CN107344731B - A kind of preparation method of the water-soluble Superparamagnetic Fe3O4 nanoparticles of single layer cladding - Google Patents
A kind of preparation method of the water-soluble Superparamagnetic Fe3O4 nanoparticles of single layer cladding Download PDFInfo
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 74
- 239000002356 single layer Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000005253 cladding Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 229920000669 heparin Polymers 0.000 claims description 40
- 229960002897 heparin Drugs 0.000 claims description 37
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 27
- -1 acyl heparin Chemical compound 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- HTTJABKRGRZYRN-UHFFFAOYSA-N Heparin Chemical compound OC1C(NC(=O)C)C(O)OC(COS(O)(=O)=O)C1OC1C(OS(O)(=O)=O)C(O)C(OC2C(C(OS(O)(=O)=O)C(OC3C(C(O)C(O)C(O3)C(O)=O)OS(O)(=O)=O)C(CO)O2)NS(O)(=O)=O)C(C(O)=O)O1 HTTJABKRGRZYRN-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000005336 cracking Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 229940014800 succinic anhydride Drugs 0.000 claims description 4
- IOTJBUQFEOYFNG-UHFFFAOYSA-N O(C1=CC=CC=C1)C1=CC=CC=C1.[N] Chemical compound O(C1=CC=CC=C1)C1=CC=CC=C1.[N] IOTJBUQFEOYFNG-UHFFFAOYSA-N 0.000 claims description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- ZFGMDIBRIDKWMY-PASTXAENSA-N heparin Chemical compound CC(O)=N[C@@H]1[C@@H](O)[C@H](O)[C@@H](COS(O)(=O)=O)O[C@@H]1O[C@@H]1[C@@H](C(O)=O)O[C@@H](O[C@H]2[C@@H]([C@@H](OS(O)(=O)=O)[C@@H](O[C@@H]3[C@@H](OC(O)[C@H](OS(O)(=O)=O)[C@H]3O)C(O)=O)O[C@@H]2O)CS(O)(=O)=O)[C@H](O)[C@H]1O ZFGMDIBRIDKWMY-PASTXAENSA-N 0.000 claims description 3
- 229960001008 heparin sodium Drugs 0.000 claims description 3
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 239000002086 nanomaterial Substances 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 3
- 239000002122 magnetic nanoparticle Substances 0.000 abstract description 3
- 238000002595 magnetic resonance imaging Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
- 239000003181 biological factor Substances 0.000 abstract 1
- 238000000015 thermotherapy Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003146 anticoagulant agent Substances 0.000 description 2
- 229940127219 anticoagulant drug Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000003102 growth factor Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RNFZFHUPJYZJBA-UHFFFAOYSA-N n,n-dimethylpurin-4-amine Chemical compound C1=NC=NC2(N(C)C)C1=NC=N2 RNFZFHUPJYZJBA-UHFFFAOYSA-N 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- ACTRVOBWPAIOHC-UHFFFAOYSA-N succimer Chemical group OC(=O)C(S)C(S)C(O)=O ACTRVOBWPAIOHC-UHFFFAOYSA-N 0.000 description 2
- RCMPDPZUFZOHKM-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;sulfuric acid Chemical compound OS(O)(=O)=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O RCMPDPZUFZOHKM-BTVCFUMJSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000010100 anticoagulation Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000004663 cell proliferation Effects 0.000 description 1
- 230000004700 cellular uptake Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 229940014144 folate Drugs 0.000 description 1
- 239000011724 folic acid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000002069 magnetite nanoparticle Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- MGXQNMLHMKAXJR-FSPDDVFZSA-N sulfuric acid (2S,3R,4R,5S)-2,3,4,5-tetrahydroxy-6-oxohexanoic acid Chemical compound S(O)(O)(=O)=O.O=C[C@@H](O)[C@H](O)[C@@H](O)[C@H](O)C(=O)O MGXQNMLHMKAXJR-FSPDDVFZSA-N 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000010415 tropism Effects 0.000 description 1
- 230000010148 water-pollination Effects 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]
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/0018—Diamagnetic or paramagnetic materials, i.e. materials with low susceptibility and no hysteresis
-
- 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)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a kind of preparation methods of the water-soluble Superparamagnetic Fe3O4 nanoparticles of single layer cladding, belong to nano material and technical field of bioengineering.This method uses high temperature thermal decomposition method to synthesize Superparamagnetic Fe3O4 nanoparticles first, and oil-soluble nano particles are surface modified with the multiple tooth polymer with a large amount of carboxyls, preparation water outlet only increases the water-soluble ferroferric oxide nano particle of 1-2nm with kinetics radius.Magnetic nano-particle pattern after modification is uniform, good dispersion, and has good biocompatibility.The present invention has many advantages, such as that operation is simple, reproducible, the water-soluble Superparamagnetic Fe3O4 nanoparticles prepared has preferable contrasting effects, and the specific groups on its surface can lay a good foundation easily in conjunction with antibody or the other biological factor for its application in fields of biomedicine such as magnetic resonance imaging, the transport of drug magnetic targeted, magnetic thermotherapy and Magneto separates.
