CN105832699B - A kind of Fe3O4@SiO2The preparation method and application of yolk-eggshell structure hollow complex microsphere - Google Patents
A kind of Fe3O4@SiO2The preparation method and application of yolk-eggshell structure hollow complex microsphere Download PDFInfo
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- 239000004005 microsphere Substances 0.000 title claims abstract description 82
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 71
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 71
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 71
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 71
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 28
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 106
- 235000019441 ethanol Nutrition 0.000 claims description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 20
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 239000000908 ammonium hydroxide Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- 239000001509 sodium citrate Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 10
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 10
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 10
- 229940038773 trisodium citrate Drugs 0.000 claims description 10
- 206010013786 Dry skin Diseases 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000008246 gaseous mixture Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003814 drug Substances 0.000 abstract description 29
- 229940079593 drug Drugs 0.000 abstract description 20
- MWWSFMDVAYGXBV-RUELKSSGSA-N Doxorubicin hydrochloride Chemical compound Cl.O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 MWWSFMDVAYGXBV-RUELKSSGSA-N 0.000 abstract description 8
- 239000007853 buffer solution Substances 0.000 abstract description 6
- 229960002918 doxorubicin hydrochloride Drugs 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- 230000005291 magnetic effect Effects 0.000 description 12
- 238000013268 sustained release Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 238000004627 transmission electron microscopy Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000011257 shell material Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 230000002459 sustained effect Effects 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 4
- 238000013270 controlled release Methods 0.000 description 4
- 102000002322 Egg Proteins Human genes 0.000 description 3
- 108010000912 Egg Proteins Proteins 0.000 description 3
- 210000003278 egg shell Anatomy 0.000 description 3
- 239000002122 magnetic nanoparticle Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000008055 phosphate buffer solution Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000012730 sustained-release form Substances 0.000 description 3
- 230000008685 targeting Effects 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000003405 delayed action preparation Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003937 drug carrier Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 206010057249 Phagocytosis Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000002975 chemoattractant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000002502 liposome Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 210000002540 macrophage Anatomy 0.000 description 1
- 238000002595 magnetic resonance imaging Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008782 phagocytosis Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000012890 simulated body fluid Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000000015 thermotherapy Methods 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
Classifications
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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]
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/70—Carbohydrates; Sugars; Derivatives thereof
- A61K31/7028—Compounds having saccharide radicals attached to non-saccharide compounds by glycosidic linkages
- A61K31/7034—Compounds having saccharide radicals attached to non-saccharide compounds by glycosidic linkages attached to a carbocyclic compound, e.g. phloridzin
- A61K31/704—Compounds having saccharide radicals attached to non-saccharide compounds by glycosidic linkages attached to a carbocyclic compound, e.g. phloridzin attached to a condensed carbocyclic ring system, e.g. sennosides, thiocolchicosides, escin, daunorubicin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5073—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals having two or more different coatings optionally including drug-containing subcoatings
- A61K9/5078—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals having two or more different coatings optionally including drug-containing subcoatings with drug-free core
-
- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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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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- Crystallography & Structural Chemistry (AREA)
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- Manufacturing Of Micro-Capsules (AREA)
Abstract
The present invention uses solvent-thermal method to prepare Fe first2O3Nano-particle under conditions of being added without any surfactant, using TEOS as silicon source, prepares the Fe of morphology controllable under mild conditions in conjunction with template and hydro-thermal method3O4@SiO2Yolk-eggshell structure hollow complex microsphere, with the hcl corrosion Fe of concentration2O3@SiO2Complex microsphere obtains Fe2O3@SiO2Yolk-eggshell structure hollow complex microsphere, then be made after carrying out reduction with superparamagnetism Fe3O4@SiO2Yolk-eggshell structure hollow complex microsphere.Obtained Fe3O4@SiO2Yolk-eggshell structure hollow complex microsphere specific surface area is 173m2/ g, drugloading rate 139mg/g, using doxorubicin hydrochloride as drug model, the release rate of drug is up to 68.4% in 72h in the PBS buffer solutions that pH is 7.4, shows good medicament slow release performance.
Description
Technical field
The invention belongs to field of biomedical materials more particularly to a kind of Fe3O4@SiO2Yolk-eggshell structure hollow is compound
The preparation method and application of microballoon.
