CN101049631A - Composition of silicon dioxide - metal hud particles, and preparation method - Google Patents
Composition of silicon dioxide - metal hud particles, and preparation method Download PDFInfo
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Abstract
A composite SiO2-metal nanoparticle with a core-shell structure for the photothermal therapy of cancer is composed of a SiO2 nanoparticle as core and a coated metal layer as shell, and has the maximal extinctivity (300-2000 nm in wavelength) and the maximal UV absorption (300-2000 nm in wavelength). It's preparing process features that a molecular cross-linking agent is used for cross-linking between SiO2 and metal layer, the metallic nanoparticles are physically adsorbed onto surface of SiO2 nanoparticle, and the solution of relative metal is chemically reduced to cover on the residual surface of SiO2 nanoparticle.
Description
Technical field
The present invention relates to a kind of nano-complex silica-metal core shell particles, especially with the Nano particles of silicon dioxide nuclear, the nano core-shell particle of at least a metal-back of surface parcel, and the preparation method of this nano-complex silica-metal core shell particles is provided, belong to the biological medicine technology field of material science.
Background technology
As everyone knows, the solid metal nano particle has special optical property, and promptly plasma resonance absorbs.It is that electronics and the coupling between the transient electromagnetic field that comes from the metal produces that this plasma resonance absorbs, this plasma resonance absorbing wavelength can be by the particle diameter of control nano particle, thereby changes the UV absorption that caused by the transient electromagnetic radiation and the wave-length coverage of scattering.But these pure metallics change particle diameter in any case, and maximal ultraviolet absorption or scattering can only be below 520nm, and intensity of variation is not obvious.If coated metal layer on the nano particle of non-conductive medium then can make it change UV absorption or scattering in a wider context, in addition to 700 to 2000nm.This photo-thermal therapy to cancer in the biology is significant: the following light source of 800nm is difficult to penetrate muscle or skin histology, the tissue of burning easily; And the above light source of 800nm is not absorbed by tissue, can penetrate tissue by the nano core-shell particle absorb, heat release, thereby make it significant in the photo-thermal therapy of cancer.In recent years, the preparation of Nano composite granules has become ten minutes active research field in the biological medicine technology.By composition, the shape and size of control nucleocapsid structure, people can customize needed Nano composite granules, thereby satisfy the application need of specific area.
Qian Weiping (preparation of gold nanoshell spheroid and potential biological applications thereof, talk usefulness, Ding Shaohua, Wang Yi, Qian Weiping, the chemistry journal, 2005,63 (10), 929-933) wait and once to have reported the RESONANCE ABSORPTION peak position, and studied its optical property in whole blood respectively about the gold nanoshell spheroid of 720nm and 760nm.The present invention prepared in the near infrared region (＞800nm) have a nano core-shell particle of maximum scattering peak and UV absorption, and can control the optical property of core-shell particles by the size of control nuclear and the thickness of shell, and further explore its potential using value in the photo-thermal therapy of cancer.
Summary of the invention
The object of the present invention is to provide a kind of good biocompatibility, good water solubility, have the nano-complex silica-metal core shell particles of particular optical properties.
Another purpose of the present invention is to provide the preparation method of a kind of nano-complex silica-metal core shell particles.
A kind of nano-complex silica of the present invention-metal core shell particles be a kind of be nuclear with the Nano particles of silicon dioxide, the nano core-shell particle of at least a metal-back of surface parcel.
The material of a kind of nano-complex silica of the present invention-metal core shell particles center is a silica, is shaped as sphere.
The metal-back of surface parcel is a metal level in a kind of nano-complex silica of the present invention-metal core shell particles, metal comprises gold, silver, tin or their alloy, the metal level of parcel comprises individual layer and multilayer, further comprise multiple metal-doped single or multiple lift, metal layer thickness is about 5nm to 30nm.
Maximum extinction value is in the wave-length coverage of 300nm to 2000nm in a kind of nano-complex silica of the present invention-metal core shell particles, and maximal ultraviolet absorption is in the wave-length coverage of 300nm to 2000nm.
