CN101125968A - Magnetism/metal/fluorescence composite silicon dioxide nano particle and preparation method thereof - Google Patents
Magnetism/metal/fluorescence composite silicon dioxide nano particle and preparation method thereof Download PDFInfo
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Abstract
The invention relates to magnetic/metal/fluorescence compound silicon dioxide nanometer particle and preparation method thereof, pertaining to nanometer material technical field. The nanometer particle is covered with an internal magnetic core, a metal layer and a lighting layer in sequence from interior to exterior; the internal magnetic core consists of organosilicon covering 6-1,000 ferrite nanometer particles; the metal layer is of a connection shell layer made of Ag or Au; the lighting layer is of SiO2 layer doped with organic lighting dye. The preparation method comprises steps of preparation of ferrite nanometer particles, laying silicon dioxide and metal layer to the internal magnetic core through inorganic silicon resource and organic silicon resource, secondary organic silicon layer coating and the coating of the layer doped with organic lighting dye. The nanometer particle of the invention has high lighting intensity and can dramatically improve detection sensitivity when being applied in biological marker, has rapid response in magnetic field, which improves separating rate; during preparation course, the control of magnetic matter content, diameter of particle and silicon dioxide shell layer through adjustment of reaction conditions.
Description
Technical field
The invention belongs to technical field of nano material, particularly a kind of magnetic/metal/fluorescence composite silicon dioxide nano particle and preparation method thereof.
Background technology
The magnetic composite fluorescent nano particle makes it be with a wide range of applications at biomedical sectors such as bioseparation, immunodetection, targeted imagings owing to have the unique magnetic property (superparamagnetism) and the characteristics of luminescence simultaneously.The magnetic composite fluorescent nano particle generally is that magnetic nano-particle and fluorescence quantum or organic light emission dyestuff are embedded in inorganic or the polymeric matrix jointly to reach the compound purpose.Because silicon-dioxide has chemistry and advantages such as colloidal stability is good, good biocompatibility make it become one of ideal material of coated magnetic and fluorescent particles.But in magnetic composite fluorescence particle, owing to exist energy to shift between magnetic nano-particle and luminescent quantum dot or the luminous organic dye, to luminous quenching effect arranged, and magnetic particle itself causes the luminous intensity of composite particles to weaken to the absorption of visible light, limited its application at biological field.
At present, the method for the synthesizing magnetic fluorescent composite nanoparticle close with the present invention is the magnetic fluorescent dual-function microballoon (ZL03150921.5) with nucleocapsid structure of people such as Zheng Yonghui invention.They have carried out surface modification with Trisodium Citrate to the inorganic magnetic particle earlier, with the tetraethoxy silicone dioxide magnetic microsphere that presoma synthesizes nucleocapsid structure with sol-gel method again, at last with being connected with the fluorescein of silane coupling agent and the method for tetraethoxy copolycondensation has synthesized the fluorescent microsphere with magnetic.The method of this synthesizing magnetic fluorescence composite particles can be controlled the distance between magnetic nano-particle and the luminophor, eliminated because energy shifts the quenching of fluorescence that causes, but can not eliminate the inhalation effects of the light that magnetic particle sends fluorophore, still reduce the luminous efficiency of particle.Over the past two years, it is found that metal nano material has very big enhancement to the luminous intensity of luminescent dye molecule, this has played technical support with regard to we that make for the problem that solves a little less than the magnetic composite fluorescence nano material luminous intensity.
Summary of the invention
The technical problem to be solved in the present invention is, at the luminous weak shortcoming of existing preparation magnetic fluorescent composite nanoparticle, invents a kind of luminous intensity height, and particle diameter is controlled, and magnetic is strong, the magnetic that chemistry and colloidal stability are good/metal/fluorescence composite nanoparticle.
