CN105366735A - Preparation method of anionic ferroferric oxide nano-particles with carboxyl groups on surfaces - Google Patents
Preparation method of anionic ferroferric oxide nano-particles with carboxyl groups on surfaces Download PDFInfo
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- CN105366735A CN105366735A CN201510981491.7A CN201510981491A CN105366735A CN 105366735 A CN105366735 A CN 105366735A CN 201510981491 A CN201510981491 A CN 201510981491A CN 105366735 A CN105366735 A CN 105366735A
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- carboxyl
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- ferroferric oxide
- caprolactone
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 44
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 title abstract 3
- 239000002245 particle Substances 0.000 claims abstract description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 9
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005642 Oleic acid Substances 0.000 claims abstract description 9
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000008187 granular material Substances 0.000 claims description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 229920001427 mPEG Polymers 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 229920001610 polycaprolactone Polymers 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000004632 polycaprolactone Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 3
- 235000019850 ferrous citrate Nutrition 0.000 claims description 3
- 239000011640 ferrous citrate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 claims description 3
- -1 poly-carboxyl caprolactone Chemical compound 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 6
- 230000036571 hydration Effects 0.000 abstract description 2
- 238000006703 hydration reaction Methods 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 abstract 1
- 229960002089 ferrous chloride Drugs 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 abstract 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 abstract 1
- 238000007885 magnetic separation Methods 0.000 abstract 1
- 230000005415 magnetization Effects 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 230000029219 regulation of pH Effects 0.000 abstract 1
- 238000009777 vacuum freeze-drying Methods 0.000 abstract 1
- 239000003814 drug Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000006249 magnetic particle Substances 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920006318 anionic polymer Polymers 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229940088623 biologically active substance Drugs 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 206010073306 Exposure to radiation Diseases 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 206010038848 Retinal detachment Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001900 immune effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- DGUKXCVHOUQPPA-UHFFFAOYSA-N phosphoric acid tungsten Chemical compound [W].OP(O)(O)=O DGUKXCVHOUQPPA-UHFFFAOYSA-N 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 230000004264 retinal detachment Effects 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000000015 thermotherapy Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Compounds Of Iron (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention discloses a preparation method of anionic ferroferric oxide nano-particles with carboxyl groups on surfaces. The preparation method comprises steps as follows: ferric chloride hexahydrate and ferrous chloride tetrahydrate are separately weighed and are separately or jointly mixed and stirred under the protection of nitrogen or other inert gases or without protection, a mixture is dissolved in deionized water, ammonia water is added for pH regulation, oleic acid is added for reaction, and a mixed product is washed by acetone for multiple times and subjected to vacuum drying; an alkane solution of ferroferric oxide is taken for stirring and mixing, a mixed solution is added to the deionized water, a product is obtained through magnetic separation, the product is washed by deionized water and subjected to vacuum freeze drying or vacuum drying at the room temperature, and white, yellowish-brown or black powder is obtained for standby application. The prepared ferroferric oxide nano-particles have good dispersibility in an aqueous solution, the grain size is 5-80 nm and is uniform, the hydration diameter is 50-400 nm, the particle surfaces are negatively charged, and the particles have high saturation magnetization strength (10-70 emu/g) and have superparamagnetism.
Description
Technical field
The invention belongs to field of nanometer technology, particularly relate to the preparation method that a kind of surface is the anionic property ferroferric oxide nano granules of carboxyl.
Background technology
The ferriferrous oxide particles of nanoscale, due to magnetic performance and the good biocompatibility of its uniqueness, makes it in industry, environmental engineering, has a wide range of applications in biomedicine and national defense construction.Particularly in biomedical sector, because Z 250 nature is stable, biocompatibility is better, intensity is higher, and the feature such as to have no side effect, be widely used especially, as Magneto separate, target medicine carrier, tumor thermotherapy technology, the cell marking of nuclear magnetic resonance, Cell and organism molecule, and as strengthening the prosthesis etc. of photographic developer, contrast medium, retinal detachment.In biomedical application, need ferroferric oxide nano granules to have good dispersion stabilization in aqueous especially, and surface has highdensity active group, be convenient to further with connections such as various biologically active substance or medicines.As surface has the anionic property ferroferric oxide nano granules of carboxyl, by carboxyl and various antigen or antibody, or other components such as polypeptide or protein directly or indirectly connect, and make it can be used for cell and protein or antibody is separated, also can be used as various immunological probe.
