CN101844983A - 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 PDFInfo
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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
Technical field
The present invention relates to the biomacromolecule separation field, particularly relate to a kind of star fluorescent polymer and initiator and their preparation method who is used for the capillary electrophoresis separation medium.
Background technology
Capillary electrophoresis is to separate at present and analyze one of the most effective means of biomacromolecule.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, the separation for the dna fragmentation of realizing different lengths or structure must add separating medium in kapillary.The separating medium of widespread use at present mainly is the polymers soln of non-crosslinked, common has: linear homopolymer (comprises linear polyacrylamide, poly-(N, the N-DMAA), polyoxyethylene, Polyvinylpyrolidone (PVP), Mierocrystalline cellulose and derivative thereof etc.), multipolymer and mixture etc.Because under the identical weight-average molecular weight, the viscosity of line polymer is very big, therefore the separating medium that non-linear polymkeric substance is used as capillary electrophoresis also has some trials, see CONTROLLED-ARCHITECTUREPOLYMERS AND USE THEREOF AS SEPARATION MEDIA Klaerner G., et al.WO:2001009204,20020417.Yet, the biomacromolecule separating effect more do not carried out systematic research for line polymer and non-line polymer.
The concentration of polymers soln is determining the separating mechanism of biomacromolecule usually.With the example that is separated into of DNA, the separating mechanism of DNA in the entanglement macromolecular solution comprises the Ogston model, the model that crawls of various corrections, entropy barrier model etc.The separating mechanism of DNA in the polymer dilute solution comprises moment entanglement coupling mechanism, collision model, " collective motion " model etc.Though the separating mechanism of DNA is numerous, the restricted application of each model can not be explained all experimental results.The mechanism that further discloses capillary electrophoresis separation DNA is extremely important: can reduce the blindness when 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, observe the motor behavior of dna molecular in sepn process then under fluorescent microscope, thereby infer the interaction between separating medium and dna molecular.Simultaneously, also the someone attempts separating medium dyeing back is observed the motor behavior of separating medium under fluorescent microscope, 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 the 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 do not do as yet.
Summary of the invention
The purpose 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 be suc as formula shown in the I,
(formula I)
In the described formula I general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 1-20 any one, any one in the straight or branched alkyl that preferred the total number of carbon atoms is 6-12, more preferably hexyl; R
2Be pi-conjugated group, described pi-conjugated group is selected from least a in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and the alkynyl oligomer, described aryl is selected from least a in phenyl, thienyl, furyl and the pyridyl, preferred repeated structural unit number is the aryl oligomer of 1-5, most preferably phenyl; M is 0 or 1, and p is 1,2 or 3.
Compound is preferably compound shown in formula II or the formula III shown in the described formula I,
(formula II)
(formula III)
M=1 in the above-mentioned formula I general structure of preparation provided by the invention, the method for the described compound of p=1 comprises the steps:
1) under the condition that palladium catalyst exists, with compound shown in the formula IV, mono methoxy substituted aryl boric acid, in organic solvent, carry out the Suzuki linked reaction with the aqueous solution of basic cpd, obtain compound shown in the formula V;
(formula IV)
In the described formula IV general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 1-20 any one;
(formula V)
In the described formula V general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 1-20 any one, R
2Be pi-conjugated group, m=1, p=1;
2) under the condition that boron tribromide exists,, obtain compound shown in the formula VI with the demethylating in organic solvent of compound shown in the described formula V;
(formula VI)
In the described formula VI general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 1-20 any one, R
2Be pi-conjugated group, m=1, p=1;
3) under the condition that triethylamine exists, compound shown in the described formula VI and 2-bromine isobutyl acylbromide are reacted in organic solvent, obtain m=1 in the described formula I general structure, the described compound of p=1.
In the step 1) of this method, in the described formula IV general structure, R
1For the total number of carbon atoms in the straight or branched alkyl of 6-12 any one, preferred hexyl; In the described formula V general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 6-12 any one, preferred hexyl, described R
2In, described pi-conjugated group is selected from least a in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and the alkynyl oligomer, described aryl is selected from least a in phenyl, thienyl, furyl and the pyridyl, preferred repeated structural unit number is the aryl oligomer of 1-5, most preferably phenyl; Described formula IV compound is 5,5,10,10,15,15-six hexyls-2,7,12-tribromo three polyindenes, described palladium catalyst is selected from least a in tetrakis triphenylphosphine palladium, two (triphenylphosphine) Palladous chloride and the 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 yellow soda ash, salt of wormwood, sodium hydroxide or potassium hydroxide; The concentration of the aqueous solution of described basic cpd is 0.5-5mol/L, preferred 2mol/L; The mol ratio of compound shown in the 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, preferred 1: 4: 15: 0.1; In the described Suzuki linked reaction, temperature is 0-30 ℃, and preferred 20 ℃, the time is 6-24 hour, preferred 12 hours;
Described step 2) in the described formula VI general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 6-12 any one, preferred hexyl; Described R
2In, described pi-conjugated group is selected from least a in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and the alkynyl oligomer, described aryl is selected from least a in phenyl, thienyl, furyl and the pyridyl, preferred repeated structural unit number is the aryl oligomer of 1-5, most preferably phenyl; The mol ratio of compound is 5-20 shown in boron tribromide and the described formula V: 1, and preferred 10: 1; Temperature of reaction is 0-30 ℃, and preferred 20 ℃, the time is 6-24 hour, preferred 12 hours;
In the described step 3), described organic solvent is at least a in methylene dichloride, chloroform, ether, toluene and the tetrahydrofuran (THF); The mol ratio of compound shown in triethylamine, the described formula VI and 2-bromine isobutyl acylbromide is 10-200: 1: 3-15, preferred 120: 1: 10; In the described reaction, temperature is 0-30 ℃, and preferred 20 ℃, the time is 6-24 hour, preferred 12 hours.
