CN104497217A - Janus structure superparamagnetic nanoparticle and prepration method thereof - Google Patents
Janus structure superparamagnetic nanoparticle and prepration method thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 title abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 17
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 13
- 239000004005 microsphere Substances 0.000 claims description 67
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 239000002131 composite material Substances 0.000 claims description 52
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 46
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 32
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 238000005530 etching Methods 0.000 claims description 25
- 230000002209 hydrophobic effect Effects 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- 229920002125 Sokalan® Polymers 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 11
- 238000009736 wetting Methods 0.000 claims description 11
- 230000001568 sexual effect Effects 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000010526 radical polymerization reaction Methods 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 9
- 230000007704 transition Effects 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002122 magnetic nanoparticle Substances 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000004945 emulsification Methods 0.000 claims description 6
- 238000000935 solvent evaporation Methods 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- -1 Poly(Hydroxyethyl Methacrylate) Polymers 0.000 claims description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 23
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical group OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 15
- 235000010378 sodium ascorbate Nutrition 0.000 description 15
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 15
- 229960005055 sodium ascorbate Drugs 0.000 description 15
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 15
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical class [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 12
- 238000013019 agitation Methods 0.000 description 10
- 229940106681 chloroacetic acid Drugs 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 8
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011553 magnetic fluid Substances 0.000 description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000013283 Janus particle Substances 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 101150098207 NAAA gene Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
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- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical group CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 244000144992 flock Species 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000703 high-speed centrifugation Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OITNBJHJJGMFBN-UHFFFAOYSA-N 4-(chloromethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CCl)C=C1 OITNBJHJJGMFBN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- Medicinal Preparation (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Soft Magnetic Materials (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
The invention discloses a Janus structure superparamagnetic nanoparticle and a prepration method thereof. The Janus structure superparamagnetic nanoparticle adopts a superparamagnetic nanoparticle as a core; two sides of the surface of the superparamagnetic nanoparticle are respectively grafted with polymer brushes with different properties; and the polymer brushes include hydrophilic-hydrophobic polymer brushes, pH sensitive-temperature sensitive polymer brushes and the like. The Janus structure superparamagnetic nanoparticle disclosed by the invention has the advantages of small particle size, narrow distribution range, functionalized surface and the like.
Description
Technical field
The present invention relates to a kind of super-paramagnetism nano grain and preparation method thereof, particularly relate to a kind of Janus structure super-paramagnetism nano grain and preparation method thereof.
Background technology
Janus is the Janus in ancient Roman's mythology, has left-right asymmetry face.1991, Nobel Prize in physics winner De Gennes will have the particle called after Janus particle (Reviews of Modern Physics, 1992,64,645-648) of left-right asymmetry structure.Janus particle due to heterogeneous structure, for nano material construct and Controllable assembly etc. provides abundant model and the platform of theoretical investigation, it also has report in the application of the biomedical sectors such as magnetic thermotherapy, asymmetry catalysis, one side drug delivery.
At present, common Janus morphology of particles type comprises: the complex microsphere of two kinds of inorganic microspheres compositions that do as one likes matter is different, the complex microsphere be made up of organic micro-spheres and inorganic microspheres, the complex microsphere of organic microspheroidal one-tenth is embedded by inorganic particulate, and cover the outer field complex microsphere of organic micro-spheres, as shown in Fig. 1 (a), (b), (c), (d) by inorganic particulate part.Existing Janus size of particles is distributed in 1 ~ 100 micron more, and specific surface area is relatively little, and such large size limits its application in biomedicine.In addition, existing Janus particle preparation method, the deficiency such as also there is complex steps, need large-scale instrument auxiliary.
Summary of the invention
Based on this, the object of the invention is to, a kind of Janus structure super-paramagnetism nano grain be provided, its have particle diameter little, be evenly distributed, and surface can the advantage of functionalization.
Another object of the present invention is, provides a kind of preparation method of Janus structure super-paramagnetism nano grain, and its technique is simple, can prepare the little and Janus structure super-paramagnetism nano grain be evenly distributed of particle diameter.
A kind of Janus structure super-paramagnetism nano grain, with super-paramagnetism nano grain for core, point both sides, surface of described super-paramagnetism nano grain are grafted with the different polymer brush of character respectively.
Wherein in an embodiment, described Janus structure super-paramagnetism nano grain is wetting ability--hydrophobic sexual type Janus structure super-paramagnetism nano grain, point both sides, surface of described super-paramagnetism nano grain are grafted with hydrophilic polymer brush and hydrophobic polymer brush respectively.
Wherein in an embodiment, described hydrophilic polymer brush is polyacrylic acid, polymethyl acrylic acid or Poly(Hydroxyethyl Methacrylate) etc.; Described hydrophobic polymer brush is polystyrene, polymethylmethacrylate or butyl polyacrylate etc.
