CN105936820B - A kind of water-soluble biological compatibility fluorescence magnetic nanocluster and preparation method thereof - Google Patents
A kind of water-soluble biological compatibility fluorescence magnetic nanocluster and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of water-soluble biological compatibility fluorescence magnetic nanoclusters and preparation method thereof.Metal precursor and biocompatibility macromolecule are dissolved in higher boiling nonpolarity or weak polar solvent by the present invention, through high-temperature decomposition while forming magnetic Nano cluster, in the surface in situ modified biological compatible polymer of nanocluster, prepare various sizes of water-soluble biological compatibility magnetic Nano cluster, the functional groups such as the carboxyl using nanocluster surface institute band couple fluorescent molecule, obtain fluorescence magnetic dual-functional nanometer cluster.Simple, easy to operate, cost of material the is low feature of present invention process, gained water-soluble biological compatibility magnetic Nano cluster size is adjustable, magnetic response is strong, good biocompatibility, the material that can be used as portable biometric sensor or the sensor in relation to environment may also used as the fields of biomedicine such as magnetic resonance imaging, fluorescence imaging, cell screening.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, in particular to a kind of water-soluble biological compatibility fluorescence/magnetism
Nanocluster and preparation method thereof.
Background technique
The Strange properties different from conventional material that magnetic Nano material is shown in physics, chemical property, in biology
As magnetic resonance imaging, medical diagnosis on disease, magnetic heat cure etc. illustrate wide application prospect in terms of medicine.Especially, high
Magnetic responsiveness magnetic material can be applied to high efficiency cell separation, drug passes since it is to the quick responding ability of external magnetic field
Defeated and magnetic heat cure.However, partial size is generally less than 30 nanometers, due to specific surface area in order to guarantee that material has superparamagnetism
Greatly, magnetic intensity is easy to be influenced by surface state and structure and reduce, these all seriously limit it and lead in biomedicine
Practical application in domain also results in particle from superparamagnetism to ferromagnetism although increasing partial size can be enhanced magnetic moment simultaneously
Transformation.Although that is, having the advantages that quick response using ferromagnetic or ferrimagnet material under magnetic field, however, i.e.
Make that magnetic field is not present, strong cohesive force is also showed that between magnetic-particle, therefore, the material containing these particles exists and has
The problem of very poor dispersion performance.Therefore, assigning the high magnetic saturation intensity of magnetic material and keeping superparamagnetism is always the research
One of the emphasis of field concern.
Magnetic Nano cluster is by reuniting primary magnetic nano crystal self assembly together, to reach higher magnetic
Saturation intensity, and the superparamagnetic characteristic of single crystal is remained, become a kind of high magnetic responsiveness material studied extensively.At present
Preparing the more common method of nanocluster is to carry out in a high pressure reaction kettle, and wherein Li et al. people is by ferric trichloride, sodium acetate, second
Glycol reacts 8-72 hours in autoclave, obtains 200-800 nanometers of partial size of Fe3O4Cluster, this method is to experimental facilities requirement
Higher, the reaction time is long and obtained Fe3O4Nanocrystal do not have superparamagnetism [H.Deng, X.Li, Q.Peng, X.Wang,
J.Chen,Y.Li,Angew.Chem.Int.Ed.,2005,44,2782].Wang et al. improves the method later, with trichlorine
Change iron is source of iron, reacts 16 hours under 200 DEG C of high temperature and pressure, obtains 7~11 nanometers of single crystal grain, 280 nanometers of average grain diameter
Super-paramagnetism nano cluster, but still to experimental facilities it is more demanding [W.Ma, Y.Zhang, L.Li, L.You, P.Zhang,
Y.Zhang,J.Li,M.Yu,J.Guo,H.Lu,C.Wang,ACS Nano,2012,6(4),3179].Yin et al. was in 2007
It reports under the conditions of 220 DEG C of high-temperature pressures, using ferric trichloride as source of iron, polyacrylic acid is stabilizer, utilizes pyrohydrolytic method
Prepare Fe3O4Magnetic Nano cluster, but this method is harsh to reagent purity requirement, and the reaction time usually requires 8 hours or more, and
Reaction condition it is more difficult to control [J.Ge, Y.Hu, M.Biasini, W.P.Beyermann, Y.Yin, Angew.Chem.Int.Ed.,
2007,46,4342].Therefore, the exploitation high magnetic responsiveness magnetic Nano cluster that low energy consumption, reaction controllability is strong is the weight of research
One of point.
