CN114014370B - Multiple-responsiveness Janus ferroferric oxide nanoparticle and preparation method thereof - Google Patents
Multiple-responsiveness Janus ferroferric oxide nanoparticle and preparation method thereof Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 60
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000004043 responsiveness Effects 0.000 title claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 18
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 16
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000004005 microsphere Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 10
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 10
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- YPCMISLZCVOUJB-UHFFFAOYSA-N 4-cyano-4-methyl-5-phenyl-5-sulfanylidenepentanoic acid Chemical compound OC(=O)CCC(C)(C#N)C(=S)C1=CC=CC=C1 YPCMISLZCVOUJB-UHFFFAOYSA-N 0.000 claims description 7
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 7
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- VMGSQCIDWAUGLQ-UHFFFAOYSA-N n',n'-bis[2-(dimethylamino)ethyl]-n,n-dimethylethane-1,2-diamine Chemical compound CN(C)CCN(CCN(C)C)CCN(C)C VMGSQCIDWAUGLQ-UHFFFAOYSA-N 0.000 claims description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000007112 amidation reaction Methods 0.000 claims description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- -1 poly 2- (2-methoxyethoxy) methyl ethyl Chemical group 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- GGXRSUUOWQBVFB-UHFFFAOYSA-N 2,3-dibromo-2-methylpropanoyl bromide Chemical group BrCC(Br)(C)C(Br)=O GGXRSUUOWQBVFB-UHFFFAOYSA-N 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000005192 partition Methods 0.000 abstract description 3
- 239000003995 emulsifying agent Substances 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 13
- 238000005119 centrifugation Methods 0.000 description 10
- 238000010257 thawing Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical group CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 description 6
- 239000013283 Janus particle Substances 0.000 description 6
- 230000009977 dual effect Effects 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000002122 magnetic nanoparticle Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention belongs to the technical field of nano materials, and particularly relates to nanoscale multiple-responsiveness Janus ferroferric oxide particles and a preparation method thereof. According to the preparation method, different kinds of chemical initiator modification is carried out on two side areas of the ferroferric oxide nano particle by a three-dimensional template auxiliary method, and different kinds of responsive polymer chains are sequentially grafted on two sides. The method has universality for functional modification of particles with the size smaller than 20 and nm. The chemical composition, the substance content and the partition ratio of the multi-responsiveness Janus ferroferric oxide nano particles can be accurately regulated and controlled. Its hydrophilicity/amphiphilicity/hydrophobicity can be controlled by external stimuli such as temperature, pH and near infrared light. When the emulsifier is used as an environment-responsive emulsifier, the material can be recycled under the action of an external magnetic field.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to nanoscale multiple-responsiveness Janus ferroferric oxide particles and a preparation method thereof.
Background
The responsive Janus nano particles can generate corresponding physical or chemical changes when being subjected to external stimulus such as temperature, pH, illumination and magnetic/electric field, and have wide application value in the fields of biomedicine, electronics, surfactants and the like (A. Synytska, L. Ionov, part. System. Charact. 2013, 30, 922-930). Grafting a responsive polymer on one or both sides of the nanoparticle is an effective method of preparing responsive Janus nanoparticles. Especially when the nanoparticle is ferroferric oxide, the magnetic responsiveness and the near infrared thermal effect of the corresponding Janus material can be endowed. However, the existing technology is limited to functional modification of nano particles above 20nm, and effective mass preparation means for particles below 20nm are still lacking. The three-dimensional interface protection method can be used for carrying out differentiation treatment on the exposed side of the particles by pre-protecting the contact surface of the particles. Pickering emulsion interface protection is commonly used to prepare Janus particles on the submicron and micron scale, but aggregates at the emulsion interface when the particles are smaller than 20nm, making the process less versatile for small size particles. The three-dimensional hard template can be in a single-layer adsorption state through specific action with the nano particles. This requires that the three-dimensional templates and the nanoparticles have functional groups capable of acting, and that the nanoparticles have repulsive interactions so that they are not easily agglomerated, while the nanoparticles are easily desorbed from the templates by changing conditions. Therefore, developing a three-dimensional template and nanoparticles that are matched in design is a key to the preparation of responsive Janus nanoparticles using interface protection.