Wherein in an embodiment, described Janus structure super-paramagnetism nano grain is that pH is responsive--responsive to temperature type Janus structure super-paramagnetism nano grain, point both sides, surface of described super-paramagnetism nano grain are grafted with pH sensitive polymer brush and temperature-sensitive polymers brush respectively.
Wherein in an embodiment, described pH sensitive polymer brush is polyacrylic acid, polymethyl acrylic acid gathers; Described responsive to temperature type polymer brush is poly N-isopropyl acrylamide, poly-N, N-acrylamide etc.
Wherein in an embodiment, described super-paramagnetism nano grain is the iron oxygen magnetic nano particle of iron oxygen magnetic nano particle or doping, and its particle diameter is 8 ± 2nm.Preferably, described iron oxygen magnetic nano particle is Z 250 (Fe
3o
4) or ferric oxide (Fe
2o
3) magnetic nano particle; The iron oxygen magnetic nano particle of described doping is for being mixed with the Z 250 (Fe of manganese (Mn), cobalt (Co) or zinc (Zn)
3o
4) or ferric oxide (Fe
2o
3) magnetic nano particle.
Wherein in an embodiment, the particle diameter of described Janus structure super-paramagnetism nano grain is 20 ~ 30nm.
It is a kind of that wetting ability--the preparation method of hydrophobic sexual type Janus structure super-paramagnetism nano grain, comprises the following steps:
1) by transfer transport regenerated catalyst atom transition free radical polymerization reaction, the hydrophobic chain shaped polymer that end group is carboxyl is prepared;
2) end group is the hydrophobic chain shaped polymer emulsification balling-up of carboxyl by employing solvent evaporation method, preparation hydrophobicity tiny balloon;
3) by ligand exchange reaction, super-paramagnetism nano grain is connected to the skin of hydrophobicity tiny balloon, forms Superparamagnetism composite microsphere;
4) carboxymethylation process is carried out to Superparamagnetism composite microsphere, then by transfer transport regenerated catalyst atom transition free radical polymerization reaction, hydrophilic polymer brush is grafted on super-paramagnetism nano grain, forms hydrophilic polymer brush grafting Superparamagnetism composite microsphere;
5) etching solution is adopted to carry out etching processing to hydrophilic polymer brush grafting Superparamagnetism composite microsphere, formed with super-paramagnetism nano grain for core, and point both sides, the surface of super-paramagnetism nano grain are grafted with the wetting ability of hydrophilic polymer brush and hydrophobic polymer brush respectively--hydrophobic sexual type Janus structure super-paramagnetism nano grain.
Wherein in an embodiment, in step 1) in, described end group is the preparation method of the hydrophobic chain shaped polymer of carboxyl, comprises the following steps:
A) preparation of reaction system: vacuumized by reaction flask, passes into nitrogen or argon gas, the oxygen in removing reaction system;
B) preparation of catalyzer: copper (II) salt, part, sodium ascorbate are dissolved in benzyl oxide respectively;
C) polyreaction: the benzyl oxide solution of copper (II) salt, part and sodium ascorbate is added in reaction system respectively, add in reaction system after hydrophobic monomer and initiator are dissolved in benzyl oxide, magnetic agitation, reacts 6 ~ 8 hours at 60 ~ 70 DEG C;
D) separation and purification: add benzyl oxide to reaction system, magnetic agitation, in homogeneous solution, then adds in methyl alcohol or ethanol, by the filtration of the white flock precipitate of generation, drying, obtains the hydrophobic chain shaped polymer that described end group is carboxyl;
Wherein, described copper (II) salt is cupric chloride (CuCl
2) or cupric bromide (CuBr
2), described part is 2,2-dipyridyl or N, N, N', N', N "-five methyl diethylentriamine (PMDETA), described hydrophobic monomer is vinylbenzene, methyl methacrylate or butyl acrylate etc., and described initiator is Mono Chloro Acetic Acid or p-chloromethyl benzoic acid; The mol ratio of copper (II) salt and part is 1 ︰ 3 ~ 1 ︰ 10, the mol ratio of copper (II) salt and sodium ascorbate is 1 ︰ 2 ~ 1 ︰ 10, the mol ratio of copper (II) salt and initiator is 1 ︰ 2 ~ 1 ︰ 10, and the mol ratio of initiator and hydrophobic monomer is 1 ︰ 100 ~ 1 ︰ 800.
