CN103524650A - Asymmetric two-block polymers as well as preparation and application thereof - Google Patents
Asymmetric two-block polymers as well as preparation and application thereof Download PDFInfo
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Abstract
The invention discloses asymmetric two-block polymers as well as preparation and application thereof. A series of asymmetric rigid-flexible two-block polymers are synthesized by reactions of Suzuki coupling and atom transfer radical polymerization (ATRP), wherein rigid chains are small-molecule 'benzene-fluorene-benzene' structures, flexible chains are polyacrylic acid or polyethylene glycol methacrylate, and the rigid-flexible structures occur as spherical assembly bodies of 50-70nm in an aqueous solution. The asymmetric two-block polymers can be well dissolved in water and have no toxicity to cells, so that the polymers can be applicable to biological cell imaging. Results show that the polymers play a specificity marking role in cytoplasm.
Description
Technical field
The invention belongs to the technical field of nano material of biological functional, be specifically related to that a kind of to take small molecules " benzene fluorenes benzene " structure be stiff chain, flexible chain be polyacrylic acid or polyethylene glycol methacrylate-styrene polymer asymmetric bi-block copolymer synthetic and self-assembly property research with and in the application in cell imaging field.
Background technology
Conjugated polymers has the character of metallic conductivity and inorganic semiconductor, and its photoelectric property can change along with the variation of external environment, and this makes them at aspects such as Organic Light Emitting Diode, solar cell and bio-sensings, have broad application prospects.The self-assembled structures of block conjugated polymer can form " core-shell " type under close hydrophobic interaction, and what also can form by the pi-pi accumulation of stiff chain is linear or bar-shaped.Hard and soft block conjugated polymer is in the past generally symmetrical structure, the present invention proposes a kind of novel asymmetric hard and soft bi-block copolymer, the small molecules " benzene fluorenes benzene " of take is stiff chain, flexible chain is introduced by ATRP reactive polymeric tert-butyl acrylate or polyethylene glycol methacrylate-styrene polymer in one end, this material water dissolubility is relatively good, but also can connect some medicines by active group, so this class self-assembled material can be easy to enter in biomass cells body, reaching the effect of detection or release of therapeutic agents, is a kind of ideal Bio-Nano-Materials.
Summary of the invention
Technical problem: the object of the present invention is to provide a kind of preparation method and the research of self-assembly behavior and application of cell imaging with the asymmetric bi-block copolymer of good photoelectric properties and water-soluble and biocompatibility.
Technical scheme: the structure of a kind of asymmetric bi-block copolymer of the present invention is as follows:
Wherein rigid chain segment (A) is " benzene fluorenes benzene " structure, and soft segment (B) is synthetic by atom transfer radical polymerization (ATRP) reaction,
N is the zip length of flexible chain monomer;
R is the repeating unit of flexible chain, is vinylformic acid when n is 20-60, or n is polyethylene glycol methacrylate-styrene polymer while being 3-10.
