CN101707109B - Functional superparamagnetic nano particle with uniform particle size and preparation method thereof - Google Patents
Functional superparamagnetic nano particle with uniform particle size and preparation method thereof Download PDFInfo
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- CN101707109B CN101707109B CN2009100354927A CN200910035492A CN101707109B CN 101707109 B CN101707109 B CN 101707109B CN 2009100354927 A CN2009100354927 A CN 2009100354927A CN 200910035492 A CN200910035492 A CN 200910035492A CN 101707109 B CN101707109 B CN 101707109B
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 33
- 239000002245 particle Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 19
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 6
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 230000005291 magnetic effect Effects 0.000 claims description 137
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 40
- 238000005119 centrifugation Methods 0.000 claims description 39
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 29
- 230000005298 paramagnetic effect Effects 0.000 claims description 22
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 20
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 20
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000005642 Oleic acid Substances 0.000 claims description 20
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 20
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 20
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 20
- 238000001556 precipitation Methods 0.000 claims description 20
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 15
- 238000013019 agitation Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- QEYMMOKECZBKAC-UHFFFAOYSA-N 3-chloropropanoic acid Chemical compound OC(=O)CCCl QEYMMOKECZBKAC-UHFFFAOYSA-N 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 10
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- FXMBKAAULHJRKL-UHFFFAOYSA-N [amino(dimethoxy)silyl]oxymethane Chemical compound CO[Si](N)(OC)OC FXMBKAAULHJRKL-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 6
- 238000005649 metathesis reaction Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims description 5
- 101710141544 Allatotropin-related peptide Proteins 0.000 claims description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 5
- 229910003321 CoFe Inorganic materials 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- -1 wherein Substances 0.000 claims description 2
- CVEPFOUZABPRMK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;styrene Chemical compound CC(=C)C(O)=O.C=CC1=CC=CC=C1 CVEPFOUZABPRMK-UHFFFAOYSA-N 0.000 claims 3
- 239000002202 Polyethylene glycol Substances 0.000 claims 3
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 239000002122 magnetic nanoparticle Substances 0.000 abstract 6
- 125000003277 amino group Chemical group 0.000 abstract 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract 2
- 229910002518 CoFe2O4 Inorganic materials 0.000 abstract 1
- 206010020843 Hyperthermia Diseases 0.000 abstract 1
- 229910000708 MFe2O4 Inorganic materials 0.000 abstract 1
- 229910017163 MnFe2O4 Inorganic materials 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 230000036031 hyperthermia Effects 0.000 abstract 1
- 239000011553 magnetic fluid Substances 0.000 abstract 1
- 150000003961 organosilicon compounds Chemical class 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 12
- 238000007789 sealing Methods 0.000 description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 3
- BZPRATGFHKWAKR-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O.CC(=O)CC(C)=O BZPRATGFHKWAKR-UHFFFAOYSA-N 0.000 description 3
- 229910021332 silicide Inorganic materials 0.000 description 3
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 3
- 208000035126 Facies Diseases 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- FOPYSAYPLMEIMI-UHFFFAOYSA-N [O].C[Si] Chemical compound [O].C[Si] FOPYSAYPLMEIMI-UHFFFAOYSA-N 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
Landscapes
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
The invention discloses a functionable superparamagnetic nano particle with uniform particle size. The nano particle is provided with a superparamagnetic nano particle core, and the magnetic nano particle core is connected with a plurality of water-soluble polymer chain segments and organic chain segments containing modifiable amino terminal groups respectively; and the magnetic nano-particle core is an MFe2O4 superparamagnetic nano particle, wherein metal M is one of Fe, Co and Mn, namely the magnetic nano particle is one of Fe3O4, CoFe2O4 or MnFe2O4, the particle size of the magnetic nano particle is between 4 and 12nm, and the particle size distribution is not more than 20 percent. The synthesized material can be widely applied to targeted release of medicaments, magnetic fluid hyperthermia, biofluorescent detection and the like. The synthesized magnetic nano-particle has uniform particle size, which ensures that the nano-particle meets the demand of biological application. At the same time, the surface of the nano-particle is modified with an organosilicon compound with an amino group remained at a terminal, and the amino group can be widely combined with bio-functional substances, thereby ensuring that the synthesized magnetic nano-particle can conveniently perform the bio-functionalization.