Among the above-mentioned preparation method, as the R of the described compound of step 1) Chinese style IV
1Be hexyl, and described mono methoxy substituted aryl boric acid is during to methoxyphenylboronic acid, promptly obtains the described compound of formula II.
M=1 among the preparation formula I provided by the invention, the described compound of p=2 comprises the steps:
1) under the condition that palladium catalyst exists, the aqueous solution of compound shown in the formula IV, dimethoxy substituted aryl boric acid and basic cpd is carried out the Suzuki linked reaction in organic solvent, obtain compound shown in the formula V;
(formula IV)
In the described formula IV general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 1-20 any one;
(formula V)
In the described formula V general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 1-20 any one, R
2Be pi-conjugated group, m=1, p=2;
2) under the condition that boron tribromide exists,, obtain compound shown in the formula VI with the demethylating in organic solvent of compound shown in the described formula V;
(formula VI)
In the described formula VI general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 1-20 any one, R
2Be pi-conjugated group, m=1, p=2;
3) under the condition that triethylamine exists, compound shown in the described formula VI and 2-bromine isobutyl acylbromide are reacted in organic solvent, obtain m=1 among the formula I, the described compound of p=2.
In the step 1) of this method, in the described formula IV general structure, R
1For the total number of carbon atoms in the straight or branched alkyl of 6-12 any one, preferred hexyl; In the described formula V general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 6-12 any one, preferred hexyl, described R
2In, described pi-conjugated group is selected from least a in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and the alkynyl oligomer, described aryl is selected from least a in phenyl, thienyl, furyl and the pyridyl, preferred repeated structural unit number is the aryl oligomer of 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 are selected from least a in tetrakis triphenylphosphine palladium, two (triphenylphosphine) Palladous chloride and the palladium, described dimethoxy substituted aryl boric acid is 3,4-dimethoxy phenylo boric acid, dimethoxy-thiophene boric acid, a kind of in the dimethoxy-pyridine boric acid, preferred 3,4-dimethoxy phenylo boric acid, described basic cpd are yellow soda ash, salt of wormwood, sodium hydroxide or potassium hydroxide; The concentration of the aqueous solution of described basic cpd is 0.5-5mol/L, preferred 2mol/L; The mol ratio of compound shown in the 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, preferred 1: 4: 15: 0.1; In the described Suzuki linked reaction, temperature is 0-30 ℃, and preferred 20 ℃, the time is 6-24 hour, preferred 12 hours;
Described step 2) in the described formula VI general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 6-12 any one, preferred hexyl; Described R
2In, described pi-conjugated group is selected from least a in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and the alkynyl oligomer, described aryl is selected from least a in phenyl, thienyl, furyl and the pyridyl, preferred repeated structural unit number is the aryl oligomer of 1-5, most preferably phenyl; The mol ratio of compound is 10-30 shown in boron tribromide and the described formula V: 1, and preferred 20: 1; Temperature of reaction is 0-30 ℃, and preferred 20 ℃, the time is 6-24 hour, preferred 12 hours;
In the described step 3), described organic solvent is at least a in methylene dichloride, chloroform, ether, toluene and the tetrahydrofuran (THF); The mol ratio of compound shown in triethylamine, the described formula VI and 2-bromine isobutyl acylbromide is 20-300: 1: 6-30, preferred 240: 1: 20; In the described reaction, temperature is 0-30 ℃, and preferred 20 ℃, the time is 6-24 hour, preferred 12 hours.
Among the above-mentioned preparation method, as the R of the described compound of step 1) Chinese style IV
1Be hexyl, and described dimethoxy substituted aryl boric acid is 3, during 4-dimethoxy phenylo boric acid, promptly obtains the described compound of formula III.
