CN105969331A - Preparation method of nano-material suitable for targeting drug carriers - Google Patents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/54—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing zinc or cadmium
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
Abstract
The invention relates to a preparation method of a nano-material suitable for targeting drug carriers. The invention relates to a preparation method of a nanocomposite which integrates magnetism and fluorescence. The method comprises the following steps: ZnO quantum dots and Fe3O4 nanometer particles with a mesoporous structure are separately prepared, a SiO2 shell layer is wrapped on the surface of the two kinds of nanoparticles, and amination is carried out; the aminated composite nanometer particles are grafted to the surface of graphene oxide by a covalent crosslinking mode, wherein the surface of graphene oxide is treated by pre-carboxylation; finally the graphene oxide composite material with magnetism and fluorescence double functions is obtained. The graphene oxide composite material has obvious magnetic performance, and graphene has a large specific surface area, so that the composite material has good application prospects in the aspect of targeting drug transportation carriers; and tracing of the transmission path of the drug carrier is hopeful to realize due to excellent fluorescence properties.
Description
The present patent application is on 09 26th, 2014 applying date, the patent of invention of application number 201410502642.1
Divisional application.
Technical field
The present invention relates to a kind of nano composite material that can be used as target medicine carrier and preparation method.
Background technology
More Graphene derivative is applied to be mainly the graphene oxide of functionalization at biomedical sector, in recent years,
Metal nanoparticle, magnetic nano-particle are loaded to surface of graphene oxide and prepares composite, and explore it in material, change
The research and development of the field application such as, biomedicine is rapid.Magnetic nanoparticle is loaded into magnetic prepared by graphenic surface
Target medicine carrier, has great application potential in actual disease is treated.About magnetic nano-particle modified graphene
The existing a small amount of report of research, these magnetic nanoparticle/graphene composite materials are expected at magnetic targeted medicine carrying, bio-separation, magnetic
Resonance image-forming, and obtain in fields such as removing in sewage condensed ring pollutant and be widely applied.More than in research, used magnetic grain
Son is all solid Fe3O4Nano-particle, wherein magnetic particle the most only plays the effect making material have magnetic property,
And the structure of nanoparticle does not the most embody significantly effect.
Quantum dot (QDs) refers to that radius is less than or close to the semiconductor nano of Exciton Bohr Radius, owing to light irradiates energy
Inspire visible fluorescence, be a kind of novel fluorescent material.Fluorescence quantum has good chemical stability, and its fluorescence
Peak position can regulate and control with the physical size of quantum dot and chemical composition, thus be expected to replace traditional organic coloring agent and
The aspects such as bioluminescence imaging, biomacromolecule identification and detection thereof are widely used.Quantum dot is used as fluorescent marker
Spike is observed living cells or the structure of tissue and activity or even carries out living animal imaging and for following the trail of drug particles at body
Interior trend and the research of effect are reported the most in a large number.In these reports, quantum dot used uses collochemistry method mostly
Organic system synthesizes, the quantum dot poorly water-soluble therefore obtained, and the chalcogen of the quantum dot composition mainly Cd synthesized
Element binary compound and nucleocapsid structure thereof.Cd is a kind of heavy metal element having severe toxicity, containing Cd quantum dot in biomarker mistake
Journey easily discharges Cd2+And damage biological body.Although the preparation of cadmium content point and properity detection are the most highly developed,
And numerous studies have shown that use surface modification technology or aqueous synthesis method can be substantially improved containing Cd quantum dot steady
Qualitative and safety, but this kind of quantum dot still can not be completely eliminated and in use can decomposite free Cd2+Possibility
Property, therefore the biological safety of cadmium content point does not the most obtain basic solution.Therefore, from biological safety and application angle
For degree, the research actively developing hypotoxicity or the preparation of bio-compatibility quanta point material, structure and performance will become future
The developing direction of quanta point material.
Summary of the invention
It is an object of the invention to provide a kind of nano combined material of magnetic fluorescent dual-function that can be used as target medicine carrier
The preparation method of material.