Background technology
In recent years, with the continuous development of medical science, medicine sustained and controlled release preparation has been increasingly becoming the weight of galenic pharmacy research
Point, and the key of medicine sustained and controlled release technology is the selection of pharmaceutical carrier.Up to the present, widely used carrier material packet
Include macromolecule carrier, embedding shaped polymer micellar carrier, dendrimer supports, liposome vectors and inorganic matter carrier.It is inorganic to receive
Rice material, such as mesoporous material, nanotube, hollow microsphere are since good with chemical stability, morphology and size of latex particals is controllable, table
Face and duct are easy to modify, also the performances such as its unique optics, magnetics and electricity and be increasingly becoming medicine sustained and controlled release field and grind
The research hotspot studied carefully.
Hollow microsphere is a kind of core-shell material with special construction, its internal cavity can accommodate a large amount of drug point
Son, porous crust can be used as the channel of drug release, thus be considered as the material of medicine sustained and controlled release field most application potential
Material.Its biggest advantage is large specific surface area, can by adjusting shell thickness, the means such as aperture, hole pattern and surface are modified come
Improve the load factor and sustained release performance of drug.It is even more to be controlled in targeting to have embedded the hollow microsphere with magnetics, optical property material
It treats, magnetic control release field causes great attention.
Magnetic Nano material has superparamagnetism and higher magnetic saturation intensity, therefore in magnetic resonance imaging, targeted drug
Prodigious application prospect is all shown with biomedical sectors such as magnetic targeted thermotherapies.Currently, magnetic carrier particle study is most
It is magnetic microsphere, but the grain size of microballoon and bearing capacity are to influence two big main problems of its practical application.It is well known that carrier
Grain size, which only reaches nanoscale just, can be effectively prevented from the phagocytosis of macrophage, maintain long circulating in vivo.On the other hand by
There is magnetism in magnetic particle itself, be easy to reunite, be unfavorable for the distribution of magnetic particle in vivo.Now, the general of reunion is reduced
It is addition surfactant all over way, but this way not only changes the surface nature of particle, influences its bearing capacity, and
Since the presence of surfactant makes the reduction of its biocompatibility.
When silica is surface modified magnetic Nano material, it can not only protect magnetic core not oxidized or rotten
Erosion, and other function chemoattractant molecules of kernel magnetic nano-particle and surface modification is separated, avoid functionalized modification layer with
Influencing each other between magnetic nano-particle.Furthermore it is possible to which the dipolar interaction between shielding magnetic nano-particle, prevents grain
Son is reunited, and the suspension characteristic and biocompatibility of core-shell particles in water are improved.Stober methods and sol-gal process are two
Silica modifies Fe3O4The common method of nano-particle, shell thickness can use TEOS and H2The proportion adjustment of O, it is high-quality to prepare
The magnetic microsphere of amount provides guarantee, this is that the surface biological modification of magnetic microsphere is carried with application of the silicon ball in biomedicine again
Important leverage is supplied.
Therefore, design that a kind of morphology controllable, stability is high, good biocompatibility, bearing capacity is high, sustained release performance significantly and
Carrier material with targeting translocation will have very important significance on the major diseases fields such as treatment tumour.
Invention content
A kind of stability is high, good biocompatibility providing for the purpose of the present invention, and bearing capacity is high, sustained release performance significantly and
Fe with targeting translocation3O4@SiO2The preparation method and application of yolk-eggshell structure hollow complex microsphere.