Wherein in an embodiment, in step 2) in, the preparation method of described hydrophobicity tiny balloon, comprises the following steps:
A) preparation of solution: be that the hydrophobic chain shaped polymer of carboxyl is dissolved in methylene dichloride by end group, polyvinyl alcohol (PVA) is dissolved in deionized water;
B) emulsification balling-up: under high speed dispersion, is added drop-wise in the aqueous solution of polyvinyl alcohol by the dichloromethane solution of hydrophobic chain shaped polymer, after being uniformly dispersed, being volatilized by methylene dichloride, obtain hydrophobicity tiny balloon emulsion under stirring at low speed;
C) separation and purification: by hydrophobicity tiny balloon emulsion high speed centrifugation, the precipitate with deionized water washing of gained, after drying, obtains described hydrophobicity tiny balloon;
Wherein, the mass concentration of the dichloromethane solution of hydrophobic chain shaped polymer is 10 ~ 30mg/mL, and be preferably 20mg/mL, the mass concentration of polyvinyl alcohol water solution is 0.5 ~ 5%; The volume ratio of dichloromethane solution and the aqueous solution is 1 ︰ 10 ~ 1 ︰ 50.
Wherein in an embodiment, in step 3) in, the preparation method of described Superparamagnetism composite microsphere, comprises the following steps:
I) adopt polyol process to prepare super-paramagnetism nano grain, obtain its magnetic fluid;
II) hydrophobicity tiny balloon is distributed in deionized water, adds magnetic fluid, under nitrogen protection, in 60 ~ 70 DEG C of lower magnetic force stirring reactions 12 ~ 24 hours;
III) carry out Magneto separate to reaction solution, gained precipitate with deionized water is washed, and obtains described Superparamagnetism composite microsphere;
Wherein, the mass ratio of hydrophobicity tiny balloon and super-paramagnetism nano grain is 3 ︰ 1 ~ 1 ︰ 2.
Wherein in an embodiment, in step 4) in, the preparation method of described hydrophilic polymer brush grafting Superparamagnetism composite microsphere, comprises the following steps:
I) carboxymethylation process: Superparamagnetism composite microsphere is scattered in ethanol, add chloroacetic ethanolic soln, magnetic agitation, react 12 ~ 24 hours at 60 ~ 70 DEG C, then Magneto separate is carried out, gained precipitation washing with alcohol, obtains carboxymethylation Superparamagnetism composite microsphere, and is scattered in ethanol;
Ii) preparation of reaction system: vacuumized by reaction flask, passes into nitrogen or argon gas, the oxygen in removing reaction system;
Iii) preparation of catalyzer: copper (II) salt, part are dissolved in ethanol, sodium ascorbate are dissolved in deionized water;
Iv) polyreaction: respectively copper (II) salt, the ethanolic soln of part and the aqueous solution of sodium ascorbate are added in reaction system, carboxymethylation Superparamagnetism composite microsphere is dissolved in ethanol, hydrophilic monomer sodium salt is dissolved in deionized water, then add in reaction system, magnetic agitation, reacts 6 ~ 8 hours at 60 ~ 70 DEG C;
V) separation and purification: Magneto separate is carried out to reaction system, gained precipitation ethanol/water mixing solutions washs, and obtains described hydrophilic polymer brush grafting Superparamagnetism composite microsphere;
Wherein, described copper (II) salt is cupric chloride (CuCl
2) or cupric bromide (CuBr
2), described part is 2,2-dipyridyl or N, N, N', N', N "-five methyl diethylentriamine (PMDETA), described hydrophilic monomer sodium salt is sodium acrylate, sodium methacrylate etc.; The mol ratio of copper (II) salt and part is 1 ︰ 3 ~ 1 ︰ 10, the mol ratio of copper (II) salt and sodium ascorbate is 1 ︰ 2 ~ 1 ︰ 10, the mol ratio of copper (II) salt and hydrophilic monomer sodium salt is 1 ︰ 100 ~ 1 ︰ 300, and the mass ratio of carboxymethylation Superparamagnetism composite microsphere and hydrophilic monomer sodium salt is 1 ︰ 1 ~ 1 ︰ 8.
Wherein in an embodiment, in step 5) in, described etching solution is DMF/water, tetrahydrofuran (THF)/water, toluene/ethanol mixed solvent; Wherein, the volume ratio of DMF/water, tetrahydrofuran (THF)/water, toluene/ethanol is 1 ︰ 1 ~ 9 ︰ 1; The final concentration of described hydrophilic polymer brush grafting Superparamagnetism composite microsphere in etching solution is 1 ~ 15mg/mL.
Wherein in an embodiment, in step 5) in, described etching processing comprises the following steps: be scattered in etching solution by hydrophilic polymer brush grafting Superparamagnetism composite microsphere, stirring reaction 4 ~ 6 hours, then Magneto separate is carried out, gained precipitation is washed with etching solution and deionized water respectively, obtains described Janus structure super-paramagnetism nano grain.