Disclosure of Invention
The invention aims to provide a component-adjustable multi-responsiveness Janus ferroferric oxide nanoparticle and a preparation method thereof.
The multi-responsiveness Janus ferroferric oxide nanoparticle is formed by grafting different responsiveness polymer chains on two sides of a magnetic ferroferric oxide nanoparticle respectively; the magnetic ferroferric oxide nano particles are ferroferric oxide nano particles with amino groups on the surfaces, and the particle size is 5-20 nm; the polymer chain is one or more of poly N-isopropyl acrylamide, poly 2- (2-methoxyethoxy) methyl ethyl acrylate, poly dimethylaminoethyl methacrylate, polymethacrylic acid and polyacrylic acid.
The multi-responsiveness Janus ferroferric oxide nanoparticle provided by the invention has adjustable chemical composition, adjustable content and adjustable partition ratio, and has universality for functional modification of particles with the size smaller than 20 nm.
The preparation method of the multi-responsiveness Janus ferroferric oxide nano-particles provided by the invention comprises the following specific steps:
(1) Dispersing the three-dimensional template in a solvent, adding acid to adjust the pH, then adding ferroferric oxide nano particles, mixing and stirring for a period of time to obtain a compound of the ferroferric oxide nano particles;
(2) Redispersing the compound obtained in the step (1) in an organic solvent, and adding an initiator A for selective modification; after purification, redispersing in water, adjusting the solution environment to desorb and collect the nano particles;
(3) Redispersing the product obtained in the step (2) in an organic solvent, adding a polymer monomer A', and adjusting the reaction conditions to carry out polymerization reaction;
(4) Reacting the product obtained in the step (3) with an initiator B; after separation and purification, the polymer monomer B' is dispersed in an organic solvent again, and the reaction conditions are adjusted to cause polymerization reaction.
In the step (1), the three-dimensional template is a microsphere with carboxyl on the surface. Preferably, the microsphere is one of silica, alumina and titania. Preferably, the microsphere is 200 nm-20 μm in size.
The solvent is one of pure water and ethanol/water mixed solution. The volume ratio of the ethanol/water mixed solution is 1:1-1:9.
The concentration of the three-dimensional template is 2 mg/mL-20 mg/mL.
The pH is 5.0-6.5. The added acid is one of hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid.
The ferroferric oxide nano particles are nano ferroferric oxide with amino groups on the surface, and the particle size is 5-20 nm. The concentration ratio of the nano ferroferric oxide to the three-dimensional template is 1:5-1:50.
The mixing time is 4-12 hours.
In the step (2), the organic solvent is one of dioxane, N-Dimethylformamide (DMF), tetrahydrofuran (THF) and dimethyl sulfoxide (DMSO).
The initiator A is a RAFT reagent with carboxyl, and can be specifically 4-cyano-4- (thiobenzoyl) valeric acid. The mass ratio of the initiator A to the compound is 1:1-3:1.
The reaction condition with the initiator A is amidation reaction. Specifically, the reaction is carried out for 24-48 hours under the action of N, N' -Dicyclohexylcarbodiimide (DCC) and N-hydroxysuccinimide (NHS) in a dark place.
The method for adjusting the solution environment comprises the steps of adding acid to adjust pH, raising temperature and carrying out ultrasonic treatment. The acid is one of hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid; the pH is 2.0-4.0; the temperature is 45-65 ℃; the ultrasonic treatment time is 2-6 hours.
In the step (3), the organic solvent is one of dioxane, N-Dimethylformamide (DMF), tetrahydrofuran (THF) and dimethyl sulfoxide (DMSO).
The polymer monomer A' is one of N-isopropyl acrylamide, dimethylaminoethyl methacrylate, tert-butyl acrylate, methyl acrylate and methyl methacrylate. The mass ratio of the monomer A' to the nano particles is 0.5:1-10:1.
The polymerization reaction conditions are carried out in the presence of an initiator, oxygen-free and high temperature. The initiator is one of Azobisisobutyronitrile (AIBN), 4 '-azobis (4-cyanovaleric acid) (ACVA) and 2,2' -azobisisobutylamidine dihydrochloride (AIBA); the anaerobic condition is that nitrogen or argon is introduced to deoxidize; the reaction temperature is 60-90 ℃; the reaction time is 12-24 hours.