To achieve the above object, the technical solution adopted by the present invention is a kind of Fe3O4@SiO2Yolk-eggshell structure hollow
The preparation method of complex microsphere, includes the following steps:1. by FeCl3•6H2O, urea, trisodium citrate be added to the water stirring it is molten
Solution, is added Sodium Polyacrylate later(Molecular weight is 20000 ~ 2000000, at room temperature gel), it is transferred to after stirring evenly anti-
It answering in kettle, 3 ~ 6h of hydro-thermal reaction under the conditions of 170 ~ 200 DEG C, after being cooled to room temperature, gained orange/yellow solid is washed with ethyl alcohol, then
It is washed with water, then in 55 ~ 65 DEG C of dryings, obtains Fe2O3Nanoparticle;2. 1. Fe that step is prepared2O3Nanoparticle presses solid-to-liquid ratio
1g:200ml~1g:350ml is distributed in the ethyl alcohol of 10-90vol%, and TEOS is added(Ethyl orthosilicate)Ethanol solution, 20 ~
It is ultrasonically treated 2 ~ 4h at 30 DEG C, ammonium hydroxide is then added, stirs evenly, reacts 1 ~ 3h at room temperature, obtained solid is washed with ethyl alcohol, then
It is washed with water, then drying obtains Fe at 55 ~ 65 DEG C2O3@ SiO2Complex microsphere;3. 2. Fe that step is obtained2O3@ SiO2
Complex microsphere is distributed in hydrochloric acid, is stirred to react 6 ~ 12h, and obtained solid uses ethyl alcohol and water washing after centrifuging, at 55 ~ 65 DEG C
Drying obtains Fe2O3@ SiO2Yolk-eggshell structure hollow complex microsphere;4. 3. Fe that step is obtained2O3@ SiO2Yolk-
Eggshell structure hollow complex microsphere is at 350 ~ 500 DEG C of tube furnace, hydrogen and nitrogen volume ratio are 1:8~1:It is protected under 3 gaseous mixture
60 ~ 120min is held, is then cooled to room temperature, ethyl alcohol washing is washed with water, Magneto separate, up to Fe after drying3O4@ SiO2Yolk-
Eggshell structure hollow complex microsphere.
Step 1. in FeCl3•6H2The mass ratio of O and urea is 1:1~5:1, FeCl3•6H2The quality of O and trisodium citrate
Than being 1:2~1:5, FeCl3•6H2The mass ratio of O and water is 1:60~1:30, the mass ratio of water and Sodium Polyacrylate is 0.75:1~
3:1。
Step 2. in TEOS ethanol solution in TEOS volume fraction be 0.5 ~ 5%;The ethyl alcohol and TEOS of 10-90vol%
Ethanol solution volume ratio be 3:1~5:1;The ethyl alcohol of 10-90vol% and the volume ratio of ammonium hydroxide are 5:1~9:1;The concentration of ammonium hydroxide
For 6 ~ 14.5 mol/L.
The step 3. in hydrochloric acid a concentration of 4 ~ 12mol/L, Fe2O3@ SiO2The solid-to-liquid ratio of complex microsphere and hydrochloric acid is
1g:300ml~1g:500ml。
The Fe3O4@SiO2Application of the yolk-eggshell structure hollow complex microsphere as pharmaceutical carrier:By hydrochloric acid Ah
Mycin is dissolved in the phosphate buffer solution of pH=7.4, and Fe is then added3O4@SiO2Yolk-eggshell structure hollow complex microsphere,
It stirs at room temperature for 24 hours, Magneto separate loads the Fe of doxorubicin hydrochloride to obtain the final product3O4@SiO2Yolk-eggshell structure hollow complex microsphere.
The beneficial effect comprise that:The present invention uses solvent-thermal method to prepare Fe first2O3Nano-particle, grain size exist
200nm or so has good monodispersity in aqueous solution by sodium citrate is modified;In conjunction with template and hydro-thermal method,
Under conditions of being added without any surfactant, using TEOS as silicon source, morphology controllable is prepared under mild conditions
Fe3O4@SiO2Yolk-eggshell structure hollow complex microsphere, the process are synthesized using ultrasonic wave added, have ensured the height of complex microsphere
Degree dispersibility;With certain density hcl corrosion Fe2O3@SiO2Complex microsphere obtains Fe2O3@ SiO2Yolk-eggshell structure hollow
Complex microsphere, then be made with superparamagnetism Fe after hydrogen reducing3O4@SiO2Yolk-eggshell structure hollow complex microsphere.With
Doxorubicin hydrochloride is drug model, realizes the performance study that medicine drug release is carried to it.Obtained Fe3O4@SiO2Yolk-eggshell knot
The hollow complex microsphere specific surface area of structure is 173m2/ g, drugloading rate 139mg/g, in the PBS buffer solutions that pH is 7.4 in 72h
The release rate of drug is up to 68.4%, shows good medicament slow release performance.