Current its surface group of anionic property ferroferric oxide nano granules is mainly carboxyl, hydroxyl, sulfydryl, the negative group such as sulfonic group.Wherein the surperficial preparation of the anionic property ferroferric oxide nano granules for carboxyl mainly contains two large classes.One class be in advance modify or not have modification Z 250 dispersion soln in add with carboxyl monomer (as, vinylformic acid, methacrylic acid, fumaric acid, toxilic acid etc.), again in every way (as, uv irradiating, other radiation exposures, microwave irradiation, or add initiator etc.) trigger monomer polymerization, thus form the anionic property ferroferric oxide nano granules of surface band carboxyl.The anionic property ferriferrous oxide particles of surface carboxyl groups prepared by this method often has the monomer residue thing do not reacted completely, unnecessary extra toxicity is brought to obtained magnetic-particle, the polymerization methods of monomer may cause certain damage to the medicine isoreactivity material added simultaneously, is therefore unfavorable for the preparation of the anionic property magnetic-particle containing medicine isoreactivity material.Another kind method adds the small-molecule substance of various band carboxyl (as citric acid in the ferriferrous oxide particles dispersion liquid modified in advance or do not modify, each amino acid etc.) or in advance polymerization or the good synthesis with carboxyl of modification or natural polymer (as, carboxylated chitosan, carboxylated cyclodextrin, carboxylated cellulose element, carboxylated polyamino acid, carboxylated dextran, polyacrylic homopolymerization or copolymerization macromole etc.), pass through ligand-displacement, electrostatic adhesion, intermolecular forces, the means that after chemical bonds, physics is coated, one step or multistep or LBL self-assembly are the anionic property ferriferrous oxide particles that surface is carboxyl.The magnetic-particle of this method gained, or can not while preparation, medicine be carried into magnetic-particle (as citric acid), or selected polymkeric substance mostly is the modifier of natural polymer, its raw material uncontrollable factor is too many, the content of modified carboxyl is also uncontrollable, or be exactly not biodegradable polymkeric substance, this brings unnecessary hidden danger all can to the bio-toxicity of magnetic-particle and stability.
Summary of the invention
A kind of surface is the object of the present invention is to provide to be the preparation method of the anionic property ferroferric oxide nano granules of carboxyl, the anionic property ferriferrous oxide particles being intended to the surface carboxyl groups that solution is prepared with current preparation method often has the monomer residue thing do not reacted completely, unnecessary extra toxicity is brought to obtained magnetic-particle, the polymerization methods of monomer causes certain damage to the medicine isoreactivity material added simultaneously, and medicine can not be carried the problem into magnetic-particle while preparation.In addition, the carboxylic anionic polymer adopted in the present invention has good biocompatibility and biodegradable, add the amphipathic of himself and emulsifying agent effect, not only can obtain the magnetic function particle that bio-toxicity is little, the stability of magnetic-particle in aqueous environment can also be increased.
The present invention is achieved in that a kind of surface is the preparation method of the anionic property ferroferric oxide nano granules of carboxyl, and this preparation method comprises the following steps:
Take FeC1 respectively
36H
2o and FeC1
24H
2o, mol ratio is 2:1, under the protection having nitrogen or other rare gas elementes or the protection not having the rare gas elementes such as nitrogen respectively or common mix and blend 1 ~ 30 minute, is dissolved in 5-1000ml deionized water, obtains molysite aqueous solution that is respective or mixing;
Add ammoniacal liquor and regulate pH to 9 ~ 13, stir 0 ~ 30 minute, then add oleic acid 1 ~ 100ml, 0 ~ 90 DEG C is reacted 1 ~ 180 minute, washing with acetone several, ambient temperature in vacuum drying 12 ~ 24 hours; Black particle is scattered in 1 ~ 100ml alkane organic solvent stand-by;
Get a certain amount of polymkeric substance to be dissolved in 1 ~ 50ml acetone, get the alkane solution 1 ~ 10ml of above-mentioned Z 250, concentration 0.2 ~ 5mg/ml, is uniformly mixed, and is added by mixing solutions in 10 ~ 1000ml deionized water, stirs 12 ~ 24 hours;
After reaction terminates, the mode of Magneto separate obtains the anionic property ferriferrous oxide particles of surface for carboxyl, and with washed with de-ionized water 3-5 all over after be again scattered in deionized water stand-by, or vacuum lyophilization 12 ~ 72 hours or vacuum drying at room temperature 12 ~ 24 hours, obtain white or yellowish brown powder is stand-by.
