or protein separation, velocity of separation is fast, good separating effect, and kapillary does not need to modify, and encapsulating is reusable and have good repeatability; And the present invention can be incorporated into comparable different topology structure in separating medium, the impact of contrast line polymer that can system on separation of biopolymer result; In addition, because this fluorescent polymer has fluorescent core, thereby this fluorescent core can be incorporated in separating medium, realize the object of simultaneously observing separating medium and biomacromolecule, thereby obtain biomacromolecule image more intuitively in sepn process, for the announcement of separating mechanism provides stronger method.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum figure that embodiment 1 prepares gained initiator S-I (being formula II).
Fig. 2 is the nucleus magnetic hydrogen spectrum figure that embodiment 2 prepares resulting polymers S-3-PDMA.
Fig. 3 is the static light scattering Zimm figure that embodiment 2 prepares resulting polymers S-3-PDMA.
Fig. 4 is the nucleus magnetic hydrogen spectrum figure that embodiment 3 prepares gained initiator S-II (being formula III).
Fig. 5 is the capillary electrophoresis separation figure of polymers soln to Φ X174/Hae III DNA Digestive system, is respectively from top to bottom that mass percentage concentration is the solution of 1%, 3%, 5% the polymkeric substance S-3-PDMA capillary electrophoresis separation figure to Φ X174/Hae IIIDNA Digestive system.
Fig. 6 is 5% the solution of the S-3-PDMA repeated experiment figure to the capillary electrophoresis separation of Φ X174/Hae III DNA Digestive system, and three curves are respectively the capillary electrophoresis separation figure of lower three sample introductions of this condition.
Fig. 7 is the capillary electrophoresis separation figure of polymers soln to Φ X174/Hae III DNA Digestive system, the capillary electrophoresis separation figure of the solution (mass percentage concentration is 3%) that is respectively polymkeric substance L-PDMA, S-3-PDMA and S-6-PDMA from top to bottom to Φ X174/Hae III DNA Digestive system.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
The preparation of initiator S-I shown in embodiment 1, formula II
With 5,5,10,10,15,15-, six hexyl-2,7,12-tribromo, three polyindenes are starting raw material, under palladium catalyst catalysis with methoxyphenylboronic acid carried out to Suzuki linked reaction obtain 5,5,10,10,15,15-, six hexyl-2,7,12-tri-(4-p-methoxy-phenyl), three polyindenes.Then under the effect of boron tribromide, demethylating obtains 5,5,10,10,15,15-, six hexyl-2,7,12-tri-(4-hydroxy phenyl), three polyindenes.Under the effect of triethylamine, obtain initiator S-I shown in formula II with 2-bromine isobutyryl bromine reaction again.Concrete reaction process is shown below:
1) prepare compound 5,5,10,10,15,15-six hexyl-2,7,12-tri-(4-p-methoxy-phenyl), three polyindenes:
By 5,5,10; 10,15,15-, six hexyl-2; 7,12-tribromo, three polyindenes (0.5g, 0.46mmol); to methoxyphenylboronic acid (0.28g; 1.84mmol), the aqueous sodium carbonate that concentration is 2M (3.7mL) and tetrahydrofuran (THF) (20mL) add in reaction flask, add four (triphenyl phosphorus) palladium (0.05g under nitrogen protection; 0.04mmol), reaction backflow 20h.After reaction finishes, use respectively saturated aqueous ammonium chloride, saturated common salt water washing organic phase.Organic phase is revolved and is desolventized after anhydrous magnesium sulfate drying, and silicagel column is separated, take ethyl acetate/petroleum ether=1/10 to obtain white solid product as eluent.Productive rate; 78%.