For obtaining a kind of nano-complex silica-metal core shell particles, the present invention adopts a kind of molecule crosslinked dose to carry out silica and metal level crosslinked, earlier by the nano-metal particle of physical absorption in Nano particles of silicon dioxide surface absorption 20～30%, with electronation respective metal salting liquid remainder silica is wrapped up again, thus the nano core-shell particle that obtains having special optical character.The corresponding salt of metal refers generally to perchlorate, hydrochloride and the nitrate of metal.
Each step is synthetic as follows:
(1) in the core-shell particles is nuclear synthetic of matrix with silica
The first step: with polar solvent ammoniacal liquor is catalyst reduction ethyl orthosilicate (TEOS), and the ratio of the consumption by regulating TEOS, the consumption of ammonia, alcohol/water, mixing speed etc. obtain the monodispersed silicon dioxide granule of different-grain diameter.Effect was best when alcohol was ethanol in this invention.
Water is secondary deionized water, unless mention especially in below describing, general water all is secondary deionized water.All glass apparatus after two hours, wash three times dry for standby under the free from dust condition with the secondary deionized water immersion before use all through the chloroazotic acid soaked overnight again with secondary deionized water.
Second step: this silicon dioxide granule reacted 2～3 hours with being with amino silane reagent in alcohol, heated again 1～2 hour with after 50～100 times of the alcoholic solution dilutions, make that the bonding of crosslinking agent and silica particle surface is more firm, form a kind of silicon dioxide granule of surperficial ammonification.Rotating speed centrifugation with 2000～4000rpm discards supernatant liquor, and sediment disperses with ultrasonic again, removes unreacted silane reagent 4～5 times repeatedly.This particle surface generally has positive charge, even do not add any surface dispersant when centrifugation, still can pass through the ultrasonic monodispersed particle that is dispersed into again, can can't not disperse because of reunion again.
(2) with silica be the preparation of the kind gold particle of nuclear
The first step: the salting liquid that the metal pair that will wrap up in the alkali condition reduction with reducing agent in the aqueous solution is answered, obtain the colloidal solution of particle diameter at the monodispersed metallic of 1nm to 3nm, filter, this solution left standstill under 4 ℃ 5～50 days.Reducing agent is with tetrakis hydroxymethyl phosphonium chloride (THPC) or sodium borohydride (NaBH in this step
4) be good.Best results when wherein metal is golden or silver-colored.The optimal sequence that reaction solution adds is the salting liquid that alkali lye, reducing agent and metal pair are answered.The salting liquid for preparing will keep in Dark Place.
Second step: on go on foot described colloidal metal solution and mix gentle agitation 2～3 hours with the silicon dioxide granule solution of the above-mentioned surperficial ammonification that makes.It is better to find among the present invention that the silicon dioxide granule solution of surperficial ammonification is joined in the colloidal metal solution effect.
The 3rd step: the rotating speed centrifugation with 1000～2000rpm discards the colloidal solution that is not adsorbed to silica particle surface, adds the ultrasonic dispersion of ethanol, and this operation repeats 4～5 times repeatedly, and obtaining with silica is the kind gold particle of nuclear.The coverage rate of this particle surface metal is about 20～30%, carries out in the step under the covering of remainder.
(3) with silica be the preparation of the core-shell particles of nuclear
The first step: preparation contains the aqueous solution of pairing salting liquid of certain density above-mentioned metal and potash, and this solution can standing over night.
Second step: the kind gold particle of above-mentioned gained and this solution according to different volume ratio mixing after, under vigorous stirring, add reducing agent, react after 0.5 hour, the nano metal particles that is not adsorbed to kind of gold surface is removed in rotating speed centrifugation with 3000～5000rpm, obtains the core-shell particles that the surface is coated with the different-thickness metal level fully.Reducing agent is preferably 1% formalin in this step.
Utilize the first step and second step in (2) neutralizations (3), or other chemical methodes, can continue to wrap up once more other metal level at this core-shell particles skin.