When the polymer monomer A 'is one of tert-butyl methacrylate, tert-butyl acrylate, methyl acrylate and methyl methacrylate, trifluoroacetic acid is used for hydrolyzing the polymer monomer A' into carboxylic acid after the polymerization reaction.
In the step (4), the initiator B is 2-bromo isobutyryl bromide. The reaction condition with the initiator B is that in dichloromethane or chloroform serving as an organic solvent, triethylamine reacts for 12-24 hours at normal temperature; the mass ratio of the amount of the initiator B to the solid product in the step (3) is 1:1-5:1.
The polymer monomer B' is one of N-isopropyl acrylamide (NIPAM), ethyl 2- (2-methoxyethoxy) methacrylate (OEGMA), dimethylaminoethyl methacrylate (DMEAMA), tert-butyl methacrylate, tert-butyl acrylate, methyl acrylate and methyl methacrylate. The mass ratio of the monomer B' to the product of the step (3) is 0.5:1-10:1.
The polymerization reaction conditions are initiator, anaerobic environment and high temperature. The initiator is a complex formed by cuprous bromide and one of 2,2' -bipyridine or tris [2- (dimethylamino) ethyl ] (Me 6 TREN) or Pentamethyldiethylenetriamine (PMDETA); the anaerobic condition is that nitrogen or argon is introduced to deoxidize; the reaction temperature is 60-90 ℃; the reaction time is 12-24 hours.
When the polymer monomer B 'is one of tert-butyl methacrylate, tert-butyl acrylate, methyl acrylate and methyl methacrylate, trifluoroacetic acid is used for hydrolyzing the polymer monomer B' into carboxylic acid after the polymerization reaction.
The separation and purification method is that the separation and purification method is collected by a magnet and washed by isopropanol or methanol for a plurality of times.
Compared with the prior art, the invention has the following advantages: the functional modification of small size nanoparticles (< 20 nm) is generic. The method can prepare the responsive Janus nano material with the chemical composition and the content-adjustable specific partition structure in batches. The Janus nanoparticle hydrophilicity/amphiphilicity/hydrophobicity can be controlled by external stimuli such as temperature, pH and near infrared light. The oil/water emulsion stabilized by the emulsion can realize a controllable emulsification-de-emulsification process under the external stimulus. The Janus nano particles can be recycled under the action of an external magnetic field.
Drawings
FIG. 1 is a TEM image of temperature/pH responsive Janus ferroferric oxide nanoparticles prepared in example 1 of the present invention.
Fig. 2 is a graph showing the change in particle size with temperature and pH of temperature/pH responsive Janus ferroferric oxide nanoparticles prepared in example 1 of the present invention.
Fig. 3 is a graph showing the variation of particle diameter of dual temperature-responsive Janus ferroferric oxide nanoparticles prepared in example 3 of the present invention with temperature.
Fig. 4 is a graph showing the change in particle size with pH of the dual pH-responsive Janus ferroferric oxide nanoparticles prepared in example 4 of the present invention.
Detailed Description
The invention is further illustrated below in conjunction with specific embodiments, it being understood that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention. Furthermore, it is to be understood that various changes and modifications may be made by one skilled in the art after reading the teachings of the invention, and that such equivalents are intended to fall within the scope of the claims appended hereto.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents, etc. used in the examples are commercially available unless otherwise specified.