The preparation method that the present invention provides is concrete according to the following steps:
(1) preparation of graphene oxide
Powdered graphite is added H2SO4、K2S2O8、P2O5Mixed liquor in, 70 ~ 85 DEG C reaction 3 ~ 6h.Then dilute, and mistake
Filter washing is to remove unnecessary acid.Gained pre-product is dried at room temperature for overnight, then the graphite of pre-oxidation is added dense H2SO4,
It is gradually added KMnO under ice-water bath is protected4, this mixture enters in 85 ~ 95 DEG C after stirring reaction 30 min at 30 ~ 35 DEG C
Row reaction 1 ~ 2h, rear dilute so that it is boiling reaction 20 ~ 40min, after being stirred for 1 ~ 2 hour, add water and the H of 30wt%2O2
Solution left standstill precipitates.Mixture rinses for several times with dilute hydrochloric acid after filtering, then rinses to neutral with water.Finally products therefrom is dialysed
Within one week, purification removes remaining metal ion, the graphite oxide the most ultrasonic stripping 30 ~ 50min obtained, and obtains dense
Degree is about 0.1 ~ 1mg mL-1Graphene oxide storing solution.Use 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide
And N-hydroxy-succinamide (NHS) makes the activated carboxylic at graphene oxide plane and edge (EDC).
(2) mesoporous Fe3O4The preparation of magnetic nanoparticle
By Fe (NO under room temperature3) 3·9H2O is dissolved in ethylene glycol, is heated to forming dry Fe in 70 ~ 80 DEG C after stirring 3 hours
(NO3)3Ethylene glycol gel.Fe (the NO that will be formed3)3Ethylene glycol gel is placed in horizontal pipe furnace 380 ~ 450 DEG C and carries out heat
Naturally cool to room temperature after solution, product is dried with after pure water and ethanol wash respectively in 70 ~ 80 DEG C of drying baker.It is eventually adding
Ferroso-ferric oxide is modified by appropriate TMA, rear ultrasonic, shake up and disperse to obtain the mesoporous of variable concentrations in deionized water
Fe3O4Nanoparticle storing solution.
(3) there is the preparation of the adjustable ZnO quantum dot of fluorescence color
Under room temperature, by Zn (OAc)2·2H2O and LiOH H2O is dissolved in TEG according to mol ratio 2:3, is stirred continuously until solution
Luminescence.After according to certain mol proportion B(Mg:Zn) by Mg (OAc)2·4H2O joins in above-mentioned solution, super under the conditions of ice-water bath
Sonication 2 ~ 5min, purification, obtain the ZnO quantum dot of different glow color.
(4) (mesoporous Fe3O4-ZnO quantum dot)@SiO2Preparation
Hexamethylene, triton x-100 and hexanol are added beaker according to volume ratio 4:1:1, adds after stirring 15 ~ 30min
The Fe of 200ul3O4Nano-particle solution and 800ulZnO quantum dot solution (concentration: 1 ~ 10mmol/l), after stirring 10 ~ 30min,
Add 120ul NH4OH and 120ul PDDA solution (0.075%V/V).Add in system after continuing stirring 20min
80ul TEOS, continues under the conditions of lucifuge to be stirred vigorously 12 ~ 24h.The last acetone adding 20 ~ 30ml again in this system, obtains
(mesoporous Fe3O4-ZnO quantum dot)@SiO2Composite nanoparticle, finally uses APS and THPMP that compound particle surface is carried out ammonia
Base functionalization.
(5) preparation of the graphene oxide composite material of magnetic fluorescent dual-function
By amidized (mesoporous Fe3O4-ZnO quantum dot)@SiO2Nano composite granules is incorporated into carboxylic by the method for covalent cross-linking
The surface of graphene oxide of base, obtains the graphene oxide composite material with magnetic fluorescent dual-function.
In the present invention, H described in step (1)2SO4、K2S2O8、P2O5Mixed liquor, in the mass ratio of each component be: 10:
1:1。
In the present invention, mol ratio B (Mg:Zn)=(0 ~ 0.1) described in step (3).