A kind of pH is responsive--and the preparation method of responsive to temperature type Janus structure super-paramagnetism nano grain, comprises the following steps:
1. by transfer transport regenerated catalyst atom transition free radical polymerization reaction, the hydrophobic chain shaped polymer that end group is carboxyl is prepared;
2. end group is the hydrophobic chain shaped polymer emulsification balling-up of carboxyl by employing solvent evaporation method, preparation hydrophobicity tiny balloon;
3. by ligand exchange reaction, super-paramagnetism nano grain is connected to the skin of hydrophobicity tiny balloon, forms Superparamagnetism composite microsphere;
4. carboxymethylation process is carried out to Superparamagnetism composite microsphere, then by transfer transport regenerated catalyst atom transition free radical polymerization reaction, responsive to temperature type polymer brush is grafted on super-paramagnetism nano grain, formation temperature sensitive polymer brush grafting Superparamagnetism composite microsphere;
5. the hydrophobicity tiny balloon in responsive to temperature type polymer brush grafting Superparamagnetism composite microsphere is replaced into pH sensitive polymer tiny balloon, forms pH responsive--responsive to temperature type Superparamagnetism composite microsphere;
6. adopting etching solution responsive to pH--responsive to temperature type Superparamagnetism composite microsphere carries out etching processing, formed with super-paramagnetism nano grain for core, and the pH that point both sides, the surface of super-paramagnetism nano grain are grafted with pH sensitive polymer brush and responsive to temperature type polymer brush is respectively responsive--responsive to temperature type Janus structure super-paramagnetism nano grain.
Janus structure super-paramagnetism nano grain of the present invention, with super-paramagnetism nano grain for core, and be grafted with the different polymer brush of character respectively in point both sides, the surface of super-paramagnetism nano grain, have that particle diameter is little, narrow distribution range, monodispersity is good, and surface can the advantage such as functionalization.The different polymer brush of described character comprises wetting ability--hydrophobic polymer brush, pH are responsive--, and temperature-sensitive polymers brush etc., its brush structure has abundant functional group and non-centrosymmetry, optionally modifies again.Polymer brush and super-paramagnetism nano grain, by chemical bonds, have satisfactory stability.This Janus structure super-paramagnetism nano grain, due to the little advantage of its unsymmetrical structure, super-paramagnetic properties and particle diameter, can be used for the fields such as mr development, drug carrier system, has biomedical applications widely.
The preparation method of Janus structure super-paramagnetism nano grain of the present invention, has that technique is simple, reaction conditions is gentle, product is easy to purify and the advantage such as collection.
In the preparation process in accordance with the present invention, with hydrophobic monomer and band carboxyl initiator for raw material, adopt transfer transport regenerated catalyst atom transition free radical polymerization reaction (ARGET-ATRP), the hydrophobic chain shaped polymer that end group is carboxyl can be prepared specifically, this hydrophobic chain shaped polymer is by solvent evaporation method emulsification balling-up, the hydrophobicity tiny balloon of carboxyl on surface can be formed, then ligand binding is carried out by the atoms metal of carboxyl and super-paramagnetism nano grain, make super-paramagnetism nano grain be bonded in the skin of hydrophobicity tiny balloon, form complex microsphere, complex microsphere forms initiator through carboxymethylation, reacted by ARGET-ATRP again, hydrophilic polymer brush in the outer grafting of super-paramagnetism nano grain, form hydrophilic polymer brush grafting complex microsphere, centered by super-paramagnetism nano grain, its skin is hydrophilic polymer brush, and internal layer is hydrophobicity tiny balloon, hydrophilic polymer brush grafting complex microsphere is added in etching solution, etching solution enters the inner chamber of complex microsphere, to not dissolve with the hydrophobic polymer of super-paramagnetism nano grain bonding, because this hydrophobic polymer is by means of only the carboxyl of end group and super-paramagnetism nano grain bonding, namely a hydrophobic polymer chains only can be bonded on a nanoparticle, and can not with many nanoparticle generation bondings, therefore, after the hydrophobic polymer that bonding does not occur is dissolved, namely this hydrophobicity tiny balloon decomposes, each super-paramagnetism nano grain is separated from one another, formed with single super-paramagnetism nano grain as core, side is grafted with hydrophilic polymer brush, opposite side is grafted with the particle of hydrophobic polymer brush, i.e. Janus structure super-paramagnetism nano grain of the present invention.The Janus structure super-paramagnetism nano grain adopting this lithographic method to be formed, has that particle diameter is little, the advantage of narrow distribution range.