Magnetic fluorescence composite nano materials not only had the advantages that superparamagnetic material can Magnetic Isolation, but also have fluorescent material
Excellent fluorescent characteristic can be widely applied to the key areas such as magnetic resonance imaging, biomarker imaging, cell screening.Using having
Engine dyeing material and magnetic Nano material synthesize this composite material, mainly have package method and modification at present, the former will be organic
Dyestuff and magnetic nano-particle are encapsulated in together in silicon shell or polymeric matrix, and the latter is combined on magnetic nano-particle surface
Engine dyeing material.Wherein the packaging efficiency of package method is not high, hydrophilic radical (such as carboxylic of the modification due to destroying particle surface
Base), lead to the bad dispersibility in water phase, and magnetic particle has extremely strong quenching effect to surface fluorescence group.
Summary of the invention
The purpose of the present invention is to provide a kind of water-soluble biological compatibility fluorescence magnetic nanoclusters and preparation method thereof.
Nanocluster obtained has excellent fluorescent characteristic but also with apparent magnetic responsiveness, is dissolved in water, has good
Stability, therefore can be used for biomarker, bio-imaging and bio-separation etc., have a good application prospect.
The technical solution of the present invention is as follows: by metal precursor and biocompatibility macromolecule be dissolved in higher boiling nonpolarity or
In weak polar solvent, through high-temperature decomposition while forming magnetic Nano cluster, life is modified in the surface in situ of nanocluster
Object compatible polymer prepares various sizes of water-soluble biological compatibility magnetic Nano cluster, utilizes nanocluster surface institute
The functional groups such as the carboxyl of band couple fluorescent molecule, obtain fluorescence magnetic dual-functional nanometer cluster.
The water-soluble biological compatibility fluorescence magnetic nanocluster that the present invention synthesizes is magnetic with water-soluble biological compatibility
Nanocluster is kernel, by bridging agent 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride by water-soluble biological
The carboxyl and fluorescent dye on compatibility magnetic Nano cluster surface pass through chemistry key connection.
The size of the water-soluble biological compatibility magnetic Nano cluster be 10-1000 nanometers, preferably 20-200 nanometers,
It is made of 2-10 nanometers of magnetic nano crystal.
The magnetic nano crystal is selected from the oxygen of iron, cobalt, nickel, manganese, ketone, zinc, the oxide of iron, the oxide of cobalt, nickel
One or more of compound, the oxide of manganese, the oxide of ketone, the oxide of zinc, cobalt ferrite, Manganese Ferrite, nickel ferrite based magnetic loaded.
The water-soluble biological compatibility magnetic Nano cluster has superparamagnetism or paramagnetism.
The water-soluble biological compatibility magnetic Nano cluster is coated with biocompatibility macromolecule.
The mass percentage that the biocompatibility macromolecule accounts for water-soluble biological compatibility magnetic Nano cluster is
10-90%.
The water-soluble biological compatibility fluorescence magnetic nanocluster, which is dispersed in, forms stable Magnetic adhesive in water phase
Body.
The preparation method of water-soluble biological compatibility magnetic Nano cluster of the present invention: by metal precursor and biology
Compatible polymer is dissolved in high boiling solvent, and the concentration for being configured to metallic element is 0.01-1mol/L, preferably 0.05-
The solution of 0.5mol/L, wherein the concentration of biocompatibility macromolecule in a solvent be 0-10mol/L, preferably 0.5-2mol/L,
It is warming up to 100-200 DEG C of holding 20-120 minutes after mixing completely, is then heated to reflux 0.5-24 hours;It is cooled to reaction solution
Room temperature is added the organic solvent that 3-10 times of reaction solution volume is measured and is precipitated, with identical organic solvent washing 2-4 times, centrifugation
Isolated water-soluble biological compatibility magnetic Nano cluster disperses obtained water-soluble biological compatibility magnetic Nano cluster
It in deionized water, dialyses 1-2 days, or is repeated using the centrifugal filter that retention relative molecular mass is 10000-100000Da
Filter 23-5 times, water-soluble biological can be obtained after freeze-drying in the water-soluble biological compatibility magnetic Nano cluster purified
Compatibility magnetic Nano cluster dry powder.