Wherein:
A. rigid chain segment is " benzene fluorenes benzene " structure, and soft segment is to react by atom transfer radical polymerization ATRP, take tert-butyl acrylate as the synthetic asymmetric bi-block copolymer of monomer, and its molecular structural formula is as follows:
B. rigid chain segment is " benzene fluorenes benzene " structure, and soft segment is to react by atom transfer radical polymerization ATRP, take polyethylene glycol methacrylate-styrene polymer as the synthetic asymmetric bi-block copolymer of monomer, and its molecular structural formula is as follows:
The concrete synthesis step of synthetic method of asymmetric bi-block copolymer of the present invention is as follows:
(1) small molecules " benzene fluorenes benzene " stiff chain is synthetic
2,7-bis-bromo-9, synthesizing of 9 '-dioctyl fluorene: by 2,7-dibromo fluorenes and Tetrabutyl amonium bromide mix and add dimethyl sulfoxide (DMSO), the aqueous solution that adds again NaOH, in mixed solution, add 1-bromooctane afterwards, under room temperature, stirring reaction is after 4～72 hours, in reaction mixture, add excessive ethyl acetate, then filter out NaOH throw out, with dilute hydrochloric acid and normal saline washing organic extraction, the sherwood oil of take utilizes silica gel chromatography as washings, dry, the concentrated and purification to organic layer, product recrystallization from ethanol is separated out, and is dried and can obtains white solid product;
Synthesizing of bromo-9, the 9 '-dioctyl fluorene of 2-phenyl-7-: by phenylo boric acid, bromo-9, the 9 '-dioctyl fluorene of 2,7-bis-, tetrakis triphenylphosphine palladium joins in two mouthfuls of flasks of lucifuge, under nitrogen protection, injects the toluene of bubbling and the K of 0.02mol/L
2cO
3the aqueous solution, was warmed up to 90 ℃ of reactions after 24～72 hours, was spin-dried for toluene, water and dichloromethane extraction, extracting has basic unit, and the sherwood oil of take utilizes silica gel chromatography as washings, dry, the concentrated and purification to organic layer, product recrystallization from ethanol is separated out, and is dried and can obtains white solid product;
2-phenyl-7-(4-methylol) phenyl-9,9 '-dioctyl fluorene synthetic: by bromo-9, the 9 '-dioctyl fluorene of 2-phenyl-7-; 4-methylol phenylo boric acid; tetrakis triphenylphosphine palladium joins in two mouthfuls of flasks of lucifuge, under nitrogen protection, injects the toluene of bubbling and the K of 0.02mol/L
2cO
3the aqueous solution, was warmed up to 90 ℃ of reactions after 24～72 hours, was spin-dried for toluene, and water and dichloromethane extraction, extract organic layer, and with sherwood oil, ethyl acetate is that washings utilizes silica gel chromatography, and to organic layer, dry, concentrated and purification, dries and obtain product;
Small molecules initiator B FB's is synthetic: by 2-phenyl-7-(4-methylol) phenyl-9,9 '-dioctyl fluorene, triethylamine and dry CH
2cl
2mix, ice-water bath is cooled to after 0 ℃, under nitrogen atmosphere vigorous stirring, dropwise adds 2-bromine isobutyl acylbromide, temperature of reaction allows to be elevated to room temperature, after stirring reaction spends the night, water extraction solution is to remove salt and excessive 2-bromine isobutyl acylbromide, with sherwood oil, methylene dichloride is that washings utilizes silica gel chromatography, dry to organic layer, concentrated and purify, vacuum lower 40 ℃～50 ℃ dry, can obtain water white thick liquid;
(2) atom transfer radical polymerization ATRP reaction
A. monomer is tert-butyl acrylate
Synthesizing of polymer P 1: by CuBr, N, N, N ', N "; N "-PMDETA, small molecules initiator B FB, methyl-phenoxide, tert-butyl acrylate joins in polymerisation tube successively, and dry ice is freezing, vacuumize, logical nitrogen, ethanol thaws, and so recirculation is three times.Then 100 ℃ of reactions 24 hours in oil bath pan, the product obtaining by neutral aluminium sesquioxide post except the catalyzer in dereaction, concentrated, in methanol/water, be sedimentation three times in 4/1V/V mixed solution, lower 40 ℃ of vacuum is dried, and can obtain product;
Asymmetric bi-block copolymer P1PAA's is synthetic: under nitrogen protection, P1 is joined in methylene dichloride, stir and add trifluoroacetic acid, room temperature reaction 24h.After reaction finishes, use normal hexane sedimentation, dry, obtain white solid;
B. monomer is polyethylene glycol methacrylate-styrene polymer
Asymmetric bi-block copolymer P1PEG's is synthetic: by CuBr, N, N, N ', N "; N "-PMDETA, small molecules initiator B FB, polyethylene glycol methacrylate-styrene polymer, methyl-phenoxide joins in polymerisation tube successively, dry ice is freezing, vacuumize, logical nitrogen, ethanol thaws, so recirculation is three times, then 100 ℃ of reactions 24 hours in oil bath pan, the product obtaining removes the catalyzer in dereaction by neutral aluminium sesquioxide post, and mixture is spin-dried for, water-soluble, with the dialysis tubing 4d that dialyses.After end, lyophilize can obtain product.