Description of the drawings
Fig. 1 is the Fe that embodiment 1 is prepared2O3The transmission electron microscope photo of nanoparticle;
Fig. 2 is the Fe that embodiment 1 is prepared2O3@ SiO2Complex microsphere transmission electron microscope photo;
Fig. 3 is the Fe that embodiment 1 is prepared2O3@ SiO2Yolk-eggshell structure hollow complex microsphere transmission electron microscopy
Mirror photo;
Fig. 4 is the Fe that embodiment 1 is prepared3O4@ SiO2Yolk-eggshell structure hollow complex microsphere transmission electron microscopy
Mirror photo;
Fig. 5 is the Fe that embodiment 1 is prepared3O4@ SiO2The XRD diagram of yolk-eggshell structure hollow complex microsphere;
Fig. 6 is the Fe that embodiment 1 is prepared3O4@ SiO2The IR of yolk-eggshell structure hollow complex microsphere schemes;
Fig. 7 is the Fe that embodiment 1 is prepared3O4@ SiO2Yolk-eggshell structure hollow complex microsphere is 7.4 in pH
In PBS buffer solutions in 72h drug releasing curve diagram;
Fig. 8 is the Fe that embodiment 2 is prepared3O4@ SiO2Yolk-eggshell structure hollow complex microsphere transmission electron microscopy
Mirror photo;
Fig. 9 is the Fe that embodiment 3 is prepared3O4@ SiO2Yolk-eggshell structure hollow complex microsphere transmission electron microscopy
Mirror photo.
Specific implementation mode
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Embodiment 1
A kind of Fe3O4@SiO2The preparation method of yolk-eggshell structure hollow complex microsphere, includes the following steps:1. will
FeCl3•6H2O, urea, trisodium citrate are added to the water stirring and dissolving, and Sodium Polyacrylate is added later, is shifted after stirring evenly
Into reaction kettle, hydro-thermal reaction 3.5h under the conditions of 190 DEG C, after being cooled to room temperature, gained orange/yellow solid is washed with ethyl alcohol, then
It is washed with water, then in 60 DEG C of dryings, obtains Fe2O3Nanoparticle;2. 1. Fe that step is prepared2O3Nanoparticle presses solid-to-liquid ratio 1:
250 are distributed in the ethyl alcohol of 60vol%, and TEOS is added(Ethyl orthosilicate)Ethanol solution, be ultrasonically treated 3h at 25 DEG C, then
Ammonium hydroxide is added, stirs 3min, reacts 2h at room temperature, obtained solid is washed with ethyl alcohol, is washed with water, and then drying is at 60 DEG C
Fe is made2O3@ SiO2Complex microsphere;3. 2. Fe that step is obtained2O3@ SiO2Complex microsphere is distributed in hydrochloric acid, and stirring is anti-
After answering 8h, obtained solid to centrifuge Fe is obtained with drying at 60 DEG C after ethyl alcohol and water washing2O3@ SiO2Yolk-eggshell knot
The hollow complex microsphere of structure;4. 3. Fe that step is obtained2O3@ SiO2Yolk-eggshell structure hollow complex microsphere is in tube furnace 500
At DEG C, hydrogen and nitrogen volume ratio be 1:120min is kept under 7 gaseous mixture, is then cooled to room temperature, ethyl alcohol washing, then use water
It washes, Magneto separate, up to Fe after drying3O4@ SiO2Yolk-eggshell structure hollow complex microsphere.
Step 1. in FeCl3•6H2The mass ratio of O and urea is 5:1, FeCl3•6H2The mass ratio of O and trisodium citrate is
1:5, FeCl3•6H2The mass ratio of O and water is 1:30, the mass ratio of water and Sodium Polyacrylate is 0.75:1.
Step 2. in TEOS ethanol solution in TEOS volume fraction be 0.5%;The ethyl alcohol of 60vol% and the ethyl alcohol of TEOS
The volume ratio of solution is 3:1;The ethyl alcohol of 60vol% and the volume ratio of ammonium hydroxide are 6:1;A concentration of 10.5 mol/L of ammonium hydroxide.