Fluorescent polymer provided by the invention, its general structure be suc as formula shown in the VII,
(formula VII)
In the described formula VII general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 1-20 any one, any one in the straight or branched alkyl that preferred the total number of carbon atoms is 6-12, more preferably hexyl; R
2Be pi-conjugated group, described pi-conjugated group is selected from least a in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and the alkynyl oligomer, described aryl is selected from least a in phenyl, thienyl, furyl and the pyridyl, preferred repeated structural unit number is the aryl oligomer of 1-5, most preferably phenyl; R
3Be the water-soluble polymers chain, described water-soluble polymers chain is selected from polyacrylamide, poly-N, at least a in N-DMAA, polyoxyethylene, Polyvinylpyrolidone (PVP), Mierocrystalline cellulose, cellulose nitrate, cellulose ethanoate, methylcellulose gum and the carboxymethyl cellulose, preferred 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 the described formula VII is 10,000-10, and 000,000, preferred 500,000-2,000,000, molecular weight dispersity is 1.5-5, preferred 2.5.
Fluorescent polymer is preferably polymkeric substance shown in the formula VIII shown in the described formula VII,
(formula VIII)
In the polymkeric substance, m is 0 or 1 shown in the described formula VIII, and n is the integer of 100-10000, and p is 1,2 or 3;
Fluorescent polymer shown in the described formula VII is fluorescent polymer shown in formula IX and the formula X more preferably,
(formula IX)
In the described formula IX general structure, n is the integer of 100-10000;
(formula X)
In the described formula X general structure, n is the integer of 100-10000.
M=1 in the described general structure of preparation formula VII provided by the invention, the method for the described polymkeric substance of p=1 comprises the steps: with the cuprous bromide to be catalyzer, with N, N, N ', N, " five methyl diethylentriamine is a part to ' N, and with m=1 in the formula I general structure, the described compound of p=1 is an initiator; cause N; the N-DMAA carries out atom transition free radical polymerization reaction, and reaction finishes and obtains m=1 in the described general structure of formula VII, the described polymkeric substance of p=1.
In this method, described cuprous bromide, N, N, N ', N, ' N " m=1 in five methyl diethylentriamine, the formula I general structure; the mol ratio of described compound of p=2 and N,N-DMAA is 3-4: 3-4: 1: 100-10000, preferred 3: 3: 1: 3000; In the described atom transition free radical polymerization reaction, temperature is 100-150 ℃, and preferred 120 ℃, the time is 1-7 days, preferred 4 days.
M=1 in the described general structure of preparation formula VII provided by the invention, the method for the described polymkeric substance of p=2 comprises the steps: with the cuprous bromide to be catalyzer, with N, N, N ', N, " five methyl diethylentriamine is a part to ' N, and with m=1 in the formula I general structure, the described compound of p=1 is an initiator; cause N; the N-DMAA carries out atom transition free radical polymerization reaction, and reaction finishes and obtains m=1 in the described general structure of formula VII, the described polymkeric substance of p=2.
In this method, described cuprous bromide, N, N, N, N, N " m=1 in five methyl diethylentriamine, the formula I general structure, the mol ratio of described compound of p=2 and N,N-DMAA is 6-8: 6-8: 1: 100-10000, preferred 6: 6: 1: 3000; In the described atom transition free radical polymerization reaction, temperature is 100-150 ℃, and preferred 120 ℃, the time is 1-7 days, preferred 4 days.
The application of fluorescent polymer separating medium in as capillary electrophoresis separation DNA or protein also belongs to protection scope of the present invention shown in the formula VII general structure that the invention described above provides.
Utilize fluorescent polymer provided by the invention to carry out DNA or protein separation, velocity of separation is fast, and good separating effect, kapillary need not modified, and encapsulating is reusable and better repeatability arranged; And the present invention can be incorporated into comparable different topology structure in the separating medium, and contrast line polymer that can system is to the influence of biomacromolecule separating resulting; In addition, because this fluorescent polymer has fluorescent core, thereby this fluorescent core can be incorporated in the separating medium, realize observing simultaneously the purpose of separating medium and biomacromolecule, thereby obtain biomacromolecule image more intuitively in sepn process, for the announcement of separating mechanism provides stronger method.
Description of drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of embodiment 1 preparation gained initiator S-I (being formula II).
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of embodiment 2 preparation resulting polymers S-3-PDMA.
Fig. 3 is the static light scattering Zimm figure of embodiment 2 preparation resulting polymers S-3-PDMA.
Fig. 4 is the nucleus magnetic hydrogen spectrum figure of embodiment 3 preparation 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, from top to bottom is respectively that mass percentage concentration is the capillary electrophoresis separation figure of the solution of 1%, 3%, 5% polymkeric substance S-3-PDMA to Φ X174/Hae IIIDNA Digestive system.