Magnetic/metal/fluorescence composite silicon dioxide nano particle of the present invention is a matrix with silicon-dioxide, and nanoparticle is embedded with magnetic kernel, metal level and luminescent layer from inside to outside successively.Described magnetic kernel is made up of the ferrite nano particles with superparamagnetism of coated with silica single magnetic domain, and 6～1000 ferrite nano particles are arranged in the kernel; Described metal level is the continuous shell that is formed by Ag or Au; Described luminescent layer is the dye adulterated SiO of organic light emission
2Layer; Whole nanoparticle globulate, particle diameter is between 50～1000nm.。Whole nanoparticle globulate, size is between 50～1000nm.
Above-mentioned metal layer thickness is between 5～50nm, and light emitting layer thickness is between 10～100nm; Distance between metal level and the luminescent layer can be regulated and control, between 5～30nm.
Above-mentioned ferrite nano particles is Fe
3O
4, CoFe
2O
4, MnFe
2O
4Or ZnFe
2O
4Nanoparticle, its particle diameter has superparamagnetism between 5～15nm.
A kind of preparation method of magnetic/metal/fluorescence composite silicon dioxide nano particle, synthesis step comprises that coprecipitation method prepares ferrite nano particles; Synthesis step carries out coated with silica by inorganic silicon source and organosilicon source to magnetic kernel in addition, and metal level coats, for the second time the coating of the dye adulterated layer of the coating of silicone layer and organic light emission;
Describedly carry out coated with silica by inorganic silicon source and organosilicon source and be, ferrite nano particles is dispersed in adds the inorganic silicon that water glass carries out ferrite nano particles in the water and coat; Then ferrite nano particles is dispersed in the ethanol, adds ammoniacal liquor and TEOS and carry out silicone covering, form magnetic kernel;
Described metal level coats, at first the magnetic kernel with surperficial coated silica is dispersed in the ethanol, add silane coupling agent with its finishing amino or sulfydryl, transfer to again that aqueous phase adds Ag or the Au nanoparticle carries out coupling, and then add the Ag ion or the tetra chlorauric acid radical ion makes it form continuous shell at the magnetic kernel surface reduction;
Described second time, the coating of silicone layer was, the particle that is coated with Ag or Au shell is dispersed in the water, added silane coupling agent and modified, and transferred in the ethanol again, added ammoniacal liquor and tetraethoxy (TEOS) growth SiO
2Layer;
The coating of the dye adulterated layer of described organic light emission is to coat SiO
2The magnetic nano-particle that has Ag or Au shell of layer is dispersed in the ethanol, adds the presoma and the TEOS of ammoniacal liquor and organic light emission dyestuff, continues reaction 6～24 hours.
Above-mentioned superparamagnetism ferrite nano particles prepares with coprecipitation method, and coprecipitation method is the method for preparing ferrite nano particles of existing technology maturation.The present invention is under 20～60 ℃, is 1: 2 Fe with mol ratio
2+(or Co
2+, Zn
2+, Mn
2+) and Fe
3+Solution join in the alkaline aqueous solution fast, and vigorous stirring, gained precipitation are collected with permanent magnet and with the high purity water washing, last ultra-sonic dispersion obtains superparamagnetic nano particle colloidal sol in water.
Above-mentioned silane coupling agent can be silane coupling agent such as the γ-sulfydryl propyl-triethoxysilicane that has sulfydryl, also can be to have amino silane coupling agent such as γ-An Jibingjisanyiyangjiguiwan.
The presoma of above-mentioned organic light emission dyestuff, be meant organic light emission dyestuff and silane coupling agent are dissolved in ethanol or/and in the tetrahydrofuran (THF), the lucifuge reaction is 3～15 hours under the magnetic agitation, makes organic light emission dyestuff and silane coupling agent compound organic light emission dye precursor; Wherein, the quality percentage composition of organic light emission dyestuff is between 0.001%～3%, and the quality percentage composition of silane coupling agent is between 0.4%～15%.
Above-mentioned golden nanometer particle or Nano silver grain, its size is between 2～40nm; Said Ag ion or tetra chlorauric acid radical ion, its concentration is between 0.001M～0.05M.