In the present invention, Fe described in step (4)3O4Nano-particle solution concentration is 1 ~ 10mmol/l, ZnO quantum dot solution
Concentration is 1 ~ 10mmol/l.
Compared with prior art, there is advantages that
The graphene nanocomposite material that the present invention prepares is by mesoporous Fe3O4The magnetic of nano-particle, Hole bottom cavity blast, Gao Bibiao
Area and the fluorescence property of ZnO quantum dot and the extra specific surface area of graphene oxide, good bio-compatibility etc. blend,
Can be as a kind of new drug carrier with magnetic target tropism, fluorescence and high drug load.Target product is possible not only to realize
The targeting transport of medicine, it is also possible to medicament transport process is carried out fluorescent tracing, has great medical application and is worth.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the magnetic fluorescent dual-function stannic oxide/graphene nano composite prepared.
Fig. 2 is the TEM figure of the magnetic fluorescent dual-function stannic oxide/graphene nano composite prepared.
Fig. 3 is the PL spectrogram of the magnetic fluorescent dual-function stannic oxide/graphene nano composite prepared.
Fig. 4 is the magnetization curve figure of the magnetic fluorescent dual-function stannic oxide/graphene nano composite prepared.
Detailed description of the invention
Below by embodiment, the present invention is further described.
Embodiment 1
(1) preparation of graphene oxide
2g graphite powder is added the dense H of 25g2SO4、2.5g K2S2O8With 2.5g P2O5Mixed liquor in, 80 DEG C reaction 3h.Then add
500ml water dilutes, and filtration washing is to remove unnecessary acid.Gained pre-product is dried at room temperature for overnight, then will pre-oxidation
Graphite add the dense H of 100ml2SO4In, under ice-water bath is protected, it is gradually added 13g KMnO4, this mixture stirs at 35 DEG C
Carry out reacting 2h, rear dilute so that it is boiling reaction 30min in 85 DEG C after reacting 30 min, after being stirred for 1 hour, add
500ml water and the H of 20ml and 30%2O2Solution left standstill precipitates.Mixture rinses 5 times with the dilute hydrochloric acid of 1:10 after filtering, then uses water
Rinse to neutral.One week purification of finally being dialysed by products therefrom removes remaining metal ion, and the graphite oxide obtained is in room temperature
Under the conditions of ultrasonic stripping 30min, be configured to concentration and be about the graphene oxide storing solution of 0.5mg/ml.To 50ml graphite oxide
The dispersion liquid of alkene adds 1 mg 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide (EDC) and 0.5 mg N-hydroxyl amber
Amber acid imide (NHS), stirs 30min, makes the activated carboxylic at GO plane and edge.
(2) mesoporous Fe3O4The preparation of magnetic nanoparticle
By 0.02mol Fe (NO under room temperature3) 3·9H2O is dissolved in 25ml ethylene glycol, is heated to shape in 80 DEG C after stirring 3 hours
Fe (the NO of Cheng Gan3)3Ethylene glycol gel.Fe (the NO that 1g is formed3)3Ethylene glycol gel is placed in horizontal pipe furnace, with 10
DEG C/heating rate to 400 DEG C of min naturally cools to room temperature after keeping 12h, by product respectively with after pure water and ethanol wash
12h it is dried in 70 DEG C of drying baker.Dried product will add appropriate TMA, be dispersed in after ultrasonic 1min 10ml go from
In sub-water, obtain the mesoporous Fe that concentration is about 10 mmol/L3O4Nanoparticle storing solution.
(3) there is the preparation of the adjustable ZnO quantum dot of fluorescence color
Under room temperature, by 0.002molZn (OAc)2·2H2The LiOH H of O and 0.003mol2O is dissolved in 40ml TEG, persistently stirs
Mix until solution luminescence, purification, be configured to the ZnO quantum dot of 10mmol/l.