The preparation method of water-soluble biological compatibility fluorescence magnetic nanocluster of the present invention: by water-soluble biological phase
Capacitive magnetic Nano cluster dry powder is configured to the solution of 0.5-5mg/mL, then preferably 1.5-2.5mg/mL adds into the solution
Enter 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride and N- hydroxysuccinimide, reacts 10-20 points at room temperature
The dimethyl sulphoxide solution for the fluorescent dye that concentration is 5-20mg/mL is added after clock, reacts 2-12 hours at room temperature, dialyse 12-
48 hours, or repeated filter 23-5 times using the centrifugal filter that retention relative molecular mass is 10000-100000Da, obtain water
Dissolubility biocompatible fluorescent magnetic Nano cluster;Wherein water-soluble biological compatibility magnetic Nano cluster dry powder and 1- (3- bis-
Methylaminopropyl) -3- ethyl-carbodiimide hydrochloride, N- hydroxysuccinimide, fluorescent dye molar ratio be 1:1-10:1-
10:1-10。
The metal precursor is selected from the oleate of iron, cobalt, nickel, manganese, ketone, zinc.
The number-average molecular weight of the biocompatibility macromolecule is 300-100000.
The biocompatibility macromolecule is polyethylene glycol and its derivative.
The biocompatibility macromolecule is selected from hydroxyl carbowax, Carboxylic-terminated Polyethylene Glycol, double-end amino
Polyethylene glycol, α-carboxyl-omega-amino polyethylene glycol, Alpha-hydroxy-ω-carboxy polyethylene glycol, hydroxyl polyethylene glycol phosphate,
The block that carboxyl polyethylene glycol phosphate, branched polyethylene glycol, branched polyethylene glycol and polyethyleneimine or chitosan are formed
Copolymer.
The high boiling solvent is phenylate or benzyl oxide.
The organic solvent is selected from one or more of ether, ethyl alcohol, acetone.
The fluorescent dye is selected from Rhodamine 123, fluorescein isothiocynate, fluorescein Cy5.5.
The present invention prepares technical method used by water-soluble biological compatibility magnetic Nano cluster with simple process, behaviour
Make feature easy, that cost of material is low, gained water-soluble biological compatibility magnetic Nano cluster size is adjustable, magnetic response is strong, raw
Object compatibility is good, high dissolution and stable dispersion in water phase and harsh water phase, and surface has functional group, can further into
Row Bioconjugation.Even if super-paramagnetism nano cluster partial size also shows superparamagnetism when being greater than 30 nanometers, and has sufficiently high
Saturation magnetization (saturation magnetization), quickly inhaled to improve dispersibility and showing by magnetic field
The characteristic drawn, therefore, the present invention can be obtained with excellent superparamagnetism (quickly recycling under magnetic field) and dispersibility (not
There are the dispersibilities under magnetic field conditions) super-paramagnetism nano cluster.In addition, water-soluble biological compatibility prepared by the present invention is glimmering
Its surface of photomagnetism nanocluster is connected with fluorescent molecule, that show can be quickly through cell membrane and selectively staining is living thin
Born of the same parents' mitochondria, therefore, fluorescence magnetic nanocluster of the invention show quick response under magnetic field, thus can be used as portable
It is raw to may also used as magnetic resonance imaging, fluorescence imaging, cell screening etc. for the material of biosensor or the sensor in relation to environment
Object medical domain.
Detailed description of the invention
Fig. 1 is the transmission electron microscope photo of 1 gained sample of the embodiment of the present invention;
Fig. 2 is the high resolution transmission electron microscope photo of 1 gained sample of the embodiment of the present invention;
Fig. 3 is the transmission electron microscope photo of 2 gained sample of the embodiment of the present invention;
Fig. 4 is the electronic diffraction photo of 2 gained sample of the embodiment of the present invention;
Fig. 5 is the x-ray diffraction pattern (XRD) of sample obtained by Example 1 and Example 2 of the present invention;
Fig. 6 is the hysteresis loop of sample obtained by Example 1 and Example 2 of the present invention;
Fig. 7 is the resulting sample of the embodiment of the present invention 5 to the laser confocal microscope photo before and after HeLa cell dyeing.