In the preparation process in accordance with the present invention, employing volume ratio is tetrahydrofuran (THF)/water, the N of 1 ︰ 1 ~ 9 ︰ 1, dinethylformamide/water, toluene/ethanol mixed solvent are as its etching solution, complex microsphere has good dispersiveness in water, ethanol, and outer field hydrophilic polymer brush extensibility in a solvent can be improved, prevent hydrophilic polymer brush from forming aggregating state in a solvent, and shielding effect is produced to etching solution, thus can promote that tetrahydrofuran (THF), DMF and toluene enter in complex microsphere and make etching processing.
Accompanying drawing explanation
Fig. 1 is existing Janus morphology of particles schematic diagram;
Fig. 2 is Janus structure super-paramagnetism nano grain PMMA/Fe
3o
4the syntheti c route figure of/PAA;
The synthetic route chart of Fig. 3 to be end group be hydrophobic chain shaped polymer PMMA of carboxyl;
Fig. 4 is the scanning electron microscope (SEM) photograph of PMMA hydrophobicity tiny balloon;
Fig. 5 is Superparamagnetism composite microsphere PMMA/Fe
3o
4scanning electron microscope (SEM) photograph;
Fig. 6 is hydrophilic polymer brush grafting Superparamagnetism composite microsphere PMMA/Fe
3o
4the scanning electron microscope (SEM) photograph of/PAA;
Fig. 7 is wetting ability--hydrophobic sexual type Janus structure super-paramagnetism nano grain PMMA/Fe
3o
4the scanning electron microscope (SEM) photograph of/PAA.
Embodiment
Embodiment one: preparation wetting ability--hydrophobic sexual type Janus structure super-paramagnetism nano grain PMMA/Fe
3o
4/ PAA
1, the hydrophobic chain shaped polymer PMMA that end group is carboxyl is prepared in ARGET-ATRP reaction
The three neck reaction flasks that oil sealing is housed are vacuumized, leads to nitrogen, three times repeatedly, guarantee reaction system anhydrous and oxygen-free.By 6.72mg (0.05mmol) CuCl
2, 86.65mg (0.5mmol) N, N, N', N', "-five methyl diethylentriamine (PMDETA), 99.06mg (0.5mmol) sodium ascorbate (SA) are dissolved in 2mL benzyl oxide N respectively, 5.006g (50mmol) methyl methacrylate (MMA) and 47.25mg (0.5mmol) Mono Chloro Acetic Acid (CA) are dissolved in 2mL benzyl oxide.Under nitrogen protection, magnetic agitation, by CuCl
2, PMDETA, SA, MMA and CA injection of solution in reaction system, at 60 ~ 70 DEG C react 8 hours, reaction terminate after be cooled to room temperature, obtain polymethylmethacrylate (PMMA) colloid.PMMA benzyl oxide is dissolved, then adds methyl alcohol to separate out precipitation, filter, repeatedly twice, obtain white flock precipitate, at room temperature dried in vacuo overnight, obtain hydrophobic chain shaped polymer PMMA.
2, solvent evaporation method prepares PMMA hydrophobicity tiny balloon
200mg hydrophobic chain shaped polymer PMMA is dissolved in 10mL methylene dichloride (CH
2cl
2) in, 500mg polyvinyl alcohol (PVA) is dissolved in 100mL deionized water.Under the high speed dispersion (8000 ~ 10000rpm) of refiner, by the CH of PMMA
2cl
2dropwise is added drop-wise in the PVA aqueous solution, continues dispersion 10 minutes, then uses mechanical stirring (300 ~ 500rpm) 12 hours, by CH
2cl
2vapor away, obtain the emulsion of PMMA hydrophobicity tiny balloon.Emulsion is carried out high speed centrifugation, and gained precipitate with deionized water is washed, dry, obtains PMMA hydrophobicity tiny balloon.
3, Superparamagnetism composite microsphere PMMA/Fe is prepared
3o
4
Get the 100mL three-necked bottle with prolong, vacuumize, lead to nitrogen, three times repeatedly, be expelled in reaction system after 720mg ferric acetyl acetonade is dissolved in 40mL triglycol; Magnetic agitation, sand-bath heats, and is slowly warming up to 180 DEG C, is incubated 30 minutes; Then be rapidly heated to 278 DEG C (triglycol boiling points), reflux 30 minutes, obtain the magnetic fluid (Fe of black
3o
4the former reaction soln of nanoparticle); Be chilled to room temperature, repeatedly wash three times, then carry out Magneto separate with ethanol/ethyl acetate mixed solvent that volume ratio is 1 ︰ 10, products therefrom disperses in ethanol, cryopreservation.