Description
Technical field
The invention belongs to nano materials and technical field of bioengineering, and in particular to a kind of water solubility of single layer cladding is super suitable
The preparation method of magnetic ferroferric oxide nano-particles, belongs to field of biomedicine.
Background technique
Nanotechnology refer in nanometer range study substance structure and its changing rule, and be applied to production and living it
In technology.Nanoparticle is also ultramicro powder, generally refers to particle of the size between 1-100nm, be in cluster and
The transitional region that macro object has a common boundary, from the usual micro and macro perspectives, such system was both atypical micro-
Sight system also atypical macrosystem is a kind of typical Mesoscopic structure.Nano material is in from single atom to block materials
Transition region, thus cause its Electronic Structure and crystal structure variation so that its have difference bulk it is special
Effect, such as small-size effect, quantum size effect, skin effect and macro quanta tunnel effect nano effect, so that they
Magnetic, light, electricity, in terms of show the notable feature that conventional material do not have, thus magnetic material, electronic material,
Wide application prospect is presented in many fields such as optical material, the sintering of high compactedness material, catalysis, sensing, ceramic toughening.
In recent years, magnetic Nano material due to its special physical and chemical performance magnetic resonance imaging (MRI), magnetic fluid,
The application aspects such as catalysis and bioengineering/biological medicine obtain the extensive concern of researcher.Ferroso-ferric oxide (Fe3O4) nanometer
Particle is to develop a kind of novel nano-material in recent years, due to its unique magnetism characteristic: superparamagnetism and high-coercive force, simultaneously
Because it has the characteristics that small-size effect, good magnetic conductance tropism, hypotoxicity and good biocompatibility, it is widely used in
The fields of biomedicine such as MRI and drug targeting, and show huge potentiality.Currently, the synthesis of magnetic ferric oxide nano particles
There are many kinds of methods, is generally divided into and reduces size method (ball-milling method), liquid-phase precipitation method, high temperature pyrolytic cracking (HTP), microbial method (magnetotactic bacterium
Culture) etc..Fe3O4Particle size, crystal form and the magnetic saturation intensity of nanoparticle have been applied to direct or indirect influence,
Thus prepare have component is uniform, pattern is uniform, narrow size distribution and it is controllable the features such as high performance magnetic nano material
It is its premise in biological and medical field application, this makes Fe3O4The synthesis of nanoparticle is of great significance with modification.Phase
For other Fe3O4Nanoparticle preparation method, the magnetic nano-particle that high temperature pyrolytic cracking (HTP) is prepared is preferable with crystal form, divides
The feature that property is good, particle diameter distribution is uniform is dissipated, but its water solubility is poor, to limit its answering in fields such as biomedicines
With.Ideal functional magnetic nano particle in order to obtain is surface modified the nano particle of synthesis modified to improve it
Dispersion stabilization in aqueous solution just seems very necessary.In recent years, many research workers attempt with different methods
To Fe3O4Nanoparticle is modified, to improve water solubility, dispersibility, stability and the biocompatibility of nanoparticle, such as
Prakash et al. is with fatty acid to oil-soluble Fe3O4Nanoparticle is modified, during forming bilayer nanocrystal,
The carbochain end of fatty acid is towards Fe3O4The original oiliness chain of nanoparticle surface, and its water-wet side is finally being received towards aqueous solution
Rice corpuscles surface forms second layer coat, while the nanoparticle after modification has good water dispersible.Xu et al. band
There is dimercaptosuccinic acid bifunctional (DMSA) to oil-soluble Fe3O4The oleic acid of nanoparticle surface carries out ligand exchange, makes to receive
Rice corpuscles is water phase by oily inversion of phases.