Specific embodiment
Illustrated by following exemplary, but non-limiting embodiment, the present invention can be better understood.
[embodiment 1]
By 0.9 gram of iron oleate and 2.4 grams of Carboxylic-terminated Polyethylene Glycol (Mn=600Da) it is dissolved in 5 grams of phenylates, it has dissolved
It is warming up to 100 DEG C after complete to be kept for 30 minutes, is then heated to reflux 5 hours, is cooled to room temperature to reaction solution, 15 milliliters of ether are added
The Fe that surface has carboxyl is settled out with acetone mixed solvent (ether and acetone volume ratio 5:1)3O4Magnetic Nano cluster is simultaneously washed
3 times, the water-soluble biological compatibility Fe that will be obtained3O4Magnetic Nano cluster is dissolved in deionized water, is dialysed 2 days, is purified
Water-soluble biological compatibility Fe3O4Water-soluble biological compatibility Fe can be obtained in magnetic Nano cluster after freeze-drying3O4Magnetic
Property nanocluster dry powder.
Obtained magnetic Nano cluster dry powder is re-dissolved in deionized water, which is dripped to the TEM for being coated with carbon film
On grid, after dry, observed with electron microscope (JEOL JEM-2100, acceleration voltage 100kV).As shown in Figure 1, using logical
Cross the water-soluble biological compatibility Fe of method preparation of the invention3O4Magnetic Nano cluster, 25 nanometers of average grain diameter;Fig. 2 is high score
Resolution transmission electron microscope photo corresponds essentially to Fe analysis shows that the spacing of striped is 0.485 nanometer3O4(111) it is brilliant
Interplanar distance.
[embodiment 2]
By 0.9 gram of iron oleate and 1.8 grams of Carboxylic-terminated Polyethylene Glycol (Mn=600Da) it is dissolved in 5 grams of phenylates, it has dissolved
It is warming up to 100 DEG C after complete to be kept for 30 minutes, is then heated to reflux 2 hours, is cooled to room temperature to reaction solution, 15 milliliters of ether are added
The Fe that surface has carboxyl is settled out with acetone mixed solvent (ether and acetone volume ratio 1:5)3O4Magnetic Nano cluster is simultaneously washed
3 times, the water-soluble biological compatibility Fe that will be obtained3O4Magnetic Nano cluster is dissolved in deionized water, uses centrifugal filter
(retention relative molecular mass is 1,0000Da) repeats filter 23, the water-soluble biological compatibility Fe purified3O4Magnetism is received
Rice cluster, can be obtained water-soluble biological compatibility Fe after freeze-drying3O4Magnetic Nano cluster dry powder.
The water-soluble biological compatibility Fe that will be obtained3O4Magnetic Nano cluster dry powder is re-dissolved in deionized water, this is molten
On drop to the TEM grid for being coated with carbon film, after dry, seen with electron microscope (JEOL JEM-2100, acceleration voltage 100kV)
It examines.As shown in figure 3, using water-soluble biological compatibility Fe prepared by the method for the present invention3O4Magnetic Nano cluster, it is average
62 nanometers of partial size;Electron diffraction diagram surface magnetic Nano cluster crystallinity in Fig. 4 is high.Attached drawing 5 is gained nanocluster
X-ray diffraction pattern (XRD), resulting nanocluster is Fe as seen from the figure3O4, the crystallinity of nano-cluster is higher.Attached drawing 6 is to implement
In example 1 in 25 nanometers of cluster and embodiment 2 62 nanometers of cluster hysteresis loop, two kinds of magnetic Nano clusters all have super suitable
Magnetism, and the saturation magnetization of crystal is respectively 49.8 and 81.8emu/ (g Fe3O4)。
[embodiment 3]
By 0.62 gram of manganese oleate and 1.8 grams of Carboxylic-terminated Polyethylene Glycol (Mn=600Da) it is dissolved in 5 grams of phenylates, it dissolves
Completely after be warming up to 100 DEG C keep 30 minutes, be then refluxed for 2 hours, be cooled to room temperature to reaction solution, be added 15 milliliters of ether and
Acetone mixed solvent (ether and acetone volume ratio 1:5) is settled out the MnO that surface has carboxyl2Magnetic Nano cluster simultaneously washs 3
It is secondary, obtained water-soluble biological compatibility magnetic Nano cluster is dissolved in deionized water, centrifugal filter (retention phase is used
It is 1,0000Da to molecular mass) repeat filter 23, the water-soluble biological compatibility MnO purified2Magnetic Nano cluster,
Water-soluble biological compatibility magnetic Nano cluster dry powder can be obtained after freeze-drying.