Above-mentioned in the coating of the SiO2 layer second time, the quality percentage composition of ammoniacal liquor is between 0.5%～5%; TEOS quality percentage composition is between 0.1%～1%.
Above-mentioned the quality percentage composition of organic dye is between 0.01%～0.1% in the reaction solution in the coating of the dye adulterated layer of organic light emission, and the percentage composition of TEOS is between 1%～4%.
The nanoparticle of method preparation of the present invention is compared with common magneto-optic compound nanoparticle, and the luminous intensity of particle has improved about 10 times, can significantly improve the sensitivity of detection in biological imaging; The magnetic substances content height of resulting particle, response has improved separation efficiency rapidly under magnetic field; In preparation process, the regulation and control reaction conditions can be realized the controlled of magnetic substance content, microspherulite diameter and silica shell; This nanoparticle has excellent biological compatibility and chemical stability, and is easy to further functionalization such as amino, carboxyl, sulfydryl.
Embodiment
Synthesizing of embodiment 1 ferrite nano particles: Fe
3O
4The preparation of nanoparticle
Take by weighing the FeCl of 1g
36H
2The FeCl of O and 0.37g
24H
2O, the water dissolution of passing through letting nitrogen in and deoxidizing with 20ml obtains mixing solutions.Get 130ml water letting nitrogen in and deoxidizing in the round-bottomed flask of 250mL, the mass percent concentration that adds 12.5ml is the strong aqua of 25-28%, rapidly to wherein pouring above-mentioned molysite mixing solutions into, reacts 1h down at 80 ℃ under vigorous stirring.After reaction finishes, isolate the solid of black with the permanent magnet of 0.1T from reaction soln, the gained solid promptly gets the Fe that particle diameter is 6～10nm 3～5 times with the high purity water cleaning
3O
4Nanoparticle.
Synthesizing of embodiment 2 ferrite nano particles: CoFe
2O
4The preparation of nanoparticle
Take by weighing the FeCl of 1g
36H
2The CoCl of O and 0.38g
24H
2O, the water dissolution of passing through letting nitrogen in and deoxidizing with 20ml obtains mixing solutions.Get 130ml water letting nitrogen in and deoxidizing in the round-bottomed flask of 250mL, the mass percent concentration that adds 12.5ml is the strong aqua of 25-28%, rapidly to wherein pouring above-mentioned mixing salt solution into, reacts 1h down at 50 ℃ under vigorous stirring.After reaction finishes, isolate the solid of black with the permanent magnet of 0.1T from reaction soln, the gained solid promptly gets the CoFe that particle diameter is 3～13nm 3～5 times with the high purity water cleaning
2O
4Nanoparticle.Can be with CoCl
2Be changed to MnCl
2Or ZnCl
2Obtain corresponding M nFe
2O
4Or ZnFe
2O
4Nanoparticle.
By inorganic silicon source and organosilicon source magnetic kernel is carried out coated with silica.
Embodiment 3 carries out coated with silica by inorganic silicon source and organosilicon source to magnetic kernel: the inorganic silicon source coats
Take by weighing 0.6g Na
2SiO
3(SiO
2Content is 45%) be dissolved in the 50ml water, be 9.6 with the pH of resin cation (R.C.) regulator solution, to wherein adding the above-mentioned synthetic Fe of 0.5g
3O
4Nanoparticle.At room temperature, in the 250mL round-bottomed flask, react 12h with the 150rpm stirring velocity.After reaction finishes, isolate the solid of black with the permanent magnet of 0.1T from reaction soln, the gained solid promptly gets the Fe that particle diameter is the coated with silica of 7～12nm 3～5 times with the high purity water cleaning
3O
4Nanoparticle.
With Fe
3O
4Nanoparticle changes CoFe into
2O
4, MnFe
2O
4Or ZnFe
2O
4Nanoparticle can obtain the magnetic nano-particle of corresponding inorganic silicon source coated with silica.