100mg PMMA hydrophobicity tiny balloon is scattered in 10mL deionized water, adds magnetic fluid (100mg Fe under magnetic stirring
3o
4nanoparticle), under nitrogen protection, in 70 DEG C of sustained reactions 24 hours, solution colour became dark-brown from black.Carry out Magneto separate after reaction terminates, products therefrom deionized water repetitive scrubbing is colourless to supernatant liquor, to guarantee to remove unreacted PMMA hydrophobicity tiny balloon and Fe
3o
4nanoparticle, obtains Superparamagnetism composite microsphere PMMA/Fe
3o
4, low-temperature dark is preserved.
4, ARGET-ATRP reaction preparation hydrophilic polymer brush grafting Superparamagnetism composite microsphere PMMA/Fe
3o
4/ PAA
The three neck reaction flasks that oil sealing is housed are vacuumized, leads to nitrogen, three times repeatedly, guarantee reaction system anhydrous and oxygen-free.By 100mg Superparamagnetism composite microsphere PMMA/Fe
3o
4after being scattered in 20mL ethanol, be expelled in reaction system; After 300mg Mono Chloro Acetic Acid (CA) is dissolved in 5mL ethanol, be expelled in reaction system.Under the condition of lucifuge, nitrogen protection, in 60 ~ 70 DEG C of lower magnetic force stirring reactions 24 hours.Then carry out Magneto separate, products therefrom ethanol repetitive scrubbing, obtain carboxymethylation Superparamagnetism composite microsphere PMMA/Fe
3o
4/ CA, low-temperature dark is preserved.
The three neck reaction flasks that oil sealing is housed are vacuumized, leads to nitrogen, three times repeatedly, guarantee reaction system anhydrous and oxygen-free.By 2.69mg (0.02mmol) CuCl
2with 15.6mg (0.1mmol) 2,2-dipyridyl (BPY) is dissolved in 1mL ethanol, 9.91mg (0.05mmol) sodium ascorbate (SA) is dissolved in 1mL deionized water, 263.31mg (2.8mmol) sodium acrylate (NaAA) is dissolved in 1mL deionized water, by 50mg carboxymethylation Superparamagnetism composite microsphere PMMA/Fe
3o
4/ CA is scattered in 1mL ethanol.Under lucifuge, nitrogen protection, magnetic agitation, by CuCl
2, BPY, SA, NaAA and PMMA/Fe
3o
4the injection of solution of/CA, in reaction system, is at room temperature reacted 6 hours.After reaction terminates, carry out Magneto separate, products therefrom volume ratio is that the ethanol/water mixed solvent of 1 ︰ 1 washs three times, after carrying out Magneto separate, three times are washed again with 0.01M dust technology, carry out Magneto separate again, be then neutral with deionized water repetitive scrubbing to supernatant liquor, obtain hydrophilic polymer brush grafting Superparamagnetism composite microsphere PMMA/Fe
3o
4/ PAA, low-temperature dark is preserved.
5, wetting ability--hydrophobic sexual type Janus structure super-paramagnetism nano grain PMMA/Fe is prepared
3o
4/ PAA
By 10mg hydrophilic polymer brush grafting Superparamagnetism composite microsphere PMMA/Fe
3o
4/ PAA is scattered in DMF/water (DMF/H that 10mL volume ratio is 9 ︰ 1
2o), in mixed solvent, magnetic agitation reacts 4 hours.Carry out Magneto separate after reaction terminates, products therefrom uses DMF/H respectively
2o mixed solvent washs three times, then uses deionized water wash three times, obtains wetting ability--hydrophobic sexual type Janus structure super-paramagnetism nano grain PMMA/Fe
3o
4/ PAA.
Wetting ability--the hydrophobic sexual type Janus structure super-paramagnetism nano grain PMMA/Fe that the present embodiment is obtained
3o
4/ PAA is particulate state, monodisperse status, and particle diameter is 20 ~ 30nm.
Embodiment two: preparation pH is responsive--responsive to temperature type Janus structure super-paramagnetism nano grain PMAA/Fe
3o
4/ PNIPAM
1, with reference to the method shown in embodiment one, Superparamagnetism composite microsphere PMMA/Fe is prepared
3o
4.
2, ARGET-ATRP reacts preparation temperature sensitive polymer brush grafting Superparamagnetism composite microsphere PMMA/Fe
3o
4/ PNIPAM
The three neck reaction flasks that oil sealing is housed are vacuumized, leads to nitrogen, three times repeatedly, guarantee reaction system anhydrous and oxygen-free.By 100mg Superparamagnetism composite microsphere PMMA/Fe
3o
4after being scattered in 20mL ethanol, be expelled in reaction system; After 300mg Mono Chloro Acetic Acid (CA) is dissolved in 5mL ethanol, be expelled in reaction system.Under the condition of lucifuge, nitrogen protection, in 60 ~ 70 DEG C of lower magnetic force stirring reactions 24 hours.Then carry out Magneto separate, products therefrom ethanol repetitive scrubbing, obtain carboxymethylation Superparamagnetism composite microsphere PMMA/Fe
3o
4/ CA, low-temperature dark is preserved.