Further, its middle-end methoxy poly (ethylene glycol) molecular weight is 500 ~ 10000g/mol, and poly-carboxyl caprolactone molecular weight is 500 ~ 5000g/mol;
Further, described polymkeric substance add-on is 0.01g ~ 20g/ml; Described stirring velocity is 300 ~ 3000r/min.
Further, described FeC1
36H
20 solubility ferric iron or employing Fe (SO
4)
37H
2one in O, ferric sulfate, iron nitrate, ironic citrate substitutes.
Further, described FeC1
24H
2o solubility ferrous iron or adopt ferrous sulfate, ferrous sulfate hydrate, Iron nitrate, one in ferrous citrate substitutes.
Further, described polymkeric substance is end methoxy poly (ethylene glycol)-poly-carboxyl caprolactone, end methoxy poly (ethylene glycol)-poly-carboxyl caprolactone-end methoxy poly (ethylene glycol), poly-carboxyl caprolactone-polyoxyethylene glycol-poly-carboxyl caprolactone, end methoxy poly (ethylene glycol)-poly-carboxyl caprolactone-polycaprolactone, end methoxy poly (ethylene glycol)-polycaprolactone-poly-carboxyl caprolactone, end methoxy poly (ethylene glycol)-poly-carboxyl caprolactone-polycaprolactone-end methoxy poly (ethylene glycol), polycaprolactone-poly-carboxyl caprolactone-polyoxyethylene glycol-poly-carboxyl caprolactone-polycaprolactone, one in poly-carboxyl caprolactone-PCL-PEG-PCL-poly-carboxyl caprolactone.
Further, described acetone solvent or employing tetrahydrofuran (THF), methyl-sulphoxide, one or more in acetonitrile substitute.
Further, the alkane solvent of described Z 250 or employing are as normal heptane, and normal hexane, iso-pentane, the one in the alkane organic solvents such as Skellysolve A substitutes.
Ferroferric oxide nano granules prepared by the present invention, there is good dispersiveness in aqueous, grain-size is 5 ~ 80nm (the controlled combinations particle size of preparation technology), even grain size, hydrated diameter is 50 ~ 400nm, particle surface electronegative (be less than or equal to-1mv, when add magnetic-particle amount with multipolymer composition and change to some extent).This particle has comparatively high saturation and magnetic intensity 10 ~ 70emu/g, has superparamagnetism.
Accompanying drawing explanation
Preparation method's schema of Fig. 1 to be surface that the embodiment of the present invention provides be anionic property ferriferrous oxide particles of carboxyl.
The TEM picture (phosphoric acid tungsten negative staining) of Fig. 2 to be surface that the embodiment of the present invention provides be anionic property ferriferrous oxide particles of carboxyl
The anionic property ferriferrous oxide particles zeta potential image in deionized water of Fig. 3 to be surface that the embodiment of the present invention provides be carboxyl.
The hydration grain size distribution of the ferriferrous oxide particles that the anionic polymer of Fig. 4 to be surface that the embodiment of the present invention provides be carboxyl is coated.
The magnetic hysteresis loop of Fig. 5 to be surface that the embodiment of the present invention provides be anionic property ferriferrous oxide particles of carboxyl.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The invention provides a kind of method preparing the surperficial anionic property ferriferrous oxide particles for carboxyl, two blocks and the segmented copolymer that adopt PEG and PCCL are raw material, to act between ligand-displacement and hydrophobic segment, preparation size is evenly distributed, in aqueous can the anionic property ferroferric oxide nano granules with high magnetic saturation intensity of stable dispersion.This particle preparation condition is gentle, is convenient to the loading of biologically active drug.