The defective that the present invention overcomes prior art provides the new method of the nano core-shell particle that a kind of preparation has special optical character, be about to connect by crosslinking agent between silica and the metal level, form the composite Nano nucleocapsid structure of the electron opaque material of metal level parcel, this nucleocapsid structure has maximal ultraviolet absorption and scattering peak in the near infrared region, significant in the photo-thermal therapy of the various cancers of the mankind.
Description of drawings
Fig. 1: synthetic particle diameter is about the TEM image (60kV) of the preparing spherical SiO 2 of 150nm
Fig. 2: synthetic particle diameter is the TEM image of the golden nanometer particle (in the gold colloid solution) of 1～3nm
Fig. 3: particle diameter is about the TEM image (60kV) of kind golden nanometer particle of the surface coating rate about 20～30% of 160nm
Fig. 4: particle diameter is about the continuous TEM image (60kV) that wraps up the nano silicon core-shell particles of gold layer in surface of 160nm
Fig. 5: particle diameter is about the UV absorption of core-shell particles of silica-Jin of 160nm.Abscissa is a wavelength, and ordinate is an absorbance.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment:
Embodiment 1:
(1) in the core-shell particles is nuclear synthetic of matrix with silica
In the beaker of 100mL cleaning, add the absolute absolute ethyl alcohol of 50mL and the ammoniacal liquor (25%) of 3.0mL, under stirring condition, the purity that adds 0.2mL (0.9mmol) in this solution is 99.999% ethyl orthosilicate (TEOS), solution becomes milky muddy liquid behind about 15～30mim, continues to stir 8h.Obtain the silicon dioxide granule that average grain diameter is 140nm.Survey the pH value of its surface charge and solution with dynamic light scattering.
By the concentration of adjustment ammoniacal liquor and the consumption of TEOS, can synthesize the silica spherical particle of particle diameter at 100～250nm.
(2) ammonification of silica surface
Get the centrifugation of above-mentioned experiment gained silicon dioxide granule suspension (1000～2000rpm), abandon the upper strata stillness of night, sediment adds the ethanol of 10mL, ultrasonic dispersion 5min.The aminopropyl triethoxysilane (APTES) that in this suspension, adds 400uL, the absolute ethyl alcohol dilution that adds 100mL under the room temperature behind the stirring 2h, dilution adds hot reflux 1h under 70 ℃, stop heating, after being cooled to room temperature, with the rotating speed centrifugation of 2500rpm, abandon supernatant liquor, repeat this operation and remove unreacted silane reagent 4～5 times.Last gained precipitation is with standby in the ultrasonic ethanol that is dispersed in 10mL.The pH value of surveying its surface charge and solution with dynamic light scattering with and particle diameter and particle diameter distribute.
(3) contain the preparation of the gold size solution of 1～3nm gold grain
Getting 80% tetrakis hydroxymethyl phosphonium chloride (THPC) aqueous solution 1.2mL, to be diluted to 100mL with secondary deionized water standby.NaOH (0.2M) aqueous solution, the THPC solution of 1mL and the perchloric acid gold (HAuCl of 2.0mL that in the aqueous solution of 45.5mL, add 1.5mL
4, 25mmol), behind the vigorous stirring 1h, at room temperature placed 1 day, be the filter membrane filtration of 200nm with the aperture, obtain the gold grain of 1～3nm.Filtrate in 4 ℃ of refrigerators, continue to place 5～50 days standby.Perchloric acid gold (HAuCl
4) be 99.9% purity.
(4) contain the preparation of the kind gold solution of 1～3nm gold grain
Get the Nano particles of silicon dioxide suspension 1mL of above-mentioned surperficial ammonification and the gold size solution of above-mentioned 100mL and mix gentle agitation 2～3 hours.Rotating speed centrifugation with 1000～2000rpm discards the colloidal solution that is not adsorbed to silica particle surface, adds the ultrasonic dispersion of ethanol, and this operation repeats 4～5 times repeatedly, and obtaining with silica is the kind gold particle of nuclear.Standby in the last ultrasonic secondary deionized water that is dispersed in 15mL of this kind gold particle.This kind gold particle particle diameter is about 150nm.And the pH value of surveying its surface charge and solution with dynamic light scattering with and particle diameter and particle diameter distribute.