Description
Technical field
The invention belongs to biological functional material technology field, what be specifically related to a kind of uniform particle diameter contains modifiable amino superparamagnetic nanoparticle and preparation method thereof.
Background technology
Superparamagnetic nanoparticle has special magnetic property, and its magnetic property can change along with the variation of external environment, and this makes them at aspects such as chemistry and bio-sensings wide application prospect be arranged.But traditional super paramagnetic nano particle also exists the not enough homogeneous of particle diameter as biological sensing material, is difficult to carry out biologic applications, and surface group be difficult to biological functional etc. shortcoming; The super paramagnetic nano particle of involutory one-tenth uniform particle diameter, and make it biological functional easily, become the focus of present research.
The present invention passes through the super paramagnetic nano particle of synthetic a series of uniform particle diameter, and introduces the amino end group that is easy to biological functional on its surface, with biocompatibility and the Biofunctional that improves super paramagnetic nano particle.
Summary of the invention
Technical problem: what the object of the present invention is to provide a kind of uniform particle diameter contains Biofunctional superparamagnetic nanoparticle of modifiable amino and preparation method thereof.
Technical scheme: but the super paramagnetic nano particle of uniform particle diameter functionalization of the present invention has a super paramagnetic nano particle core, and on this magnetic nanometer nuclear, connect some water soluble polymer segments respectively and contain the organic segment that can modify amino end group;
Described magnetic nanometer nuclear is MFe
2O
4Super paramagnetic nano particle, wherein, metal M is a kind of among Fe, Co, the Mn, that is, magnetic nanometer is Fe
3O
4, CoFe
2O
4Or MnFe
2O
4In a kind of, the particle diameter of magnetic nanometer is between 4-12nm, particle size distribution is not more than 20%.
The water soluble polymer segment is poly-(ethylene glycol) methacrylate macromolecular chain, and concrete structure is:
M is the degree of polymerization, and m is 5-100,
N is the zip length of polyalkylene glycol monomer, and n is 6-7,
Macromolecular chain by on the end group-COO
-Group is connected with the magnetic nanometer nuclear phase.
Contain the organic segment that can modify amino end group, its structure is
Be connected with magnetic nanometer nuclear by the Si-O-key.
The synthetic method concrete steps are as follows:
A. magnetic nanometer is synthetic:
Ferric acetyl acetonade is 1 in the benzyl ether solvent, and under the acting in conjunction of 2-16 glycol, oleic acid, oleyl amine, pyrolysis becomes monodispersed magnetic nanometer,
Concrete steps are: with ferric acetyl acetonade (III), 1; 2-16 glycol, oleic acid, oleyl amine are dissolved in the benzyl ether; in the condition magnetic agitation that constantly feeds nitrogen; under nitrogen protection, mixed solution is heated to 200 ℃ and continues 2 hours; be warmed up to then and heated again under 300 ℃ one hour; remove the thermal source cool to room temperature, add ethanol, have black precipitate to generate.Isolate black precipitate with centrifugal separation, and it is dispersed in the hexane solution that contains oleic acid and oleyl amine, the black precipitate that centrifugation goes out is magnetic nanometer, with the magnetic nanometer drying under reduced pressure, preserves down at 0-4 ℃;
B. the introducing of initator on the magnetic nanometer:
The surface that 3-chloropropionic acid initator is introduced magnetic nanometer by metathesis,
Concrete steps are: the magnetic nanometer that oleic acid is stable is dispersed in the n-hexane Ji liquid of 3-chloropropionic acid, the normal temperature magnetic agitation is 24 hours under argon shield, centrifugation obtains introducing the magnetic nanometer of initator, with three drying under reduced pressure of n-hexane washing, preserves down at 0-4 ℃;
C. water-soluble magnetic nanometer is synthetic:
With the 3-chloropropionic acid that is connected on the magnetic nanometer is initator, by the water-soluble magnetic nanometer of ATRP reaction with poly-(ethylene glycol) methacrylate polymers parcel,