The step 3. in hydrochloric acid a concentration of 6mol/L, Fe2O3@ SiO2The solid-to-liquid ratio of complex microsphere and hydrochloric acid is 1g:
300ml。
Fe prepared by embodiment 12O3The transmission electron microscope photo of nanoparticle as shown in Figure 1, it will be seen from figure 1 that
Fe2O3Nanoparticle arranged regular, size have good monodispersity in 200nm or so;What embodiment 1 was prepared
Fe2O3@ SiO2Complex microsphere transmission electron microscope photo is as shown in Fig. 2, figure it is seen that SiO2Successfully it is coated on
Fe2O3Nanoparticle surface, size is about 50nm, and coats SiO2Good monodispersity is still kept after shell;Embodiment 1
The Fe being prepared2O3@ SiO2The transmission electron microscope photo of yolk-eggshell structure hollow complex microsphere as shown in figure 3, from
Fig. 3 can be seen that Fe2O3@ SiO2Complex microsphere passes through the corrosion of 6mol/L hydrochloric acid, Fe2O3Core forms yolk-by partial corrosion
Eggshell structure hollow Fe2O3@ SiO2Complex microsphere, SiO2Its integrality is still kept after shell;What embodiment 1 was prepared
Fe3O4@ SiO2Yolk-eggshell structure hollow complex microsphere transmission electron microscope photo as shown in figure 4, from fig. 4, it can be seen that
Through tube furnace calcination processing, Fe2O3@ SiO2Yolk-eggshell structure hollow is compound to become the Fe with superparamagnetism3O4@ SiO2
Yolk-eggshell structure hollow complex microsphere, it is found that microballoon core becomes smaller after calcining, cavity becomes larger for comparison.
Medicine sustained and controlled release performance test:
(1)Drug is loaded into
With the phosphate buffer solution of pH=7.4(PBS)For solvent, by doxorubicin hydrochloride(DOX)It is dissolved in PBS, is made into one
Determine the solution of concentration(0.2mg/mL), it is denoted as DOX-PBS.Weigh Fe prepared by the embodiment 1 of 5mg3O4@ SiO2Yolk-eggshell
Structure hollow complex microsphere, is added 10mL DOX-PBS solution, and ultrasound makes it dissolve, then seals container, stirs at room temperature
For 24 hours, sample is made fully to adsorb drug.Finally by sample Magneto separate, with UV spectrophotometer measuring supernatant at 480nm
Absorbance, with the drugloading rate of minusing unit of account quality hollow microsphere, 60 DEG C of dryings of sample, Fe obtained3O4@ SiO2Egg
Huang-eggshell structure hollow complex microsphere specific surface area is 173m2/ g, drugloading rate 139mg/g.Drugloading rate QeDOX in=load
Quality/support samples quality, can be calculated by following formula:
C in formula0- drug initial concentration(mg/mL);
CeConcentration when-reaction is completed(mg/mL);
The volume of V-drug solution(mL);
M-carrier quality(g).
(2)Drug release
With the phosphate buffer solution of pH=7.4(PBS)Carry out the research that simulated body fluid carries out drug release in vitro.It will
It is loaded with the Fe of DOX drugs3O4@ SiO2Yolk-eggshell structure hollow complex microsphere is distributed in the PBS solution of 10mL, after sealing
It is put into 37 DEG C of constant temperature oscillator and slowly shakes, solution is centrifuged every 2h, until discharging 72h, with ultraviolet point
Light photometer detects absorbance of the centrifuged supernatant at 480nm, then supplements the phosphorus of 10mLpH=7.4 again in the reactor
Hydrochlorate buffer solution continues to discharge.The quality that the drug of every section of time interval release is calculated according to the standard curve demarcated, into
And the drug release rate accumulated.Calculation formula is as follows:, MtIt is the t times
The quality of doxorubicin hydrochloride released in buffer solution, M0It is Fe3O4@ SiO2Yolk-eggshell structure hollow complex microsphere
In contained doxorubicin hydrochloride quality.As shown in Figure 7, the release rate of drug reaches in 72h in the PBS buffer solutions that pH is 7.4
To 68.4%, good medicament slow release performance is shown.