It is as follows that this compound structure detects data: 1h NMR (CDCl 3, 300MHz, ppm): 8.45-8.43 (d, J=8.1Hz, 3H, Ar-H), 7.73-7.70 (d, J=8.7Hz, 6H, Ar-H), 7.68 (s, 3H, Ar-H), 7.65-7.63 (d, J=8.1Hz, 3H, Ar-H), 7.07-7.04 (d, J=8.7Hz, 6H, Ar-H), 3.81 (s, 9H, OCH 3), 3.07-3.00 (m, 6H, CH 2), 2.23-2.13 (m, 6H, CH 2), 0.98-0.90 (m, 36H, CH 2), 0.63-0.59 (m, 30H, CH 2cH 3).
From said structure, detect data, this compound structure is correct.
2) prepare compound 5,5,10,10,15,15-six hexyl-2,7,12-tri-(4-hydroxy phenyl), three polyindenes:
By 5,5,10,10,15,15-, six hexyl-2,7,12-tri-(4-p-methoxy-phenyl), three polyindene (0.26g, 0.22mmol) be dissolved in methylene dichloride (10mL), drip boron tribromide (0.56g, 2.23mmol) under ice bath, reaction system at room temperature stirs and spends the night.After reaction finishes, in reaction system, add the saturated aqueous solution of sodium bicarbonate, and use dichloromethane extraction water.The organic phase merging is revolved and is desolventized after anhydrous sodium sulfate drying, and silicagel column is separated, take ethyl acetate/petroleum ether=1/5 to obtain white solid product as eluent.Productive rate: 99%.
It is as follows that this compound structure detects data: 1h NMR (CDCl 3, 300MHz, ppm): 8.41-8.37 (d, J=12Hz, 3H, Ar-H), 7.68-7.58 (m, 12H, Ar-H), 7.00-7.96 (d, J=12Hz, 6H, Ar-H), 4.84 (s, 3H, OH), 3.04-2.97 (m, 6H, CH 2), 2.20-2.06 (m, 6H, CH 2), 0.88 (m, 36H, CH 2), 0.62-0.56 (m, 30H, CH 2cH 3). 13c NMR (CDCl 3, 75MHz, ppm): δ 155.0,154.3, and 144.8,139.2,138.5,138.0,134.2,128.3,124.8,124.6,120.1,115.7,55.7,37.1,31.5,29.7,29.5,23.9,22.3,13.9.MS (MALDI-TOF): Calcd for C 84h 108o 3: 1123.Found:1123.
From said structure, detect data, this compound structure is correct.
(3) prepare compound S-I:
By 5,5,10,10,15,15-, six hexyl-2,7,12-tri-(4-hydroxy phenyl) three polyindene (0.26g, 0.23mmol), triethylamine (2mL, 28mmol) and tetrahydrofuran (THF) (10mL) add in reaction flask, drips 2-bromine isobutyl acylbromide (0.53g under ice bath, 2.3mmol), reaction system at room temperature stirs 12 hours.After reaction finishes, remove by filter ammonium salt, and revolve and desolventize.Silicagel column is separated, take ethyl acetate/petroleum ether=1/10 as eluent obtains white solid product, is compound S-I.Productive rate: 89%.
As shown in Figure 1, hydrogen spectrum and the carbon concrete detection of spectrum data are as follows for the nucleus magnetic hydrogen spectrum figure of this compound: 1h NMR (CDCl 3, 300MHz, ppm): δ 8.45-8.42 (d, J=8.4Hz, 3H, Ar-H), 7.80-7.77 (dd, J=8.4Hz, J=2.1Hz, 6H, Ar-H), 7.67 (s, 3H, Ar-H), 7.67-7.64 (d, J=8.4Hz, 3H, Ar-H), 7.29-7.27 (dd, J=6.8Hz, J=1.8Hz, 6H, Ar-H), 3.04-2.99 (m, 6H, CH 2), 2.19-2.09 (m, 6H, CH 2), 2.12 (s, 18H, CH 3), 0.96-0.89 (m, 36H, CH 2), 0.63-0.56 (m, 30H, CH 2cH 3). 13c NMR (CDCl 3, 75MHz, ppm): δ 170.4,154.3, and 150.1,154.3,139.7,139.5,138.2,138.0,128.1,125.1,124.9,121.3,120.6,55.8,55.4,37.1,31.5,30.7,29.7,29.5,23.9,22.2,13.9,1.0.MS (MALDI-TOF): Calcd for C 93h 117br 3o 6: 1570.Found:1571.
From said structure, detect data, this compound structure is correct.
The preparation of polymkeric substance shown in embodiment 2, formula IX (S3-PDMA)