Fig. 6 is the repeated experiment figure of 5% the solution of S-3-PDMA to the capillary electrophoresis separation of Φ X174/Hae III DNA Digestive system, and three curves are respectively the capillary electrophoresis separation figure of following 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, is respectively the capillary electrophoresis separation figure of the solution (mass percentage concentration is 3%) of polymkeric substance L-PDMA, S-3-PDMA and S-6-PDMA to Φ X174/Hae III DNA Digestive system from top to bottom.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
The preparation of initiator S-I shown in embodiment 1, the formula II
With 5,5,10,10,15,15-six hexyls-2,7,12-tribromo three polyindenes are starting raw material, under palladium catalyst catalysis with methoxyphenylboronic acid carried out the Suzuki linked reaction obtain 5,5,10,10,15,15-six hexyls-2,7,12-three (4-p-methoxy-phenyl) three polyindenes.Demethylating obtains 5,5,10,10,15 under the effect of boron tribromide then, 15-six hexyls-2,7,12-three (4-hydroxy phenyl) three polyindenes.Under the effect of triethylamine, obtain initiator S-I shown in the formula II again with 2-bromine isobutyryl bromine reaction.Concrete reaction process is shown below:
1) preparation compound 5,5,10,10,15,15-six hexyls-2,7,12-three (4-p-methoxy-phenyl) three polyindenes:
With 5,5,10; 10,15,15-six hexyls-2; 7, and 12-tribromo three polyindenes (0.5g, 0.46mmol); to methoxyphenylboronic acid (0.28g; 1.84mmol), concentration is that aqueous sodium carbonate (3.7mL) and the tetrahydrofuran (THF) (20mL) of 2M adds in the reaction flask, nitrogen protection adds four (triphenyl phosphorus) palladium (0.05g down; 0.04mmol), reaction backflow 20h.Reaction is used saturated aqueous ammonium chloride, saturated common salt water washing organic phase respectively after finishing.Organic phase is revolved behind anhydrous magnesium sulfate drying and is desolventized, and silicagel column separates, and is that eluent obtains the white solid product with ethyl acetate/petroleum ether=1/10.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), and 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).
Detect data as can be known by said structure, this compound structure is correct.
2) preparation compound 5,5,10,10,15,15-six hexyls-2,7,12-three (4-hydroxy phenyl) three polyindenes:
With 5,5,10,10,15,15-six hexyls-2,7, (0.26g 0.22mmol) is dissolved in the methylene dichloride (10mL) 12-three (4-p-methoxy-phenyl) three polyindenes, and ice bath drips boron tribromide down, and (0.56g, 2.23mmol), reaction system at room temperature stirs spends the night.After reaction finishes, in reaction system, add the saturated aqueous solution of sodium bicarbonate, and use the dichloromethane extraction water.The organic phase that merges is revolved behind anhydrous sodium sulfate drying and is desolventized, and silicagel column separates, and is that eluent obtains the white solid product with ethyl acetate/petroleum ether=1/5.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 155.0,154.3,144.8,139.2,138.5,138.0,134.2,128.3,124.8,124.6,120.1,115.7,55.7,37.1,31.5,29.7,29.5,23.9,22.3,13.9.MS (MALDI-TOF): Calcd for C
84H
108O
3: 1123.Found:1123.
Detect data as can be known by said structure, this compound structure is correct.
(3) preparation compound S-I:
With 5,5,10,10,15,15-six hexyls-2,7,12-three (4-hydroxy phenyl) three polyindene (0.26g, 0.23mmol), triethylamine (2mL, 28mmol) and tetrahydrofuran (THF) (10mL) add in the reaction flask, ice bath drips 2-bromine isobutyl acylbromide (0.53g down, 2.3mmol), reaction system at room temperature stirred 12 hours.After reaction finishes, remove by filter ammonium salt, and revolve and desolventize.Silicagel column separates, and is that eluent obtains the white solid product with ethyl acetate/petroleum ether=1/10, is compound S-I.Productive rate: 89%.
The nucleus magnetic hydrogen spectrum figure of this compound as shown in Figure 1, hydrogen spectrum and the carbon concrete detection of spectrum data are as follows:
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.
Detect data as can be known by said structure, this compound structure is correct.
The preparation of polymkeric substance shown in embodiment 2, the formula IX (S3-PDMA)
Compound is an initiator shown in the formula II for preparing with embodiment 1, consumption is 0.01mmol, with the N,N-DMAA is monomer, and consumption is 30mmol, with CuBr is catalyzer, consumption is 0.03mmol, is part with PMDETA, and consumption is 0.03mmol, reacted four days down at 120 ℃, obtain polymkeric substance shown in the formula IX structural formula.The molecular weight that static light scattering records this polymkeric substance is 9 * 10
5G/mol, molecular weight dispersity are 2.5.