Embodiment 2
A kind of Fe3O4@SiO2The preparation method of yolk-eggshell structure hollow complex microsphere, includes the following steps:1. will
FeCl3•6H2O, urea, trisodium citrate are added to the water stirring and dissolving, and Sodium Polyacrylate is added later, is shifted after stirring evenly
Into reaction kettle, hydro-thermal reaction 3h under the conditions of 170 DEG C, after being cooled to room temperature, gained orange/yellow solid is washed with ethyl alcohol, then is used
Washing, then in 55 DEG C of dryings, obtains Fe2O3Nanoparticle;2. 1. Fe that step is prepared2O3Nanoparticle presses solid-to-liquid ratio 1g:
200ml is distributed in the ethyl alcohol of 90vol%, and TEOS is added(Ethyl orthosilicate)Ethanol solution, be ultrasonically treated 4h at 20 DEG C, with
After be added ammonium hydroxide, stir 1min, react 3h at room temperature, obtained solid is washed with ethyl alcohol, is washed with water, then dry at 65 DEG C
Obtain Fe2O3@ SiO2Complex microsphere;3. 2. Fe that step is obtained2O3@ SiO2Complex microsphere is distributed in hydrochloric acid, stirring
6h is reacted, obtained solid uses ethyl alcohol and water washing, dried at 55 DEG C and obtain Fe after centrifuging2O3@ SiO2Yolk-eggshell knot
The hollow complex microsphere of structure;4. 3. Fe that step is obtained2O3@ SiO2Yolk-eggshell structure hollow complex microsphere is in tube furnace 450
At DEG C, hydrogen and nitrogen volume ratio be 1:100min is kept under 8 gaseous mixture, is then cooled to room temperature, ethyl alcohol washing, then use water
It washes, Magneto separate, up to Fe after drying3O4@ SiO2Yolk-eggshell structure hollow complex microsphere.
Step 1. in FeCl3•6H2The mass ratio of O and urea is 3:1, FeCl3•6H2The mass ratio of O and trisodium citrate is
1:2, FeCl3•6H2The mass ratio of O and water is 1:60, the mass ratio of water and Sodium Polyacrylate is 3:1.
Step 2. in TEOS ethanol solution in TEOS volume fraction be 5%;The ethyl alcohol of 90vol% and the ethyl alcohol of TEOS are molten
The volume ratio of liquid is 4:1;The ethyl alcohol of 90vol% and the volume ratio of ammonium hydroxide are 9:1;A concentration of 14.5 mol/L of ammonium hydroxide.
The step 3. in hydrochloric acid a concentration of 4mol/L, Fe2O3@ SiO2The solid-to-liquid ratio of complex microsphere and hydrochloric acid is 1g:
500ml。
Embodiment 3
A kind of Fe3O4@SiO2The preparation method of yolk-eggshell structure hollow complex microsphere, includes the following steps:1. will
FeCl3•6H2O, urea, trisodium citrate are added to the water stirring and dissolving, and Sodium Polyacrylate is added later, is shifted after stirring evenly
Into reaction kettle, hydro-thermal reaction 6h under the conditions of 200 DEG C, after being cooled to room temperature, gained orange/yellow solid is washed with ethyl alcohol, then is used
Washing, then in 65 DEG C of dryings, obtains Fe2O3Nanoparticle;2. 1. Fe that step is prepared2O3Nanoparticle presses solid-to-liquid ratio 1g:
350ml is distributed in the ethyl alcohol of 10vol%, and TEOS is added(Ethyl orthosilicate)Ethanol solution, be ultrasonically treated 2h at 30 DEG C, with
After be added ammonium hydroxide, stir 5min, react 1h at room temperature, obtained solid is washed with ethyl alcohol, is washed with water, then dry at 55 DEG C
Obtain Fe2O3@ SiO2Complex microsphere;3. 2. Fe that step is obtained2O3@ SiO2Complex microsphere is distributed in hydrochloric acid, stirring
12h is reacted, obtained solid uses ethyl alcohol and water washing, dried at 65 DEG C and obtain Fe after centrifuging2O3@ SiO2Yolk-eggshell
Structure hollow complex microsphere;4. 3. Fe that step is obtained2O3@ SiO2Yolk-eggshell structure hollow complex microsphere is in tube furnace
At 350 DEG C, hydrogen and nitrogen volume ratio be 1:60min is kept under 3 gaseous mixture, is then cooled to room temperature, ethyl alcohol washing, then use
Washing, Magneto separate, up to Fe after drying3O4@ SiO2Yolk-eggshell structure hollow complex microsphere.
Step 1. in FeCl3•6H2The mass ratio of O and urea is 1:1, FeCl3•6H2The mass ratio of O and trisodium citrate is
1:3, FeCl3•6H2The mass ratio of O and water is 1:45, the mass ratio of water and Sodium Polyacrylate is 2:1.