Shown in the formula II that the embodiment 1 of take prepares, compound is initiator, consumption is 0.01mmol, take N,N-DMAA as monomer, and consumption is 30mmol, take CuBr as catalyzer, consumption is 0.03mmol, take PMDETA as part, and consumption is 0.03mmol, at 120 ℃, react four days, obtain polymkeric substance shown in formula IX structural formula.The molecular weight that static light scattering records this polymkeric substance is 9 * 10 5g/mol, molecular weight dispersity is 2.5.
The preparation of initiator shown in embodiment 3, formula III (S-II)
According to the identical experimental technique of embodiment 1 and condition, only by step 1) in p-methoxyphenylboronic acid used replace with 3,4-dimethoxy phenylo boric acid, described 3, the consumption of 4-dimethoxy phenylo boric acid is 1.84mmol, prepares initiator shown in formula III.With 5,5,10,10,15,15-, six hexyl-2,7,12-tribromo, three polyindenes are starting raw material, carry out Suzuki linked reaction obtain 5,5,10 under palladium catalyst catalysis with 3,4-dimethoxy phenylo boric acid, 10,15,15-, six hexyl-2,7,12-tri-(3,4-Dimethoxyphenyl), three polyindenes.Then under the effect of boron tribromide, demethylating obtains 5,5,10,10,15,15-, six hexyl-2,7,12-tri-(3,4-dihydroxy phenyl), three polyindenes.Under the effect of triethylamine, obtain initiator S-II with 2-bromine isobutyryl bromine reaction again.Concrete reaction process is shown below:
As shown in Figure 4, hydrogen spectrum and the carbon concrete detection of spectrum data are as follows for the nucleus magnetic hydrogen spectrum figure of this compound S-II: 1hNMR (CDCl 3, 300MHz, ppm): δ 8.46-8.43 (d, J=8.7Hz, 3H, Ar-H), 7.70-7.64 (m, 9H, Ar-H), 7.59-7.58 (d, J=1.8Hz, 3H, Ar-H), 7.40-7.37 (d, J=8.4Hz, 3H, Ar-H), 3.02-2.98 (m, 6H, CH 2), 2.23-2.10 (m, 6H, CH 2), 2.13 (s, 18H, CH 3), 2.11 (s, 18H, CH 3), 0.95-0.90 (m, 36H, CH 2), 0.64-0.55 (m, 30H, CH 2cH 3). 13c NMR (CDCl 3, 75MHz, ppm): δ 169.2,154.4, and 145.6,142.2,141.2,140.8,140.1,137.9,137.3,125.6,125.3,124.9,123.1,121.5,120.6,55.9,55.1,55.0,37.0,32.8,31.5,30.8,30.82,30.80,29.7,29.4,24.0,22.2,13.9,1.0.
From said structure, detect data, this compound structure is correct.
The preparation of embodiment 4, polymkeric substance S-6-PDMA (formula X)
Shown in the formula III that the embodiment 3 of take prepares, compound is initiator, consumption is 0.01mmol, take N,N-DMAA as monomer, and consumption is 30mmol, take cuprous bromide CuBr as catalyzer, consumption is 0.06mmol, take PMDETA as part, and consumption is 0.06mmol, at 120 ℃, react four days, obtain polymkeric substance S-6-PDMA.The molecular weight that static light scattering method records this polymkeric substance is 9 * 10 5g/mol, molecular weight dispersity is 2.5.
Embodiment 2 is prepared to polymkeric substance (S-3-PDMA) shown in gained formula IX structural formula as separating medium, the Φ X174/Hae III DNA Digestive system (this Digestive system is purchased from sigmaaldrich company) that is 100 μ g/mL to concentration by the following method carries out capillary electrophoresis separation: first prepare the Φ X174/Hae III DNA Digestive system of 100 μ g/mL, use fluorescence dye GeneFinder tM(purchased from Xiamen Baiweixin Biological Technology Co., Ltd.) dyeing.Recycling is prepared polymkeric substance shown in gained formula IX structural formula, and to be dissolved in mass percentage concentration be in 1% TBE (Tris-borate buffer) solution, to be mixed with the macromolecular solution of a series of different concns.The kapillary