The preparation of initiator shown in embodiment 3, the formula III (S-II)
According to embodiment 1 identical experimental technique and condition, only with in the step 1) used right-methoxyphenylboronic acid replaces with 3,4-dimethoxy phenylo boric acid, described 3, the consumption of 4-dimethoxy phenylo boric acid is 1.84mmol, initiator shown in the preparation formula III.Promptly with 5,5,10,10,15,15-six hexyls-2,7,12-tribromo three polyindenes are starting raw material, and with 3,4-dimethoxy phenylo boric acid carries out the Suzuki linked reaction and obtains 5,5,10 under palladium catalyst catalysis, 10,15,15-six hexyls-2,7,12-three (3, the 4-Dimethoxyphenyl) three polyindenes.Demethylating obtains 5,5,10,10,15 under the effect of boron tribromide then, 15-six hexyls-2,7,12-three (3, the 4-dihydroxy phenyl) three polyindenes.Under the effect of triethylamine, obtain initiator S-II again with 2-bromine isobutyryl bromine reaction.Concrete reaction process is shown below:
The nucleus magnetic hydrogen spectrum figure of this compound S-II as shown in Figure 4, hydrogen spectrum and the carbon concrete detection of spectrum data are as follows:
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.
Detect data as can be known by said structure, this compound structure is correct.
The preparation of embodiment 4, polymkeric substance S-6-PDMA (formula X)
Compound is an initiator shown in the formula III for preparing with embodiment 3, consumption is 0.01mmol, with the N,N-DMAA is monomer, and consumption is 30mmol, with cuprous bromide CuBr is catalyzer, consumption is 0.06mmol, is part with PMDETA, and consumption is 0.06mmol, reacted four days down at 120 ℃, obtain polymkeric substance S-6-PDMA.The molecular weight that the static light scattering method records this polymkeric substance is 9 * 10
5G/mol, molecular weight dispersity are 2.5.
Embodiment 2 is prepared polymkeric substance (S-3-PDMA) shown in the gained formula IX structural formulas as separating medium, is that the Φ X174/Hae III DNA Digestive system (this Digestive system is available from sigmaaldrich company) of 100 μ g/mL carries out capillary electrophoresis separation according to following method to concentration: the Φ X174/Hae III DNA Digestive system of preparation 100 μ g/mL earlier, use fluorescence dye GeneFinder
TM(available from Xiamen Baiweixin Biological Technology Co., Ltd.) dyeing.Utilizing polymkeric substance shown in the preparation gained formula IX structural formula to be dissolved in mass percentage concentration again is the macromolecular solution that is mixed with a series of different concns in 1% TBE (Tris-borate buffer) solution.The kapillary that is adopted is 75 microns of internal diameters, total pipe range 31cm, effectively pipe range 21cm.During operation, the hydrochloric acid soln with 1M washed 10 minutes kapillary earlier, used deionized water rinsing then 2 minutes, under 30kpa the macromolecular solution for preparing was pressed in the kapillary again, continued 8 minutes, and this base line reaches balance substantially.Follow the negative pole electrokinetic injection, voltage is-5kV/cm that sample injection time is 5s.After sample introduction was finished, the TBE solution with 1% was as damping fluid, at 25 ℃, separation voltage be-condition of 8kV/cm under, carry out the DNA separating experiment.Detect with fluorimetric detector, excitation wavelength is 488nm, and the 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.Be 9 * 10 at first with molecular weight
5The polymkeric substance S-3-PDMA of g/mol is an example, it is made into mass percentage concentration is respectively 1%, 3% and 5% polymers soln, and solvent is TBE (Tris-borate buffer), its capillary electrophoresis separation result such as Fig. 5 in this solution.As seen increase with concentration, its separating effect improves, and illustrates that in the finite concentration scope, high density helps the raising of separating effect.Reusable behind encapsulating of kapillary, the S-3-PDMA with 5% is an example, and three times electrophoresis has good repeatability, repeated experiment result such 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 mass percentage concentration respectively with it, and solvent for use is TBE (Tris-borate buffer), is used for DNA and separates.Its capillary electrophoresis separation result such as Fig. 7.As seen the separating effect of S-3-PDMA is best, and S-6-PDMA to separate the time when obtaining close separating effect with the L-PDMA polymkeric substance of line style the shortest obtaining.Above experimental fact explanation: under molecular weight, starlike PDMA has separating property preferably when DNA isolation.
(formula XI)
Wherein, the structural formula of described L-PDMA polymkeric substance is suc as formula shown in the X, and its preparation method is as follows:
1) preparation compound 9,9-dihexyl-2,7-two (p-methoxyphenyl) fluorenes:
With 9,9-dihexyl-2,7-dibromo fluorenes (1.5g, 3mmol); the 4-methoxyphenylboronic acid (1.4g, 9mmol), yellow soda ash (2M, 13mL) and tetrahydrofuran (THF) (30mL) join in the reaction flask; nitrogen protection adds four (triphenyl phosphorus) palladium down, and (0.2g 0.018mmol), reacts backflow 20h.Reaction is used saturated aqueous ammonium chloride, saturated common salt water washing organic phase respectively after finishing.Organic phase is revolved behind anhydrous magnesium sulfate drying and is desolventized, and silicagel column separates, and is that eluent carries out wash-out with the sherwood oil, obtains the white solid product, is compound 9,9-dihexyl-2,7-two (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.