Example 1 preparation of temperature/pH responsive Janus ferroferric oxide nanoparticles
Adding 0.4 g surface carboxyl-bearing silica microsphere into 100 mL water/ethanol (v: v=1:1), and adding 40 mg surface amino Fe 3 O 4 Ph=5.5 was adjusted with hydrochloric acid. Stir 4h. After lyophilization by centrifugation, 0.2. 0.2 g of the material was added to a solution of 4-cyano-4- (thiobenzoyl) pentanoic acid in THF (20 mL,5 mg/mL) activated by DCC and NHS, reacted in the absence of light 48h, collected by centrifugation and washed with THF. The above product was redispersed in water, ph=2 was adjusted with hydrochloric acid, warmed to 50 ℃, sonicated 2h, and the product was collected with a magnet. 20mg of the above product, 1 mg of AIBN, 40 mg of NIPAM and 5 mL of dioxane are added into a reaction bottle, and after three freezing-vacuumizing-thawing cycles, the temperature is raised to 60 ℃ under vacuum to react 24h, and air is introduced to terminate the reaction. The product was collected by magnet and re-dispersed in CH after repeated washing with THF 2 Cl 2 To the mixture, 0.16. 0.16 mL of triethylamine and 0.2 mL of 2-bromoisobutyryl bromide were added and reacted at room temperature 24. 24h. Magnet collection, CH 2 Cl 2 Washed and dried in vacuo. The product 20mg, 5mg Me6TREN, 0.1 mL DMEAMA and 5 mL isopropanol were taken and added to a reaction flask, after three freeze-vacuum-thaw cycles, 3 mg CuBr was added under refrigeration and nitrogen flow protection. After re-evacuation, the temperature is raised to 70 ℃ to react 12h. Air is introduced to terminate the reaction, the magnet is collected and washed by isopropanol, and vacuum drying is carried out to obtain PNIPAM-Fe 3 O 4 PEMEAMA Janus particles. Fig. 1 is a TEM image of temperature/pH responsive Janus ferroferric oxide nanoparticles in the examples. Fig. 2 is a graph showing the variation of particle size of temperature/pH responsive Janus ferroferric oxide nanoparticles prepared in examples with temperature and pH.
Example 2 preparation of temperature/pH responsive Janus ferroferric oxide nanoparticles
Adding 0.4 g surface carboxyl-bearing silica microsphere into 100 mL water/ethanol (v: v=1:1), and adding 40 mg surface amino Fe 3 O 4 By hydrochloric acidPh=5.5 was adjusted. Stir 4h. After lyophilization by centrifugation, 0.2. 0.2 g of the material was added to a solution of 4-cyano-4- (thiobenzoyl) pentanoic acid in THF (20 mL,5 mg/mL) activated by DCC and NHS, reacted in the absence of light 48h, collected by centrifugation and washed with THF. The above product was redispersed in water, ph=2 was adjusted with hydrochloric acid, warmed to 50 ℃, sonicated 2h, and the product was collected with a magnet. 20mg of the above product, 1 mg of AIBN, 80 mg of NIPAM and 8 mL of dioxane are added into a reaction bottle, and after three freezing-vacuumizing-thawing cycles, the temperature is raised to 60 ℃ under vacuum to react 24h, and air is introduced to terminate the reaction. The product was collected by magnet and re-dispersed in CH after repeated washing with THF 2 Cl 2 To the mixture, 0.16. 0.16 mL of triethylamine and 0.2 mL of 2-bromoisobutyryl bromide were added and reacted at room temperature 24. 24h. Magnet collection, CH 2 Cl 2 Washed and dried in vacuo. The above product 20mg, 5mg of Me6TREN, 0.1 mL of t-butyl acrylate and 5 mL of isopropanol were taken and added to a reaction flask, and 3 mg of CuBr was added under nitrogen flow protection in a frozen state after three freeze-vacuum-thaw cycles. After re-evacuation, the temperature is raised to 70 ℃ to react 12h. Air is introduced to stop the reaction, and the magnet is collected and then is redispersed in CH 2 Cl 2 Adding 5 times of trifluoroacetic acid, reacting 48 and h at room temperature to hydrolyze tert-butyl polyacrylate into polyacrylic acid, CH 2 Cl 2 Washing and vacuum drying to obtain PNIPAM-Fe 3 O 4 -PAA Janus particles.