adopting is 75 microns of internal diameters, total pipe range 31cm, effectively pipe range 21cm.During operation, first with the hydrochloric acid soln of 1M, kapillary is rinsed 10 minutes, then use deionized water rinsing 2 minutes, then under 30kpa, the macromolecular solution preparing is pressed in kapillary, continue 8 minutes, this base line reaches balance substantially.Follow negative pole electrokinetic injection, voltage is-5kV/cm that sample injection time is 5s.After sample introduction completes, with 1% TBE solution as damping fluid, at 25 ℃, separation voltage, be-condition of 8kV/cm under, carry out DNA separating experiment.With fluorimetric detector, detect, excitation wavelength is 488nm, and detection wavelength is 520nm.
Separating resulting as shown in Figure 5.As seen from the figure, Φ X174/Hae III DNA Digestive system contains 11 DNA fragmentations altogether, and each fragment is expressed as a peak in capillary electrophoresis figure.First take molecular weight as 9 * 10 5the polymkeric substance S-3-PDMA of g/mol is example, is made into mass percentage concentration and is respectively 1%, 3% and 5% polymers soln, and in this solution, solvent is TBE (Tris-borate buffer), and its capillary electrophoresis separation result is as Fig. 5.Visible with concentration increase, its separating effect improves, and illustrates within the scope of finite concentration, and high density is conducive to the raising of separating effect.Reusable after encapsulating of kapillary, 5% the S-3-PDMA of take is example, and three times electrophoresis has good repeatability, and repeated experiment result is as Fig. 6.Choose molecular weight and be 9 * 10 5it is 3% polymers soln that polymkeric substance S-3-PDMA, the S-6-PDMA of g/mol and L-PDMA are made into respectively mass percentage concentration by it, and solvent for use is TBE (Tris-borate buffer), separated for DNA.Its capillary electrophoresis separation result is as Fig. 7.The separating effect of visible S-3-PDMA is best, and S-6-PDMA is obtaining separated shortest time while obtaining close separating effect with the L-PDMA polymkeric substance of line style.Above experimental fact explanation: under molecular weight, starlike PDMA has good separating property when DNA isolation.
(formula XI)
Wherein, the structural formula of described L-PDMA polymkeric substance is suc as formula shown in X, and its preparation method is as follows:
1) prepare compound 9,9-dihexyl-2,7-bis-(p-methoxyphenyl) fluorenes:
By 9; 9-dihexyl-2; 7-dibromo fluorenes (1.5g, 3mmol), 4-methoxyphenylboronic acid (1.4g; 9mmol); sodium carbonate (2M, 13mL) and tetrahydrofuran (THF) (30mL) join in reaction flask, add four (triphenyl phosphorus) palladium (0.2g under nitrogen protection; 0.018mmol), reaction backflow 20h.After reaction finishes, use respectively saturated aqueous ammonium chloride, saturated common salt water washing organic phase.Organic phase is revolved and is desolventized after anhydrous magnesium sulfate drying, and silicagel column is separated, take sherwood oil as eluent carries out wash-out, obtains white solid product, is compound 9,9-dihexyl-2,7-bis-(p-methoxyphenyl) fluorenes.Productive rate; 96%.