The present invention adopts two-step approach to prepare.First prepare in aqueous the ferroferric oxide nano granules of oleic acid modified, then to add two blocks of PEG and PCCL and the carboxylic anionic polymer of many blocks be the anionic property ferriferrous oxide particles of carboxyl with solvent evaporation method preparation surface in aqueous.Here carboxylic anionic polymer is amphipathic owing to having in aqueous, is namely anionic property reagent, is again the tensio-active agent of system, and the medicine of loading can also be protected not by environmental injury.Prepared particle surface band carboxyl is electronegativity, and carboxyl density and electronegativity power can carry out regulation and control according to the add-on of the length of PCCL fragment and polymkeric substance, and can uniform and stablely disperse in water, its size tunable, magnetic saturation intensity is high.The carboxyl on surface is convenient to be connected with biologically active substance or other drug further, and the biodegradable of polymkeric substance is convenient to the loading of medicine and the design of controlled release durg delivery system.
Below in conjunction with accompanying drawing, application principle of the present invention is further described.
S101: take FeC1 respectively
36H
2o and FeC1
24H
2o, mol ratio is 2:1, under the protection having nitrogen or other rare gas elementes or the protection not having the rare gas elementes such as nitrogen respectively or common mix and blend 1 ~ 30 minute, is dissolved in 5-1000ml deionized water, obtains molysite aqueous solution that is respective or mixing;
S102: add ammoniacal liquor and regulate pH to 9 ~ 13, stir 0 ~ 30 minute, then add oleic acid 1 ~ 100ml, 0 ~ 90 DEG C is reacted 1 ~ 180 minute, washing with acetone several, ambient temperature in vacuum drying 12 ~ 24 hours; Black particle is scattered in 1 ~ 100ml alkane organic solvent stand-by;
S103: get a certain amount of polymkeric substance and be dissolved in 1 ~ 50ml acetone, get the alkane solution 1 ~ 10ml of above-mentioned Z 250, concentration 0.2 ~ 5mg/ml, is uniformly mixed, and is added by mixing solutions in 10 ~ 1000ml deionized water, stirs 12 ~ 24 hours;
S104: after reaction terminates, the mode of Magneto separate obtains with the coated ferriferrous oxide particles of carboxylic anionic polymer, and with washed with de-ionized water 3-5 all over after be again scattered in deionized water stand-by, or vacuum lyophilization 12 ~ 72 hours or vacuum drying at room temperature 12 ~ 24 hours, obtain white or yellowish brown or black powder stand-by.
End methoxy poly (ethylene glycol) molecular weight is 500 ~ 10000g/mol, and poly-carboxyl caprolactone molecular weight is 500 ~ 5000g/mol;
Polymkeric substance add-on is 0.01g ~ 20g/ml; Stirring velocity is 300 ~ 3000r/min.
Described FeC1
36H
20 solubility ferric iron or employing Fe (SO
4)
37H
2one in O, ferric sulfate, iron nitrate, ironic citrate substitutes.
Described FeC1
24H
2o solubility ferrous iron or adopt ferrous sulfate, ferrous sulfate hydrate, Iron nitrate, one in ferrous citrate substitutes.
Described polymkeric substance is end methoxy poly (ethylene glycol)-poly-carboxyl caprolactone (MPEG-PCCL), end methoxy poly (ethylene glycol)-poly-carboxyl caprolactone-end methoxy poly (ethylene glycol) (MPEG-PCCL-MPEG), poly-carboxyl caprolactone-polyoxyethylene glycol-poly-carboxyl caprolactone (PCCL-PEG-PCCL), end methoxy poly (ethylene glycol)-poly-carboxyl caprolactone-polycaprolactone (mPEG-PCCL-PCL), end methoxy poly (ethylene glycol)-polycaprolactone-poly-carboxyl caprolactone (mPEG-PCL-PCCL), end methoxy poly (ethylene glycol)-poly-carboxyl caprolactone-polycaprolactone-end methoxy poly (ethylene glycol) (mPEG-PCCL-PCL-mPEG), polycaprolactone-poly-carboxyl caprolactone-polyoxyethylene glycol-poly-carboxyl caprolactone-polycaprolactone (PCL-PCCL-PEG-PCCL-PCL), one in poly-carboxyl caprolactone-PCL-PEG-PCL-poly-carboxyl caprolactone (PCCL-PCL-PEG-PCL-PCCL).