[embodiment 4]
By 0.62 gram of manganese oleate and 1.8 grams of Carboxylic-terminated Polyethylene Glycol (Mn=600Da) it is dissolved in 5 grams of phenylates, it dissolves
Completely after be warming up to 100 DEG C keep 30 minutes, be then refluxed for 2 hours, be cooled to room temperature to reaction solution, be added 15 milliliters of ether and
Acetone mixed solvent (ether and acetone volume ratio 1:5) is settled out the MnO that surface has carboxyl2Magnetic Nano cluster simultaneously washs 3
It is secondary, obtained water-soluble biological compatibility magnetic Nano cluster is dissolved in deionized water, centrifugal filter (retention phase is used
It is 1,0000Da to molecular mass) repeat filter 23, the water-soluble biological compatibility MnO purified2Magnetic Nano cluster,
Water-soluble biological compatibility magnetic Nano cluster dry powder can be obtained after freeze-drying.
[embodiment 5]
The water-soluble biological compatibility Fe that embodiment 2 is obtained3O4Magnetic Nano cluster dry powder is configured to the molten of 2mg/mL
Then 76 milligrams of 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochlorides (EDC) are added in liquid into 1 milliliter of solution
With 26 milligrams of N- hydroxysuccinimides (NHS) by activated carboxylic, react 20 minutes at room temperature, the backward reaction solution in be added
The dimethyl sulphoxide solution (9mg/mL) of 1 milliliter of fluorescent molecule Rhodamine 123 reacts 4 hours at room temperature, uses centrifugal filter
(retention relative molecular mass is 1,0000Da) repeats filter 23, obtains water-soluble biological compatibility fluorescence magnetic nanocluster.
Water-soluble biological compatibility fluorescence magnetic nanocluster obtained above is with water-soluble biological compatibility Fe3O4Magnetic
Property nanocluster be kernel, it is by bridging agent 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride that water solubility is raw
The carboxyl and Rhodamine 123 on object compatibility magnetic Nano cluster surface pass through chemistry key connection.Water-soluble biological compatibility Fe3O4
The size of magnetic Nano cluster is 20-200 nanometers, is by 2-10 nanometers of Fe3O4Magnetic nano crystal composition, surface package
Carboxylic-terminated Polyethylene Glycol, Carboxylic-terminated Polyethylene Glycol account for the mass percentage of water-soluble biological compatibility magnetic Nano cluster
75%.Water-soluble biological compatibility magnetic Nano cluster obtained has superparamagnetism, is dispersed in water phase and is formed surely
Fixed magnetic colloid.
Attached drawing 7 is the fluorescence magnetic nanocluster to the laser confocal microscope photo after the dyeing of HeLa cell.
Water-soluble biological compatibility fluorescence magnetic nanocluster obtained by above-described embodiment have apparent magnetic responsiveness,
Good water-soluble and fluorescence, and good stability is all had in water phase and harsh water phase, therefore, this kind of fluorescence magnetic
Double-bang firecracker answers nanocluster to can be applied to the fields of biomedicine such as cell marking, fluorescence imaging and magnetic resonance imaging.
Claims (3)
1. a kind of water-soluble biological compatibility fluorescence magnetic nanocluster, which is characterized in that it is with water-soluble biological compatibility
Magnetic Nano cluster is kernel, will be water-soluble by bridging agent 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride
The carboxyl and fluorescent dye on biological compatibility magnetic nanocluster surface pass through chemistry key connection;Water-soluble biological compatibility is glimmering
Photomagnetism nanocluster, which is dispersed in, forms stable magnetic colloid in water phase;The water-soluble biological compatibility magnetic Nano group
Cluster is made of 2-10 nanometers of magnetic nano crystal, has superparamagnetism or paramagnetism;The water-soluble biological compatibility magnetic
Property nanocluster size be 25-62 nanometers, be coated with biocompatibility macromolecule;The biocompatibility macromolecule
The mass percentage for accounting for water-soluble biological compatibility magnetic Nano cluster is 10-90%;The magnetic nano crystal is selected from
Iron, cobalt, nickel, manganese, copper, the oxide of iron, the oxide of cobalt, the oxide of nickel, the oxide of manganese, the oxide of copper, cobalt ferrite,
One or more of Manganese Ferrite, nickel ferrite based magnetic loaded.