(5) preparation of nano core-shell particle
The K of 25mg
2CO
3HAuCl with 1.5mL
4(25mmol) solution joins in the secondary deionized water of 100mL, and this mixed solution (PCG) can use after placing one day under the lucifuge.The PCG solution of getting above-mentioned kind of gold solution 1mL and 60mL mixes, after violent speed stirs 10mim, the formalin (1%) that adds 5mL fast, after continuing to stir 0.5h, the nano metal particles that is not adsorbed to kind of gold surface is removed in rotating speed centrifugation with 3000～5000rpm, repeats this minimal manipulation 5 times repeatedly.Gained precipitation is ultrasonic to be scattered in the water of 5mL again, and the concentration of nano particle is about 4 * 10 in this solution
11Individual/mL.Survey its particle diameter and survey its UV absorption with transmission electricity border with ultraviolet spectrometer, and the pH value of surveying its surface charge and solution with dynamic light scattering with and particle diameter and particle diameter distribution.Nano-silica surface has wrapped up one deck gold continuously, and this gold layer thickness is about 10nm.Uv atlas shows that it has maximal ultraviolet absorption at about 850nm.
Embodiment 2:
(1) in the core-shell particles is nuclear synthetic of matrix with silica
In the beaker of 100mL cleaning, add the absolute absolute ethyl alcohol of 50mL and the ammoniacal liquor (5.0%) of 15.0mL, under stirring condition, the purity that adds 0.2mL (0.9mmol) in this solution is 99.999% ethyl orthosilicate (TEOS), solution becomes translucent muddy liquid behind about 15～30mim, continues to stir 8h.Obtain the silicon dioxide granule that average grain diameter is 100nm.
The consumption of regulating TEOS in the example 1 (1) is 0.4mL and other reagent dosages are constant, through similarly obtaining the silicon dioxide granule that average grain diameter is 250nm after the reaction.
Generally speaking, under other reagent dosage same cases, the concentration of ammoniacal liquor is got over the end, and gained silicon dioxide granule particle diameter is more little; The consumption of TEOS is many more, and gained silicon dioxide granule particle diameter is big more.
(2) ammonification of silica surface
Get experiment averaging of income particle diameters in the above-mentioned example 2 (1) and be 100nm the centrifugation of silicon dioxide granule suspension (1000～2000rpm), abandon the upper strata stillness of night, sediment adds the ethanol of 10mL, ultrasonic dispersion 5min.The aminopropyl triethoxysilane (APTES) that in this suspension, adds 250uL, the absolute ethyl alcohol dilution that adds 100mL under the room temperature behind the stirring 2h, dilution adds hot reflux 1h under 70 ℃, stop heating, after being cooled to room temperature, with the rotating speed centrifugation of 2500rpm, abandon supernatant liquor, repeat this operation and remove unreacted silane reagent 4～5 times.Last gained precipitation is with standby in the ultrasonic ethanol that is dispersed in 10mL.The pH value of surveying its surface charge and solution with dynamic light scattering with and particle diameter and particle diameter distribute.
(3) contain the preparation of the kind gold solution of 1～3nm gold grain
The Nano particles of silicon dioxide suspension 1mL and the gold size solution 100mL in the above-mentioned example 1 (3) that get this surface ammonification mix gentle agitation 2～3 hours.Rotating speed centrifugation with 2000rpm discards the colloidal solution that is not adsorbed to silica particle surface, adds the ultrasonic dispersion of ethanol, and this operation repeats 4～5 times repeatedly, and obtaining with silica is the kind gold particle of nuclear.Standby in the last ultrasonic secondary deionized water that is dispersed in 15mL of this kind gold particle.And the pH value of surveying its surface charge and solution with dynamic light scattering with and particle diameter and particle diameter distribute.This kind gold particle particle diameter is about 120nm.