Example 3 preparation of Dual temperature responsive Janus magnetic nanoparticles
Adding 0.4. 0.4 g surface carboxyl group-containing alumina microsphere into 100 mL water/ethanol (v: v=2:1), and adding 40 mg surface amino Fe 3 O 4 Ph=6 was adjusted with acetic acid. Stir 4h. After lyophilization by centrifugation, 0.2. 0.2 g of the material was added to a solution of 4-cyano-4- (thiobenzoyl) pentanoic acid in THF (20 mL,5 mg/mL) activated by DCC and NHS, reacted in the absence of light 48h, collected by centrifugation and washed with THF. The above product was redispersed in water, ph=2 was adjusted with hydrochloric acid, warmed to 60 ℃, sonicated 3 h, and the product was collected with a magnet. Adding 20mg above product, 1 mg ACVA, 60 mg NIPAM and 5 mL dioxane into a reaction bottle, freezing, vacuumizing and thawing for three timesAnd (3) circulating, heating to 70 ℃ under vacuum to react 24-h, and introducing air to terminate the reaction. The product was collected by magnet and re-dispersed in CH after repeated washing with THF 2 Cl 2 To the mixture, 0.24. 0.24 mL of triethylamine and 0.3 mL of 2-bromoisobutyryl bromide were added and reacted at room temperature 24. 24h. Magnet collection, CH 2 Cl 2 Washed and dried in vacuo. 20mg of the above product, 5mg of 2,2' -bipyridine, 100 mg of OEGMA and 5 mL of methanol were taken and added into a reaction flask, and 3 mg of CuBr was added under the protection of nitrogen stream in a frozen state after three freeze-vacuum-thawing cycles. After re-evacuation, the temperature is raised to 70 ℃ to react 12h. Air is introduced to terminate the reaction, the magnet is collected and washed by methanol, and vacuum drying is carried out to obtain PNIPAM-Fe 3 O 4 POEGMA Janus particles. Fig. 3 is a change in particle size of dual temperature-responsive Janus ferroferric oxide nanoparticles prepared in example 3 with temperature.
Example 4 preparation of double pH responsive Janus magnetic nanoparticles
Adding titanium dioxide microspheres with carboxyl groups on the surfaces of 0.4 and g into 100 mL water/ethanol (v: v=4:1), and adding 40 mg of Fe with amino groups on the surfaces 3 O 4 Ph=6 was adjusted with phosphoric acid. Reaction 4h. After lyophilization by centrifugation, 0.2. 0.2 g of the material was added to a solution of 4-cyano-4- (thiobenzoyl) pentanoic acid in THF (20 mL,5 mg/mL) activated by DCC and NHS, reacted in the absence of light 48h, collected by centrifugation and washed with THF. The above product was redispersed in water, ph=2 was adjusted with hydrochloric acid, warmed to 60 ℃, sonicated to 2.5 h, and the product was collected with a magnet. 20mg of the above product, 1 mg of AIBA, 50 mg of tert-butyl methacrylate and 5 mL of dioxane are taken and added into a reaction bottle, and after three freezing-vacuumizing-thawing cycles, the temperature is increased to 60 ℃ under vacuum to react 24h, and air is introduced to terminate the reaction. The product was collected by magnet and re-dispersed in CH after repeated washing with THF 2 Cl 2 To the mixture, 0.2. 0.2 mL triethylamine and 0.25 mL 2-bromoisobutyryl bromide were added and reacted at room temperature 24. 24h. After collection of the magnet, redispersion in CH 2 Cl 2 Adding 5 times of trifluoroacetic acid, reacting 48 and h at room temperature to hydrolyze the poly-tert-butyl methacrylate into the poly-methacrylic acid, CH 2 Cl 2 Washed and dried in vacuo. Taking the above products 20mg,5 mg PMDETA, 200mg of DMEAMA and 5 mL of methanol are added to the reaction flask, and 3 mg of CuBr are added in a frozen state under the protection of nitrogen flow after three freeze-vacuum-thawing cycles. After re-evacuation, the temperature is raised to 70 ℃ to react 12h. Introducing air to terminate the reaction, collecting magnet, washing with methanol, and vacuum drying to obtain PMAA-Fe 3 O 4 Pdmecma Janus particles. Fig. 4 is a graph showing the change in particle size of the dual pH-responsive Janus ferroferric oxide nanoparticle prepared in example 4 with pH.