It is as follows that this compound structure detects data: 1h NMR (CDCl 3, 200MHz, ppm): 7.78-7.74 (d.J=8.2Hz, 2H, Ar-H), 7.66-7.62 (d, J=8.6Hz, 4H, Ar-H), 7.57-7.54 (m, 4H, Ar-H), 7.06-7.02 (d, J=8.6Hz, 4H, Ar-H), 3.89 (s, 6H, OCH 3), 2.09-2.01 (m, 4H, CH 2), 1.09 (m, 12H, CH 2), 0.81-0.75 (m, 10H, CH 2cH 3). 13c NMR (CDCl 3, 50MHz, ppm): δ 159.1,151.6,139.6,139.5,134.3,128.2,125.5,121.0,119.8,114.2,55.3,55.2,40.5,31.4,29.7,23.8,22.6,14.0.MS (EI): Calcd for C 39h 46o 2: 546.Found:546. (M +, 100%) and .Anal.Calcdfor C 39h 46o 2: C, 85.67; H, 8.48.Found:C, 85.50; H, 8.39.
From said structure, detect data, this compound structure is correct.
2) prepare compound 9,9-dihexyl-2,7-bis-(4-hydroxy phenyl) fluorenes:
By 9,9-dihexyl-2,7-bis-(4-p-methoxy-phenyl) fluorenes (0.1g, 0.18mmol) is dissolved in methylene dichloride (10mL), drips boron tribromide (0.18g, 0.74mmol) under ice bath, and reaction system at room temperature stirs and spends the night.After reaction finishes, in reaction system, add the saturated aqueous solution of sodium bicarbonate, and use dichloromethane extraction water.The organic phase merging is revolved and is desolventized after anhydrous sodium sulfate drying, and silicagel column is separated, take volume ratio as ethyl acetate: sherwood oil=1: 8 eluents that mix carry out wash-out, obtain white solid product, be compound 9,9-dihexyl-2,7-bis-(4-hydroxy phenyl) fluorenes.Productive rate: 99%.
It is as follows that this compound structure detects data: 1h NMR (CDCl 3, 300MHz, ppm): δ 7.74-7.71 (d, J=8.1Hz, 2H, Ar-H), 7.57-7.54 (d, J=8.7Hz, 4H, Ar-H), 7.53-7.50 (m, 4H, Ar-H), 6.96-6.94 (d, J=8.7Hz, 4H, Ar-H), 4.84 (s, 2H, OH), 2.04-1.99 (m, 4H, CH 2), 1.14-1.04 (m, 12H, CH 2), 0.77-0.73 (m, 10H, CH 2cH 3). 13c NMR (CDCl 3, 75MHz, ppm): δ 154.9,151.6,139.6,139.5,134.5,128.4,125.5,121.0,119.8,115.7,55.1,40.5,31.4,29.7,23.8,22.5,14.0.HRMS (EI): Calcd for C 37h 42o 2: 518.3185.Found:518.3192. (M +, 100%).
From said structure, detect data, this compound structure is correct.
(3) prepare line style initiator:
By 9,9-dihexyl-2,7-bis-(4-hydroxy phenyl) fluorenes (0.14g, 0.27mmol), triethylamine (1.5mL, 21mmol) and tetrahydrofuran (THF) (10mL) add in reaction flask, drip 2-bromine isobutyl acylbromide (0.24g under ice bath, 1mmol), reaction system at room temperature stirs and spends the night.After reaction finishes, remove by filter ammonium salt, and revolve and desolventize.Silicagel column is separated, take volume ratio as ethyl acetate: sherwood oil=1: the eluent of 10 mixing carries out wash-out, obtains white solid product, obtains described line style initiator.Productive rate: 95%.
It is as follows that this compound structure detects data: 1h NMR (CDCl 3, 200MHz, ppm): δ 7.79-7.76 (d, J=7.8Hz, 2H, Ar-H), 7.71-7.67 (d, J=8Hz, 4H, Ar-H), 7.58-7.54 (m, 4H, Ar-H), 7.26-7.22 (d, J=8Hz, 4H, Ar-H), 2.11 (s, 12H, CH 3), 2.11-1.94 (m, 4H, CH 2), 1.07 (m, 12H, CH 2), 0.76-0.72 (m, 10H, CH 2cH 3). 13c NMR (CDCl 3, 50MHz, ppm): δ 170.3,151.7,150.1,140.1,139.8,139.2,128.2,126.1,121.5,121.3,120.1,55.4,55.3,40.4,31.4,30.7,29.6,23.8,22.5,14.0.MS (MALDI-TOF): Calcd for C 45h 52br 2o 4: 816.Found:815.Anal.Calcd for C 45h 52br 2o 4: C, 66.18; H, 6.42.Found:C, 66.05; H, 6.35.
From said structure, detect data, this compound structure is correct.
Get aforesaid method and prepare gained line style initiator 0.01mmol, with N, N-DMAA is monomer, and consumption is 30mmol, take CuBr as catalyzer, consumption is 0.02mmol, take PMDETA as part, and consumption is 0.02mmol, reacts four days at 120 ℃, obtain described line style L-PDMA polymkeric substance, the molecular weight that static light scattering method records this polymkeric substance is 9 * 10 5g/mol, molecular weight dispersity is 2.5.