Embodiment 4 carries out coated with silica by inorganic silicon source and organosilicon source to magnetic kernel: the organosilicon source coats Fe
3O
4Nanoparticle
The strong aqua, 0.01g that add 100ml ethanol, 5ml water, 2ml mass percent concentration successively and be 25-28% in the 250mL round-bottomed flask are through inorganic silicon source coated with silica synthetic Fe
3O
4Nanoparticle and 0.03mlTEOS behind the reaction 12h, isolate the solid of black with the permanent magnet of 0.1T from reaction soln, the gained solid promptly gets the multinuclear Fe that mean sizes is 40nm 3～5 times with the high purity water cleaning
3O
4/ SiO
2Core-shell particle, its average check figure is 6.
Embodiment 5 carries out coated with silica by inorganic silicon source and organosilicon source to magnetic kernel: the organosilicon source coats CoFe
2O
4Nanoparticle
The strong aqua, 0.05g that add 100ml ethanol, 5ml water, 3ml mass percent concentration successively and be 25-28% in the 250mL round-bottomed flask are through inorganic silicon source coated with silica synthetic CoFe
2O
4Nanoparticle and 0.3ml TEOS behind the reaction 12h, isolate the solid of black with the permanent magnet of 0.1T from reaction soln, the gained solid promptly gets the multinuclear CoFe that mean sizes is 400nm 3～5 times with the high purity water cleaning
2O
4/ SiO
2Core-shell particle, its average check figure is about 400.
Embodiment 6 carries out coated with silica by inorganic silicon source and organosilicon source to magnetic kernel: the organosilicon source coats MnFe
2O
4Or ZnFe
2O
4Nanoparticle
The strong aqua, 0.1g that add 100ml ethanol, 5ml water, 5ml mass percent concentration successively and be 25-28% in the 250mL round-bottomed flask are through inorganic silicon source coated with silica synthetic MnFe
2O
4Or ZnFe
2O
4Nanoparticle and 0.5ml TEOS behind the reaction 12h, isolate the solid of black with the permanent magnet of 0.1T from reaction soln, the gained solid promptly gets the multinuclear MnFe that mean sizes is 800nm 3～5 times with the high purity water cleaning
2O
4/ SiO
2Or ZnFe
2O
4/ SiO
2Core-shell particle, its average check figure is about 1000.
Embodiment 7 metal levels coat: carry out finishing with silane coupling agent
With the Fe that obtains among the embodiment 4
3O
4/ SiO
2The core-shell particle constant volume is in 100ml ethanol, join in the three-necked bottle of 250ml, add 2ml ammoniacal liquor and 10 μ l γ-An Jibingjisanyiyangjiguiwans (APS) again, react after 12 hours with the solid of isolating black with the permanent magnet of 0.1T from reaction soln, the gained solid cleans with high purity water and promptly gets amido modified Fe 3～5 times
3O
4/ SiO
2Nanoparticle.
With Fe
3O
4/ SiO
2Core-shell particle changes resulting CoFe in embodiment 5 or 6 into
2O
4/ SiO
2, MnFe
2O
4/ SiO
2Or ZnFe
2O
4/ SiO
2Nanoparticle can obtain corresponding other amido modified magnetic nano-particle.
Change APS into γ-sulfydryl propyl-triethoxysilicane (MPS) and can obtain the magnetic nano-particle of sulfydryl modification.
Embodiment 8 metal levels coat: the preparation of Au layer
With the amido modified Fe that obtains among the embodiment 7
3O
4/ SiO
2The nanoparticle constant volume is in 100ml water, Au (10mg/ml) nanoparticle that adds 10ml 2nm, react permanent magnet separating particle from reaction soln of using 0.1T after 2 hours, it is inferior to give a baby a bath on the third day after its birth with high purity water, add the HAuCl4 of 1ml 0.1M and the aqueous hydroxylamine of 10ml 0.2M, react after 2 hours, obtain the magnetic particle that 5nmAu coats.Whole size of particles is 45nm.