Detect data as can be known by said structure, this compound structure is correct.
2) preparation compound 9,9-dihexyl-2,7-two (4-hydroxy phenyl) fluorenes:
With 9,9-dihexyl-2, (0.1g 0.18mmol) is dissolved in methylene dichloride (10mL) to 7-two (4-p-methoxy-phenyl) fluorenes, and ice bath drips boron tribromide down, and (0.18g, 0.74mmol), reaction system at room temperature stirs spends the night.After reaction finishes, in reaction system, add the saturated aqueous solution of sodium bicarbonate, and use the dichloromethane extraction water.The organic phase that merges is revolved behind anhydrous sodium sulfate drying and is desolventized, and silicagel column separates, and be ethyl acetate with the volume ratio: sherwood oil=the blended eluent carried out wash-out in 1: 8, obtain the white solid product, be compound 9,9-dihexyl-2,7-two (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%).
Detect data as can be known by said structure, this compound structure is correct.
(3) preparation line style initiator:
With 9,9-dihexyl-2,7-two (4-hydroxy phenyl) fluorenes (0.14g, 0.27mmol), triethylamine (1.5mL, 21mmol) and tetrahydrofuran (THF) (10mL) add in the reaction flask, ice bath drips 2-bromine isobutyl acylbromide down, and (0.24g, 1mmol), reaction system at room temperature stirs spends the night.After reaction finishes, remove by filter ammonium salt, and revolve and desolventize.Silicagel column separates, and is ethyl acetate with the volume ratio: the blended eluent of sherwood oil=1: 10 carries out wash-out, obtains the 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.
Detect data as can be known by said structure, this compound structure is correct.
Get method for preparing gained line style initiator 0.01mmol, with N, the N-DMAA is a monomer, and consumption is 30mmol, is catalyzer with CuBr, consumption is 0.02mmol, with PMDETA is part, and consumption is 0.02mmol, reacts four days down at 120 ℃, obtain described line style L-PDMA polymkeric substance, the molecular weight that the static light scattering method records this polymkeric substance is 9 * 10
5G/mol, molecular weight dispersity are 2.5.
Claims (16)
1. compound shown in the formula I,
(formula I)
In the described formula I general structure, R
1For the total number of carbon atoms in the straight or branched alkyl of 1-20 any one, R
2Be pi-conjugated group, m is 0 or 1, and p is 1,2 or 3.
2. compound according to claim 1 is characterized in that: in the described formula I general structure, and R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 6-12 any one, preferred hexyl; R
2In, described pi-conjugated group is selected from any one in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and the alkynyl oligomer, described aryl is selected from least a in phenyl, thienyl, furyl and the pyridyl, preferred repeated structural unit number is the aryl oligomer of 1-5, most preferably phenyl;
Compound shown in the described formula I is a compound shown in formula II or the formula III,
(formula II)
(formula III)
3. one kind prepares m=1 in the described formula I general structure of claim 1, and the method for the described compound of p=1 comprises the steps:
1) under the condition that palladium catalyst exists, the aqueous solution of compound shown in the formula IV, mono methoxy substituted aryl boric acid and basic cpd is carried out the Suzuki linked reaction in organic solvent, obtain compound shown in the formula V;
(formula IV)
In the described formula IV general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 1-20 any one;
(formula V)
In the described formula V general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 1-20 any one, R
2Be pi-conjugated group, m=1, p=1;
2) under the condition that boron tribromide exists,, obtain compound shown in the formula VI with the demethylating in organic solvent of compound shown in the described formula V;
(formula VI)
In the described formula VI general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 1-20 any one, R
2Be pi-conjugated group, m=1, p=1;
3) under the condition that triethylamine exists, compound shown in the described formula VI and 2-bromine isobutyl acylbromide are reacted in organic solvent, obtain m=1 in the described formula I general structure of claim 1, the described compound of p=1.
4. method according to claim 3 is characterized in that: in the described formula IV general structure of described step 1), and R
1For the total number of carbon atoms in the straight or branched alkyl of 6-12 any one, preferred hexyl; In the described formula V general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 6-12 any one, preferred hexyl, described R
2In, described pi-conjugated group is selected from least a in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and the alkynyl oligomer, described aryl is selected from least a in phenyl, thienyl, furyl and the pyridyl, preferred repeated structural unit number is the aryl oligomer of 1-5, most preferably phenyl; Described formula IV compound is 5,5,10,10,15,15-six hexyls-2,7,12-tribromo three polyindenes, described palladium catalyst are selected from least a in tetrakis triphenylphosphine palladium, two (triphenylphosphine) Palladous chloride and the palladium, and described basic cpd is yellow soda ash, salt of wormwood, sodium hydroxide or potassium hydroxide; Described mono methoxy substituted aryl boric acid is to methoxyphenylboronic acid, methoxythiophene boric acid or methoxypyridine boric acid, preferably to methoxyphenylboronic acid;
Described step 2) in the described formula VI general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 6-12 any one, preferred hexyl; Described R
2In, described pi-conjugated group is selected from least a in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and the alkynyl oligomer, described aryl is selected from least a in phenyl, thienyl, furyl and the pyridyl, preferred repeated structural unit number is the aryl oligomer of 1-5, most preferably phenyl;
In the described step 3), described organic solvent is at least a in methylene dichloride, chloroform, ether, toluene and the tetrahydrofuran (THF).