Described acetone solvent or employing tetrahydrofuran (THF), methyl-sulphoxide, one or more in acetonitrile substitute.
The alkane of described Z 250 or employing are as normal heptane, and normal hexane, iso-pentane, the one in the alkane organic solvents such as Skellysolve A substitutes.
Below in conjunction with embodiment, application principle of the present invention is described in detail.
Example 1
Take 0.2gFeC1
36H
2o and 0.074gFeC1
24H
2o, mixes 10min with 10ml deionized water dissolving respectively under nitrogen protection; Add ammoniacal liquor under nitrogen protection and regulate pH to 11.Add oleic acid 10ml to stir;
In nitrogen atmosphere, be slowly warmed up to 90 DEG C under stirring, keep stirring, react 120 minutes
Products therefrom acetone precipitation is washed three times.Dry 18 hours of room temperature in vacuo.The ferriferrous oxide particles of gained oleic acid modified is prepared as the hexane solution that concentration is 2mg/ml;
MPEG-PCCL-mPEG (mPEG molecular weight 1000g/mol, PCCL molecular weight 1000g/mol, then polymericular weight is 3000g/mol) 1g is dissolved in 4ml acetone, add in 50ml deionized water solution after mixing with the ferriferrous oxide particles hexane solution (2mg/ml) of the above-mentioned preparation of 1ml, stir 20 hours, magnetic resolution, dry 24 hours of room temperature in vacuo, obtains sundown powder.
Institute's X-ray diffraction method that is able to (XRD) test is high purity inverse spinel structure ferriferrous oxide particles, and its grain-size is 11nm.Transmission electron microscope observing particle, for being uniformly dispersed, subsphaeroidal particle.It is 112.0 ± 13.5nm that Dynamic laser scattering records its hydrated diameter.Fourier infrared spectrum (FT-IR) and thermal weight loss (TGA) method confirm, its surface is mPEG-PCCL.Zeta potential measure its in aqueous surface potential be-1.96 ± 0.15mv.Vibrating sample magnetometer (VSM) is tested, and its saturated magnetic intensity is 46.35emu/g.
Embodiment 2:
Take 0.1gFeC1
36H
2o and 0.037gFeC1
24H
2o, mixes 10min with 5ml deionized water dissolving respectively under nitrogen protection; Add ammoniacal liquor under nitrogen protection and regulate pH to 10.Add oleic acid 6ml to stir;
In nitrogen atmosphere, be slowly warmed up to 90 DEG C under stirring, keep stirring, react 90 minutes;
Products therefrom acetone precipitation is washed three times.Dry 18 hours of room temperature in vacuo.The ferriferrous oxide particles of gained oleic acid modified is prepared as the hexane solution that concentration is 1.5mg/ml;
MPEG-PCCL (mPEG molecular weight 2000g/mol, PCCL molecular weight 4000g/mol, then the molecular weight of polymkeric substance is 6000g/mol) 1g is dissolved in 4ml acetone, add in 50ml deionized water solution after mixing with the ferriferrous oxide particles hexane solution (2mg/ml) of the above-mentioned preparation of 1ml, stir 20 hours, magnetic resolution, dry 24 hours of room temperature in vacuo, obtains sundown powder.