Step 2. in TEOS ethanol solution in TEOS volume fraction be 2.5%;The ethanol water and TEOS of 10vol%
Ethanol solution volume ratio be 5:1;The ethyl alcohol of 10vol% and the volume ratio of ammonium hydroxide are 5:1;A concentration of 6 mol/L of ammonium hydroxide.
The step 3. in hydrochloric acid a concentration of 12mol/L, Fe2O3@ SiO2The solid-to-liquid ratio of complex microsphere and hydrochloric acid is
1g:400ml。
Fig. 8 is the Fe that embodiment 2 is prepared3O4@ SiO2Yolk-eggshell structure hollow complex microsphere transmission electron microscopy
Mirror photo, Fig. 9 are the Fe that embodiment 3 is prepared3O4@ SiO2Yolk-eggshell structure hollow complex microsphere transmission electron microscopy
Mirror photo, the present invention can control the shell thickness of complex microsphere by controlling the amount of TEOS, regulate and control the concentration of hydrochloric acid, influence
Fe2O3@ SiO2The extent of corrosion of complex microsphere, to control Fe3O4@ SiO2The knot of yolk-eggshell structure hollow complex microsphere
Structure and pattern.
Claims (1)
1. a kind of Fe3O4@SiO2The preparation method of yolk-eggshell structure hollow complex microsphere, which is characterized in that including following step
Suddenly:1. by FeCl3•6H2O, urea, trisodium citrate are added to the water stirring and dissolving, and Sodium Polyacrylate is added later, and stirring is equal
It is transferred in reaction kettle after even, 3 ~ 6h of hydro-thermal reaction under the conditions of 170 ~ 200 DEG C, after being cooled to room temperature, gained orange/yellow solid
It is washed, is washed with water with ethyl alcohol, then in 55 ~ 65 DEG C of dryings, obtain Fe2O3Nanoparticle;2. 1. Fe that step is prepared2O3It receives
Meter Wei Qiu presses solid-to-liquid ratio 1g:200ml~1g:350ml is distributed in the ethyl alcohol of 10-90vol%, is added the ethanol solution of TEOS, and 20
It is ultrasonically treated 2 ~ 4h at ~ 30 DEG C, ammonium hydroxide is then added, stirs evenly, reacts 1 ~ 3h at room temperature, obtained solid is washed with ethyl alcohol,
It is washed with water, then drying obtains Fe at 55 ~ 65 DEG C2O3@ SiO2Complex microsphere;3. 2. Fe that step is obtained2O3@
SiO2Complex microsphere is distributed in hydrochloric acid, is stirred to react 6 ~ 12h, obtained solid centrifuge after with after ethyl alcohol and water washing 55 ~
Drying obtains Fe at 65 DEG C2O3@ SiO2Yolk-eggshell structure hollow complex microsphere;4. 3. Fe that step is obtained2O3@
SiO2Yolk-eggshell structure hollow complex microsphere is at 350 ~ 500 DEG C, hydrogen and nitrogen volume ratio are 1:8~1:3 gaseous mixture
60 ~ 120min of lower holding, then cools to room temperature, and ethyl alcohol washing is washed with water, Magneto separate, up to Fe after drying3O4@ SiO2
Yolk-eggshell structure hollow complex microsphere;Step 1. in FeCl3•6H2The mass ratio of O and urea is 1:1~5:1, FeCl3•6H2O
Mass ratio with trisodium citrate is 1:2~1:5, FeCl3•6H2The mass ratio of O and water is 1:60~1:30, water and Sodium Polyacrylate
Mass ratio be 0.75:1~3:1;Step 2. in TEOS ethanol solution in TEOS volume fraction be 0.5 ~ 5%;10-
The volume ratio of the ethyl alcohol of 90vol% and the ethanol solution of TEOS is 3:1~5:1;The ethyl alcohol of 10-90vol% and the volume ratio of ammonium hydroxide are
5:1~9:1;A concentration of 6 ~ 14.5 mol/L of ammonium hydroxide;The step 3. in hydrochloric acid a concentration of 4 ~ 12mol/L, Fe2O3@
SiO2The solid-to-liquid ratio of complex microsphere and hydrochloric acid is 1g:300ml~1g:500ml.
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