5. according to claim 3 or 4 described methods, it is characterized in that: in the described step 1), the concentration of the aqueous solution of described basic cpd is 0.5-5mol/L, preferred 2mol/L; The mol ratio of compound shown in the described formula IV, mono methoxy substituted aryl boric acid, described basic cpd and described palladium catalyst is 1: 3-6: 10-20: 0.05-0.2, preferred 1: 4: 15: 0.1; In the described Suzuki linked reaction, temperature is 0-30 ℃, and preferred 20 ℃, the time is 6-24 hour, preferred 12 hours;
Described step 2) in, the mol ratio of compound is 5-20 shown in boron tribromide and the described formula V: 1, and preferred 10: 1; Temperature of reaction is 0-30 ℃, and preferred 20 ℃, the time is 6-24 hour, preferred 12 hours;
In the described step 3), the mol ratio of compound shown in triethylamine, the described formula VI and 2-bromine isobutyl acylbromide is 10-200: 1: 3-15, preferred 120: 1: 10; In the described reaction, temperature is 0-30 ℃, and preferred 20 ℃, the time is 6-24 hour, preferred 12 hours.
6. one kind prepares m=1 in the I of formula described in the claim 1 general structure, and the method for the described compound of p=2 comprises the steps:
1) under the condition that palladium catalyst exists, the aqueous solution of compound shown in the formula IV, dimethoxy substituted aryl boric acid and basic cpd is carried out the Suzuki linked reaction in organic solvent, obtain compound shown in the formula V;
(formula IV)
In the described formula IV general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 1-20 any one;
(formula V)
In the described formula V general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 1-20 any one, R
2Be pi-conjugated group, m=1, p=2;
2) under the condition that boron tribromide exists,, obtain compound shown in the formula VI with the demethylating in organic solvent of compound shown in the described formula V;
(formula VI)
In the described formula VI general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 1-20 any one, R
2Be pi-conjugated group, m=1, p=2;
3) under the condition that triethylamine exists, compound shown in the described formula VI and 2-bromine isobutyl acylbromide are reacted in organic solvent, obtain m=1 in the I of formula described in the claim 1 general structure, the described compound of p=2.
7. method according to claim 6 is characterized in that: in the described formula IV general structure of described step 1), and R
1For the total number of carbon atoms in the straight or branched alkyl of 6-12 any one, preferred hexyl; In the described formula V general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 6-12 any one, preferred hexyl, described R
2In, described pi-conjugated group is selected from least a in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and the alkynyl oligomer, described aryl is selected from least a in phenyl, thienyl, furyl and the pyridyl, preferred repeated structural unit number is the aryl oligomer of 1-5, most preferably phenyl; Described formula IV compound is 5,5,10,10,15,15-six hexyls-2,7,12-tribromo three polyindenes, described palladium catalyst are selected from least a in tetrakis triphenylphosphine palladium, two (triphenylphosphine) Palladous chloride and the palladium, described dimethoxy substituted aryl boric acid is 3,4-dimethoxy phenylo boric acid, dimethoxy-thiophene boric acid, a kind of in the dimethoxy-pyridine boric acid, preferred 3,4-dimethoxy phenylo boric acid, described basic cpd are yellow soda ash, salt of wormwood, sodium hydroxide or potassium hydroxide;
Described step 2) in the described formula VI general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 6-12 any one, preferred hexyl; Described R
2In, described pi-conjugated group is selected from least a in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and the alkynyl oligomer, described aryl is selected from least a in phenyl, thienyl, furyl and the pyridyl, preferred repeated structural unit number is the aryl oligomer of 1-5, most preferably phenyl;
In the described step 3), described organic solvent is at least a in methylene dichloride, chloroform, ether, toluene and the tetrahydrofuran (THF).