2. a kind of preparation method of water-soluble biological compatibility magnetic Nano cluster as described in claim 1, which is characterized in that
Its concrete operations condition are as follows: metal precursor and biocompatibility macromolecule are dissolved in high boiling solvent, are configured to metal
The concentration of element is 0.01-1mol/L, and wherein the concentration of biocompatibility macromolecule in a solvent is 0-10mol/L, has been mixed
It is warming up to 100-200 DEG C of holding 20-120 minutes after complete, is then heated to reflux 0.5-24 hours;It is cooled to room temperature to reaction solution,
The organic solvent that 3-10 times of reaction solution volume is measured is added to be precipitated, with identical organic solvent washing 2-4 times, is centrifugated
To water-soluble biological compatibility magnetic Nano cluster, by obtained water-soluble biological compatibility magnetic Nano cluster be scattered in from
It in sub- water, dialyses 1-2 days, or repeats filter 23-using the centrifugal filter that retention relative molecular mass is 10000-100000Da
5 times, water-soluble biological compatibility can be obtained in the water-soluble biological compatibility magnetic Nano cluster purified after freeze-drying
Magnetic Nano cluster dry powder;The metal precursor is selected from the oleate of iron, cobalt, nickel, manganese, copper;The high boiling solvent
For phenylate or benzyl oxide;The biocompatibility macromolecule is polyethylene glycol and its derivative, number-average molecular weight 300-
100000;The organic solvent is the ether and acetone mixed solvent that volume ratio is 5:1.
3. a kind of preparation method of water-soluble biological compatibility fluorescence magnetic nanocluster as described in claim 1, feature
It is, concrete operations condition are as follows: water-soluble biological compatibility magnetic Nano cluster dry powder is configured to the molten of 0.5-5mg/mL
Liquid, is then added 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride into the solution and N- maloyl is sub-
The dimethyl sulphoxide solution for the fluorescent dye that concentration is 5-20mg/mL is added, at room temperature in amine after reacting 10-20 minutes at room temperature
Reaction 2-12 hours is dialysed 12-48 hours, or the centrifugal filter for the use of retention relative molecular mass being 10000-100000Da
It repeats filter 23-5 times, obtains water-soluble biological compatibility fluorescence magnetic nanocluster;Wherein water-soluble biological compatibility magnetism is received
Rice cluster dry powder and 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, N- hydroxysuccinimide, fluorescent dye
Molar ratio be 1:1-10:1-10:1-10;The fluorescent dye uses concentration for the two of 9mg/mL fluorescent molecule Rhodamine 123
Methyl sulfoxide solution.
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Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102112158A (en) * | 2008-04-22 | 2011-06-29 | 财团法人工业技术研究院 | Biocompatible polymer and magnetic nanoparticle with biocompatibility |
-
2016
- 2016-04-20 CN CN201610249289.XA patent/CN105936820B/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102112158A (en) * | 2008-04-22 | 2011-06-29 | 财团法人工业技术研究院 | Biocompatible polymer and magnetic nanoparticle with biocompatibility |
Non-Patent Citations (4)
Title |
---|
Carbodiimide versus Click Chemistry for Nanoparticle Surface Functionalization: A Comparative Study for the Elaboration of Multimodal Superparamagnetic Nanoparticles Targeting αvβ3 Integrins;Julie Bolley等;《Langmuir》;20131231;第29卷;14639-14647 |
One-pot fabrication of carboxyl-functionalized biocompatible magnetic nanocrystals for conjugation with targeting agents;Chichong Lu等;《New J. Chem.》;20101231;第34卷;2040-2046 |
Structural and magnetic properties of uniform magnetite nanoparticles prepared by high temperature decomposition of organic precursors;A G Roca等;《Nanotechnology》;20061231;第17卷;2783-2788 |
Water-Dispersible Iron Oxide Magnetic Nanoparticles with Versatile Surface Functionalities;Haiou Qu等;《Langmuir》;20111231;第27卷;2271-2278 |
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