(4) (mesoporous Fe3O4-ZnO quantum dot)@SiO2Preparation
15ml hexamethylene, 3.6ml triton x-100 and 3.6ml hexanol are added beaker, after stirring 15min, adds 200ul's
The Fe of concentration 10mmol/l3O4The ZnO quantum dot solution of nano-particle solution and 800ul concentration 10mmol/l, stirs 10min
After, add 120ul NH4OH and 120ul PDDA solution (0.075%V/V).Add in system after continuing stirring 20min
80ul TEOS, continues under the conditions of lucifuge to be stirred vigorously 24h.The last acetone adding 20ml again in this system, obtains (mesoporous
Fe3O4-ZnO quantum dot)@SiO2Composite nanoparticle.30ulAPS and 80ulTHPMP is joined (the mesoporous Fe of preparation3O4 -
ZnO quantum dot)@SiO2In composite nanoparticle, stir 24h, finally obtain (the mesoporous Fe of surface amination3O4-ZnO quantum
Point)@SiO2Composite nanoparticle.
(5) preparation of the graphene oxide composite material of magnetic fluorescent dual-function
By 20ml(4) in amino functional (the mesoporous Fe that obtains3O4-ZnO quantum dot)@SiO2Composite nanoparticle joins
The GO dispersion liquid of 50ml concentration 0.5mg/ml activated carboxylic reacts 2 h, makes (mesoporous Fe3O4-ZnO quantum dot)@SiO2Compound
The amino of nanoparticle surface forms amido link with the carboxyl covalent cross-linking of GO.Then by step with Magneto separate is cleaned multiple times
Suddenly, target product magnetic fluorescence polyfunctional GO composite nanometer particle is obtained.
Embodiment 2
(1) preparation of graphene oxide
2g graphite powder is added the dense H of 25g2SO4、2.5g K2S2O8With 2.5g P2O5Mixed liquor in, 70 DEG C reaction 5h.Then add
500ml water dilutes, and filtration washing is to remove unnecessary acid.Gained pre-product is dried at room temperature for overnight, then will pre-oxidation
Graphite add the dense H of 150ml2SO4In, under ice-water bath is protected, it is gradually added 20g KMnO4, this mixture stirs at 30 DEG C
Carry out reacting 2h, rear dilute so that it is boiling reaction 30min in 85 DEG C after reacting 30 min, after being stirred for 1 hour, add
The H of 500ml water 20ml and 30%2O2Solution left standstill precipitates.Mixture rinses 5 times with the dilute hydrochloric acid of 1:10 after filtering, then rushes with water
It is washed till neutrality.One week purification of finally being dialysed by products therefrom removes remaining metal ion, and the graphite oxide obtained is at room temperature bar
Under part, ultrasonic stripping 30min, is configured to concentration and is about the graphene oxide storing solution of 0.2 mg/ml.To 50ml graphite oxide
The dispersion liquid of alkene adds 0.5 mg 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide (EDC) and 0.2 mg N-hydroxyl
Butanimide (NHS), stirs 30min, makes the activated carboxylic at GO plane and edge.
(2) mesoporous Fe3O4The preparation of magnetic nanoparticle
By 0.02mol Fe (NO under room temperature3) 3·9H2O is dissolved in 25ml ethylene glycol, is heated to shape in 70 DEG C after stirring 3 hours
Fe (the NO of Cheng Gan3)3Ethylene glycol gel.Fe (the NO that 1g is formed3)3Ethylene glycol gel is placed in horizontal pipe furnace, with 10
DEG C/heating rate to 400 DEG C of min naturally cools to room temperature after keeping 12h, by product respectively with after pure water and ethanol wash
12h it is dried in 70 DEG C of drying baker.Dried product will add appropriate TMA, be dispersed in after ultrasonic 1min 100ml go from
In sub-water, obtain the mesoporous Fe that concentration is about 1 mmol/L3O4Nanoparticle storing solution.
(3) there is the preparation of the adjustable ZnO quantum dot of fluorescence color
Under room temperature, by 0.002molZn (OAc)2·2H2The LiOH H of O and 0.003mol2O is dissolved in 40ml TEG, persistently stirs
Mix until solution luminescence.By the Mg (OAc) of 0.0002mol2·4H2O joins in above-mentioned solution, ultrasonic under the conditions of ice-water bath
Process 5min, purification, be configured to the ZnO quantum dot of 10mmol/l.