8. according to claim 6 or 7 described methods, it is characterized in that: in the described step 1), the concentration of the aqueous solution of described basic cpd is 0.5-5mol/L, preferred 2mol/L; The mol ratio of compound shown in the described formula IV, dimethoxy substituted aryl boric acid, described basic cpd and described palladium catalyst is 1: 3-6: 10-20: 0.05-0.2, preferred 1: 4: 15: 0.1; In the described Suzuki linked reaction, temperature is 0-30 ℃, and preferred 20 ℃, the time is 6-24 hour, preferred 12 hours;
Described step 2) in, the mol ratio of compound is 10-30 shown in boron tribromide and the described formula V: 1, and preferred 20: 1; Temperature of reaction is 0-30 ℃, and preferred 20 ℃, the time is 6-24 hour, preferred 12 hours;
In the described step 3), the mol ratio of compound shown in triethylamine, the described formula VI and 2-bromine isobutyl acylbromide is 20-300: 1: 6-30, preferred 240: 1: 20; In the described reaction, temperature is 0-30 ℃, and preferred 20 ℃, the time is 6-24 hour, preferred 12 hours.
9. fluorescent polymer shown in the formula VII,
(formula VII)
In the described formula VII general structure, R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 1-20 any one; R
2Be pi-conjugated group; R
3Be the water-soluble polymers chain; M is 0 or 1; P is 1,2 or 3; The number-average molecular weight of fluorescent polymer shown in the described formula VII is 10,000-10, and 000,000, molecular weight dispersity is 1.5-5.
10. polymkeric substance according to claim 9 is characterized in that: in the described formula VII general structure, and R
1Be selected from the total number of carbon atoms and be in the straight or branched alkyl of 6-12 any one, preferred hexyl; Described R
2In, described pi-conjugated group is selected from least a in aryl, thiazolinyl, alkynyl, aryl oligomer, thiazolinyl oligomer and the alkynyl oligomer, described aryl is selected from least a in phenyl, thienyl, furyl and the pyridyl, preferred repeated structural unit number is the aryl oligomer of 1-5, most preferably phenyl; Described R
3In, described water-soluble polymers chain is selected from polyacrylamide, poly-N, at least a in N-DMAA, polyoxyethylene, Polyvinylpyrolidone (PVP), Mierocrystalline cellulose, cellulose nitrate, cellulose ethanoate, methylcellulose gum and the carboxymethyl cellulose, preferred poly-N,N-DMAA; The number-average molecular weight of fluorescent polymer shown in the described formula VII is 500,000-2, and 000,000, molecular weight dispersity is 2.5.
11. according to claim 9 or 10 described polymkeric substance, it is characterized in that: fluorescent polymer shown in the described formula VII is a fluorescent polymer shown in the formula VIII,
(formula VIII)
In the polymkeric substance, m is 0 or 1 shown in the described formula VIII, and n is the integer of 100-10000, and p is 1,2 or 3; Fluorescent polymer shown in preferred formula IX and the formula X,
(formula IX)
In the described formula IX general structure, n is the integer of 100-10000;
(formula X)
In the described formula X general structure, n is the integer of 100-10000.
12. one kind prepares m=1 in the described general structure of claim 9 formula VII, the method of the described polymkeric substance of p=1, comprise the steps: with the cuprous bromide to be catalyzer, with N, N, N ', N, " five methyl diethylentriamine is a part to ' N, and with m=1 in the claim 1 formula I general structure, the described compound of p=1 is an initiator; cause N; the N-DMAA carries out atom transition free radical polymerization reaction, and reaction finishes and obtains m=1 in the described general structure of claim 9 formula VII, the described polymkeric substance of p=1.
13. method according to claim 12, it is characterized in that: described cuprous bromide, N, N, N ', N, ' N " m=1 in five methyl diethylentriamine, the claim 1 formula I general structure, described compound of p=1 and N; the mol ratio of N-DMAA is 3-4: 3-4: 1: 100-10000, preferred 3: 3: 1: 3000; In the described atom transition free radical polymerization reaction, temperature is 100-150 ℃, and preferred 120 ℃, the time is 1-7 days, preferred 4 days.
14. one kind prepares m=1 in the described general structure of claim 9 formula VII, the method of the described polymkeric substance of p=2, comprise the steps: with the cuprous bromide to be catalyzer, with N, N, N ', N, " five methyl diethylentriamine is a part to ' N, and with m=1 in the claim 1 formula I general structure, the described compound of p=2 is an initiator; cause N; the N-DMAA carries out atom transition free radical polymerization reaction, and reaction finishes and obtains m=1 in the described general structure of claim 9 formula VII, the described polymkeric substance of p=2.
15. method according to claim 13, it is characterized in that: described cuprous bromide, N, N, N ', N, ' N " m=1 in five methyl diethylentriamine, the claim 1 formula I general structure, described compound of p=2 and N; the mol ratio of N-DMAA is 6-8: 6-8: 1: 100-10000, preferred 6: 6: 1: 3000; In the described atom transition free radical polymerization reaction, temperature is 100-150 ℃, and preferred 120 ℃, the time is 1-7 days, preferred 4 days.
16. the application of the described fluorescent polymer of claim 9 separating medium in as capillary electrophoresis separation DNA or protein.
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