The application concrete grammar of asymmetric bi-block copolymer of the present invention in cell imaging is as follows
1) in the aqueous solution, be spontaneously self-assembled into the spherical assembly of 50-70nm, wherein n is 50;
2) described polymkeric substance is dissolved in deionized water, adds in cell culture fluid for cell cultures, under fluorescent microscope, can see that this material is to cytoplasmic mark effect.
Beneficial effect: the present invention, by Suzuki linked reaction synthesized micromolecule initiator, introduces the flexible group polyacrylic acid tert-butyl ester and the polyethylene glycol methacrylate-styrene polymer with biocompatibility very easily with atom transition free radical polymerization reaction (ATRP).This asymmetric bi-block copolymer has well water-solublely owing to can introducing a large amount of flexible chains, and the material of containing in the present invention has good luminescent properties, chemical stability, thermostability.In the aqueous solution, have the spherical assembly of 50-70nm to occur, this material can spontaneously wrap up inorganic nano-particle (magnetic, golden nanometer particle) or the drug molecule of some functionalization in self assembling process, reaches the effect detecting with medicine carrying.Some functional modifications make it have specific recognition capability in addition, will have far-reaching application so at biomedical sector.
Accompanying drawing explanation
Fig. 1 is the nuclear-magnetism (CDCl of P1
3),
Fig. 2 is the nuclear-magnetism (DMSO) of P1PAA,
Fig. 3 is the TEM figure of P1PAA in the aqueous solution.
Embodiment
The structure of asymmetric two block conjugated polymers of the present invention is as follows:
Wherein rigid chain segment (A) is " benzene fluorenes benzene " structure, and soft segment (B) is synthetic by atom transfer radical polymerization (ATRP) reaction.
N is the zip length of flexible chain monomer;
R is the repeating unit of flexible chain, is vinylformic acid when n is 20-60, or n is polyethylene glycol methacrylate-styrene polymer while being 3-10.
In above-claimed cpd, typical its molecular structural formula of particle P1PAA-50 is as follows:
The synthetic method of above-claimed cpd of the present invention is as follows:
2,7-bis-bromo-9, synthesizing of 9 '-dioctyl fluorene: by 2,7-dibromo fluorenes and Tetrabutyl amonium bromide mix and add dimethyl sulfoxide (DMSO), the aqueous solution that adds again NaOH, in mixed solution, add 1-bromooctane afterwards, under room temperature, stirring reaction is after 4～72 hours, in reaction mixture, add excessive ethyl acetate, then filter out NaOH throw out, with dilute hydrochloric acid and normal saline washing organic extraction, the sherwood oil of take utilizes silica gel chromatography as washings, dry, the concentrated and purification to organic layer, product recrystallization from ethanol is separated out, and is dried and can obtains white solid product;
Synthesizing of bromo-9, the 9 '-dioctyl fluorene of 2-phenyl-7-: by phenylo boric acid, bromo-9, the 9 '-dioctyl fluorene of 2,7-bis-, tetrakis triphenylphosphine palladium joins in two mouthfuls of flasks of lucifuge, under nitrogen protection, injects the toluene of bubbling and the K of 0.02mol/L
2cO
3the aqueous solution, was warmed up to 90 ℃ of reactions after 24～72 hours, was spin-dried for toluene, water and dichloromethane extraction, extracting has basic unit, and the sherwood oil of take utilizes silica gel chromatography as washings, dry, the concentrated and purification to organic layer, product recrystallization from ethanol is separated out, and is dried and can obtains white solid product;
2-phenyl-7-(4-methylol) phenyl-9,9 '-dioctyl fluorene synthetic: by bromo-9, the 9 '-dioctyl fluorene of 2-phenyl-7-; 4-methylol phenylo boric acid; tetrakis triphenylphosphine palladium joins in two mouthfuls of flasks of lucifuge, under nitrogen protection, injects the toluene of bubbling and the K of 0.02mol/L
2cO
3the aqueous solution, was warmed up to 90 ℃ of reactions after 24～72 hours, was spin-dried for toluene, and water and dichloromethane extraction, extract organic layer, and with sherwood oil, ethyl acetate is that washings utilizes silica gel chromatography, and to organic layer, dry, concentrated and purification, dries and obtain product.