(4) preparation of nano core-shell particle
The K of 25mg
2CO
3HAuCl with 1.5mL
4(25mmol) solution joins in the secondary deionized water of 100mL, and this mixed solution (PCG) can be placed under lucifuge after one day and use.The PCG solution of getting above-mentioned kind of gold solution 1mL and 80mL mixes, after violent speed stirs 10mim, the formalin (1%) that adds 6mL fast, after continuing to stir 0.5h, the nano metal particles that is not adsorbed to kind of gold surface is removed in rotating speed centrifugation with 3000～5000rpm, repeats this minimal manipulation 5 times repeatedly.Gained precipitation is ultrasonic to be scattered in the water of 5mL again.Survey its particle diameter and survey its UV absorption with transmission electricity border with ultraviolet spectrometer, and the pH value of surveying its surface charge and solution with dynamic light scattering with and particle diameter and particle diameter distribution.Nano-silica surface has wrapped up one deck gold continuously, and this gold layer thickness is about 10nm.Uv atlas shows that it has maximal ultraviolet absorption at about 750nm.
Embodiment 3:
The PCG solution of getting kind gold solution 1mL in the above-mentioned example 1 (4) and 30mL mixes, after violent speed stirs 10mim, the formalin (1%) that adds 3mL fast, after continuing to stir 0.5h, the nano metal particles that is not adsorbed to kind of gold surface is removed in rotating speed centrifugation with 3000～5000rpm, repeats this minimal manipulation 5 times repeatedly.Gained precipitation is ultrasonic to be scattered in the water of 5mL again, and the concentration of nano particle is about 4 * 10 in this solution
11Individual/mL.Survey its particle diameter and survey its UV absorption with transmission electricity border with ultraviolet spectrometer, and the pH value of surveying its surface charge and solution with dynamic light scattering with and particle diameter and particle diameter distribution.Nano-silica surface has wrapped up one deck gold continuously, and this gold layer thickness is about 5nm.Uv atlas shows that it has maximal ultraviolet absorption about 700nm.
The PCG solution of getting kind gold solution 1mL in the above-mentioned example 1 (4) and 100mL mixes, after violent speed stirs 10mim, the formalin (1%) that adds 8mL fast, after continuing to stir 0.5h, the nano metal particles that is not adsorbed to kind of gold surface is removed in rotating speed centrifugation with 3000～5000rpm, repeats this minimal manipulation 5 times repeatedly.Gained precipitation is ultrasonic to be scattered in the water of 5mL again, and the concentration of nano particle is about 4 * 10 in this solution
11Individual/mL.Survey its particle diameter and survey its UV absorption with transmission electricity border with ultraviolet spectrometer, and the pH value of surveying its surface charge and solution with dynamic light scattering with and particle diameter and particle diameter distribution.Nano-silica surface has wrapped up one deck gold continuously, and this gold layer thickness is about 30nm.Uv atlas shows that it has maximal ultraviolet absorption about 650nm.
For the solution of the identical kind gold particle of particle diameter, under the certain condition of concentration, PCG consumption many more (are used to reduce PCG formaldehyde consumption also increase in proportion), SiO
2The gold layer that particle surface covers is thick more, and its uv-absorption maximum wavelength value is more little; The consumption of PCG is few more, and surface gold layer is thin more, and its uv-absorption maximum wavelength value is big more.Its Volume Changes of formaldehyde influences very little in 3-10mL.
Concerning a certain amount of kind of gold, particle diameter is more little, and covering gold layer required PCG consumption is many more fully to reach the surface; It is more little to plant the goldc grains footpath, the easy more reunion of the core-shell nano of generation, and its maximal ultraviolet absorption moves to the shortwave direction more.