(4) (mesoporous Fe3O4-ZnO quantum dot)@SiO2Preparation
15ml hexamethylene, 3.6ml triton x-100 and 3.6ml hexanol are added beaker, after stirring 15min, adds 200ul's
The Fe of concentration 1mmol/l3O4The ZnO quantum dot solution of nano-particle solution and 800ul concentration 10mmol/l, stirs 10min
After, add 120ul NH4OH and 120ul PDDA solution (0.075%V/V).Add in system after continuing stirring 20min
80ul TEOS, continues under the conditions of lucifuge to be stirred vigorously 24h.The last acetone adding 20ml again in this system, obtains (mesoporous
Fe3O4-ZnO quantum dot)@SiO2Composite nanoparticle.30ulAPS and 80ulTHPMP is joined (the mesoporous Fe of preparation3O4 -
ZnO quantum dot)@SiO2In composite nanoparticle, stir 24h, finally obtain (the mesoporous Fe of surface amination3O4-ZnO quantum
Point)@SiO2Composite nanoparticle.
(5) preparation of the graphene oxide composite material of magnetic fluorescent dual-function
By 20ml(4) in amino functional (the mesoporous Fe that obtains3O4-ZnO quantum dot)@SiO2Composite nanoparticle solution adds
In the activated carboxylic GO dispersion liquid of 50ml concentration 0.2 mg/ml, react 2 h, make (mesoporous Fe3O4-ZnO quantum dot)@SiO2Multiple
The carboxyl covalent cross-linking of the amino and GO that close nanoparticle surface forms amido link.Then by step with Magneto separate is cleaned multiple times
Suddenly, target product magnetic fluorescence polyfunctional GO composite nanometer particle is obtained.
Embodiment 3
(1) preparation of graphene oxide
2g graphite powder is added the dense H of 25g2SO4、2.5g K2S2O8With 2.5g P2O5Mixed liquor in, 80 DEG C reaction 3h.Then add
500ml water dilutes, and filtration washing is to remove unnecessary acid.Gained pre-product is dried at room temperature for overnight, then will pre-oxidation
Graphite add the dense H of 100ml2SO4In, under ice-water bath is protected, it is gradually added 13g KMnO4, this mixture stirs at 35 DEG C
Carry out reacting 2h, rear dilute so that it is boiling reaction 30min in 85 DEG C after reacting 30 min, after being stirred for 1 hour, add
500ml water and the H of 20ml and 30%2O2Solution left standstill precipitates.Mixture rinses 5 times with the dilute hydrochloric acid of 1:10 after filtering, then uses water
Rinse to neutral.One week purification of finally being dialysed by products therefrom removes remaining metal ion, and the graphite oxide obtained is in room temperature
Under the conditions of ultrasonic stripping 30min, be configured to concentration and be about the graphene oxide storing solution of 0.1mg/ml.To 50ml graphite oxide
The dispersion liquid of alkene adds 2mg 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide (EDC) and 0.1mg N-hydroxysuccinimidyl
Acid imide (NHS), stirs 30min, makes the activated carboxylic at GO plane and edge.
(2) mesoporous Fe3O4The preparation of magnetic nanoparticle
By 0.02mol Fe (NO under room temperature3) 3·9H2O is dissolved in 25ml ethylene glycol, is heated to shape in 80 DEG C after stirring 3 hours
Fe (the NO of Cheng Gan3)3Ethylene glycol gel.Fe (the NO that 1g is formed3)3Ethylene glycol gel is placed in horizontal pipe furnace, with 10
DEG C/heating rate to 400 DEG C of min naturally cools to room temperature after keeping 12h, by product respectively with after pure water and ethanol wash
12h it is dried in 70 DEG C of drying baker.Dried product will add appropriate TMA, be dispersed in after ultrasonic 1min 10ml go from
In sub-water, obtain the mesoporous Fe that concentration is about 10 mmol/L3O4Nanoparticle storing solution.
