CN104162665A - Gold-organic silicon-gold multilayer core-shell nano-structure and preparing method and application thereof - Google Patents
Gold-organic silicon-gold multilayer core-shell nano-structure and preparing method and application thereof Download PDFInfo
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Abstract
The invention provides a gold-organic silicon-gold multilayer core-shell nano-structure and a preparing method and application of the multilayer core-shell nano-structure. The multilayer core-shell nano-structure comprises an inner core, a middle dielectric layer and an outer shell, wherein the inner core is made of gold nanoparticles, the middle dielectric layer is made of organic silicon and encircles the inner core, and the outer shell is made of gold nano materials and encircles the middle dielectric layer. The preparing method includes the steps that a, gold chloride and trisodium citrate are used for preparing a colloidal solution where the gold nanoparticles are dispersed; b, ammonia water and sulfydryl silane are added to form the middle dielectric layer made of the organic silicon, and sulfydryl on the surface of the middle dielectric layer is functionalized; c, gold chloride and a reducing agent are added, and a in-situ reduction seed growing method is used for forming the outer shell made of the gold nano materials. The preparing method is simple, efficient and good in repeatability. The multilayer core-shell nano-structure is uniform in appearance and good in monodispersity, has a better photo-thermal effect under irradiation of near-infrared laser compared with a common single-layer gold nano-shell and can serve as an ace enhanced Raman scattering substrate material used for Raman biological imaging.
Description
Technical field
The present invention relates to nanometer and technical field of biological material, relate more specifically to multi-layer core-shell nanostructured of a kind of gold-organosilicon-Jin and its preparation method and application.
Background technology
In recent years, gold nanoshell is because its adjustable plasma optical property and wide biomedical applications and optical application prospect are just being subject to paying close attention to more and more widely.Gold nanoshell can produce adjustable plasma primitive resonance, thereby causes strong optical absorption and scattering.By regulating the relative size (being nucleocapsid ratio) of core and shell, visible ray can be crossed near infrared region (650-1300nm) in its delustring peak.For adjusting plasma resonance characteristic that can be more meticulous, the multi-layer core-shell nanostructured of a kind of special gold-silica-Jin is mentioned by people.In theory, compare with common single layer of gold nanoshell, multi-layer core-shell nanostructured has more complicated excellent optical property.First, can there is plasma effect in inner core particles and outer golden shell, and this makes multi-layer core-shell nanostructured occur more plasma resonance peak.In addition, by regulating the interlevel dielectric layer thickness of multi-layer core-shell nanostructured, the absorption of multi-layer core-shell nanostructured and scattering phase can be conditioned power, and this makes multi-layer core-shell nanostructured application potential aspect bio-imaging and treatment huge.And multi-layer core-shell structure multi-layer core-shell nanostructured can also be supported " Fano " resonance." Fano " resonates aspect detection sensitivity or larger breakthrough, and therefore, multi-layer core-shell nanostructured has larger advantage as biological response reagent of future generation.Near field distribution is calculated and is shown, the kernel gold grain surface of multi-layer core-shell nanostructured has good near field and strengthens.This result is indicating that multi-layer core-shell nanostructured, as SERS (SERS) substrate, has wide application potential in environmental monitoring and basic biomedical research field.
Although multi-layer core-shell nanostructured has very excellent optical property, up to now, the controlled preparation report of relevant multi-layer core-shell nanostructured is few.Limited report demonstration, the intermediate dielectric layer of multi-layer core-shell nanostructured is all to adopt silica to form (R.Bardhan, S.Mukherjee, N.A.Mirin, S.D.Levit, P.Nordlander, N.J.Halas, J.Phys.Chem.C2010,114,7378; X.H.Xia, Y.Liu, V.Backman, G.A.Ameer, Nanotechnology2006,17,5435; C.S.Bell, S.S.Yu, T.D.Giorgio, Small2011,7,1158; C.Ayala-Orozco, J.G.Liu, M.W.Knight, Y.Wang, J.K.Day, P.Nordlander, N.J.Halas, Nano Lett.2014,14,2926).Its preparation process is roughly: first, prepare the gold nano grain of certain particle diameter, through centrifugal, ultrasonic dispersion again, be replaced into ethanol phase; Then add ammoniacal liquor and ethyl orthosilicate (TEOS) to form Au-SiO
2alcosol, disperses also in triplicate with the removal of impurity through centrifugal, ultrasonic again; Cleaned Au-SiO
2alcosol mixes with aminopropyl triethoxysilane (APTES), by APTES, modifies Au-SiO
2particle makes its surface amination; Then, with sodium borohydride reduction, prepare the colloidal gold solution of 1-3nm as the seed of subsequent experimental; Then, gold nano grain seed is adsorbed onto SiO by electrostatic interaction
2particle surface; Finally, at formaldehyde or CO
2under effect Deng weak reductant, more gold is reduced, and usings the gold nano grain seed of colloid surface and as nucleus, on surface, form outermost layer gold shell.But this seed mediated growth method step is many, complicated, and gold nano grain seed grafting effect is not good enough.Summary is got up, and its preparation exists the problem of following three aspects::
(1) the method needs phase transfer frequently (water-ol) and eccentric cleaning, takes time and effort very much.