Concrete steps are: the magnetic nanometer of introducing initator directly is dissolved in poly-(ethylene glycol) methacrylate monomers, logical argon gas 15 minutes adds CuCl and bipyridine, logical again argon gas 10 minutes, with the mixed solution sealing, stirred 18 hours at 30 ℃ of water-bath lower magnetic forces.With oxolane diluting reaction mixed liquor, centrifugation gained mixed liquor was removed the cupric precipitation, and residual mixed liquor is splashed in the ether, obtains the dark brown precipitation after reaction was finished.Precipitation is dissolved in the ethanol, the remaining precipitation of centrifugation, redissolve-precipitation-centrifugal process three times, vacuumize obtains water-soluble magnetic nanometer;
D. the magnetic nanometer of biological functional is synthetic:
By metathesis, will contain amino trimethoxy silicon displacement on water-soluble magnetic nanometer surface,
Concrete steps are: will contain amino trimethoxy silicon (CH
3O)
3SiCH
2CH
2NH
2) be dissolved in the ether, adding the above-mentioned magnetic nanometer that makes, the normal temperature magnetic agitation is 24 hours under the situation of logical argon gas, centrifugation gained magnetic nanometer, with ether washing three times, vacuumize, obtain the water-soluble magnetic nanometer of final biological functional.
In magnetic nanometer synthetic,, 2-16 glycol, oleic acid, when oleyl amine is dissolved in benzyl ether, then also need add manganese acetylacetonate (II) or acetylacetone cobalt (II) as the synthetic magnetic nanometer that contains manganese or cobalt of need with ferric acetyl acetonade (III), 1.
Beneficial effect: the present invention is by steps such as employing high temperature organic facies co-electrodeposition methods, synthesized the equal ultra-fine magnetic nanometer (size is less than 10nm) of size, utilize ATRP to be aggregated in poly-(ethylene glycol) methacrylate that its surface articulates biocompatibility, articulate the trimethoxy silicon that contains amino on the magnetic nanometer surface, make its can be on amino the functional fluorophor of modified biological, realize biological functional.
Synthetic this super paramagnetic nano particle diameter homogeneous, the variation of the magnetic nanometer physical property of having avoided particle diameter to differ may bringing and to the injury of organism can apply in the organism it preferably.Simultaneously, introduced the three oxygen methyl silicon that contain amino on the synthetic this super paramagnetic nano particle, amino can be used to connect the Biofunctional group that has the biomolecule of specific recognition with some, realizes the detection to specific biological molecules.In addition, the macromolecule chain section that introduce on the surface is poly-(ethylene glycol) methacrylate (PEGMA), PEGMA has well water-soluble and biocompatibility, makes this super paramagnetic nano particle have good biocompatibility, has reduced the toxicity of conjugated polymer to organism greatly.
Embodiment
Adopt steps such as high temperature organic facies co-electrodeposition method, the ultra-fine magnetic nanometer (size is less than 10nm) that has synthesized the size homogeneous, utilize ATRP to be aggregated in poly-(ethylene glycol) methacrylate that its surface articulates biocompatibility, articulate the trimethoxy silicon that contains amino on the magnetic nanometer surface, make it can on amino, modify various Biofunctional groups, realize biological functional.
Synthetic this super paramagnetic nano particle diameter is equal, and the variation of the magnetic nanometer physical property of having avoided particle diameter to differ may bringing and to the injury of organism can apply in the organism it preferably.Simultaneously, introduced the three oxygen methyl silicon that contain amino on the synthetic this super paramagnetic nano particle, amino can be used to connect the Biofunctional group that has the biomolecule of specific recognition with some, realizes the detection to specific biological molecules.In addition, the macromolecule chain section that introduce on the surface is poly-(ethylene glycol) methacrylate (PEGMA), PEGMA has well water-soluble and biocompatibility, makes this super paramagnetic nano particle have good biocompatibility, has reduced the toxicity of conjugated polymer to organism greatly.