(3) there is the preparation of the adjustable ZnO quantum dot of fluorescence color
Under room temperature, by 0.002molZn (OAc)2·2H2The LiOH H of O and 0.003mol2O is dissolved in 40ml TEG, persistently stirs
Mix until solution luminescence, by the Mg (OAc) of 0.0001mol2·4H2O joins in above-mentioned solution, ultrasonic under the conditions of ice-water bath
Process 5min, purification, be configured to the ZnO quantum dot of 10mmol/l
(4) (mesoporous Fe3O4-ZnO quantum dot)@SiO2Preparation
15ml hexamethylene, 3.6ml triton x-100 and 3.6ml hexanol are added beaker, after stirring 15min, adds 200ul's
The Fe of concentration 10mmol/l3O4The ZnO quantum dot solution of nano-particle solution and 800ul concentration 10mmol/l, stirs 10min
After, add 120ul NH4OH and 120ul PDDA solution (0.075%V/V).Add in system after continuing stirring 20min
80ul TEOS, continues under the conditions of lucifuge to be stirred vigorously 24h.The last acetone adding 20ml again in this system, obtains (mesoporous
Fe3O4-ZnO quantum dot)@SiO2Composite nanoparticle.30ulAPS and 80ulTHPMP is joined (the mesoporous Fe of preparation3O4 -
ZnO quantum dot)@SiO2In composite nanoparticle, stir 24h, finally obtain (the mesoporous Fe of surface amination3O4-ZnO quantum
Point)@SiO2Composite nanoparticle.
(5) preparation of the graphene oxide composite material of magnetic fluorescent dual-function
By 20ml(4) in amino functional (the mesoporous Fe that obtains3O4-ZnO quantum dot)@SiO2Composite nanoparticle joins
The GO dispersion liquid of 50ml concentration 0.1mg/ml activated carboxylic reacts 2 h, makes (mesoporous Fe3O4-ZnO quantum dot)@SiO2Compound
The amino of nanoparticle surface forms amido link with the carboxyl covalent cross-linking of GO.Then by step with Magneto separate is cleaned multiple times
Suddenly, target product magnetic fluorescence polyfunctional GO composite nanometer particle is obtained.
Claims (2)
1. the preparation method of the nano material being applicable to target medicine carrier, it is characterised in that prepare as follows:
(1) preparation of graphene oxide
Powdered graphite is added H2SO4、K2S2O8、P2O5Mixed liquor in, 70 ~ 85 DEG C of reactions 3 ~ 6h, then dilutes, and mistake
Filter washing is to remove unnecessary acid, and gained pre-product is dried at room temperature for overnight, is subsequently adding dense H2SO4, under ice-water bath is protected
It is gradually added KMnO4, this mixture stir at 30 ~ 35 DEG C reaction 30 min after carry out reacting 1 ~ 2h in 85 ~ 95 DEG C, after add
Water dilutes so that it is boiling reaction 20 ~ 40min, after being stirred for 1 ~ 2 hour, adds water and the H of 30%2O2Solution left standstill precipitates, mixing
Thing rinses for several times with dilute hydrochloric acid after filtering, then rinses to neutral with water, and one week purification of finally being dialysed by products therefrom removes residue
Metal ion, the graphite oxide the most ultrasonic stripping 30 ~ 50min obtained, obtain concentration and be about 0.1 ~ 1mg
mL-1Graphene oxide storing solution；Use 1-(3-dimethylamino-propyl)-3-ethyl carbodiimide (EDC) and N-hydroxysuccinimidyl
Acid imide (NHS) makes the activated carboxylic at graphene oxide plane and edge；
(2) mesoporous Fe3O4The preparation of magnetic nanoparticle
By Fe (NO under room temperature3) 3·9H2O is dissolved in ethylene glycol, is heated to forming dry Fe in 70 ~ 80 DEG C after stirring 3 hours
(NO3)3Ethylene glycol gel, the Fe (NO that will be formed3)3Ethylene glycol gel is placed in horizontal pipe furnace 380 ~ 450 DEG C and carries out heat
Naturally cool to room temperature after solution, product is dried with after pure water and ethanol wash respectively in 70 ~ 80 DEG C of drying baker, is eventually adding
Ferroso-ferric oxide is modified by TMA, rear ultrasonic, shake up and disperse to obtain in deionized water the mesoporous Fe of variable concentrations3O4Receive