(2) carrier surface needs complicated amino functional to modify, and this modification easily causes the reunion of material, affects the dispersiveness of material.
(3) pass through-NH of gold nano grain seed
2be adsorbed onto carrier surface with the electrostatic interaction of seed, this classical absorption is insecure, and seed easily comes off, and affects the growth of follow-up shell.
Summary of the invention
The invention provides multi-layer core-shell nanostructured of a kind of gold-organosilicon-Jin and its preparation method and application, thereby solve the problems such as the complicated process of preparation of multi-layer core-shell nanostructured in prior art, preparation effect is not good enough, unstable properties.
For addressing the above problem, the technical solution used in the present invention is:
A multi-layer core-shell nanostructured of gold-organosilicon-Jin, comprising: the kernel consisting of gold nano grain; By organosilicon, form and surround the intermediate dielectric layer of described kernel; And the shell that forms and surround described intermediate dielectric layer by gold nano-material.
The multi-layer core-shell nanostructured of described gold-organosilicon-Jin has the integral diameter of 60-250nm, and wherein, the diameter of described kernel is 10-100nm, and the thickness of described intermediate dielectric layer is 10-50nm, and the thickness of described shell is 15-25nm.
The multi-layer core-shell nanostructured of described gold-organosilicon-Jin has and presents bimodal ultraviolet-visible-near-infrared Spectral Extinction, the near infrared region of one of them peak in 700-900nm scope, the visible region of another peak in 550-650nm scope.
The present invention also provides the preparation method of the multi-layer core-shell nanostructured of a kind of gold-organosilicon-Jin, comprising:
Step a: utilize chlorauride and trisodium citrate preparation to be dispersed with the colloidal solution of gold nano grain;
Step b: add ammoniacal liquor and hydrosulphonyl silane in the colloidal solution obtaining to step a, form on described gold nano grain surface the mercapto-functionalized intermediate dielectric layer in surface being formed by organosilicon;
Step c: add chlorauride and reducing agent in the colloidal solution obtaining to step b, utilize in-situ reducing seed mediated growth method to form on described intermediate dielectric layer surface the shell being formed by gold nano-material.
Wherein, described step a comprises:
Step a1: by chlorauride and trisodium citrate according to mol ratio (15-50): (250-400) mix, add ultra-pure water, under 100 ℃ of boiling conditions, obtain cerise colloidal solution, be then cooled to 70-90 ℃;
Step a2: by chlorauride and trisodium citrate according to mol ratio (20-40): (50-200) join in described cerise colloidal solution simultaneously, at 70-90 ℃, continue to stir the kermesinus colloidal solution that obtains being dispersed with gold nano grain.
Wherein, in described step b, the mol ratio of described gold nano grain, ammoniacal liquor and organosilan is (1-10): (100-300): (5-20).
Wherein, in described step b, described hydrosulphonyl silane is 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane or 3-sulfydryl propyl group tripropoxy silane.
Wherein, described step c comprises:
C1: adding successively mol ratio in the colloidal solution obtaining to step b is 6 * 10
4: the ultra-pure water of 1.5:1, chlorauride and the first reducing agent, form gold nano grain on described intermediate dielectric layer surface;
C2: adding successively mol ratio in the colloidal solution obtaining to step c1 is 2 * 10
4: the ultra-pure water of 1.5:0.01:30, chlorauride, potash and the second reducing agent, so that the gold nano grain continued growth on described intermediate dielectric layer surface forms the shell consisting of gold nano-material.
Wherein, described the first reducing agent is preferably sodium borohydride, and described the second reducing agent is preferably ascorbic acid, should be appreciated that, other is any, and chlorauride can be reduced to golden reducing agent all in the present invention available.
The application of the multi-layer core-shell nanostructured that the present invention also provides described gold-organosilicon-Jin on SERS.
The multi-layer core-shell nanostructured of described gold-organosilicon-Jin, under 808nm Ear Mucosa Treated by He Ne Laser Irradiation, under equal delustring intensity (intensity is 2) condition, is compared with single layer of gold nanoshell and is had better photo-thermal changing effect.Described multi-layer core-shell nanostructure concentration is that 50 μ g/ml have obvious photo-thermal and kill cancer cell ability.