Synthesizing of small molecules initiator (BFB): by 2-phenyl-7-(4-methylol) phenyl-9,9 '-dioctyl fluorene, triethylamine and dry CH
2cl
2mix, ice-water bath is cooled to after 0 ℃, under nitrogen atmosphere vigorous stirring, dropwise adds 2-bromine isobutyl acylbromide, temperature of reaction allows to be elevated to room temperature, after stirring reaction spends the night, water extraction solution is to remove salt and excessive 2-bromine isobutyl acylbromide, with sherwood oil, methylene dichloride is that washings utilizes silica gel chromatography, dry to organic layer, concentrated and purify, vacuum lower 40 ℃～50 ℃ dry, can obtain water white thick liquid.
Synthesizing of polymer P 1: by CuBr, N, N, N ', N "; N "-PMDETA, small molecules initiator (BFB), methyl-phenoxide, tert-butyl acrylate joins in polymerisation tube successively, and dry ice is freezing, vacuumize, logical nitrogen, ethanol thaws, and so recirculation is three times.Then 100 ℃ of reactions 24 hours in oil bath pan, the product obtaining is by neutral aluminium sesquioxide post except the catalyzer in dereaction, and concentrated, in methanol/water (4/1V/V) mixed solution, sedimentation is three times, and lower 40 ℃ of vacuum is dried, and can obtain product.
Asymmetric bi-block copolymer P1PAA's is synthetic: under nitrogen protection, P1 is joined in methylene dichloride, stir and add trifluoroacetic acid, room temperature reaction 24h.After reaction finishes, use normal hexane sedimentation, dry.Obtain white solid.
In order to understand better the present invention, below by specific examples, further illustrate technical scheme of the present invention.
The synthetic method of example 1P1PAA-50 is as follows:
2, 7-bis-bromo-9, synthesizing of 9 '-dioctyl fluorene: by 2, 7-dibromo fluorenes 10.0g and Tetrabutyl amonium bromide 1.0g mix and add dimethyl sulfoxide (DMSO) 50mL, the aqueous solution (50%w/w) 12mL that adds again NaOH, in mixed solution, add 1-bromooctane 13.5mL afterwards, under room temperature, stirring reaction is after 4～72 hours, in reaction mixture, add excessive ethyl acetate 200mL, then filter out NaOH throw out, with dilute hydrochloric acid 200mL and salt solution 2 * 150mL, rinse organic extraction, the sherwood oil of take utilizes silica gel chromatography as washings, dry to organic layer, concentrate and purify, product recrystallization from ethanol is separated out, be dried and can obtain 2, 7-bis-bromo-9, 9 '-dioctyl fluorene 15.2g(productive rate 90%).
1HNMR(400MHz,CDCl
3,ppm)δ：7.53(s，1H)，7.51(s,1H)，7.46(d,1H,J=1.6Hz)，7.44(s,3H)，1.91(t,4H,J=16.8Hz)，1.23-1.05（br,20H），0.83（t,6H,J=14Hz），0.57(br,4H)。
2-phenyl-7-bromo-9; synthesizing of 9 '-dioctyl fluorene: by phenylo boric acid 0.5g(4mmol); 2; 7-bis-bromo-9; 9 '-dioctyl fluorene 5.48g(10mmol); tetrakis triphenylphosphine palladium 80mg joins in bis-mouthfuls of flasks of 50mL of lucifuge, under nitrogen protection, injects the toluene 20mL of bubbling and the K of 0.02mol/L
2cO
3aqueous solution 5mL, be warmed up to 90 ℃ of reactions after 24～72 hours, be spin-dried for toluene, water and dichloromethane extraction, extracting has basic unit, and the sherwood oil of take utilizes silica gel chromatography as washings, dry, the concentrated and purification to organic layer, product recrystallization from ethanol is separated out, and is dried and can obtains white solid product, and productive rate is 63%.