In the structure of super paramagnetic nano particle provided by the invention,
Be MFe
2O
4Magnetic nanometer nuclear, wherein, metal M is a kind of among Fe, Co, the Mn, and the particle diameter of magnetic nanometer is between 4-12nm, and particle size distribution is not more than 20%
M is the degree of polymerization, and m is 5-100,
N is the zip length of polyalkylene glycol monomer, and n is 6-7,
Macromolecular chain by on the end group-COO
-Group is connected with the magnetic nanometer nuclear phase.
In the above-mentioned magnetic nanometer, three following examples are the typical case relatively.
(1) magnetic nanometer nuclear is Fe
3O
4, adhering to the organic silicide that gathers (ethylene glycol) methacrylate and the band amino of energy biological functional around the magnetic nanometer with biocompatibility, its architectural feature is as follows:
Perhaps, (2) magnetic nanometer nuclear is CoFe
2O
4, adhering to the organic silicide that gathers (ethylene glycol) methacrylate and the band amino of energy biological functional around the magnetic nanometer with biocompatibility, its architectural feature is as follows:
Perhaps, (3) magnetic nanometer nuclear is MnFe
2O
4, adhering to the organic silicide that gathers (ethylene glycol) methacrylate and the band amino of energy biological functional around the magnetic nanometer with biocompatibility, its architectural feature is as follows:
The synthetic method of above-claimed cpd of the present invention is as follows:
(1) magnetic nanometer is synthetic
Ferric acetyl acetonade is 1 in the benzyl ether solvent, and under the acting in conjunction of 2-16 glycol, oleic acid, oleyl amine, pyrolysis becomes monodispersed magnetic nanometer.
Concrete steps are as follows:
With ferric acetyl acetonade (III) (then also need add manganese acetylacetonate (II) or acetylacetone cobalt (II)), 1 as the synthetic magnetic nanometer that contains manganese or cobalt of need; 2-16 glycol, oleic acid, oleyl amine are dissolved in the benzyl ether; in the condition magnetic agitation that constantly feeds nitrogen; under nitrogen protection, mixed solution is heated to 200 ℃ and continues 2 hours; be warmed up to then and heated again under 300 ℃ one hour; remove the thermal source cool to room temperature, add ethanol, have black precipitate to generate.Isolate black precipitate with centrifugal separation, and it is dispersed in the hexane solution that contains oleic acid and oleyl amine, the black precipitate that centrifugation goes out is magnetic nanometer, with the magnetic nanometer drying under reduced pressure, preserves down at 0-4 ℃.
(2) introducing of initator on the magnetic nanometer
3-chloropropionic acid initator is by the table of metathesis introducing magnetic nanometer.Concrete steps are as follows:
The magnetic nanometer that oleic acid is stable is dispersed in the hexane solution of 3-chloropropionic acid, and the normal temperature magnetic agitation is 24 hours under argon shield, and centrifugation obtains introducing the magnetic nanometer of initator, with three drying under reduced pressure of n-hexane washing, preserves down at 0-4 ℃.
(3) water-soluble magnetic nanometer is synthetic
With the 3-chloropropionic acid that is connected on the magnetic nanometer is initator, by the water-soluble magnetic nanometer of ATRP reaction with poly-(ethylene glycol) methacrylate polymers parcel.Concrete steps are as follows:
The magnetic nanometer of introducing initator directly is dissolved in poly-(ethylene glycol) methacrylate monomers, and logical argon gas 15 minutes adds CuCl and bipyridine, and logical again argon gas 10 minutes with the mixed solution sealing, stirred 18 hours at 30 ℃ of water-bath lower magnetic forces.With oxolane diluting reaction mixed liquor, centrifugation gained mixed liquor was removed the cupric precipitation, and residual mixed liquor is splashed in the ether, obtains the dark brown precipitation after reaction was finished.Precipitation is dissolved in the ethanol, the remaining precipitation of centrifugation, redissolve-precipitation-centrifugal process three times, vacuumize obtains water-soluble magnetic nanometer.