The multi-layer core-shell nanostructured of described gold-organosilicon-Jin is as SERS (SERS) substrate, under equal kernel gold grain concentration conditions, multi-layer core-shell nanostructured has the Raman enhancing effect than strong nearly 10 times of the gold-organic silicon nano particle without outermost layer gold shell.
By above-mentioned technological means, the advantage of multi-layer core-shell nanostructured of gold-organosilicon-Jin of the present invention and its preparation method and application comprises:
(1) the preparation building-up process of this multi-layer core-shell nanostructured is simply efficient, reproducible.Whole building-up process is all carried out at aqueous phase system, does not need phase transfer frequently and cleaning process, time saving and energy saving; Intermediate dielectric layer adopts hydrosulphonyl silane directly from polycondensation, to form as single silane, and the intermediate dielectric layer surface of formation has been sulfydryl (SH) functionalization, has avoided the functional modification of loaded down with trivial details and poor effect; Gold nano grain seed is surperficial to intermediate dielectric layer by the direct step grafting of method of in-situ reducing, and seed and carrier close by chemical bond Au-S bond, than traditional Electrostatic Absorption better effects if, difficult drop-off.
(2) this multi-layer core-shell nanostructured has splendid dispersiveness, and pattern uniform particle diameter, and multi-layer core-shell structure is clear and legible, is the theoretical gedanken experiment model calculating.
(3) each layer thickness parameter of this multi-layer core-shell nanostructured all can be by regulating reactant addition to regulate easily, and therefore plasma resonance characteristic also can obtain interior free adjustment in a big way.
(4) this multi-layer core-shell nanostructured has good photo-thermal treatment ability, can be used for SERS substrate simultaneously, is expected at biomedicine field, particularly the advantage of the Clinics and Practices aspect of cancer performance Nano medication.
Accompanying drawing explanation
Fig. 1 is preparation technology's flow chart of the multi-layer core-shell nanostructured of gold-organosilicon-Jin of the present invention;
Fig. 2 is the scanning transmission electron microscope photo of the multi-layer core-shell nanostructured of gold-organosilicon-Jin of preparing according to one embodiment of the invention, wherein, (a) is scanned photograph, is (b) transmission electron microscope brightfield mode photo;
Fig. 3 is the transmission electron microscope photo of the multi-layer core-shell nanostructured of gold-organosilicon-Jin of preparing according to one embodiment of the invention, wherein, (a) is 4000 times, (b) is 60000 times;
Fig. 4 is ultraviolet-visible-near-infrared extinction spectra figure of the multi-layer core-shell nanostructured of gold-organosilicon-Jin of preparing according to one embodiment of the invention;
Fig. 5 is under identical dullness condition, the temperature variation of the multi-layer core-shell nanostructured of ultra-pure water, single layer of gold nanoshell and gold-organosilicon-Jin of preparing according to one embodiment of the invention after 808nm Ear Mucosa Treated by He Ne Laser Irradiation;
Fig. 6 is that the multi-layer core-shell nanostructured of gold-organosilicon-Jin of preparing according to one embodiment of the invention is at 808nm Ear Mucosa Treated by He Ne Laser Irradiation with without under laser irradiation condition, the toxicity of cancer cell being characterized;
When Fig. 7 is the multi-layer core-shell nanostructured of gold-organosilicon-Jin of preparing according to one embodiment of the invention with gold-organic silicon nano particle without outermost layer gold shell as SERS (SERS) substrate, Raman signal strengthens effect contrast figure;
The transmission electron microscope photo of the multi-layer core-shell nanostructured that Fig. 8 is gold-organosilicon-Jin of preparing according to another embodiment of the present invention, wherein, (a) is 4000 times, is (b) 60000 times;
The transmission electron microscope photo of the multi-layer core-shell nanostructured that Fig. 9 is gold-organosilicon-Jin of preparing according to further embodiment of this invention, wherein, (a) is 4000 times, is (b) 60000 times.
The specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described.Should be understood that following examples are only for the present invention is described but not for limiting the scope of the invention.
Embodiment 1
At ambient temperature, by chlorauride, according to mol ratio, be that 25:300 mixes with trisodium citrate, add 72ml ultra-pure water to mix and obtain cerise colloidal solution, heat this solution to boiling and keep being cooled to 85 ℃ of left and right after 15min.Continuation is that 30:75 joins in above-mentioned solution by chlorauride and trisodium citrate according to mol ratio, under 85 ℃ of conditions, stir half an hour after the centrifugal 70ml of obtaining be dispersed with the kermesinus colloidal solution of gold nano grain.
Getting above-mentioned colloidal solution 16ml, by gold nano grain, ammoniacal liquor and hydrosulphonyl silane mol ratio, be that 2:300:15 directly adds standing 12h after 0.2mg ammoniacal liquor and 0.03mg3-sulfydryl propyl-triethoxysilicane (MPTES) vibration 90s, to form on described gold nano grain surface the mercapto-functionalized intermediate dielectric layer in surface that one deck consists of organosilicon, thereby obtain the mercapto-functionalized gold-organic silicon nano particle in surface.