As a kind of natural bioactive polysaccharide compound, heparin is to obtain Food and Drug Adminstration of the US (FDA) to recognize
One of most effective, the most popular anticoagulation medicine of card.Heparin (Heparin) was purified and names first in nineteen thirty-five,
The same year is applied to treatment thrombotic diseases as anti-coagulants, mainly by sulfuric acid-D-Glucose amine, sulfuric acid-D- iduronic acid
It is alternately formed by connecting with two kinds of dissacharide units in D-Glucose aldehydic acid, is the mixture that molecular weight is 4~40kDa.In addition to anticoagulant
Blood acts on, and can also promote growth factor cell proliferation, group containing the site in conjunction with a variety of growth factors in heparin molecule
It knits or organ reparation and regenerated effect.Therefore, in recent years, heparin functionalization biomaterial receives great attention.
Since binding ability of the carboxyl to ferric oxide nano particles surface is stronger, in order to which heparin is preferably coated on nanometer
Particle surface, the invention are first esterified heparin with succinic anhydride to increase the carboxyl in heparin structure, then by the amber
Amber acyl heparin is to oil-soluble Fe3O4Nanoparticle is modified, to improve water solubility, dispersibility, stability and the life of nanoparticle
Object compatibility.
Summary of the invention:
The water-soluble superparamagnetic iron oxide that the technical issues of present invention intends to solve is to provide a kind of single layer cladding is received
The preparation method of rice corpuscles synthesizes Superparamagnetic Fe3O4 nanoparticles using high temperature thermal decomposition method first, and big with band
The multiple tooth polymer of amount carboxyl is surface modified obtained oil-soluble ferriferrous oxide nano-particle, prepares and has in water
There is the Superparamagnetic Fe3O4 nanoparticles of good dispersion.The succinyl heparin that product of the present invention uses has preferable
The excellent properties such as hydrophily and biocompatibility can influence in lesser situation on nano particle diameter,
Effectively improve water solubility, dispersibility, stability and the biocompatibility of ferriferrous oxide nano-particle.
Product of the present invention is prepared by following steps:
1. high temperature pyrolytic cracking (HTP) prepares ferriferrous oxide nano-particle reference literature [Sun, Shouheng, and Hao
Zeng.″Size-controlled synthesis of magnetite nanoparticles.″Journal of the
American Chemical Society 124.28 (2002): 8204-8205.].
2. the preparation of succinyl heparin: reference literature [Wang, Ying, et al. " Target-specific cellular
uptake of taxol-loased heparin-PEG-folate nanoparticles.″Biomacromolecules
11.12 (2010): 3531-3538.].
3. the preparation of the water-soluble Superparamagnetic Fe3O4 nanoparticles of single layer cladding: by 1mg-100mg (1) step
Resulting Superparamagnetic Fe3O4 nanoparticles is dissolved in the dry solvent chloroform of 10mL-500mL, and by 1mg-
The tributyl ammonium salt of the resulting succinyl heparin of 500mg (2) step is added in reaction solution, after stirring 48h-96h at room temperature, is used
Magnet separation, obtained black solid is washed 1-5 times respectively with appropriate hexane and methylene chloride, finally, by the single layer packet of formation
The water-soluble Superparamagnetic Fe3O4 nanoparticles covered is held in deionized water, for use.
The mass ratio of the tributyl ammonium salt of Superparamagnetic Fe3O4 nanoparticles and succinyl heparin in the step 3
It is 1: 0.1-1: 100.
The concentration of Superparamagnetic Fe3O4 nanoparticles is 0.01mg/mL~10mg/mL in the step 3.
The molecular weight of the tributyl ammonium salt of succinyl heparin is 2000~20000 in the step 3.