The three neck reaction flasks that oil sealing is housed are vacuumized, leads to nitrogen, three times repeatedly, guarantee reaction system anhydrous and oxygen-free.By 4.03mg (0.03mmol) CuCl
2with 24.43mg (0.15mmol) 2,2-dipyridyl (BPY) is dissolved in 1mL ethanol, 19.81mg (0.1mmol) sodium ascorbate (SA) is dissolved in 1mL deionized water, 339.48mg (3mmol) N-isopropylacrylamide (NIPAM) is dissolved in 1mL deionized water, by 50mg carboxymethylation Superparamagnetism composite microsphere PMMA/Fe
3o
4/ CA is scattered in 1mL ethanol.Under lucifuge, nitrogen protection, magnetic agitation, by CuCl
2, BPY, SA, NaAA and PMMA/Fe
3o
4the injection of solution of/CA, in reaction system, is at room temperature reacted 6 hours.After reaction terminates, carry out Magneto separate, products therefrom volume ratio is that the ethanol/water mixed solvent of 1 ︰ 1 washs three times, after carrying out Magneto separate, three times are washed again with 0.01M dust technology, carry out Magneto separate again, be then neutral with deionized water repetitive scrubbing to supernatant liquor, obtain responsive to temperature type polymer brush grafting Superparamagnetism composite microsphere PMMA/Fe
3o
4/ PNIPAM, low-temperature dark is preserved.
3, pH is prepared responsive--responsive to temperature type Superparamagnetism composite microsphere PMAA/Fe
3o
4/ PNIPAM
By the PMMA/Fe of 100mg
3o
4/ PNIPAM adds in the NaOH solution of 10mL 0.1M, and under the condition of nitrogen protection, magnetic agitation, saponification 40 hours at 40 DEG C, is converted into sodium polymethacrylate (PMAA) by polymethylmethacrylate (PMMA).After reaction terminates, carry out Magneto separate, wash three times with 0.01M dust technology, then carry out Magneto separate, be neutral with deionized water repetitive scrubbing to supernatant liquor, obtain pH sensitivity--responsive to temperature type Superparamagnetism composite microsphere PMAA/Fe
3o
4/ PNIPAM.
4, pH is prepared responsive--responsive to temperature type Janus structure super-paramagnetism nano grain PMMA/Fe
3o
4/ PNIPAM
10mg pH is responsive--responsive to temperature type Superparamagnetism composite microsphere PMAA/Fe
3o
4/ PNIPAM is scattered in DMF/water (DMF/H that 5mL volume ratio is 9 ︰ 1
2o) in mixed solvent, in 40 DEG C of lower magnetic force stirring reactions 4 hours.Carry out Magneto separate after reaction terminates, products therefrom uses DMF/H respectively
2o mixed solvent washs three times, then uses deionized water wash three times, obtains pH sensitivity--responsive to temperature type Janus structure super-paramagnetism nano grain PMMA/Fe
3o
4/ PNIPAM.
PH sensitivity--the responsive to temperature type Janus structure super-paramagnetism nano grain PMMA/Fe that the present embodiment is obtained
3o
4/ PNIPAM is particulate state, monodisperse status, and particle diameter is 20 ~ 30nm.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a Janus structure super-paramagnetism nano grain, is characterized in that: with super-paramagnetism nano grain for core, and point both sides, surface of described super-paramagnetism nano grain are grafted with the different polymer brush of character respectively.
2. Janus structure super-paramagnetism nano grain according to claim 1, it is characterized in that: described Janus structure super-paramagnetism nano grain is wetting ability--hydrophobic sexual type Janus structure super-paramagnetism nano grain, point both sides, surface of described super-paramagnetism nano grain are grafted with hydrophilic polymer brush and hydrophobic polymer brush respectively; Described hydrophilic polymer brush is polyacrylic acid, polymethyl acrylic acid or Poly(Hydroxyethyl Methacrylate), and described hydrophobic polymer brush is polystyrene, polymethylmethacrylate or butyl polyacrylate etc.
3. Janus structure super-paramagnetism nano grain according to claim 1, it is characterized in that: described Janus structure super-paramagnetism nano grain is that pH is responsive--responsive to temperature type Janus structure super-paramagnetism nano grain, point both sides, surface of described super-paramagnetism nano grain are grafted with pH sensitive polymer brush and temperature-sensitive polymers brush respectively; Described pH sensitive polymer brush is polyacrylic acid or polymethyl acrylic acid; Described responsive to temperature type polymer brush is poly N-isopropyl acrylamide or poly-N, N-acrylamide.