In colloidal solution obtained above, in molar ratio 6 * 10
4: 1.5:1 adds 75ml ultra-pure water, 3ml successively, the chlorauride (HAuCl of 0.01M
4) and 2ml, the sodium borohydride (NaBH of 0.01M
4), after mixing, continue to stir 2h, so that described intermediate dielectric layer surface forms the gold nano grain as seed, then centrifugal concentrating is 2ml left and right.This 2ml colloidal solution is added in 300ml ultra-pure water, then in molar ratio for 1.5:0.01:30 adds 11ml, the chlorauride (HAuCl of 0.01M
4), 73mg potash (K
2cO
3) and 5.5ml, 0.4M ascorbic acid, rapid stirring 3min, so that described gold nano grain seed continued growth forms the shell consisting of gold nano-material, the then centrifugal multi-layer core-shell nanostructured that obtains gold-organosilicon-Jin.
The multi-layer core-shell nanostructured making according to the present embodiment is carried out respectively to ESEM and transmission electron microscope sign, and its shape characteristic and structure are as shown in Fig. 2 (a)-Fig. 3 (b).As figure shows, the integral diameter of this multi-layer core-shell nanostructured is 150nm left and right, and wherein, the diameter of kernel is 50nm left and right, and the thickness of intermediate dielectric layer is 30nm left and right, and the thickness of shell is 20nm left and right.
The colloidal solution of this multi-layer core-shell nanostructured is carried out to ultraviolet-visible-near-infrared spectrum sign, and result as shown in Figure 4.Result demonstration, there are two plasma peaks in multi-layer core-shell nanostructured, lays respectively at 790nm and 590nm.
Further this multi-layer core-shell nanostructured is carried out to photo-thermal conversion and characterize, quantitatively dullness is the multi-layer core-shell nanostructured colloidal solution of 2.0 concentration, is placed under 808nm Ear Mucosa Treated by He Ne Laser Irradiation, with thermocouple, measures in real time its variations in temperature, and result as shown in Figure 5.As shown in Figure 5, after 15min irradiates, the temperature of multi-layer core-shell nanostructured solution rises to 55 ℃ of left and right, and the temperature of single layer of gold nanoshell only rises to 50 ℃ of left and right, and pure water does not have obvious variations in temperature.After multi-layer core-shell nanostructured and breast cancer cell being hatched jointly, under 808nm Ear Mucosa Treated by He Ne Laser Irradiation, there is the function of significantly killing and wounding cancer cell simultaneously, confirmed significant photo-thermal therapeutic effect (Fig. 6).In addition, gold nanoshell itself does not have toxicity to cancer cell.
Basic recipe is constant, is only adding ammoniacal liquor and the front 2ml of adding of 3-sulfydryl propyl-triethoxysilicane (MPTES), and 0.01mM mercaptobenzoic acid (MBA), as Raman reporter molecules, obtains the multi-layer core-shell nanostructured of MBA mark.It is carried out to Raman Characterization, and result as shown in Figure 7.As shown in Figure 7, multi-layer core-shell nanostructured has the ability of obvious enhancing MBA Raman signal.And contrasting the gold-organic silicon nano particle without outermost layer gold shell, this multi-layer core-shell nanostructured provides the Raman signal of nearly 10 times to strengthen effect, has proved that the multi-layer core-shell nanostructured making is the good SERS matrix material of a class.
Embodiment 2
At ambient temperature, by chlorauride, according to mol ratio, be that 25:250 mixes with trisodium citrate, add 72ml ultra-pure water to mix and obtain cerise colloidal solution, heat this solution to boiling and keep being cooled to 70 ℃ of left and right after 15min.Continuation is that 20:100 joins in above-mentioned solution by chlorauride and trisodium citrate according to mol ratio, under 70 ℃ of conditions, stir half an hour after the centrifugal 70ml of obtaining be dispersed with the kermesinus colloidal solution of gold nano grain.
Getting above-mentioned colloidal solution 16ml, by gold nano grain, ammoniacal liquor and hydrosulphonyl silane mol ratio, be that 1:300:20 directly adds standing 12h after 0.2mg ammoniacal liquor and 0.04mg3-sulfydryl propyl-triethoxysilicane (MPTES) vibration 90s, to form on described gold nano grain surface the mercapto-functionalized intermediate dielectric layer in surface that one deck consists of organosilicon, thereby obtain the mercapto-functionalized gold-organic silicon nano particle in surface.