Example 5 preparation of double pH responsive Janus magnetic nanoparticles
Adding titanium dioxide microspheres with carboxyl groups on the surfaces of 0.4 and g into 100 mL water/ethanol (v: v=3:1), and adding 40 mg of Fe with amino groups on the surfaces 3 O 4 Ph=5.5 was adjusted with phosphoric acid. Reaction 3 h. After lyophilization by centrifugation, 0.2. 0.2 g of the material was added to a solution of 4-cyano-4- (thiobenzoyl) pentanoic acid in THF (20 mL,5 mg/mL) activated by DCC and NHS, reacted in the absence of light 48h, collected by centrifugation and washed with THF. The above product was redispersed in water, ph=2 was adjusted with hydrochloric acid, warmed to 60 ℃, sonicated 2h, and the product was collected with a magnet. 20mg of the above product, 1 mg of AIBA, 100 mg of tert-butyl acrylate and 5 mL of dioxane are added into a reaction bottle, and after three freezing-vacuumizing-thawing cycles, the temperature is raised to 60 ℃ under vacuum to react 24h, and air is introduced to terminate the reaction. The product was collected by magnet and re-dispersed in CH after repeated washing with THF 2 Cl 2 To the mixture, 0.2. 0.2 mL triethylamine and 0.25 mL 2-bromoisobutyryl bromide were added and reacted at room temperature 24. 24h. After collection of the magnet, redispersion in CH 2 Cl 2 Adding 5 times of trifluoroacetic acid, reacting at room temperature 40 and h to hydrolyze tert-butyl polyacrylate into polyacrylic acid, CH 2 Cl 2 Washed and dried in vacuo. The product 20mg,5 mg Me6TREN, 300 mg of DMEAMA and 5 mL of isopropyl alcohol were taken and added to a reaction flask, and 3 mg of CuBr was added under the protection of nitrogen flow in a frozen state through three freeze-vacuum-thaw cycles. After re-evacuation, the temperature is raised to 70 ℃ to react 12h. Air is introduced to terminate the reaction, a magnet is collected and washed by isopropanol, and the PAA-Fe is obtained after vacuum drying 3 O 4 Pdmecma Janus particles.
Claims (9)
1. A preparation method of multi-responsiveness Janus ferroferric oxide nano-particles is characterized in that the nano-particles are Janus nano-particles formed by grafting polymer chains with different responsiveness on two sides of magnetic ferroferric oxide nano-particles respectively; wherein the magnetic ferroferric oxide nano-particles are ferroferric oxide nano-particles with amino groups on the surfaces, and the particle size is 5-20 nm; the polymer chain is one or more of poly N-isopropyl acrylamide, poly 2- (2-methoxyethoxy) methyl ethyl acrylate, poly dimethylaminoethyl methacrylate, polymethacrylic acid and polyacrylic acid;
the method comprises the following specific steps:
(1) Dispersing the three-dimensional template in a solvent, adding acid to adjust the pH, adding ferroferric oxide nano particles, and mixing and stirring to obtain a compound of the ferroferric oxide nano particles;
(2) Redispersing the compound obtained in the step (1) in an organic solvent, and adding an initiator A for selective modification; re-dispersing in water after purification, adjusting the solution environment to desorb and collect the nano particles;
(3) Redispersing the product obtained in the step (2) in an organic solvent, adding a polymer monomer A', and adjusting the reaction conditions to carry out polymerization reaction;
(4) Reacting the product obtained in the step (3) with an initiator B; after separation and purification, redispersing in an organic solvent, adding a polymer monomer B', and adjusting reaction conditions to cause polymerization reaction to occur, thus obtaining a final product of the multi-responsiveness Janus ferroferric oxide nano particles;
in the step (1), the three-dimensional template is a microsphere with carboxyl on the surface; the microsphere is one of silicon dioxide, aluminum oxide and titanium dioxide microsphere; the microsphere size is 200 nm-20 mu m;
in the step (1), the ferroferric oxide nano particles are nano ferroferric oxide with amino groups on the surface, and the particle size is 5-20 nm; the mass concentration ratio of the nano ferroferric oxide to the three-dimensional template is 1:5-1:50;
in the step (2), the initiator A is a RAFT reagent with carboxyl, specifically 4-cyano-4- (thiobenzoyl) pentanoic acid; the mass ratio of the initiator A to the compound is 1:1-3:1;