Institute's X-ray diffraction method that is able to (XRD) test is high purity inverse spinel structure ferriferrous oxide particles, and its grain-size is 16nm.Transmission electron microscope observing particle, for being uniformly dispersed, subsphaeroidal particle.It is 199.9 ± 3.3nm that Dynamic laser scattering records its hydrated diameter.Fourier infrared spectrum (FT-IR) and thermal weight loss (TGA) method confirm, its surface is mPEG-PCCL.Zeta potential measure its in aqueous surface potential be-11.3 ± 0.3mv.Vibrating sample magnetometer (VSM) is tested, and its saturated magnetic intensity is 37.28emu/g.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. surface is a preparation method for the anionic property ferroferric oxide nano granules of carboxyl, it is characterized in that, this preparation method comprises the following steps:
Take FeCl respectively
36H
2o and FeCl
24H
2o, mol ratio is 2:1, is having the protection of nitrogen or other rare gas elementes or is being dissolved in respectively or jointly in 5ml-1000ml deionized water under not having the protection of the rare gas elementes such as nitrogen, stirring 1 minute ~ 30 minutes, obtains molysite aqueous solution that is respective or mixing;
Add ammoniacal liquor and regulate pH to 9 ~ 13, stir 0 minute ~ 30 minutes, then add oleic acid 1ml ~ 100ml, 0 DEG C ~ 90 DEG C are reacted 1 minute ~ 180 minutes, washing with acetone several, dry 12 hours ~ 24 hours of ambient temperature in vacuum; Black ferroferric oxide Granular composite is stand-by in 1ml ~ 100ml alkane solvent;
The polymkeric substance getting 0.01-20g is dissolved in 1ml ~ 50ml acetone, get the alkane solution 1ml ~ 10ml of above-mentioned Z 250, concentration 0.2mg/ml ~ 5mg/ml, is uniformly mixed, mixing solutions is added in 10ml ~ 1000ml deionized water, stir 12 hours ~ 24 hours;
After reaction terminates, the mode of Magneto separate obtains the anionic property ferriferrous oxide particles of surface for carboxyl, and with washed with de-ionized water 3-5 all over after, again be scattered in deionized water stand-by, or vacuum lyophilization 12 hours ~ 72 hours or vacuum drying at room temperature 12 hours ~ 24 hours, obtain white or yellowish brown or black powder stand-by.
2. surface as claimed in claim 1 is the preparation method of the anionic property ferroferric oxide nano granules of carboxyl, it is characterized in that, described polymkeric substance is end methoxy poly (ethylene glycol)-poly-carboxyl caprolactone, end methoxy poly (ethylene glycol)-poly-carboxyl caprolactone-end methoxy poly (ethylene glycol), poly-carboxyl caprolactone-polyoxyethylene glycol-poly-carboxyl caprolactone, end methoxy poly (ethylene glycol)-poly-carboxyl caprolactone-polycaprolactone, end methoxy poly (ethylene glycol)-polycaprolactone-poly-carboxyl caprolactone, end methoxy poly (ethylene glycol)-poly-carboxyl caprolactone-polycaprolactone-end methoxy poly (ethylene glycol), polycaprolactone-poly-carboxyl caprolactone-polyoxyethylene glycol-poly-carboxyl caprolactone-polycaprolactone, one in poly-carboxyl caprolactone-PCL-PEG-PCL-poly-carboxyl caprolactone.
3. surface as claimed in claim 1 is the preparation method of the anionic property ferroferric oxide nano granules of carboxyl, it is characterized in that, described end methoxy poly (ethylene glycol) molecular weight is 500g/mol ~ 10000g/mol, and poly-carboxyl caprolactone molecular weight is 500g/mol ~ 10000g/mol.
4. surface as claimed in claim 1 is the preparation method of the anionic property ferroferric oxide nano granules of carboxyl, it is characterized in that, described polymkeric substance add-on 0.01g ~ 20g/ml; Described stirring velocity is 300r/min ~ 3000r/min.
5. surface as claimed in claim 1 is the preparation method of the anionic property ferroferric oxide nano granules of carboxyl, it is characterized in that, described FeCl
36H
2o solubility ferric iron or employing Fe (SO
4)
37H
2one in O, ferric sulfate, iron nitrate, ironic citrate substitutes.
6. surface as claimed in claim 1 is the preparation method of the anionic property ferroferric oxide nano granules of carboxyl, it is characterized in that, described FeCl
24H
2o solubility ferrous iron or adopt ferrous sulfate, ferrous sulfate hydrate, Iron nitrate, one in ferrous citrate substitutes.
7. surface as claimed in claim 1 is the preparation method of the anionic property ferroferric oxide nano granules of carboxyl, it is characterized in that, described acetone solvent or employing tetrahydrofuran (THF), and methyl-sulphoxide, one or more in acetonitrile substitute.
8. surface as claimed in claim 1 is the preparation method of the anionic property ferroferric oxide nano granules of carboxyl, it is characterized in that, the alkane organic solvent of described dispersion ferriferrous oxide particles or employing normal heptane, normal hexane, iso-pentane, the one in the alkane organic solvents such as Skellysolve A substitutes.
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| CN112429895A (en) * | 2020-01-22 | 2021-03-02 | 江苏久吾高科技股份有限公司 | Petrochemical high-salt wastewater resource utilization process and device |
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