In above-mentioned colloidal solution, in molar ratio 6 * 10
4: 1.5:1 adds 75ml ultra-pure water, 3ml successively, the chlorauride (HAuCl of 0.01M
4) and 2ml, the sodium borohydride (NaBH of 0.01M
4), after mixing, continue to stir 2h, so that described intermediate dielectric layer surface forms the gold nano grain as seed, then centrifugal concentrating is 2ml left and right.This 2ml colloidal solution is added in 300ml ultra-pure water, then in molar ratio for 1.5:0.01:30 adds 11ml, the chlorauride (HAuCl of 0.01M
4), 73mg potash (K
2cO
3) and 5.5ml, 0.4M ascorbic acid, rapid stirring 3min, so that described gold nano grain seed continued growth forms the shell consisting of gold nano-material, the then centrifugal multi-layer core-shell nanostructured that obtains gold-organosilicon-Jin.
The multi-layer core-shell nanostructured making according to the present embodiment is carried out to transmission electron microscope sign, and result as shown in Figure 8.As seen from the figure, the integral diameter of this multi-layer core-shell nanostructured be about 150nm wherein, the diameter of kernel is 30nm left and right, the thickness of intermediate dielectric layer is 40nm left and right, the thickness of shell is 20nm left and right.
The colloidal solution of this multi-layer core-shell nanostructured is carried out to ultraviolet-visible-near-infrared spectrum sign, result demonstration, there are two plasma peaks in multi-layer core-shell nanostructured, lays respectively at 750nm and 550nm.
Embodiment 3
At ambient temperature, by chlorauride, according to mol ratio, be that 30:250 mixes with trisodium citrate, add 72ml ultra-pure water to mix and obtain cerise colloidal solution, heat this solution to boiling and keep being cooled to 90 ℃ of left and right after 15min.Continuation is that 40:100 joins in above-mentioned solution by chlorauride and trisodium citrate according to mol ratio, under 90 ℃ of conditions, stir half an hour after the centrifugal 70ml of obtaining be dispersed with the kermesinus colloidal solution of gold nano grain.
Getting above-mentioned colloidal solution 16ml, by gold nano grain, ammoniacal liquor and hydrosulphonyl silane mol ratio, be that 6:300:9 directly adds standing 12h after 0.2mg ammoniacal liquor and 0.018mg3-sulfydryl propyl-triethoxysilicane (MPTES) vibration 90s, to form on described gold nano grain surface the mercapto-functionalized intermediate dielectric layer in surface that one deck consists of organosilicon, thereby obtain the mercapto-functionalized gold-organic silicon nano particle in surface.
In above-mentioned colloidal solution, in molar ratio 6 * 10
4: 1.5:1 adds 75ml ultra-pure water, 3ml successively, the chlorauride (HAuCl of 0.01M
4) and 2ml, the sodium borohydride (NaBH of 0.01M
4), after mixing, continue to stir 2h, so that described intermediate dielectric layer surface forms the gold nano grain as seed, then centrifugal concentrating is 2ml left and right.This 2ml colloidal solution is added in 300ml ultra-pure water, then in molar ratio for 1.5:0.01:30 adds 11ml, the chlorauride (HAuCl of 0.01M
4), 73mg potash (K
2cO
3) and 5.5ml, 0.4M ascorbic acid, rapid stirring 3min, so that described gold nano grain seed continued growth forms the shell consisting of gold nano-material, the then centrifugal multi-layer core-shell nanostructured that obtains gold-organosilicon-Jin.
The multi-layer core-shell nanostructured making according to the present embodiment is carried out to transmission electron microscope sign, and result as shown in Figure 9.As seen from the figure, the integral diameter of this multi-layer core-shell nanostructured is 150nm left and right, and wherein, the diameter of kernel is 70nm left and right, and the thickness of intermediate dielectric layer is 20nm left and right, and the thickness of shell is 20nm left and right.
The colloidal solution of this multi-layer core-shell nanostructured is carried out to ultraviolet-visible-near-infrared spectrum sign, result demonstration, there are two plasma peaks in multi-layer core-shell nanostructured, lays respectively at 820nm and 620nm.
Embodiment 4
At ambient temperature, by chlorauride, according to mol ratio, be that 25:300 mixes with trisodium citrate, add 72ml ultra-pure water to mix and obtain cerise colloidal solution, heat this solution to boiling and keep being cooled to 85 ℃ of left and right after 15min.Continuation is that 30:75 joins in above-mentioned solution by chlorauride and trisodium citrate according to mol ratio, under 85 ℃ of conditions, stir half an hour after the centrifugal 70ml of obtaining be dispersed with the kermesinus colloidal solution of gold nano grain.
Getting above-mentioned colloidal solution 16ml, by gold nano grain, ammoniacal liquor and hydrosulphonyl silane mol ratio, be that 2:100:12 is directly added in colloidal solution obtained above, directly add standing 6h after 0.05mg ammoniacal liquor and 0.025mg3-sulfydryl propyl trimethoxy silicane (MPTMS) vibration 90s, to form on described gold nano grain surface the mercapto-functionalized intermediate dielectric layer in surface that one deck consists of organosilicon, thereby obtain the mercapto-functionalized gold-organic silicon nano particle in surface.