1HNMR(400MHz,CDCl
3,ppm)δ：7.72（d,1H,J=8Hz），7.66（d,2H,J=7.6Hz），7.58（d,2H,J=12.8Hz），7.53(S,1H)，7.47（br,4H），7.37（br,1H），1.96（t,3H,J=25.2Hz），1.22-1.01（br,20H），0.90（t,6H,J=54.4Hz），0.65（br,4H）。
2-phenyl-7-(4-methylol) phenyl-9; synthesizing of 9 '-dioctyl fluorene: by 2-phenyl-7-bromo-9; 9 '-dioctyl fluorene 2g(3.67mmol); 4-methylol phenylo boric acid 1.11g(7.34mmo); tetrakis triphenylphosphine palladium 50mmg joins in bis-mouthfuls of flasks of 50mL of lucifuge; under nitrogen protection, inject the toluene 20mL of bubbling and the K of 0.02mol/L
2cO
3aqueous solution 5mL, was warmed up to 90 ℃ of reactions after 24～72 hours, was spin-dried for toluene, water and dichloromethane extraction, extract organic layer, take sherwood oil: ethyl acetate (V/V5:1) is utilized silica gel chromatography as washings, to organic layer, dry, concentrated and purification, dries and obtains product, and productive rate is 71%.
1HNMR（400MHz,CDCl
3,ppm）δ：7.78（d,2H,J=11.6Hz），7.68（d,4H,J=8Hz），7.60-7.56（br,4H），7.49-7.46（br,4H），7.40-7.35(br,1H)，4.77(br,2H)，2.0(t,4H,J=16.4Hz)，1.20-1.06(br,20H)，0.80(t,6H,J=54Hz)，0.72(br,4H)。
Synthesizing of small molecules initiator (BFB): by 2-phenyl-7-(4-methylol) phenyl-9,9 '-dioctyl fluorene 1g (1.75mmol), triethylamine 15mL and dry CH
2cl
220mL mixes, ice-water bath is cooled to after 0 ℃, under nitrogen atmosphere vigorous stirring, dropwise add 2-bromine isobutyl acylbromide 0.8g (3.5mmol), temperature of reaction allows to be elevated to room temperature, after stirring reaction spends the night, water extraction solution is to remove salt and excessive 2-bromine isobutyl acylbromide, the mixing solutions (V/V4:1) of sherwood oil and methylene dichloride of take utilizes silica gel chromatography as washings, dry, the concentrated and purification to organic layer, vacuum lower 40 ℃～50 ℃ dry, can obtain water white thick liquid, productive rate 90%.
1HNMR(400MHz,CDCl
3,ppm)δ：7.78(d,2H,J=12Hz),7.70-7.67(br,4H),7.60-7.57(br,4H),7.50-7.46(br,4H),7.39-7.35(br,1H),2.03(t,4H,J=16Hz),1,99(s,6H),1.18-1.06(br,20H),0.80(t,6H,J=14Hz),0.72(br,4H)。
Synthesizing of polymer P 1: by CuBr7mg, N, N, N ', N ", N " and-PMDETA 21 μ L, small molecules initiator (BFB) 27.2mg, methyl-phenoxide 0.1mL, tert-butyl acrylate 0.33g joins in polymerisation tube successively, and dry ice is freezing, vacuumize, logical nitrogen, ethanol thaws, and so recirculation is three times.Then 100 ℃ of reactions 24 hours in oil bath pan, the product obtaining is by neutral aluminium sesquioxide post except the catalyzer in dereaction, and concentrated, in methanol/water (4/1V/V) mixed solution, sedimentation is three times, and lower 40 ℃ of vacuum is dried, and can obtain faint yellow solid.Fig. 1.