Embodiment 4:
Aminopropyl triethoxysilane (APTES) among the embodiment 1 in (2) step substitutes with aminopropyl trimethoxysilane, two aminopropyl diethoxy silanes, 4-ammonia butyl dimethyl methyl TMOS or phenyl triethoxysilane respectively silica surface is carried out oxidation.Other are with embodiment 1.
The particle diameter of this project gained nano particle distributes with the MARLVEN Zetasizer Nano-ZS of company type dynamic light scattering (DLS) test, and probe temperature is 25 ℃, and laser wavelength of incidence is 633nm.Transmission electricity border picture is tested (60kV) with the Philips120C type transmission electricity border of PGILIPS company.Ultraviolet spectrometer is that ultraviolet spectrometer grinds the UV1900PC of Electronics Co., Ltd. type ultraviolet device for the Asia, Shanghai.
Only in order to explanation the present invention but be not limited thereto, should be appreciated that in not breaking away from spiritual scope of the present invention also can have multiple accommodation or alternative to the foregoing description.
Claims (8)
1. nano-complex silica-metal core shell particles, comprise silica core and metal-back, it is characterized in that examining into particle diameter at the silica between the 100nm to 250nm, shell is gold, silver, tin or their alloy, and the thickness of shell is between the 5nm to 30nm, and shell is connected the surface of silica nuclear particle by crosslinking agent.
2. nano-complex silica as claimed in claim 1-metal core shell particles is characterized in that the silica core shape of particle is for spherical.
3. nano-complex silica as claimed in claim 1-metal core shell particles, the metal level that it is characterized in that forming shell are the individual layer that a kind of metal forms, or the multilayer that forms of different metal, perhaps are the single or multiple lift of metal alloy formation.
4. nano-complex silica as claimed in claim 1-metal core shell particles is characterized in that crosslinking agent is aminopropyl triethoxysilane, aminopropyl trimethoxysilane, two aminopropyl diethoxy silanes, 4-ammonia butyl dimethyl methyl TMOS or phenyl triethoxysilane.
5. nano-complex silica as claimed in claim 1-metal core shell particles is characterized in that the sphere that is shaped as of nano-complex silica-metal core shell particles.
6. nano-complex silica as claimed in claim 1-metal core shell particles is characterized in that the metal level of nano core-shell particle wraps up the part of silicon dioxide granule for nuclear fully.
7. the preparation method of nano-complex silica-metal core shell particles is characterized in that comprising the steps:
(1) in the core-shell particles is nuclear synthetic of matrix with silica
The first step: in polar solvent, be catalyst reduction ethyl orthosilicate (TEOS), obtain monodispersed Nano particles of silicon dioxide with ammonia;
Second step: in alcohol, the crosslinking agent binding is arrived silica particle surface, form a kind of silicon dioxide granule of surperficial ammonification;
(2) with silica be the preparation of the kind gold particle of nuclear
The first step: in the aqueous solution,, obtain the colloidal solution of particle diameter at the monodispersed metallic of 1nm to 3nm with perchlorate, hydrochloride or the nitrate solution of the reducing agent reduction coated metal of being wanted;
Second step: on go on foot described metallic colloidal solution mix stirring with the silicon dioxide granule solution of the above-mentioned surperficial ammonification that makes;
The 3rd step: centrifugation discards the colloidal solution that is not adsorbed to silica particle surface, ultrasonic dispersion, and obtaining with silica is the kind gold particle of nuclear, the coverage rate of this particle surface conductive materials is about 20～30%;
(3) with silica be the preparation of the core-shell particles of nuclear
The first step: preparation contains the aqueous solution of pairing salting liquid of above-mentioned metal and potash;
Second step: will plant after the solution in first step mixes in gold particle and (3), and add reducing agent under vigorous stirring, the centrifugation removal is not adsorbed to the nano metal particles of kind of gold surface, obtains the surperficial core-shell particles that is coated with metal level fully.
8. the preparation method of nano-complex silica as claimed in claim 7-metal core shell particles is characterized in that the polar solvent in the first step is alcohol, water or the mixture of the two in (1).
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