In above-mentioned colloidal solution, in molar ratio 6 * 10
4: 1.5:1 adds 75ml ultra-pure water, 3ml successively, the chlorauride (HAuCl of 0.01M
4) and 2ml, the sodium borohydride (NaBH of 0.01M
4), after mixing, continue to stir 2h, so that described intermediate dielectric layer surface forms the gold nano grain as seed, then centrifugal concentrating is 2ml left and right.This 2ml colloidal solution is added in 300ml ultra-pure water, then in molar ratio for 1.5:0.01:30 adds 11ml, the chlorauride (HAuCl of 0.01M
4), 73mg potash (K
2cO
3) and 5.5ml, 0.4M ascorbic acid, rapid stirring 3min, so that described gold nano grain seed continued growth forms the shell consisting of gold nano-material, the then centrifugal multi-layer core-shell nanostructured that obtains gold-organosilicon-Jin.
The multi-layer core-shell nanostructured making according to the present embodiment is carried out to transmission electron microscope sign, result demonstration, the integral diameter of this multi-layer core-shell nanostructured is 150nm left and right, wherein, the diameter of kernel is 50nm left and right, and the thickness of intermediate dielectric layer is 30nm left and right, and the thickness of shell is 20nm left and right.
Embodiment 5
At ambient temperature, by chlorauride, according to mol ratio, be that 25:300 mixes with trisodium citrate, add 72ml ultra-pure water to mix and obtain cerise colloidal solution, heat this solution to boiling and keep being cooled to 85 ℃ of left and right after 15min.Continuation is that 30:75 joins in above-mentioned solution by chlorauride and trisodium citrate according to mol ratio, under 85 ℃ of conditions, stir half an hour after the centrifugal 70ml of obtaining be dispersed with the kermesinus colloidal solution of gold nano grain.
Getting above-mentioned colloidal solution 16ml, by gold nano grain, ammoniacal liquor and hydrosulphonyl silane mol ratio, be that 2:300:20 is directly added in colloidal solution obtained above, directly add after 0.2mg ammoniacal liquor and 0.04mg3-sulfydryl propyl group tripropoxy silane (MPTPS) vibration 90s and obtain mercapto-functionalized gold-organic silicon nano particle after standing 24h.
In above-mentioned colloidal solution, in molar ratio 6 * 10
4: 1.5:1 adds 75ml ultra-pure water, 3ml successively, the chlorauride (HAuCl of 0.01M
4) and 2ml, the sodium borohydride (NaBH of 0.01M
4), after mixing, continue to stir 2h, so that described intermediate dielectric layer surface forms the gold nano grain as seed, then centrifugal concentrating is 2ml left and right.This 2ml colloidal solution is added in 300ml ultra-pure water, then in molar ratio for 1.5:0.01:30 adds 11ml, the chlorauride (HAuCl of 0.01M
4), 73mg potash (K
2cO
3) and 5.5ml, 0.4M ascorbic acid, rapid stirring 3min, so that described gold nano grain seed continued growth forms the shell consisting of gold nano-material, the then centrifugal multi-layer core-shell nanostructured that obtains gold-organosilicon-Jin.
The multi-layer core-shell nanostructured making according to the present embodiment is carried out to transmission electron microscope sign, result demonstration, the integral diameter of this multi-layer core-shell nanostructured is 150nm left and right, wherein, the diameter of kernel is 50nm left and right, and the thickness of intermediate dielectric layer is 30nm left and right, and the thickness of shell is 20nm left and right.
Embodiment 6
At ambient temperature, by chlorauride, according to mol ratio, be that 50:250 mixes with trisodium citrate, add 72ml ultra-pure water to mix and obtain cerise colloidal solution, heat this solution to boiling and keep being cooled to 90 ℃ of left and right after 15min.Continuation is that 40:50 joins in above-mentioned solution by chlorauride and trisodium citrate according to mol ratio, under 90 ℃ of conditions, stir half an hour after the centrifugal 70ml of obtaining be dispersed with the kermesinus colloidal solution of gold nano grain.
Getting above-mentioned colloidal solution 16ml, by gold nano grain, ammoniacal liquor and hydrosulphonyl silane mol ratio, be that 10:300:20 is directly added in colloidal solution obtained above, directly add after 0.2mg ammoniacal liquor and 0.04mg3-sulfydryl propyl-triethoxysilicane (MPTES) vibration 90s and obtain mercapto-functionalized gold-organic silicon nano particle after standing 24h.