Claims (14)

1. compound shown in formula II or formula III,
2. prepare a method for compound shown in formula II described in claim 1, comprise the steps:
1) under the condition existing at palladium catalyst, by compound shown in formula IV, to the aqueous solution of methoxyphenylboronic acid and basic cpd, in organic solvent, carry out Suzuki linked reaction, obtain compound shown in formula V;
In described formula IV, R 1for hexyl;
In described formula V, R 1for hexyl, R 2for phenyl, m=1, p=1;
2), under the condition existing at boron tribromide, by the demethylating in organic solvent of compound shown in described formula V, obtain compound shown in formula VI;
In described formula VI, R 1for hexyl, R 2for phenyl, m=1, p=1;
3) under the condition existing at triethylamine, compound shown in described formula VI is reacted in organic solvent with 2-bromine isobutyl acylbromide, obtain compound shown in formula II described in claim 1.
3. method according to claim 2, it is characterized in that: in described step 1), described palladium catalyst is selected from least one in tetrakis triphenylphosphine palladium, two (triphenylphosphine) Palladous chloride and palladium, and described basic cpd is sodium carbonate, salt of wormwood, sodium hydroxide or potassium hydroxide;
In described step 3), described organic solvent is at least one in methylene dichloride, chloroform, ether, toluene and tetrahydrofuran (THF).
4. according to the method in claim 2 or 3, it is characterized in that: in described step 1), the concentration of the aqueous solution of described basic cpd is 0.5-5mol/L; Compound shown in described formula IV, to the mol ratio of methoxyphenylboronic acid, described basic cpd and described palladium catalyst, be 1:3-6:10-20:0.05-0.2; In described Suzuki linked reaction, temperature is 0-30 ℃, and the time is 6-24 hour;
Described step 2), in, shown in boron tribromide and described formula V, the mol ratio of compound is 5-20:1; Temperature of reaction is 0-30 ℃, and the time is 6-24 hour;
In described step 3), the mol ratio of compound shown in triethylamine, described formula VI and 2-bromine isobutyl acylbromide is 10-200:1:3-15; In described reaction, temperature is 0-30 ℃, and the time is 6-24 hour.
5. method according to claim 4, is characterized in that: in described step 1), the concentration of the aqueous solution of described basic cpd is 2mol/L; Compound shown in described formula IV, to the mol ratio of methoxyphenylboronic acid, described basic cpd and described palladium catalyst, be 1:4:15:0.1; In described Suzuki linked reaction, temperature is 20 ℃, and the time is 12 hours;
Described step 2), in, shown in boron tribromide and described formula V, the mol ratio of compound is 10:1; Temperature of reaction is 20 ℃, and the time is 12 hours;
In described step 3), the mol ratio of compound shown in triethylamine, described formula VI and 2-bromine isobutyl acylbromide is 120:1:10; In described reaction, temperature is 0 ℃, and the time is 12 hours.
6. a method of preparing compound shown in formula III described in claim 1, comprises the steps:
1), under the condition existing at palladium catalyst, by compound, 3 shown in formula IV, the aqueous solution of 4-dimethoxy phenylo boric acid and basic cpd carries out Suzuki linked reaction in organic solvent, obtains compound shown in formula V;
In described formula IV, R 1for hexyl;
In described formula V, R 1for hexyl, R 2for phenyl, m=1, p=2;
2), under the condition existing at boron tribromide, by the demethylating in organic solvent of compound shown in described formula V, obtain compound shown in formula VI;
In described formula VI, R 1for hexyl, R 2for phenyl, m=1, p=2;
3) under the condition existing at triethylamine, compound shown in described formula VI is reacted in organic solvent with 2-bromine isobutyl acylbromide, obtain compound shown in formula III described in claim 1.