(4) magnetic nanometer of biological functional is synthetic
By metathesis, will contain amino trimethoxy silicon displacement on water-soluble magnetic nanometer surface.
Concrete steps are as follows:
To contain amino trimethoxy silicon (CH
3O)
3SiCH
2CH
2NH
2) be dissolved in the ether, adding the above-mentioned magnetic nanometer that makes, the normal temperature magnetic agitation is 24 hours under the situation of logical argon gas, centrifugation gained magnetic nanometer, with ether washing three times, vacuumize, obtain the water-soluble magnetic nanometer of final biological functional.
In order to understand the present invention better, further specify technical scheme of the present invention below by specific embodiment.
Embodiment 1, Fe
3O
4As synthesizing of the super paramagnetic nano particle of biological functional of magnetic nanometer nuclear
(1) magnetic nanometer is synthetic
Concrete steps are as follows:
With ferric acetyl acetonade (III) (1.766g, 0.337mL, 5mmol), 1; 2-16 glycol (6.461g, 25mmol), oleic acid (4.237g, 4.761mL; 15mmol), (4.012g, 4.935mL 15mmol) are dissolved in the 50mL benzyl ether oleyl amine; in the condition magnetic agitation that constantly feeds nitrogen; under nitrogen protection, mixed solution is heated to 200 ℃ and continues 2 hours, be warmed up to then and heated again under 300 ℃ one hour, remove the thermal source cool to room temperature; add 100mL ethanol, have black precipitate to generate.Centrifugation is 10 minutes under 6000 rev/mins speed, centrifugation goes out black precipitate, and it is dispersed in the 40mL hexane solution that contains 1mL oleic acid and 1mL oleyl amine, centrifugation is 10 minutes under 6000 rev/mins speed, the black precipitate that centrifugation goes out is magnetic nanometer, with the magnetic nanometer drying under reduced pressure, preserve down at 0-4 ℃.
(2) introducing of initator on the magnetic nanometer
Concrete steps are as follows:
The magnetic nanometer that 100mg oleic acid is stable is dispersed in the hexane solution of 3-chloropropionic acid of 100mL0.25mol/L; the normal temperature magnetic agitation is 24 hours under argon shield; centrifugation is 4 minutes under 6000 rev/mins the speed; centrifugation obtains introducing the magnetic nanometer of initator; with three drying under reduced pressure of n-hexane washing, preserve down at 0-4 ℃.
(3) water-soluble magnetic nanometer is synthetic
The magnetic nanometer of 60.0mg being introduced initator directly is dissolved in poly-(ethylene glycol) methacrylate monomers of 6mL, obtain a transparent brown solution, logical argon gas 15 minutes, add 5.1mgCuCl and 24mg bipyridine, logical again argon gas 10 minutes, with the mixed solution sealing, stirred 18 hours at 30 ℃ of water-bath lower magnetic forces.With 1: 5 ratio oxolane diluting reaction mixed liquor, 4 minutes centrifugation gained of centrifugation mixed liquor under 4000 rev/mins speed was removed the cupric precipitation, and residual mixed liquor is splashed in the 200mL ether, obtains the dark brown precipitation after reaction was finished.Precipitation is dissolved in the ethanol, 4 minutes remaining precipitations of centrifugation of centrifugation under 2000 rev/mins speed, redissolve-precipitation-centrifugal process three times, vacuumize obtains water-soluble magnetic nanometer.
(4) magnetic nanometer of biological functional is synthetic
2g is contained amino trimethoxy silicon (CH
3O)
3SiCH
2CH
2NH
2) be dissolved in the 50mL ether, add the above-mentioned magnetic nanometer that makes of 30mg, the normal temperature magnetic agitation is 24 hours under the situation of logical argon gas, 4 minutes centrifugation gained of centrifugation magnetic nanometer under 4000 rev/mins speed, with ether washing three times, vacuumize obtains the water-soluble magnetic nanometer of final biological functional.