The tributyl ammonium salt of succinyl heparin is dissolvable in water in non-polar organic solvent-chloroform in the step 3, and
Good stable state is presented.
The concentration of the tributyl ammonium salt of succinyl heparin is 0.01mg/mL~10mg/mL in the step 3.
(1) high temperature pyrolytic cracking (HTP) prepares oil-soluble Superparamagnetic Fe3O4 nanoparticles: by 0.1g-5.0g acetylacetone,2,4-pentanedione
It is mixed evenly under iron, 0.1g-5.0g oleic acid, 0.1g-5.0g oleyl amine and 5mL-50mL diphenyl ether nitrogen protection, and gradually rises
Temperature is to 100 DEG C -300 DEG C, after reacting 0.5h-3h, generates partial size and is one Superparamagnetic Fe3O4 nanoparticles, and use this
Method prepares partial size by seed of the ferriferrous oxide nano-particle of small particle as the superparamagnetic iron oxide of 6nm-20nm
Nanoparticle；
(2) preparation of succinyl heparin: the heparin sodium of 0.1g-1.0g is dissolved in 10mL-20mL water, and the solution is seeped
The gel column acidified by 50mL-200mL thoroughly, is adjusted to 6.0-7.0 for the pH of solution with tri-n-butylamine solution later, by the solution
Freeze-drying, obtains the tributyl ammonium salt of 0.1g-2.0g heparin.The tributyl ammonium salt of 0.1g-2.0g heparin is dissolved in 5mL-
In the drying solvent n,N dimethylformamide (DMF) of 40mL, under protecting under a nitrogen, by 0.1g-5.0g succinic anhydride, 0.1g-
5.0g triethylamine and 0.01g-5.0g 4- dimethylaminopurine (DMAP) sequentially add reaction solution, and reaction carries out at room temperature
For 24 hours after -72h, excessive solvent is evaporated, after the dilution of suitable deionized water, which is penetrated through into 50mL-
The pH of solution is adjusted to 6.0-7.0 with tri-n-butylamine solution later, which is freeze-dried, is obtained by 200mL acidified gel column
To the tributyl ammonium salt of 0.1g-5.0g succinyl heparin；
(3) preparation of the water-soluble Superparamagnetic Fe3O4 nanoparticles of single layer cladding: by 1mg-100mg (1) step
Rapid resulting Superparamagnetic Fe3O4 nanoparticles is dissolved in the dry solvent chloroform of 10mL-500mL, and by 1mg-
The tributyl ammonium salt of the resulting succinyl heparin of 500mg (2) step is added in reaction solution, after stirring 48h-96h at room temperature, is used
Magnet separation, obtained black solid is washed 1-5 times respectively with appropriate hexane and methylene chloride, finally, by the single layer packet of formation
The water-soluble Superparamagnetic Fe3O4 nanoparticles covered is held in deionized water, for use.
Specific embodiment
Embodiment 1:
(1) high temperature pyrolytic cracking (HTP) prepares oil-soluble Superparamagnetic Fe3O4 nanoparticles: by 0.706g ferric acetyl acetonade,
It is mixed evenly under 0.565g oleic acid, 0.535g oleyl amine and 20mL diphenyl ether nitrogen protection, and is gradually heated to 265 DEG C, instead
After answering 1h, the 4nm Superparamagnetic Fe3O4 nanoparticles that partial size is one is generated, and with the method, with four oxygen of small particle
Changing three Fe nanometer particles is that seed prepares the Superparamagnetic Fe3O4 nanoparticles that partial size is 12nm；
(2) preparation of succinyl heparin: the heparin sodium of 1.0g is dissolved in 5mL water, and the solution is penetrated through 200mL
The pH of solution is adjusted to 7.0 with tri-n-butylamine solution later, which is freeze-dried, obtains 1.5g liver by acidified gel column
The tributyl ammonium salt of element.The tributyl ammonium salt of 1.5g heparin is dissolved in the drying solvent n,N dimethylformamide (DMF) of 30mL
In, under protecting under a nitrogen, by 5.0g succinic anhydride, 0.5g triethylamine and 1.0g 4- dimethylaminopurine (DMAP) are successively
Reaction solution is added to evaporate excessive solvent after reaction carries out 48h at room temperature, it, will after the dilution of suitable deionized water
The solution penetrates through the acidified gel column of 200mL, and the pH of solution is adjusted to 7.0 with tri-n-butylamine solution later, by the solution
Freeze-drying, obtains the tributyl ammonium salt of 2.0g succinyl heparin；
(3) preparation of the water-soluble Superparamagnetic Fe3O4 nanoparticles of single layer cladding: will be obtained by 10mg (1) step
Superparamagnetic Fe3O4 nanoparticles be dissolved in the dry solvent chloroform of 50mL, and it is 50mg (2) step is resulting
The tributyl ammonium salt of succinyl heparin is added in reaction solution, after stirring 48h at room temperature, is separated with magnet, and obtained black is solid
Body is washed 2 times respectively with appropriate hexane and methylene chloride, finally, four oxygen of water-soluble superparamagnetism that the single layer of formation is coated
Change three Fe nanometer particles to be held in deionized water, for use.