7. method according to claim 6, it is characterized in that: in described step 1), described palladium catalyst is selected from least one in tetrakis triphenylphosphine palladium, two (triphenylphosphine) Palladous chloride and palladium, and described basic cpd is sodium carbonate, salt of wormwood, sodium hydroxide or potassium hydroxide;
In described step 3), described organic solvent is at least one in methylene dichloride, chloroform, ether, toluene and tetrahydrofuran (THF).
8. according to the method described in claim 6 or 7, it is characterized in that: in described step 1), the concentration of the aqueous solution of described basic cpd is 0.5-5mol/L; Compound, 3 shown in described formula IV, the mol ratio of 4-dimethoxy phenylo boric acid, described basic cpd and described palladium catalyst is 1:3-6:10-20:0.05-0.2; In described Suzuki linked reaction, temperature is 0-30 ℃, and the time is 6-24 hour;
Described step 2), in, shown in boron tribromide and described formula V, the mol ratio of compound is 10-30:1; Temperature of reaction is 0-30 ℃, and the time is 6-24 hour;
In described step 3), the mol ratio of compound shown in triethylamine, described formula VI and 2-bromine isobutyl acylbromide is 20-300:1:6-30; In described reaction, temperature is 0-30 ℃, and the time is 6-24 hour.
9. method according to claim 8, is characterized in that: in described step 1), the concentration of the aqueous solution of described basic cpd is 2mol/L; Compound, 3 shown in described formula IV, the mol ratio of 4-dimethoxy phenylo boric acid, described basic cpd and described palladium catalyst is 1:4:15:0.1; In described Suzuki linked reaction, temperature is 20 ℃, and the time is 12 hours;
Described step 2), in, shown in boron tribromide and described formula V, the mol ratio of compound is 20:1; Temperature of reaction is 20 ℃, and the time is 12 hours;
In described step 3), the mol ratio of compound shown in triethylamine, described formula VI and 2-bromine isobutyl acylbromide is 240:1:20; In described reaction, temperature is 20 ℃, and the time is 12 hours.
10. fluorescent polymer shown in formula IX or formula X,
In described formula IX general structure, the integer that n is 100-10000;
In described formula X general structure, the integer that n is 100-10000.
11. 1 kinds of methods of preparing polymkeric substance described in claim 10, comprise the steps: take that cuprous bromide is as catalyzer, with N, N, N', N', " five methyl diethylentriamine is part to N, and the compound described in claim 1 of take is initiator, causes N; N-DMAA carries out atom transition free radical polymerization reaction, reacts the complete described polymkeric substance that obtains.
12. methods according to claim 11, is characterized in that: described cuprous bromide, N, N, N', N', N " described in five methyl diethylentriamine, claim 1, the mol ratio of compound and N,N-DMAA is 3-4:3-4:1:100-10000; In described atom transition free radical polymerization reaction, temperature is 100-150 ℃, and the time is 1-7 days.
13. methods according to claim 12, is characterized in that: described cuprous bromide, N, N, N', N', N, and " described in five methyl diethylentriamine, claim 1, the mol ratio of compound and N,N-DMAA is 3:3:1:3000; In described atom transition free radical polymerization reaction, temperature is 120 ℃, and the time is 4 days.
The application of fluorescent polymer separating medium in as capillary electrophoresis separation DNA or protein described in 14. claims 10.
CN201010140590.XA 2010-04-02 2010-04-02 Start fluorescent polymer, initiator thereof and preparation methods for start fluorescent polymer and initiator Active CN101844983B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201010140590.XA CN101844983B (en) 2010-04-02 2010-04-02 Start fluorescent polymer, initiator thereof and preparation methods for start fluorescent polymer and initiator