Embodiment 2, CoFe
2O
4As synthesizing of the super paramagnetic nano particle of biological functional of magnetic nanometer nuclear
(1) magnetic nanometer is synthetic
Concrete steps are as follows:
With ferric acetyl acetonade (III) (1.413g; 4mmol), acetylacetone cobalt (II) (0.5503g; 2mmol), 1; 2-16 glycol (7.753g; 30mmol), oleic acid (5.084g; 5.713mL; 18mmol), (4.814g, 5.922mL 18mmol) are dissolved in the 60mL benzyl ether oleyl amine; in the condition magnetic agitation that constantly feeds nitrogen; under nitrogen protection, mixed solution is heated to 200 ℃ and continues 2 hours, be warmed up to then and heated again under 300 ℃ one hour, remove the thermal source cool to room temperature; add 100mL ethanol, have black precipitate to generate.Centrifugation is 10 minutes under 6000 rev/mins speed, centrifugation goes out black precipitate, and it is dispersed in the 40mL hexane solution that contains 1mL oleic acid and 1mL oleyl amine, centrifugation is 10 minutes under 6000 rev/mins speed, the black precipitate that centrifugation goes out is magnetic nanometer, with the magnetic nanometer drying under reduced pressure, preserve down at 0-4 ℃.
(2) introducing of initator on the magnetic nanometer
Concrete steps are as follows:
The magnetic nanometer that 100mg oleic acid is stable is dispersed in the hexane solution of 3-chloropropionic acid of 100mL0.25mol/L; the normal temperature magnetic agitation is 24 hours under argon shield; centrifugation is 4 minutes under 6000 rev/mins the speed; centrifugation obtains introducing the magnetic nanometer of initator; with three drying under reduced pressure of n-hexane washing, preserve down at 0-4 ℃.
(3) water-soluble magnetic nanometer is synthetic
The magnetic nanometer of 60.0mg being introduced initator directly is dissolved in poly-(ethylene glycol) methacrylate monomers of 6mL, obtain a transparent brown solution, logical argon gas 15 minutes, add 5.1mgCuCl and 24mg bipyridine, logical again argon gas 10 minutes, with the mixed solution sealing, stirred 18 hours at 30 ℃ of water-bath lower magnetic forces.With 1: 5 ratio oxolane diluting reaction mixed liquor, 4 minutes centrifugation gained of centrifugation mixed liquor under 4000 rev/mins speed was removed the cupric precipitation, and residual mixed liquor is splashed in the 200mL ether, obtains the dark brown precipitation after reaction was finished.Precipitation is dissolved in the ethanol, 4 minutes remaining precipitations of centrifugation of centrifugation under 2000 rev/mins speed, redissolve-precipitation-centrifugal process three times, vacuumize obtains water-soluble magnetic nanometer.
(4) magnetic nanometer of biological functional is synthetic
2g is contained amino trimethoxy silicon (CH
3O)
3SiCH
2CH
2NH
2) be dissolved in the 50mL ether, add the above-mentioned magnetic nanometer that makes of 30mg, the normal temperature magnetic agitation is 24 hours under the situation of logical argon gas, 4 minutes centrifugation gained of centrifugation magnetic nanometer under 4000 rev/mins speed, with ether washing three times, vacuumize obtains the water-soluble magnetic nanometer of final biological functional.
Claims (3)
1. but the super paramagnetic nano particle of a uniform particle diameter functionalization, it is characterized in that this nano particle has a super paramagnetic nano particle core, and on this magnetic nanometer nuclear, connect some water soluble polymer segments respectively and contain the organic segment that to modify amino end group;
Described magnetic nanometer nuclear is MFe
2O
4Super paramagnetic nano particle, wherein, metal M is a kind of among Fe, Co, the Mn, that is, magnetic nanometer is Fe
3O
4, CoFe
2O
4Or MnFe
2O
4In a kind of, the particle diameter of magnetic nanometer is between 4-12nm, particle size distribution is not more than 20%;
The water soluble polymer segment is the polyethylene glycol methacrylate-styrene polymer macromolecular chain, and concrete structure is:
M is the degree of polymerization, and m is 5-100,
N is the zip length of polyalkylene glycol monomer, and n is 6-7,
Macromolecular chain by on the end group-COO
-Group is connected with the magnetic nanometer nuclear phase;
Contain the organic segment that can modify amino end group, its structure is
Be connected with magnetic nanometer nuclear by the Si-O-key.