in the step (2), the reaction condition with the initiator A is amidation reaction, specifically, light-shielding reaction is carried out for 24-48 h under the action of N, N' -dicyclohexylcarbodiimide and N-hydroxysuccinimide;
in the step (3), the polymer monomer A' is one of N-isopropyl acrylamide, dimethylaminoethyl methacrylate, tert-butyl acrylate, methyl acrylate and methyl methacrylate; the mass ratio of the monomer A' to the nano particles is 0.5:1-10:1;
in step (3), the polymerization reaction conditions are carried out in an initiator, oxygen-free and high temperature; the initiator is one of azodiisobutyronitrile, 4 '-azobis (4-cyano valeric acid) and 2,2' -azodiisobutyl amidine dihydrochloride; the anaerobic condition is that nitrogen or argon is introduced to deoxidize; the reaction temperature is 60-90 ℃; the reaction time is 12-24 hours;
in the step (4), the initiator B is dibromoisobutyryl bromide; the reaction condition with the initiator B is that in dichloromethane or chloroform which is an organic solvent, triethylamine reacts for 12-24 hours at normal temperature; the mass ratio of the amount of the initiator B to the solid product in the step (3) is 1:1-5:1;
in the step (4), the polymer monomer B' is one of N-isopropyl acrylamide, ethyl 2- (2-methoxyethoxy) methacrylate, dimethylaminoethyl methacrylate, tert-butyl acrylate, methyl acrylate and methyl methacrylate; the mass ratio of the monomer B' to the product of the step (3) is 0.5:1-10:1;
in the step (4), the polymerization reaction condition is that the initiator, the anaerobic environment and the high temperature are carried out; the initiator is a complex formed by cuprous bromide and one of 2,2' -bipyridine or tris [2- (dimethylamino) ethyl ] or pentamethyl diethylenetriamine; the anaerobic condition is that nitrogen or argon is introduced to deoxidize; the reaction temperature is 60-90 ℃; the reaction time is 12-24 h.
2. The method for preparing multi-responsive Janus ferroferric oxide nanoparticles according to claim 1, wherein the solvent in the step (1) is one of pure water and ethanol/water mixture; the volume ratio of the ethanol/water mixed solution is 1:1-1:9; the concentration of the three-dimensional template is 2 mg/mL-20 mg/mL.
3. The method for preparing multi-responsive Janus ferroferric oxide nanoparticles according to claim 1, wherein the pH in step (1) is 5.0 to 6.5; the acid is one of hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid.
4. The method for preparing multi-responsive Janus ferroferric oxide nano particles according to claim 1, wherein the mixing and stirring time in the step (1) is 4-12 h.
5. The method for preparing multi-responsive Janus ferroferric oxide nano-particles according to claim 1, wherein the organic solvent in the step (2) is one of dioxane, N-dimethylformamide, tetrahydrofuran and dimethyl sulfoxide.
6. The method for preparing the multi-responsiveness Janus ferroferric oxide nano-particles according to claim 1, wherein the method for adjusting the solution environment in the step (2) is that the pH is adjusted by adding acid, the temperature is increased and the ultrasonic treatment is performed; the acid is one of hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid; the pH is 2.0-4.0; the temperature is 45-65 ℃; the ultrasonic treatment time is 2-6 h.
7. The method for preparing multi-responsive Janus ferroferric oxide nanoparticles according to claim 1, wherein the organic solvent in the step (3) is one of dioxane, N-dimethylformamide, tetrahydrofuran and dimethyl sulfoxide.
8. The method for preparing multi-responsive Janus ferroferric oxide nanoparticles according to claim 1, wherein in the step (3), when the polymer monomer a' is one of t-butyl methacrylate, t-butyl acrylate, methyl acrylate and methyl methacrylate, it is hydrolyzed into carboxylic acid by trifluoroacetic acid after the polymerization reaction.
9. The method for preparing multi-responsive Janus ferroferric oxide nanoparticles according to claim 1, wherein in the step (4), when the polymer monomer B' is one of t-butyl methacrylate, t-butyl acrylate, methyl acrylate and methyl methacrylate, it is hydrolyzed into carboxylic acid by trifluoroacetic acid after the polymerization reaction.
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