In above-mentioned colloidal solution, in molar ratio 6 * 10
4: 1.5:1 adds 112ml ultra-pure water, 4.5ml successively, the chlorauride (HAuCl of 0.01M
4) and 3ml, the sodium borohydride (NaBH of 0.01M
4), after mixing, continue to stir 2h, so that described intermediate dielectric layer surface forms the gold nano grain as seed, then centrifugal concentrating is 2ml left and right.This 2ml colloidal solution is added in 450ml ultra-pure water, then in molar ratio for 1.5:0.01:30 adds 17.6ml, the chlorauride (HAuCl of 0.01M
4), 117mg potash (K
2cO
3) and 8.8ml, 0.4M ascorbic acid, rapid stirring 3min, so that described gold nano grain seed continued growth forms the shell consisting of gold nano-material, the then centrifugal multi-layer core-shell nanostructured that obtains gold-organosilicon-Jin.
The multi-layer core-shell nanostructured making according to the present embodiment is carried out to transmission electron microscope sign, result demonstration, the integral diameter of this multi-layer core-shell nanostructured is 250nm left and right, wherein, the diameter of kernel is 100nm left and right, and the thickness of intermediate dielectric layer is 50nm left and right, and the thickness of shell is 25nm left and right.The colloidal solution of this multi-layer core-shell nanostructured is carried out to ultraviolet-visible-near-infrared spectrum sign, result demonstration, there are two plasma peaks in multi-layer core-shell nanostructured, lays respectively at 900nm and 650nm.
Embodiment 7
At ambient temperature, by chlorauride, according to mol ratio, be that 15:400 mixes with trisodium citrate, add 72ml ultra-pure water to mix and obtain cerise colloidal solution, heat this solution to boiling and keep being cooled to 70 ℃ of left and right after 15min.Continuation is that 20:200 joins in above-mentioned solution by chlorauride and trisodium citrate according to mol ratio, under 70 ℃ of conditions, stir half an hour after the centrifugal 70ml of obtaining be dispersed with the kermesinus colloidal solution of gold nano grain.
Getting above-mentioned colloidal solution 16ml, by gold nano grain, ammoniacal liquor and hydrosulphonyl silane mol ratio, be that 1:100:5 is directly added in colloidal solution obtained above, directly add after 0.05mg ammoniacal liquor and 0.01mg3-sulfydryl propyl-triethoxysilicane (MPTES) vibration 90s and obtain mercapto-functionalized gold-organic silicon nano particle after standing 24h.
In above-mentioned colloidal solution, in molar ratio 6 * 10
4: 1.5:1 adds 75ml ultra-pure water, 3ml successively, the chlorauride (HAuCl of 0.01M
4) and 2ml, the sodium borohydride (NaBH of 0.01M
4), after mixing, continue to stir 2h, so that described intermediate dielectric layer surface forms the gold nano grain as seed, then centrifugal concentrating is 2ml left and right.This 2ml colloidal solution is added in 150ml ultra-pure water, then in molar ratio for 1.5:0.01:30 adds 5.5ml, the chlorauride (HAuCl of 0.01M
4), 36.5mg potash (K
2cO
3) and 2.75ml, 0.4M ascorbic acid, rapid stirring 3min, so that described gold nano grain seed continued growth forms the shell consisting of gold nano-material, the then centrifugal multi-layer core-shell nanostructured that obtains gold-organosilicon-Jin.
The multi-layer core-shell nanostructured making according to the present embodiment is carried out to transmission electron microscope sign, result demonstration, the integral diameter of this multi-layer core-shell nanostructured is 60nm left and right, wherein, the diameter of kernel is 10nm left and right, and the thickness of intermediate dielectric layer is 10nm left and right, and the thickness of shell is 15nm left and right.The colloidal solution of this multi-layer core-shell nanostructured is carried out to ultraviolet-visible-near-infrared spectrum sign, result demonstration, there are two plasma peaks in multi-layer core-shell nanostructured, lays respectively at 700nm and 550nm.
In sum, the advantage of multi-layer core-shell nanostructured of gold-organosilicon-Jin of the present invention and its preparation method and application comprises:
(1) the preparation building-up process of this multi-layer core-shell nanostructured is simply efficient, reproducible.Whole building-up process is all carried out at aqueous phase system, does not need phase transfer frequently and cleaning process, time saving and energy saving; Intermediate dielectric layer adopts hydrosulphonyl silane directly from polycondensation, to form as single silane, and the intermediate dielectric layer surface of formation is-SH functionalization, has avoided the functional modification of loaded down with trivial details and poor effect; Gold nano grain seed is surperficial to intermediate dielectric layer by the direct step grafting of method of in-situ reducing, and seed and carrier close by chemical bond Au-S bond, than traditional Electrostatic Absorption better effects if, difficult drop-off.