Asymmetric bi-block copolymer P1PAA's is synthetic: under nitrogen protection, P1 (0.1g) is joined in 15mL methylene dichloride, stir and add 1.5mL trifluoroacetic acid, room temperature reaction 24h.After reaction finishes, use normal hexane sedimentation, dry and obtain white solid.Fig. 2.Compared to Figure 1, δ: 1.43 peak obviously reduces.
Applied research
1. method: utilize hydrophobic stiff chain can spontaneous extending to form inwards " core " in the aqueous solution and hydrophilic flexible chain can be spontaneous stretch out and form the spherical self-assembly of " shell " structure.And the carboxyl of the flexible end of the chain can connect some medicines and enter in biomass cells body, reach the effect that detects or discharge medicine, be a kind of very potential Bio-Nano-Materials.
2. experimental procedure: add 1.0mg material (P1PAA-50) in sample bottle, then add 5mL deionized water, stirring at room 36h.By TEM, SEM, these class materials of sign proof such as DLS are spontaneously self-assembled into the spherical assembly of 50-70nm, Fig. 3 in the aqueous solution.Self-assembled material, for PANC-1 cell cultures, can be seen under fluorescent microscope to this material is to cytoplasmic mark effect.
Claims (4)
1. an asymmetric bi-block copolymer, is characterized in that this polymkeric substance has following molecular structural formula:
Wherein rigid chain segment (A) is " benzene fluorenes benzene " structure, and soft segment (B) is synthetic by atom transfer radical polymerization ATRP reaction,
N is the zip length of flexible chain monomer;
R is the repeating unit of flexible chain, is vinylformic acid when n is 20-60, or n is polyethylene glycol methacrylate-styrene polymer while being 3-10.
2. asymmetric bi-block copolymer according to claim 1, is characterized in that:
A. rigid chain segment is " benzene fluorenes benzene " structure, and soft segment is to react by atom transfer radical polymerization ATRP, take tert-butyl acrylate as the synthetic asymmetric bi-block copolymer of monomer, and its molecular structural formula is as follows:
B. rigid chain segment is " benzene fluorenes benzene " structure, and soft segment is to react by atom transfer radical polymerization ATRP, take polyethylene glycol methacrylate-styrene polymer as the synthetic asymmetric bi-block copolymer of monomer, and its molecular structural formula is as follows:
3. a synthetic method for asymmetric bi-block copolymer as claimed in claim 1, is characterized in that concrete synthesis step is as follows:
(1) small molecules " benzene fluorenes benzene " stiff chain is synthetic
2,7-bis-bromo-9, synthesizing of 9 '-dioctyl fluorene: by 2,7-dibromo fluorenes and Tetrabutyl amonium bromide mix and add dimethyl sulfoxide (DMSO), the aqueous solution that adds again NaOH, in mixed solution, add 1-bromooctane afterwards, under room temperature, stirring reaction is after 4～72 hours, in reaction mixture, add excessive ethyl acetate, then filter out NaOH throw out, with dilute hydrochloric acid and normal saline washing organic extraction, the sherwood oil of take utilizes silica gel chromatography as washings, dry, the concentrated and purification to organic layer, product recrystallization from ethanol is separated out, and is dried and can obtains white solid product;
Synthesizing of bromo-9, the 9 '-dioctyl fluorene of 2-phenyl-7-: by phenylo boric acid, bromo-9, the 9 '-dioctyl fluorene of 2,7-bis-, tetrakis triphenylphosphine palladium joins in two mouthfuls of flasks of lucifuge, under nitrogen protection, injects the toluene of bubbling and the K of 0.02mol/L
2cO