CoFe with the sulfydryl modification that obtains among the embodiment 7
2O
4/ SiO
2The nanoparticle constant volume is in 100ml water, Au (10mg/ml) nanoparticle that adds 10ml 2nm, react permanent magnet separating particle from reaction soln of using 0.1T after 2 hours, it is inferior to give a baby a bath on the third day after its birth with high purity water, add the HAuCl4 of 10ml 0.1M and the aqueous hydroxylamine of 10ml 0.2M, react after 2 hours, obtain the magnetic particle that 25nm Au coats.Whole particle mean sizes is 425nm.
Embodiment 9 metal levels coat: the preparation of Ag layer
With the amido modified MnFe that obtains among the embodiment 7
2O
4/ SiO
2Or ZnFe
2O
4/ SiO
2The nanoparticle constant volume is in 100ml water, Ag (10mg/ml) nanoparticle that adds 10ml 30nm, react permanent magnet separating particle from reaction soln of using 0.1T after 2 hours, it is inferior to give a baby a bath on the third day after its birth with high purity water, add the AgNO3 of 5ml 0.1M and the sodium citrate aqueous solution of 5ml 0.2M, react after 2 hours, obtain the magnetic particle that 50nmAg coats.Whole particle mean sizes is 850nm.
Embodiment 10 coating of silicone layer for the second time and the coating of the dye adulterated layer of organic light emission
The magnetic particle that resulting 5nm Au shell among the embodiment 8 is coated is dispersed in the 100ml water, add 10 μ lAPS, react permanent magnet separating particle from reaction soln of using 0.1T after 10 hours, particle is joined in the 100ml ethanol again, add 0.5ml ammoniacal liquor, 0.1ml TEOS, react after 10 hours, add the different thiocyanate fluorescein of 0.1ml 1mg/L and the presoma of APS reaction again, 0.1ml the TEOS reaction obtains magnetic/metal/fluorescence composite nanoparticle of 55nm after 24 hours, wherein golden shell thickness is 5nm, with luminescent layer distance be 5nm, light emitting layer thickness is 5nm.
Embodiment 11 coating of silicone layer for the second time and the coating of the dye adulterated layer of organic light emission
The magnetic particle that resulting 25nm Au shell among the embodiment 8 is coated is dispersed in the 100ml water, add 10 μ lAPS, react permanent magnet separating particle from reaction soln of using 0.1T after 10 hours, particle is joined in the 100ml ethanol again, add 1.5ml ammoniacal liquor, 0.5mlTEOS, react after 10 hours, the phenanthroline connection ruthenium that adds 0.5ml 1mg/L again, 1ml TEOS reaction obtains magnetic/metal/fluorescence composite nanoparticle of 490nm after 12 hours, wherein golden shell thickness is 25nm, with luminescent layer distance be 15nm, light emitting layer thickness is 50nm.
Embodiment 12 coating of silicone layer for the second time and the coating of the dye adulterated layer of organic light emission
The magnetic particle that resulting 50nmAg shell among the embodiment 9 is coated is dispersed in the 100ml water, add 10 μ lAPS, react permanent magnet separating particle from reaction soln of using 0.1T after 10 hours, particle is joined in the 100ml ethanol again, add 5ml ammoniacal liquor, 1ml TEOS, react after 10 hours, add the different thiocyanate fluorescein of 1ml 1mg/L and the presoma of APS reaction again, 2ml TEOS reaction obtains magnetic/metal/fluorescence composite nanoparticle of 1000nm after 6 hours, wherein silver-colored shell thickness is 50nm, with luminescent layer distance be 30nm, light emitting layer thickness is 100nm.
Claims (7)
1. a magnetic/metal/fluorescence composite silicon dioxide nano particle is characterized in that, nanoparticle is embedded with magnetic kernel, metal level and luminescent layer from inside to outside successively; Described magnetic kernel is made up of the ferrite nano particles with superparamagnetism of coated with silica single magnetic domain, and 6～1000 ferrite nano particles are arranged in the kernel; Described metal level is the continuous shell that is formed by Ag or Au; Described luminescent layer is the dye adulterated SiO of organic light emission
2Layer; Whole nanoparticle globulate, particle diameter is between 50～1000nm.