(2) this multi-layer core-shell nanostructured has splendid dispersiveness, and pattern uniform particle diameter, and multi-layer core-shell structure is clear and legible, is the theoretical gedanken experiment model calculating.
(3) each layer thickness parameter of this multi-layer core-shell nanostructured all can be by regulating reactant addition to regulate easily, and therefore plasma resonance characteristic also can obtain interior free adjustment in a big way.
(4) this multi-layer core-shell nanostructured has good photo-thermal treatment ability, can be used for SERS substrate simultaneously, is expected at biomedicine field, particularly the advantage of the Clinics and Practices aspect of cancer performance Nano medication.
Above-described, be only preferred embodiment of the present invention, not in order to limit scope of the present invention, the above embodiment of the present invention can also make a variety of changes.Be that simple, the equivalence that every claims according to the present patent application and description are done changes and modify, all fall into the claim protection domain of patent of the present invention.The present invention not detailed description be routine techniques content.
Claims (10)
1. a multi-layer core-shell nanostructured of gold-organosilicon-Jin, is characterized in that, comprising:
The kernel being formed by gold nano grain;
By organosilicon, form and surround the intermediate dielectric layer of described kernel; And
By gold nano-material, form and surround the shell of described intermediate dielectric layer.
2. the multi-layer core-shell nanostructured of gold-organosilicon-Jin according to claim 1, it is characterized in that, the multi-layer core-shell nanostructured of described gold-organosilicon-Jin has the integral diameter of 60-250nm, wherein, the diameter of described kernel is 10-100nm, the thickness of described intermediate dielectric layer is 10-50nm, and the thickness of described shell is 15-25nm.
3. the multi-layer core-shell nanostructured of gold-organosilicon-Jin according to claim 1, it is characterized in that, the multi-layer core-shell nanostructured of described gold-organosilicon-Jin has and presents bimodal ultraviolet-visible-near-infrared Spectral Extinction, the near infrared region of one of them peak in 700-900nm scope, the visible region of another peak in 550-650nm scope.
4. a preparation method for the multi-layer core-shell nanostructured of gold-organosilicon-Jin, is characterized in that, comprising:
Step a: utilize chlorauride and trisodium citrate preparation to be dispersed with the colloidal solution of gold nano grain;
Step b: add ammoniacal liquor and hydrosulphonyl silane in the colloidal solution obtaining to step a, form on the surface of described gold nano grain the mercapto-functionalized intermediate dielectric layer in surface being formed by organosilicon;
Step c: add chlorauride and reducing agent in the colloidal solution obtaining to step b, utilize in-situ reducing seed mediated growth method to form on described intermediate dielectric layer surface the shell being formed by gold nano-material.
5. the preparation method of the multi-layer core-shell nanostructured of gold-organosilicon-Jin as claimed in claim 4, is characterized in that, described step a comprises:
Step a1: by chlorauride and trisodium citrate according to mol ratio (15-50): (250-400) mix, add ultra-pure water, under 100 ℃ of boiling conditions, obtain cerise colloidal solution, be then cooled to 70-90 ℃;
Step a2: by chlorauride and trisodium citrate according to mol ratio (20-40): (50-200) join in described cerise colloidal solution simultaneously, at 70-90 ℃, continue to stir the kermesinus colloidal solution that obtains being dispersed with gold nano grain.
6. the preparation method of the multi-layer core-shell nanostructured of gold-organosilicon-Jin as claimed in claim 4, it is characterized in that, in described step b, the mol ratio of described gold nano grain, ammoniacal liquor and organosilan is (1-10): (100-300): (5-20).
7. the preparation method of the multi-layer core-shell nanostructured of gold-organosilicon-Jin as claimed in claim 4, it is characterized in that, in described step b, described hydrosulphonyl silane is 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane or 3-sulfydryl propyl group tripropoxy silane.
8. the preparation method of the multi-layer core-shell nanostructured of gold-organosilicon-Jin as claimed in claim 4, is characterized in that, described step c comprises:
C1: adding successively mol ratio in the colloidal solution obtaining to step b is 6 * 10
4: the ultra-pure water of 1.5:1, chlorauride and the first reducing agent, form gold nano grain on described intermediate dielectric layer surface;
C2: adding successively mol ratio in the colloidal solution obtaining to step c1 is 2 * 10
4: the ultra-pure water of 1.5:0.01:30, chlorauride, potash and the second reducing agent, so that the gold nano grain continued growth on described intermediate dielectric layer surface forms the shell consisting of gold nano-material.
9. the preparation method of the multi-layer core-shell nanostructured of gold-organosilicon-Jin as claimed in claim 8, is characterized in that, described the first reducing agent is sodium borohydride, and described the second reducing agent is ascorbic acid.
10. the application on SERS according to the multi-layer core-shell nanostructured of the gold-organosilicon-Jin described in claim 1-3.
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