3the aqueous solution, was warmed up to 90 ℃ of reactions after 24～72 hours, was spin-dried for toluene, water and dichloromethane extraction, extracting has basic unit, and the sherwood oil of take utilizes silica gel chromatography as washings, dry, the concentrated and purification to organic layer, product recrystallization from ethanol is separated out, and is dried and can obtains white solid product;
2-phenyl-7-(4-methylol) phenyl-9,9 '-dioctyl fluorene synthetic: by bromo-9, the 9 '-dioctyl fluorene of 2-phenyl-7-; 4-methylol phenylo boric acid; tetrakis triphenylphosphine palladium joins in two mouthfuls of flasks of lucifuge, under nitrogen protection, injects the toluene of bubbling and the K of 0.02mol/L
2cO
3the aqueous solution, was warmed up to 90 ℃ of reactions after 24～72 hours, was spin-dried for toluene, and water and dichloromethane extraction, extract organic layer, and with sherwood oil, ethyl acetate is that washings utilizes silica gel chromatography, and to organic layer, dry, concentrated and purification, dries and obtain product;
Small molecules initiator B FB's is synthetic: by 2-phenyl-7-(4-methylol) phenyl-9,9 '-dioctyl fluorene, triethylamine and dry CH
2cl
2mix, ice-water bath is cooled to after 0 ℃, under nitrogen atmosphere vigorous stirring, dropwise adds 2-bromine isobutyl acylbromide, temperature of reaction allows to be elevated to room temperature, after stirring reaction spends the night, water extraction solution is to remove salt and excessive 2-bromine isobutyl acylbromide, with sherwood oil, methylene dichloride is that washings utilizes silica gel chromatography, dry to organic layer, concentrated and purify, vacuum lower 40 ℃～50 ℃ dry, can obtain water white thick liquid;
(2) atom transfer radical polymerization ATRP reaction
A. monomer is tert-butyl acrylate
Synthesizing of polymer P 1: by CuBr, N, N, N ', N "; N "-PMDETA, small molecules initiator B FB, methyl-phenoxide, tert-butyl acrylate joins in polymerisation tube successively, and dry ice is freezing, vacuumize, logical nitrogen, ethanol thaws, and so recirculation is three times.Then 100 ℃ of reactions 24 hours in oil bath pan, the product obtaining by neutral aluminium sesquioxide post except the catalyzer in dereaction, concentrated, in methanol/water, be sedimentation three times in 4/1V/V mixed solution, lower 40 ℃ of vacuum is dried, and can obtain product;
Asymmetric bi-block copolymer P1PAA's is synthetic: under nitrogen protection, P1 is joined in methylene dichloride, stir and add trifluoroacetic acid, room temperature reaction 24h.After reaction finishes, use normal hexane sedimentation, dry, obtain white solid;
B. monomer is polyethylene glycol methacrylate-styrene polymer
Asymmetric bi-block copolymer P1PEG's is synthetic: by CuBr, N, N, N ', N "; N "-PMDETA, small molecules initiator B FB, polyethylene glycol methacrylate-styrene polymer, methyl-phenoxide joins in polymerisation tube successively, dry ice is freezing, vacuumize, logical nitrogen, ethanol thaws, so recirculation is three times, then 100 ℃ of reactions 24 hours in oil bath pan, the product obtaining removes the catalyzer in dereaction by neutral aluminium sesquioxide post, and mixture is spin-dried for, water-soluble, with the dialysis tubing 4d that dialyses.After end, lyophilize can obtain product.
4. the application of asymmetric bi-block copolymer as claimed in claim 1 in cell imaging, concrete grammar is as follows
1) in the aqueous solution, be spontaneously self-assembled into the spherical assembly of 50-70nm, wherein n is 50;
2) described polymkeric substance is dissolved in deionized water, adds in cell culture fluid for cell cultures, under fluorescent microscope, can see that this material is to cytoplasmic mark effect.
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| KR102545566B1 (en) | 2020-04-16 | 2023-06-21 | 서울대학교산학협력단 | 2-dimensional polymer nanosheet and width, length, and height tunable method of preparing the same |
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