2. according to the described a kind of magnetic/metal/fluorescence composite silicon dioxide nano particle of claim 1, it is characterized in that: metal layer thickness is between 5～50nm, and light emitting layer thickness is between 10～100nm; Distance between metal level and the luminescent layer is between 5～30nm.
3. according to claim 1 or 2 described magnetic/metal/fluorescence composite silicon dioxide nano particles, it is characterized in that described ferrite nano particles is Fe
3O
4, CoFe
2O
4, MnFe
2O
4Or ZnFe
2O
4Nanoparticle, its particle diameter is between 5～15nm.
4. the preparation method of a magnetic/metal/fluorescence composite silicon dioxide nano particle as claimed in claim 1, synthesis step comprises that coprecipitation method prepares ferrite nano particles; It is characterized in that: synthesis step carries out coated with silica, metal level coating, the coating of silicone layer for the second time and the coating of the dye adulterated layer of organic light emission by inorganic silicon source and organosilicon source to magnetic kernel in addition;
Describedly carry out coated with silica by inorganic silicon source and organosilicon source and be, ferrite nano particles is dispersed in adds the inorganic silicon that water glass carries out ferrite nano particles in the water and coat; Then ferrite nano particles is dispersed in the ethanol, adds ammoniacal liquor and tetraethoxy and carry out silicone covering, form magnetic kernel;
Described metal level coats, at first the magnetic kernel with surperficial coated silica is dispersed in the ethanol, add silane coupling agent with its finishing amino or sulfydryl, transfer to again that aqueous phase adds Ag or the Au nanoparticle carries out coupling, and then add the Ag ion or the tetra chlorauric acid radical ion makes it form continuous shell at the magnetic kernel surface reduction;
Described second time, the coating of silicone layer was, the particle that is coated with Ag or Au shell is dispersed in the water, added silane coupling agent and modified, and transferred in the ethanol again, added ammoniacal liquor and tetraethoxy growth SiO
2Layer;
The coating of the dye adulterated layer of described organic light emission is to coat SiO
2The magnetic nano-particle that has Ag or Au shell of layer is dispersed in the ethanol, adds the presoma and the tetraethoxy of ammoniacal liquor and organic light emission dyestuff, continues reaction 6～24 hours.
5. according to the preparation method of the described magnetic/metal/fluorescence composite silicon dioxide nano particle of claim 4, it is characterized in that, described silane coupling agent is the γ-sulfydryl propyl-triethoxysilicane that has sulfydryl, or has amino γ-An Jibingjisanyiyangjiguiwan.
6. according to the preparation method of claim 4 or 5 described described magnetic/metal/fluorescence composite silicon dioxide nano particles, it is characterized in that, the presoma of described organic light emission dyestuff, be meant organic light emission dyestuff and silane coupling agent are dissolved in ethanol or/and in the tetrahydrofuran (THF), the lucifuge reaction is 3～15 hours under the magnetic agitation, makes organic light emission dyestuff and silane coupling agent compound organic light emission dye precursor; Wherein, the quality percentage composition of organic light emission dyestuff is between 0.001%～3%, and the quality percentage composition of silane coupling agent is between 0.4%～15%.
7. according to the preparation method of claim 4 or 5 described described magnetic/metal/fluorescence composite silicon dioxide nano particles, it is characterized in that, described golden nanometer particle or Nano silver grain, its size is between 2～40nm; Described Ag ion or tetra chlorauric acid radical ion, its concentration is between 0.001M～0.05M; In the coating of the silicone layer second time, the quality percentage composition of ammoniacal liquor is between 0.5%～5%; Tetraethoxy quality percentage composition is between 0.1%～1%; In the coating of the dye adulterated layer of organic light emission, the quality percentage composition of organic light emission dyestuff is between 0.01%～0.1% in the reaction solution, and the percentage composition of tetraethoxy is between 1%～4%.
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