4. Janus structure super-paramagnetism nano grain according to claim 1, is characterized in that: described super-paramagnetism nano grain is the iron oxygen magnetic nano particle of iron oxygen magnetic nano particle or doping, and its particle diameter is 8 ± 2nm.
5. according to Claims 1-4 one of them described in Janus structure super-paramagnetism nano grain, it is characterized in that: the particle diameter of described Janus structure super-paramagnetism nano grain is 20 ~ 30nm.
6. the preparation method of Janus structure super-paramagnetism nano grain according to claim 2, comprises the following steps:
1) by transfer transport regenerated catalyst atom transition free radical polymerization reaction, the hydrophobic chain shaped polymer that end group is carboxyl is prepared;
2) end group is the hydrophobic chain shaped polymer emulsification balling-up of carboxyl by employing solvent evaporation method, preparation hydrophobicity tiny balloon;
3) by ligand exchange reaction, super-paramagnetism nano grain is connected to the skin of hydrophobicity tiny balloon, forms Superparamagnetism composite microsphere;
4) carboxymethylation process is carried out to Superparamagnetism composite microsphere, then by transfer transport regenerated catalyst atom transition free radical polymerization reaction, hydrophilic polymer brush is grafted on super-paramagnetism nano grain, forms hydrophilic polymer brush grafting Superparamagnetism composite microsphere;
5) etching solution is adopted to carry out etching processing to hydrophilic polymer brush grafting Superparamagnetism composite microsphere, formed with super-paramagnetism nano grain for core, and point both sides, the surface of super-paramagnetism nano grain are grafted with the wetting ability of hydrophilic polymer brush and hydrophobic polymer brush respectively--hydrophobic sexual type Janus structure super-paramagnetism nano grain.
7. preparation method according to claim 6, is characterized in that: in step 5) in, described etching solution is DMF/water, tetrahydrofuran (THF)/water, toluene/ethanol mixed solvent; The volume ratio of DMF/water, tetrahydrofuran (THF)/water, toluene/ethanol is 1 ︰ 1 ~ 9 ︰ 1; The final concentration of described hydrophilic polymer brush grafting Superparamagnetism composite microsphere in etching solution is 1 ~ 15mg/mL.
8. preparation method according to claim 7, it is characterized in that, in step 5) in, described etching processing comprises the following steps: be scattered in etching solution by hydrophilic polymer brush grafting Superparamagnetism composite microsphere, stirring reaction 4 ~ 6 hours, then carry out Magneto separate, gained precipitation is washed with etching solution and deionized water respectively, obtains described Janus structure super-paramagnetism nano grain.
9. the preparation method of Janus structure super-paramagnetism nano grain according to claim 3, comprises the following steps:
1. by transfer transport regenerated catalyst atom transition free radical polymerization reaction, the hydrophobic chain shaped polymer that end group is carboxyl is prepared;
2. end group is the hydrophobic chain shaped polymer emulsification balling-up of carboxyl by employing solvent evaporation method, preparation hydrophobicity tiny balloon;
3. by ligand exchange reaction, super-paramagnetism nano grain is connected to the skin of hydrophobicity tiny balloon, forms Superparamagnetism composite microsphere;
4. carboxymethylation process is carried out to Superparamagnetism composite microsphere, then by transfer transport regenerated catalyst atom transition free radical polymerization reaction, responsive to temperature type polymer brush is grafted on super-paramagnetism nano grain, formation temperature sensitive polymer brush grafting Superparamagnetism composite microsphere;
5. the hydrophobicity tiny balloon in responsive to temperature type polymer brush grafting Superparamagnetism composite microsphere is replaced into pH sensitive polymer tiny balloon, forms pH responsive--responsive to temperature type Superparamagnetism composite microsphere;
6. adopting etching solution responsive to pH--responsive to temperature type Superparamagnetism composite microsphere carries out etching processing, formed with super-paramagnetism nano grain for core, and the pH that point both sides, the surface of super-paramagnetism nano grain are grafted with pH sensitive polymer brush and responsive to temperature type polymer brush is respectively responsive--responsive to temperature type Janus structure super-paramagnetism nano grain.
10. preparation method according to claim 9, is characterized in that: step 6. in, described etching solution is DMF/water, tetrahydrofuran (THF)/water, toluene/ethanol mixed solvent; The volume ratio of DMF/water, tetrahydrofuran (THF)/water, toluene/ethanol is 1 ︰ 1 ~ 9 ︰ 1; Described pH is responsive--and the final concentration of responsive to temperature type Superparamagnetism composite microsphere in etching solution is 1 ~ 15mg/mL.
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