2. but the preparation method of the super paramagnetic nano particle of a uniform particle diameter functionalization as claimed in claim 1 is characterized in that concrete steps are as follows:
A. magnetic nanometer is synthetic:
Ferric acetyl acetonade is 1 in the benzyl ether solvent, and under the acting in conjunction of 2-16 glycol, oleic acid, oleyl amine, pyrolysis becomes monodispersed magnetic nanometer,
Concrete steps are: with ferric acetyl acetonade, 1,2-16 glycol, oleic acid, oleyl amine is dissolved in the benzyl ether, in the condition magnetic agitation that constantly feeds nitrogen, under nitrogen protection, mixed solution is heated to 200 ℃ and continues 2 hours, be warmed up to then and heated again under 300 ℃ one hour, remove the thermal source cool to room temperature, add ethanol, there is black precipitate to generate, isolate black precipitate with centrifugal separation, and it is dispersed in the hexane solution that contains oleic acid and oleyl amine, the black precipitate that centrifugation goes out is magnetic nanometer, with the magnetic nanometer drying under reduced pressure, preserve down at 0-4 ℃;
B. the introducing of initator on the magnetic nanometer:
The surface that 3-chloropropionic acid initator is introduced magnetic nanometer by metathesis,
Concrete steps are: the magnetic nanometer that oleic acid is stable is dispersed in the hexane solution of 3-chloropropionic acid, the normal temperature magnetic agitation is 24 hours under argon shield, centrifugation obtains introducing the magnetic nanometer of initator, with three drying under reduced pressure of n-hexane washing, preserves down at 0-4 ℃;
C. water-soluble magnetic nanometer is synthetic:
With the 3-chloropropionic acid that is connected on the magnetic nanometer is initator, by the water-soluble magnetic nanometer of ATRP reaction with polyethylene glycol methacrylate-styrene polymer polymer parcel,
Concrete steps are: the magnetic nanometer of introducing initator directly is dissolved in the polyethylene glycol methacrylate-styrene polymer monomer, logical argon gas 15 minutes, add CuCl and bipyridine, logical again argon gas 10 minutes, mixed solution is sealed, stirred 18 hours at 30 ℃ of water-bath lower magnetic forces, use oxolane diluting reaction mixed liquor after reaction is finished, centrifugation gained mixed liquor, removal cupric precipitation, residual mixed liquor is splashed in the ether, obtain the dark brown precipitation, precipitation is dissolved in the ethanol, the remaining precipitation of centrifugation, redissolve-precipitation-centrifugal process three times, vacuumize obtains water-soluble magnetic nanometer;
D. the magnetic nanometer of biological functional is synthetic:
By metathesis, will contain amino trimethoxy silicon displacement on water-soluble magnetic nanometer surface,
Concrete steps are: will contain amino trimethoxy silicon (CH
3O)
3SiCH
2CH
2NH
2Be dissolved in the ether, add the above-mentioned magnetic nanometer that makes, the normal temperature magnetic agitation is 24 hours under the situation of logical argon gas, centrifugation gained magnetic nanometer, with ether washing three times, vacuumize, obtain the water-soluble magnetic nanometer of final biological functional.
3. but the preparation method of the super paramagnetic nano particle of uniform particle diameter functionalization as claimed in claim 2, it is characterized in that in magnetic nanometer synthetic, with ferric acetyl acetonade, 1,2-16 glycol, oleic acid, when oleyl amine is dissolved in benzyl ether, then also need add manganese acetylacetonate or acetylacetone cobalt as the synthetic magnetic nanometer that contains manganese or cobalt of need.
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