Embodiment 2:
(1) with embodiment 1；
(2) with embodiment 1；
(3) preparation of the water-soluble Superparamagnetic Fe3O4 nanoparticles of single layer cladding: will be obtained by 20mg (1) step
Superparamagnetic Fe3O4 nanoparticles be dissolved in the dry solvent chloroform of 50mL, and it is 50mg (2) step is resulting
The tributyl ammonium salt of succinyl heparin is added in reaction solution, after stirring 72h at room temperature, is separated with magnet, and obtained black is solid
Body is washed 2 times respectively with appropriate hexane and methylene chloride, finally, four oxygen of water-soluble superparamagnetism that the single layer of formation is coated
Change three Fe nanometer particles to be held in deionized water, for use.
Embodiment 3:
(1) high temperature pyrolytic cracking (HTP) prepares oil-soluble Superparamagnetic Fe3O4 nanoparticles: by 0.706g ferric acetyl acetonade,
0.565g oleic acid is mixed evenly under bis- Bian ether nitrogen protection of 0.535g oleyl amine and 20mL, and is gradually heated to 300 DEG C, instead
After answering 3h, the 6nm Superparamagnetic Fe3O4 nanoparticles that partial size is one is generated, and with the method, with four oxygen of small particle
Changing three Fe nanometer particles is that seed prepares the Superparamagnetic Fe3O4 nanoparticles that partial size is 14nm；
(2) with embodiment 1；
(3) preparation of the water-soluble Superparamagnetic Fe3O4 nanoparticles of single layer cladding: will be obtained by 30mg (1) step
Superparamagnetic Fe3O4 nanoparticles be dissolved in the dry solvent chloroform of 40mL, and it is 40mg (2) step is resulting
The tributyl ammonium salt of succinyl heparin is added in reaction solution, after stirring 72h at room temperature, is separated with magnet, and obtained black is solid
Body is washed 3 times respectively with appropriate hexane and methylene chloride, finally, four oxygen of water-soluble superparamagnetism that the single layer of formation is coated
Change three Fe nanometer particles to be held in deionized water, for use.
The water-soluble Superparamagnetic Fe3O4 nanoparticles prepared in example 3 carries out dynamic light scattering test, as a result
The thickness for showing multiple tooth polymer coating is only 2nm, and the water solubility Superparamagnetic Fe3O4 nanoparticles is in water
Dispersion stabilization is up to 6 months.
Claims (8)
1. a kind of water-soluble Superparamagnetic Fe3O4 nanoparticles of single layer cladding, it is characterised in that high temperature pyrolytic cracking (HTP) synthesis
Superparamagnetic Fe3O4 nanoparticles surface is coated with the multiple tooth polymer of 1.5nm-2nm, and the multiple tooth polymer is amber
Amber acyl heparin.
2. a kind of water-soluble Superparamagnetic Fe3O4 nanoparticles of single layer cladding, it is characterised in that this method includes following
Step:
(1) high temperature pyrolytic cracking (HTP) prepares oil-soluble Superparamagnetic Fe3O4 nanoparticles: by 0.1g-5.0g ferric acetyl acetonade,
It is mixed evenly, and is gradually warmed up under 0.1g-5.0g oleic acid, 0.1g-5.0g oleyl amine and 5mL-50mL diphenyl ether nitrogen protection
To 100 DEG C -300 DEG C, after reacting 0.5h-3h, the Superparamagnetic Fe3O4 nanoparticles that partial size is one is generated, and with this side
Method prepares partial size by seed of the ferriferrous oxide nano-particle of small particle and receives for the superparamagnetic iron oxide of 6nm-20nm
Rice corpuscles；
(2) preparation of succinyl heparin: the heparin sodium of 0.1g-1.0g is dissolved in 10mL-20mL water, and the solution is permeated and is led to
The acidified gel column of 50mL-200mL is crossed, the pH of solution is adjusted to 6.0-7.0 with tri-n-butylamine solution later, which is freezed
It is dry, obtain 0.1g-2.0g heparin tributyl ammonium salt.The tributyl ammonium salt of 0.1g-2.0g heparin is dissolved in 5mL-40mL's
In dry solvent n,N dimethylformamide (DMF), under protecting under a nitrogen, by 0.1g-5.0g succinic anhydride, 0.1g-5.0g tri-
Ethamine and 0.01g-5.0g4- dimethylaminopurine (DMAP) sequentially add reaction solution, and reaction carries out -72h for 24 hours at room temperature
Afterwards, excessive solvent is evaporated, after the dilution of suitable deionized water, it is acidified which is penetrated through into 50mL-200mL
Gel column, the pH of solution is adjusted to 6.0-7.0 with tri-n-butylamine solution later, which is freeze-dried, 0.1g-5.0g is obtained
The tributyl ammonium salt of succinyl heparin；
(3) preparation of the water-soluble Superparamagnetic Fe3O4 nanoparticles of single layer cladding: by 1mg-100mg step (1) institute
Superparamagnetic Fe3O4 nanoparticles be dissolved in the dry solvent chloroform of 10mL-500mL, and by 1mg-500mg
The tributyl ammonium salt of the resulting succinyl heparin of step (2) is added in reaction solution, after stirring 48h-96h at room temperature, uses magnet
Separation, obtained black solid are washed 1-5 times respectively with appropriate hexane and methylene chloride, finally, the single layer of formation is coated
Water-soluble Superparamagnetic Fe3O4 nanoparticles is held in deionized water, for use.
3. the preparation method of the water-soluble Superparamagnetic Fe3O4 nanoparticles of single layer cladding as claimed in claim 2,
It is organic molten to be characterized in that the Superparamagnetic Fe3O4 nanoparticles being prepared in the step (1) is dissolvable in water nonpolarity
In agent-chloroform, and good stable state is presented.
4. the preparation method of the water-soluble Superparamagnetic Fe3O4 nanoparticles of single layer cladding as claimed in claim 2,
The molecular weight for being characterized in that the tributyl ammonium salt for the succinyl heparin being prepared in the step (2) is 2000~20000.
5. the preparation method of the water-soluble Superparamagnetic Fe3O4 nanoparticles of single layer cladding as claimed in claim 2,
It is characterized in that the tributyl ammonium salt for the succinyl heparin being prepared in the step (2) is dissolvable in water non-polar organic solvent-
In chloroform, and good stable state is presented.
6. the preparation method of the water-soluble Superparamagnetic Fe3O4 nanoparticles of single layer cladding as claimed in claim 2,
It is characterized in that the quality of the tributyl ammonium salt of Superparamagnetic Fe3O4 nanoparticles and succinyl heparin in the step (3)
Than being 1: 0.1-1: 100.
7. the preparation method of the water-soluble Superparamagnetic Fe3O4 nanoparticles of single layer cladding as claimed in claim 2,
The concentration for being characterized in that Superparamagnetic Fe3O4 nanoparticles in the step (3) is 0.01mg/mL~10mg/mL.
8. the preparation method of the water-soluble Superparamagnetic Fe3O4 nanoparticles of single layer cladding as claimed in claim 2,
The concentration for being characterized in that the tributyl ammonium salt of succinyl heparin in the step (3) is 0.01mg/mL~10mg/mL.
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