Rice grain storing solution；
(3) there is the preparation of the adjustable ZnO quantum dot of fluorescence color
Under room temperature, by Zn (OAc)2·2H2O and LiOH H2O is dissolved in TEG according to mol ratio 2:3, is stirred continuously until solution
Luminescence, after according to different mol ratio B(Mg:Zn) by Mg (OAc)2·4H2O joins in above-mentioned solution, super under the conditions of ice-water bath
Sonication 2 ~ 5min, purification, obtain the ZnO quantum dot of different glow color；
(4) (mesoporous Fe3O4-ZnO quantum dot)@SiO2Preparation
Hexamethylene, triton x-100 and hexanol are added beaker according to volume ratio 4:1:1, adds after stirring 15 ~ 30min
The Fe of 200ul3O4Nanoparticles solution and 800ulZnO quantum dot solution (concentration: 1 ~ 10mmol/l), after stirring 10 ~ 30min,
Add 120ul NH4OH and 120ul PDDA solution (0.075%V/V), adds after continuing stirring 20min in system
80ul TEOS, continues under the conditions of lucifuge to be stirred vigorously 12 ~ 24h, adds the acetone of 20 ~ 30ml the most again, obtain in this system
(mesoporous Fe3O4-ZnO quantum dot)@SiO2Composite nanoparticle, finally uses APS and THPMP that compound particle surface is carried out ammonia
Base functionalization；
(5) preparation of the graphene oxide composite material of magnetic fluorescent dual-function
By amidized (mesoporous Fe3O4-ZnO quantum dot)@SiO2Nano composite granules is incorporated into carboxylic by the method for covalent cross-linking
The surface of graphene oxide of base, obtains the graphene oxide composite material with magnetic fluorescent dual-function.
It is applicable to the preparation method of the nano material of target medicine carrier the most as claimed in claim 1, it is characterised in that: described step
Suddenly H in (1)2SO4、K2S2O8、P2O5Mixed liquor in the mass ratio of each component be: 10:1:1；Described in described step (3) mole
Change between 0 ~ 0.1 than B=Mg:Zn；Fe in described step (4)3O4Nanoparticles solution concentration is 1 ~ 10mmol/l, ZnO amount
Son point solution concentration is 1 ~ 10mmol/l.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610301971.9A CN105969331B (en) | 2014-09-26 | 2014-09-26 | A kind of preparation method of nano material suitable for target medicine carrier |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610301971.9A CN105969331B (en) | 2014-09-26 | 2014-09-26 | A kind of preparation method of nano material suitable for target medicine carrier |
| CN201410502642.1A CN104263358B (en) | 2014-09-26 | 2014-09-26 | A kind of magnetic fluorescent dual-function stannic oxide/graphene nano matrix material and preparation method |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410502642.1A Division CN104263358B (en) | 2014-09-26 | 2014-09-26 | A kind of magnetic fluorescent dual-function stannic oxide/graphene nano matrix material and preparation method |
Publications (2)
| Publication Number | Publication Date |
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| CN105969331A true CN105969331A (en) | 2016-09-28 |
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| CN108578703A (en) * | 2018-05-25 | 2018-09-28 | 河北工业大学 | A kind of preparation method of function medicine carrying material |
| CN108578703B (en) * | 2018-05-25 | 2020-07-28 | 河北工业大学 | Preparation method of functional drug-loaded material |
| CN114806551A (en) * | 2021-06-01 | 2022-07-29 | 四川大学 | Graphene fluorescent nano material and preparation method and application thereof |
Also Published As
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| CN105860957B (en) | 2017-10-17 |
| CN105969330B (en) | 2017-12-26 |
| CN105969330A (en) | 2016-09-28 |
| CN104263358B (en) | 2016-04-13 |
| CN105860957A (en) | 2016-08-17 |
| CN104263358A (en) | 2015-01-07 |
| CN105969331B (en) | 2017-12-26 |
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