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201010140590.XA CN101844983B (en) 2010-04-02 2010-04-02 Start fluorescent polymer, initiator thereof and preparation methods for start fluorescent polymer and initiator

Publications (2)

Publication Number Publication Date
CN101844983A CN101844983A (en) 2010-09-29
CN101844983B true CN101844983B (en) 2014-07-16

Family

ID=42769820

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201010140590.XA Active CN101844983B (en) 2010-04-02 2010-04-02 Start fluorescent polymer, initiator thereof and preparation methods for start fluorescent polymer and initiator

Country Status (1)

Country Link
CN (1) CN101844983B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109776290B (en) * 2019-01-21 2021-03-16 中国科学院化学研究所 Fluorescent material for detecting mustard gas simulant based on sulfur-pi interaction as well as preparation method and application of fluorescent material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001009204A2 (en) * 1999-07-31 2001-02-08 Symyx Technologies, Inc. Controlled-architecture polymers and use thereof as separation media
US20030196896A1 (en) * 2002-04-17 2003-10-23 Mcwaid Thomas Harding Method and apparatus for screening flowable separation media for electrophoresis and related applications
CN1587344A (en) * 2004-07-15 2005-03-02 复旦大学 Star shape double block conjugate polymer and its preparing method
CN1594314A (en) * 2004-06-24 2005-03-16 复旦大学 Fluorene based water soluble conjugated polymer and process for preparing same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001009204A2 (en) * 1999-07-31 2001-02-08 Symyx Technologies, Inc. Controlled-architecture polymers and use thereof as separation media
US20030196896A1 (en) * 2002-04-17 2003-10-23 Mcwaid Thomas Harding Method and apparatus for screening flowable separation media for electrophoresis and related applications
CN1594314A (en) * 2004-06-24 2005-03-16 复旦大学 Fluorene based water soluble conjugated polymer and process for preparing same
CN1587344A (en) * 2004-07-15 2005-03-02 复旦大学 Star shape double block conjugate polymer and its preparing method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Synthesis of poly(N-isopropylacrylamide) by ATRP using a fluorescein-based initiator;Xiaoju Lu et al.;《Polymer Bulletin》;20070317;第59卷;第195-206页 *
Xiaoju Lu et al..Synthesis of poly(N-isopropylacrylamide) by ATRP using a fluorescein-based initiator.《Polymer Bulletin》.2007,第59卷第195-206页.

Also Published As

Publication number Publication date
CN101844983A (en) 2010-09-29

Similar Documents

Publication Publication Date Title
CN107011469A (en) A kind of side chain type liquid crystal macromolecule with aggregation-induced emission performance and preparation method thereof
CN107200832B (en) A kind of polymer and preparation method thereof with aggregation-induced emission effect, graphene composite material and preparation method thereof
CN101139319A (en) Substituted quinoline trimer indene derivative and method for making same
CN109608564A (en) A kind of side chain liquid crystalline polymer containing azobenzene and preparation method thereof with micro phase separation structure
CN111056987B (en) Aggregation-induced emission compound and preparation method and application thereof
CN108424349A (en) A kind of preparation method of the rare earth nano line for the tetraphenyl ethylene Derivatives Modified can be used for organic carboxyl acid detection
CN101844983B (en) Start fluorescent polymer, initiator thereof and preparation methods for start fluorescent polymer and initiator
CN107254032A (en) A kind of conjugated polymer based on anthra indenofluorene unit and preparation method and application
CN103992271A (en) Organic fluorescent gel compound based on naphthalimide and preparation method and application thereof
CN113929659B (en) Preparation and application of pressure-induced color-changing material with AIE (aluminum-doped aluminum-oxide) property
CN101787275B (en) Preparation and application method of phosphorescent conjugated polymer photoelectric material containing iridium complex
CN109111475B (en) Preparation method and application of aggregation-induced emission probe material
CN102295743A (en) Fluorescent conjugated polymer containing polyhedral oligomeric silsesquioxane (POSS), its preparation method and application
CN105348308A (en) Bridged bis-boron-dipyrromethene (BODIPY) derivative containing fluorene at meso-position and preparation method thereof
CN101302154B (en) Acrylic ester type benzocyclobutene monomer and preparation thereof
JP2010095514A (en) Linear tetraphosphine tetraoxide, rare-earth metal complex comprising the linear tetraphosphine tetraoxide as ligand and use of the complex
CN107011244A (en) Benzocyclobutane diene with AEE effects and azole derivatives and its preparation
CN106083694A (en) A kind of 3,6 2 (anthraquinone 2 vinyl) N ethyl carbazole and preparation method thereof
CN106835327B (en) A kind of preparation method of the photochromic nano micron fibre of multiple bases
CN109232654B (en) Eu/Tb-TCP-COOH complex luminescent material and preparation method and application thereof
CN104558427A (en) Preparation method of ring brush polymer containing polystyrene main chain
CN101481455A (en) Method for synthesizing white light emitting polymer with polyhexylfluorene as main chain
CN110305659A (en) A kind of aggregation-induced emission compound and the preparation method and application thereof
CN107793652A (en) Thin polymer film with changing color resulting from acid and aggregation-induced emission performance and preparation method thereof
CN107759775A (en) The condensed cyclic structure containing sulfuryl gives receptor type alternating polymer, preparation method and application with strong two-photon effect

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant