CN104162665B - 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 a kind of gold-organosilicon-gold many
Layer nanometer nuclear shell nano-structure and its preparation method and application.
Background technology
In recent years, gold nanoshell is due to its adjustable Plasma-Optical character and wide biomedical applications
Just paid close attention to by the most widely with optical application prospect.Gold nanoshell can produce adjustable plasma base
Unit's resonance, thus cause strong optical absorption and scattering.By the relative size of regulation core and shell (i.e.
Nucleocapsid than), its delustring peak may span across visible ray near infrared region (650-1300nm).The most smart in order to enable
Thin regulation plasma resonance characteristic, the multi-layer core-shell nanostructured of a kind of special gold-silicon dioxide-gold
Mentioned by people.In theory, compared with common single layer of gold nanoshell, multi-layer core-shell nanostructured has more
For complicated excellent optical property.First, inner core particles and outer layer gold shell can occur plasma effect, this
Make multi-layer core-shell nanostructured that more plasma resonance peak occur.Additionally, by regulation multi-layer core-shell
The interlevel dielectric layer thickness of nanostructured, absorption and the scattering phase of multi-layer core-shell nanostructured can quilts to power
Regulation, this makes multi-layer core-shell nanostructured application potential in terms of bio-imaging and treatment huge.And,
Multi-layer core-shell structure multi-layer core-shell nanostructured can also support that " Fano " resonates." Fano " resonance is in detection
The breakthrough of sensitivity aspect or bigger, therefore, multi-layer core-shell nanostructured is as biological response of future generation
Reagent has bigger advantage.Near field distribution calculates and shows, the kernel gold grain of multi-layer core-shell nanostructured
Surface has preferable near field and strengthens.This result imply that multi-layer core-shell nanostructured is as surface enhanced
Raman scattering (SERS) substrate, has wide answering in environmental monitoring and basic biomedical research field
Use potentiality.
Although multi-layer core-shell nanostructured has a most excellent optical property, but up to now, relevant
The controlled preparation report of multi-layer core-shell nanostructured is few.Limited report shows, multi-layer core-shell nano junction
The intermediate dielectric layer of structure is all to use silicon dioxide to constitute (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 substantially is: first, prepares the gold nano grain of certain particle diameter, by centrifugation,
Ultrasonic redispersion is replaced into ethanol phase；It is subsequently adding ammonia and tetraethyl orthosilicate (TEOS) forms Au-SiO2
Alcosol, by centrifugation, ultrasonic redispersion in triplicate with the removal of impurity；Cleaned Au-SiO2Alcohol is molten
Glue mixes with aminopropyl triethoxysilane (APTES), modifies Au-SiO by APTES2Granule makes
Its surface amination；Then, the colloidal gold solution of 1-3nm is prepared with sodium borohydride reduction as follow-up
The seed of experiment；Then, gold nano grain seed is adsorbed onto SiO by electrostatic interaction2Particle surface；?
After, at formaldehyde or CO2Deng under the effect of weak reductant, more gold is reduced, and with colloid surface
Gold nano grain seed as nucleus surface formed outermost layer gold shell.But this seed mediated growth method step
Many, complicated, gold nano grain seed grafting less effective.Summary is got up, and its preparation exists following tripartite
The problem in face:
(1) the method needs phase transfer frequently (water-alcohol) and eccentric cleaning, takes time and effort very much.
(2) carrier surface needs complicated amino functional to modify, and this modification is easily caused the group of material
Poly-, affect the dispersibility of material.
(3) gold nano grain seed passes through-NH2It is adsorbed onto carrier surface with the electrostatic interaction of seed, this
Planting classics absorption insecure, seed easily comes off, and affects the growth of follow-up shell.
Summary of the invention
The present invention provides multi-layer core-shell nanostructured of a kind of gold-organosilicon-gold and preparation method thereof and answers
With, thus solve the complicated process of preparation of multi-layer core-shell nanostructured in prior art, prepare less effective,
The problems such as unstable properties.
For solving the problems referred to above, the technical solution used in the present invention is:
A kind of multi-layer core-shell nanostructured of gold-organosilicon-gold, including: in being made up of gold nano grain
Core；It is made up of and surrounds the intermediate dielectric layer of described kernel organosilicon；And be made up of gold nano-material and
Surround the shell of described intermediate dielectric layer.
The multi-layer core-shell nanostructured of described gold-organosilicon-gold has the integral diameter of 60-250nm, its
In, a diameter of 10-100nm of described kernel, the thickness of described intermediate dielectric layer is 10-50nm, institute
The thickness stating shell is 15-25nm.
The multi-layer core-shell nanostructured of described gold-organosilicon-gold has and presents bimodal ultraviolet-visible-the reddest
Outer Spectral Extinction, one of them peak is in the near infrared region of 700-900nm scope, and another peak is in
The visible region of 550-650nm scope.
The present invention also provides for the preparation method of the multi-layer core-shell nanostructured of a kind of gold-organosilicon-gold, including:
Step a: utilize auric chloride and trisodium citrate preparation to be dispersed with the colloid solution of gold nano grain；
Step b: add ammonia and hydrosulphonyl silane in the colloid solution that step a obtains, described Jenner
Rice grain surface forms the intermediate dielectric layer that the surface being made up of organosilicon is mercapto-functionalized；
Step c: add auric chloride and reducing agent in the colloid solution that step b obtains, utilize the most also
Former seed mediated growth method forms the shell being made up of gold nano-material on described intermediate dielectric layer surface.
Wherein, described step a includes:
Step a1: by auric chloride and trisodium citrate according to mol ratio (15-50): (250-400) mixes
Uniformly, add ultra-pure water, under the conditions of 100 DEG C of boilings, obtain cerise colloid solution, be then cooled to
70-90℃；
Step a2: by auric chloride and trisodium citrate according to mol ratio (20-40): (50-200) adds simultaneously
Enter in described cerise colloid solution, at 70-90 DEG C, continue stirring obtain being dispersed with gold nano grain
Kermesinus colloid solution.
Wherein, in described step b, the mol ratio of described gold nano grain, ammonia and organosilan is
(1-10): (100-300): (5-20).
Wherein, in described step b, described hydrosulphonyl silane is 3-mercaptopropyi trimethoxy silane, 3-mercapto
Base propyl-triethoxysilicane or 3-mercaptopropyi tripropoxy silane.
Wherein, described step c includes:
C1: being sequentially added into mol ratio in the colloid solution that step b obtains is 6 × 104: 1.5:1's is super
Pure water, auric chloride and the first reducing agent, form gold nano grain on described intermediate dielectric layer surface；
C2: being sequentially added into mol ratio in the colloid solution that step c1 obtains is 2 × 104: 1.5:0.01:
Ultra-pure water, auric chloride, potassium carbonate and second reducing agent of 30, so that the gold on described intermediate dielectric layer surface
Nano-particle continued growth forms the shell being made up of gold nano-material.
Wherein, described first reducing agent is preferably sodium borohydride, and described second reducing agent is preferably Vitamin C
Acid, it should be appreciated that other any reducing agent that auric chloride can be reduced to gold all can use in the present invention.
The present invention also provides for the multi-layer core-shell nanostructured of described gold-organosilicon-gold and dissipates at surface-enhanced Raman
The application penetrated.
The multi-layer core-shell nanostructured of described gold-organosilicon-gold 808nm laser irradiate under, equal delustring
Under the conditions of intensity (intensity is 2), there is compared with single layer of gold nanoshell more preferable photothermal conversion effect.
Described multi-layer core-shell nanostructure concentration is that 50 μ g/ml have obvious light heat-killed cancerous cell ability.
The multi-layer core-shell nanostructured of described gold-organosilicon-gold is as surface enhanced raman spectroscopy (SERS)
Substrate, under equal kernel gold grain concentration conditions, multi-layer core-shell nanostructured has ratio without outermost layer
The Raman reinforced effects of gold-the nearlyest 10 times of the organic silicon nano granule of gold shell.
By above-mentioned technological means, the multi-layer core-shell nanostructured of the gold-organosilicon-gold of the present invention and system thereof
The advantage of Preparation Method and application includes:
(1) the preparation building-up process of this multi-layer core-shell nanostructured is simply efficient, reproducible.Whole conjunction
One-tenth process is all carried out at aqueous phase system, it is not necessary to phase transfer and cleaning process frequently, time saving and energy saving；In
Between dielectric layer use hydrosulphonyl silane as single silane directly from polycondensation formed, the intermediate dielectric layer table of formation
Face has been sulfydryl (-SH) functionalization, it is to avoid the loaded down with trivial details and functional modification of poor effect；Gold
Nano-particle seed is grafted onto intermediate dielectric layer surface by the direct step of the method for in-situ reducing, seed with
Carrier is closed by chemical bond Au-S bond, more preferable than traditional Electrostatic Absorption effect, difficult drop-off.
(2) this multi-layer core-shell nanostructured has splendid dispersibility, and pattern uniform particle diameter, multilayer core
Shell structure is clear and legible, is the gedanken experiment model of Theoretical Calculation.
(3) each layer thickness parameter of this multi-layer core-shell nanostructured all can by regulation reactant addition very
Being adjusted easily, the most therefore plasma resonance characteristic can obtain freely regulating in a big way.
(4) this multi-layer core-shell nanostructured has excellent light thermotherapy ability, is simultaneously available for SERS base
Plate, is expected at biomedicine field, and the particularly Clinics and Practices aspect of cancer plays the excellent of Nano medication
Gesture.
Accompanying drawing explanation
Fig. 1 is the preparation technology flow chart of the multi-layer core-shell nanostructured of the gold-organosilicon-gold of the present invention；
Fig. 2 is the multi-layer core-shell nanostructured of the gold-organosilicon-gold prepared according to one embodiment of the invention
Scanning transmission electron microscope photo, wherein, (a) is scanned photograph, (b) be transmission electron microscope brightfield mode shine
Sheet；
Fig. 3 is the multi-layer core-shell nanostructured of the gold-organosilicon-gold prepared according to one embodiment of the invention
Transmission electron microscope photo, wherein, (a) is 4000 times, and (b) is 60000 times；
Fig. 4 is the multi-layer core-shell nanostructured of the gold-organosilicon-gold prepared according to one embodiment of the invention
Ultraviolet-visible-near-infrared extinction spectra figure；
Fig. 5 is under the conditions of identical dullness, ultra-pure water, single layer of gold nanoshell with according to the present invention one
The multi-layer core-shell nanostructured of gold-organosilicon-gold prepared by embodiment temperature after 808nm laser irradiates
Variation diagram；
Fig. 6 is the multi-layer core-shell nanostructured of the gold-organosilicon-gold prepared according to one embodiment of the invention
808nm laser irradiate and without laser irradiation condition under Toxicological Characterization to cancerous cell；
Fig. 7 is the multi-layer core-shell nanostructured of the gold-organosilicon-gold prepared according to one embodiment of the invention
With the gold-organic silicon nano granule without outermost layer gold shell as surface enhanced raman spectroscopy (SERS)
During substrate, Raman signal reinforced effects comparison diagram；
Fig. 8 is the multi-layer core-shell nanostructured of the gold-organosilicon-gold prepared according to another embodiment of the present invention
Transmission electron microscope photo, wherein, (a) is 4000 times, and (b) is 60000 times；
Fig. 9 is the multi-layer core-shell nanostructured of the gold-organosilicon-gold prepared according to further embodiment of this invention
Transmission electron microscope photo, wherein, (a) is 4000 times, and (b) is 60000 times.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described.Should be understood that following example are only
For illustrating rather than for limiting the scope of the present invention.
Embodiment 1
At ambient temperature, it is that 25:300 mix with trisodium citrate according to mol ratio by auric chloride, adds
72ml ultra-pure water mix homogeneously obtains cerise colloid solution, heats this solution and keeps 15min to boiling
After be cooled to about 85 DEG C.Continuing auric chloride and trisodium citrate according to mol ratio is that 30:75 adds
In above-mentioned solution, stir under the conditions of 85 DEG C and centrifugal after half an hour obtain 70ml and be dispersed with gold nano
The kermesinus colloid solution of granule.
Taking above-mentioned colloid solution 16ml, by gold nano grain, ammonia and hydrosulphonyl silane mol ratio be
2:300:15 is directly added into 0.2mg ammonia and 0.03mg3-Mercaptopropyltriethoxysilane (MPTES)
12h is stood, in order to be made up of organosilicon described gold nano grain surface formation one layer after vibration 90s
The intermediate dielectric layer that surface is mercapto-functionalized, thus obtain gold-organic silicon nano that surface is mercapto-functionalized
Grain.
In colloid solution obtained above, in molar ratio 6 × 104: it is ultrapure that 1.5:1 is sequentially added into 75ml
Water, 3ml, the auric chloride (HAuCl of 0.01M4) and the sodium borohydride (NaBH of 2ml, 0.01M4),
Stirring 2h is continued, in order to described intermediate dielectric layer surface forms the gold nano grain as seed after mixing,
It is then centrifuged for concentrating as about 2ml.This 2ml colloid solution is added in 300ml ultra-pure water, then
Auric chloride (the HAuCl of 11ml, 0.01M is added in molar ratio for 1.5:0.01:304), 73mg potassium carbonate
(K2CO3) and 5.5ml, 0.4M ascorbic acid, quickly stir 3min, so that described gold nano grain
Seed continued growth forms the shell being made up of gold nano-material, is then centrifuged for obtaining gold-organosilicon-gold
Multi-layer core-shell nanostructured.
The multi-layer core-shell nanostructured prepared according to the present embodiment is scanned Electronic Speculum and transmission electron microscope respectively
Characterize, shown in its shape characteristic and structure such as Fig. 2 (a) Fig. 3 (b).As figure shows, this multilayer core
The integral diameter of shell nanostructured is about 150nm, wherein, and a diameter of about 50nm of kernel,
The thickness of intermediate dielectric layer is about 30nm, and the thickness of shell is about 20nm.
The colloid solution of this multi-layer core-shell nanostructured is carried out ultraviolet-visible-near-infrared spectrum sign, knot
Fruit is as shown in Figure 4.Result shows, two plasma peaks occurs in multi-layer core-shell nanostructured, lays respectively at
790nm and 590nm.
Further this multi-layer core-shell nanostructured being carried out photothermal deformation sign, quantitative dullness is 2.0 dense
The multi-layer core-shell nanostructured colloid solution of degree, is placed under the irradiation of 808nm laser, uses thermocouple
Measuring its variations in temperature in real time, result is as shown in Figure 5.As shown in Figure 5, after 15min irradiates, multilamellar
The temperature of nanometer nuclear shell nano-structure solution rises to about 55 DEG C, and the temperature of single layer of gold nanoshell only rises
To about 50 DEG C, pure water does not has obvious variations in temperature.Simultaneously by multi-layer core-shell nanostructured and breast carcinoma
After cell is hatched jointly, there is under 808nm laser irradiates the function significantly killing cancerous cell, card
Real significant light thermotherapy effect (Fig. 6).It addition, gold nanoshell itself does not has toxicity to cancerous cell.
Basic recipe is constant, only front at addition ammonia and 3-Mercaptopropyltriethoxysilane (MPTES)
Addition 2ml, 0.01mM mercaptobenzoic acid (MBA), as Raman reporter molecules, obtains MBA mark
The multi-layer core-shell nanostructured of note.It is carried out Raman Characterization, and result is as shown in Figure 7.By Fig. 7
Understanding, multi-layer core-shell nanostructured has the ability significantly strengthening MBA Raman signal.And contrast
Without the gold-organic silicon nano granule of outermost layer gold shell, this multi-layer core-shell nanostructured provides nearly 10
Times Raman signal reinforced effects, it was demonstrated that the multi-layer core-shell nanostructured prepared is a class is good
SERS matrix material.
Embodiment 2
At ambient temperature, it is that 25:250 mix with trisodium citrate according to mol ratio by auric chloride, adds
72ml ultra-pure water mix homogeneously obtains cerise colloid solution, heats this solution and keeps 15min to boiling
After be cooled to about 70 DEG C.Continuing auric chloride with trisodium citrate is that 20:100 adds according to mol ratio
Enter in above-mentioned solution, stir under the conditions of 70 DEG C and centrifugal after half an hour obtain 70ml and be dispersed with Jenner
The kermesinus colloid solution of rice grain.
Taking above-mentioned colloid solution 16ml, by gold nano grain, ammonia and hydrosulphonyl silane mol ratio be
1:300:20 is directly added into 0.2mg ammonia and 0.04mg3-Mercaptopropyltriethoxysilane (MPTES)
12h is stood, in order to be made up of organosilicon described gold nano grain surface formation one layer after vibration 90s
The intermediate dielectric layer that surface is mercapto-functionalized, thus obtain gold-organic silicon nano that surface is mercapto-functionalized
Grain.
In above-mentioned colloid solution, in molar ratio 6 × 104: 1.5:1 is sequentially added into 75ml ultra-pure water, 3ml,
Auric chloride (the HAuCl of 0.01M4) and the sodium borohydride (NaBH of 2ml, 0.01M4), after mixing
Continue stirring 2h, in order to described intermediate dielectric layer surface is formed as the gold nano grain of seed, then from
The heart concentrates as about 2ml.This 2ml colloid solution is added in 300ml ultra-pure water, then by mole
Than the auric chloride (HAuCl adding 11ml, 0.01M for 1.5:0.01:304), 73mg potassium carbonate (K2CO3)
And 5.5ml, 0.4M ascorbic acid, quickly stir 3min, so that described gold nano grain seed continues raw
The shell that long formation is made up of gold nano-material, the multi-layer core-shell being then centrifuged for obtaining gold-organosilicon-gold is received
Rice structure.
The multi-layer core-shell nanostructured prepared according to the present embodiment is carried out transmission electron microscope sign, result such as figure
Shown in 8.As seen from the figure, the integral diameter of this multi-layer core-shell nanostructured be about 150nm wherein, interior
A diameter of about 30nm of core, the thickness of intermediate dielectric layer is about 40nm, and the thickness of shell is 20
About nm.
The colloid solution of this multi-layer core-shell nanostructured is carried out ultraviolet-visible-near-infrared spectrum sign, knot
Fruit display, there are two plasma peaks, lays respectively at 750nm and 550nm in multi-layer core-shell nanostructured.
Embodiment 3
At ambient temperature, it is that 30:250 mix with trisodium citrate according to mol ratio by auric chloride, adds
72ml ultra-pure water mix homogeneously obtains cerise colloid solution, heats this solution and keeps 15min to boiling
After be cooled to about 90 DEG C.Continuing auric chloride with trisodium citrate is that 40:100 adds according to mol ratio
Enter in above-mentioned solution, stir under the conditions of 90 DEG C and centrifugal after half an hour obtain 70ml and be dispersed with Jenner
The kermesinus colloid solution of rice grain.
Taking above-mentioned colloid solution 16ml, by gold nano grain, ammonia and hydrosulphonyl silane mol ratio be
6:300:9 is directly added into 0.2mg ammonia and 0.018mg3-Mercaptopropyltriethoxysilane (MPTES)
12h is stood, in order to be made up of organosilicon described gold nano grain surface formation one layer after vibration 90s
The intermediate dielectric layer that surface is mercapto-functionalized, thus obtain gold-organic silicon nano that surface is mercapto-functionalized
Grain.
In above-mentioned colloid solution, in molar ratio 6 × 104: 1.5:1 is sequentially added into 75ml ultra-pure water, 3ml,
Auric chloride (the HAuCl of 0.01M4) and the sodium borohydride (NaBH of 2ml, 0.01M4), after mixing
Continue stirring 2h, in order to described intermediate dielectric layer surface is formed as the gold nano grain of seed, then from
The heart concentrates as about 2ml.This 2ml colloid solution is added in 300ml ultra-pure water, then by mole
Than the auric chloride (HAuCl adding 11ml, 0.01M for 1.5:0.01:304), 73mg potassium carbonate (K2CO3)
And 5.5ml, 0.4M ascorbic acid, quickly stir 3min, so that described gold nano grain seed continues raw
The shell that long formation is made up of gold nano-material, the multi-layer core-shell being then centrifuged for obtaining gold-organosilicon-gold is received
Rice structure.
The multi-layer core-shell nanostructured prepared according to the present embodiment is carried out transmission electron microscope sign, result such as figure
Shown in 9.As seen from the figure, the integral diameter of this multi-layer core-shell nanostructured is about 150nm, wherein,
A diameter of about 70nm of kernel, the thickness of intermediate dielectric layer is about 20nm, and the thickness of shell is
About 20nm.
The colloid solution of this multi-layer core-shell nanostructured is carried out ultraviolet-visible-near-infrared spectrum sign, knot
Fruit display, there are two plasma peaks, lays respectively at 820nm and 620nm in multi-layer core-shell nanostructured.
Embodiment 4
At ambient temperature, it is that 25:300 mix with trisodium citrate according to mol ratio by auric chloride, adds
72ml ultra-pure water mix homogeneously obtains cerise colloid solution, heats this solution and keeps 15min to boiling
After be cooled to about 85 DEG C.Continuing auric chloride and trisodium citrate according to mol ratio is that 30:75 adds
In above-mentioned solution, stir under the conditions of 85 DEG C and centrifugal after half an hour obtain 70ml and be dispersed with gold nano
The kermesinus colloid solution of granule.
Taking above-mentioned colloid solution 16ml, by gold nano grain, ammonia and hydrosulphonyl silane mol ratio be
2:100:12 is directly added in colloid solution obtained above, is directly added into 0.05mg ammonia and 0.025
6h is stood, in order at described gold after mg3-mercaptopropyi trimethoxy silane (MPTMS) vibration 90s
Nano grain surface forms the intermediate dielectric layer that one layer of surface being made up of organosilicon is mercapto-functionalized, thus
Obtain the mercapto-functionalized gold in surface-organic silicon nano granule.
In above-mentioned colloid solution, in molar ratio 6 × 104: 1.5:1 is sequentially added into 75ml ultra-pure water, 3ml,
Auric chloride (the HAuCl of 0.01M4) and the sodium borohydride (NaBH of 2ml, 0.01M4), after mixing
Continue stirring 2h, in order to described intermediate dielectric layer surface is formed as the gold nano grain of seed, then from
The heart concentrates as about 2ml.This 2ml colloid solution is added in 300ml ultra-pure water, then by mole
Than the auric chloride (HAuCl adding 11ml, 0.01M for 1.5:0.01:304), 73mg potassium carbonate (K2CO3)
And 5.5ml, 0.4M ascorbic acid, quickly stir 3min, so that described gold nano grain seed continues raw
The shell that long formation is made up of gold nano-material, the multi-layer core-shell being then centrifuged for obtaining gold-organosilicon-gold is received
Rice structure.
The multi-layer core-shell nanostructured prepared according to the present embodiment is carried out transmission electron microscope sign, and result shows,
The integral diameter of this multi-layer core-shell nanostructured is about 150nm, wherein, and a diameter of 50nm of kernel
Left and right, the thickness of intermediate dielectric layer is about 30nm, and the thickness of shell is about 20nm.
Embodiment 5
At ambient temperature, it is that 25:300 mix with trisodium citrate according to mol ratio by auric chloride, adds
72ml ultra-pure water mix homogeneously obtains cerise colloid solution, heats this solution and keeps 15min to boiling
After be cooled to about 85 DEG C.Continuing auric chloride and trisodium citrate according to mol ratio is that 30:75 adds
In above-mentioned solution, stir under the conditions of 85 DEG C and centrifugal after half an hour obtain 70ml and be dispersed with gold nano
The kermesinus colloid solution of granule.
Taking above-mentioned colloid solution 16ml, by gold nano grain, ammonia and hydrosulphonyl silane mol ratio be
2:300:20 is directly added in colloid solution obtained above, is directly added into 0.2mg ammonia and 0.04mg
Obtain mercapto-functionalized after standing 24h after 3-mercaptopropyi tripropoxy silane (MPTPS) vibration 90s
Gold-organic silicon nano granule.
In above-mentioned colloid solution, in molar ratio 6 × 104: 1.5:1 is sequentially added into 75ml ultra-pure water, 3ml,
Auric chloride (the HAuCl of 0.01M4) and the sodium borohydride (NaBH of 2ml, 0.01M4), after mixing
Continue stirring 2h, in order to described intermediate dielectric layer surface is formed as the gold nano grain of seed, then from
The heart concentrates as about 2ml.This 2ml colloid solution is added in 300ml ultra-pure water, then by mole
Than the auric chloride (HAuCl adding 11ml, 0.01M for 1.5:0.01:304), 73mg potassium carbonate (K2CO3)
And 5.5ml, 0.4M ascorbic acid, quickly stir 3min, so that described gold nano grain seed continues raw
The shell that long formation is made up of gold nano-material, the multi-layer core-shell being then centrifuged for obtaining gold-organosilicon-gold is received
Rice structure.
The multi-layer core-shell nanostructured prepared according to the present embodiment is carried out transmission electron microscope sign, and result shows,
The integral diameter of this multi-layer core-shell nanostructured is about 150nm, wherein, and a diameter of 50nm of kernel
Left and right, the thickness of intermediate dielectric layer is about 30nm, and the thickness of shell is about 20nm.
Embodiment 6
At ambient temperature, it is that 50:250 mix with trisodium citrate according to mol ratio by auric chloride, adds
72ml ultra-pure water mix homogeneously obtains cerise colloid solution, heats this solution and keeps 15min to boiling
After be cooled to about 90 DEG C.Continuing auric chloride and trisodium citrate according to mol ratio is that 40:50 adds
In above-mentioned solution, stir under the conditions of 90 DEG C and centrifugal after half an hour obtain 70ml and be dispersed with gold nano
The kermesinus colloid solution of granule.
Taking above-mentioned colloid solution 16ml, by gold nano grain, ammonia and hydrosulphonyl silane mol ratio be
10:300:20 is directly added in colloid solution obtained above, is directly added into 0.2mg ammonia and 0.04
Sulfydryl merit is obtained after standing 24h after mg3-Mercaptopropyltriethoxysilane (MPTES) vibration 90s
The gold of energyization-organic silicon nano granule.
In above-mentioned colloid solution, in molar ratio 6 × 104: 1.5:1 be sequentially added into 112ml ultra-pure water,
4.5ml, the auric chloride (HAuCl of 0.01M4) and the sodium borohydride (NaBH of 3ml, 0.01M4),
Stirring 2h is continued, in order to described intermediate dielectric layer surface forms the gold nano grain as seed after mixing,
It is then centrifuged for concentrating as about 2ml.This 2ml colloid solution is added in 450ml ultra-pure water, then
Auric chloride (the HAuCl of 17.6ml, 0.01M is added in molar ratio for 1.5:0.01:304), 117mg carbon
Acid potassium (K2CO3) and 8.8ml, 0.4M ascorbic acid, quickly stir 3min, so that described gold nano
Grain seed continued growth forms the shell that is made up of gold nano-material, be then centrifuged for obtaining gold-organosilicon-
The multi-layer core-shell nanostructured of gold.
The multi-layer core-shell nanostructured prepared according to the present embodiment is carried out transmission electron microscope sign, and result shows,
The integral diameter of this multi-layer core-shell nanostructured is about 250nm, wherein, and a diameter of 100nm of kernel
Left and right, the thickness of intermediate dielectric layer is about 50nm, and the thickness of shell is about 25nm.This is many
The colloid solution of layer nanometer nuclear shell nano-structure carries out ultraviolet-visible-near-infrared spectrum sign, and result shows, many
There are two plasma peaks in layer nanometer nuclear shell nano-structure, lays respectively at 900nm and 650nm.
Embodiment 7
At ambient temperature, it is that 15:400 mix with trisodium citrate according to mol ratio by auric chloride, adds
72ml ultra-pure water mix homogeneously obtains cerise colloid solution, heats this solution and keeps 15min to boiling
After be cooled to about 70 DEG C.Continuing auric chloride with trisodium citrate is that 20:200 adds according to mol ratio
Enter in above-mentioned solution, stir under the conditions of 70 DEG C and centrifugal after half an hour obtain 70ml and be dispersed with Jenner
The kermesinus colloid solution of rice grain.
Taking above-mentioned colloid solution 16ml, by gold nano grain, ammonia and hydrosulphonyl silane mol ratio be
1:100:5 is directly added in colloid solution obtained above, is directly added into 0.05mg ammonia and 0.01mg
Obtain mercapto-functionalized after standing 24h after 3-Mercaptopropyltriethoxysilane (MPTES) vibration 90s
Gold-organic silicon nano granule.
In above-mentioned colloid solution, in molar ratio 6 × 104: 1.5:1 is sequentially added into 75ml ultra-pure water, 3ml,
Auric chloride (the HAuCl of 0.01M4) and the sodium borohydride (NaBH of 2ml, 0.01M4), after mixing
Continue stirring 2h, in order to described intermediate dielectric layer surface is formed as the gold nano grain of seed, then from
The heart concentrates as about 2ml.This 2ml colloid solution is added in 150ml ultra-pure water, then by mole
Than the auric chloride (HAuCl adding 5.5ml, 0.01M for 1.5:0.01:304), 36.5mg potassium carbonate
(K2CO3) and 2.75ml, 0.4M ascorbic acid, quickly stir 3min, so that described gold nano
Grain seed continued growth forms the shell being made up of gold nano-material, is then centrifuged for obtaining gold-organosilicon-gold
Multi-layer core-shell nanostructured.
The multi-layer core-shell nanostructured prepared according to the present embodiment is carried out transmission electron microscope sign, and result shows,
The integral diameter of this multi-layer core-shell nanostructured is about 60nm, wherein, and a diameter of 10nm of kernel
Left and right, the thickness of intermediate dielectric layer is about 10nm, and the thickness of shell is about 15nm.This is many
The colloid solution of layer nanometer nuclear shell nano-structure carries out ultraviolet-visible-near-infrared spectrum sign, and result shows, many
There are two plasma peaks in layer nanometer nuclear shell nano-structure, lays respectively at 700nm and 550nm.
In sum, multi-layer core-shell nanostructured of gold-organosilicon-gold of the present invention and preparation method thereof and
The advantage of application includes:
(1) the preparation building-up process of this multi-layer core-shell nanostructured is simply efficient, reproducible.Whole conjunction
One-tenth process is all carried out at aqueous phase system, it is not necessary to phase transfer and cleaning process frequently, time saving and energy saving；In
Between dielectric layer use hydrosulphonyl silane as single silane directly from polycondensation formed, the intermediate dielectric layer table of formation
Face has been-SH functionalization, it is to avoid the loaded down with trivial details and functional modification of poor effect；Gold nano grain
Seed is grafted onto intermediate dielectric layer surface by the direct step of the method for in-situ reducing, and seed passes through with carrier
Chemical bond Au-S bond is closed, more preferable than traditional Electrostatic Absorption effect, difficult drop-off.
(2) this multi-layer core-shell nanostructured has splendid dispersibility, and pattern uniform particle diameter, multilayer core
Shell structure is clear and legible, is the gedanken experiment model of Theoretical Calculation.
(3) each layer thickness parameter of this multi-layer core-shell nanostructured all can by regulation reactant addition very
Being adjusted easily, the most therefore plasma resonance characteristic can obtain freely regulating in a big way.
(4) this multi-layer core-shell nanostructured has excellent light thermotherapy ability, is simultaneously available for SERS base
Plate, is expected at biomedicine field, and the particularly Clinics and Practices aspect of cancer plays the excellent of Nano medication
Gesture.
Above-described, only presently preferred embodiments of the present invention, it is not limited to the scope of the present invention,
The above embodiment of the present invention can also make a variety of changes.The most every right according to the present patent application is wanted
Ask change simple, equivalent and modification that book and description made, fall within the right of patent of the present invention
Claimed scope.The most detailed description of the present invention be routine techniques content.
Claims (10)
1. the preparation method of the multi-layer core-shell nanostructured of gold-organosilicon-gold, it is characterised in that bag
Include:
Step a: utilize auric chloride and trisodium citrate preparation to be dispersed with the colloid solution of gold nano grain；
Step b: add ammonia and hydrosulphonyl silane in the colloid solution that step a obtains, described Jenner
The surface of rice grain forms the intermediate dielectric layer that the surface being made up of organosilicon is mercapto-functionalized；
Step c: add auric chloride and reducing agent in the colloid solution that step b obtains, utilize the most also
Former seed mediated growth method forms the shell being made up of gold nano-material on described intermediate dielectric layer surface.
2. the preparation method of the multi-layer core-shell nanostructured of gold-organosilicon-gold as claimed in claim 1,
It is characterized in that, described step a includes:
Step a1: by auric chloride and trisodium citrate according to mol ratio (15-50): (250-400) mixes
Uniformly, add ultra-pure water, under the conditions of 100 DEG C of boilings, obtain cerise colloid solution, be then cooled to
70-90℃；
Step a2: by auric chloride and trisodium citrate according to mol ratio (20-40): (50-200) adds simultaneously
Enter in described cerise colloid solution, at 70-90 DEG C, continue stirring obtain being dispersed with gold nano grain
Kermesinus colloid solution.
3. the preparation method of the multi-layer core-shell nanostructured of gold-organosilicon-gold as claimed in claim 1,
It is characterized in that, in described step b, the mol ratio of described gold nano grain, ammonia and hydrosulphonyl silane is
(1-10): (100-300): (5-20).
4. the preparation method of the multi-layer core-shell nanostructured of gold-organosilicon-gold as claimed in claim 1,
It is characterized in that, in described step b, described hydrosulphonyl silane is 3-mercaptopropyi trimethoxy silane, 3-
Mercaptopropyltriethoxysilane or 3-mercaptopropyi tripropoxy silane.
5. the preparation method of the multi-layer core-shell nanostructured of gold-organosilicon-gold as claimed in claim 1,
It is characterized in that, described step c includes:
C1: being sequentially added into mol ratio in the colloid solution that step b obtains is 6 × 104: 1.5:1's is super
Pure water, auric chloride and the first reducing agent, form gold nano grain on described intermediate dielectric layer surface；
C2: being sequentially added into mol ratio in the colloid solution that step c1 obtains is 2 × 104: 1.5:0.01:
Ultra-pure water, auric chloride, potassium carbonate and second reducing agent of 30, so that the gold on described intermediate dielectric layer surface
Nano-particle continued growth forms the shell being made up of gold nano-material.
6. the preparation method of the multi-layer core-shell nanostructured of gold-organosilicon-gold as claimed in claim 5,
It is characterized in that, described first reducing agent is sodium borohydride, and described second reducing agent is ascorbic acid.
7. gold-the organosilicon obtained according to the preparation method according to any one of claim 1-6-
The multi-layer core-shell nanostructured of gold, it is characterised in that including:
The kernel being made up of gold nano grain；
It is made up of and surrounds the intermediate dielectric layer of described kernel organosilicon；And
It is made up of and surrounds the shell of described intermediate dielectric layer gold nano-material.
The multi-layer core-shell nanostructured of gold-organosilicon-gold the most according to claim 7, its feature exists
In, the multi-layer core-shell nanostructured of described gold-organosilicon-gold has the integral diameter of 60-250nm, its
In, a diameter of 10-100nm of described kernel, the thickness of described intermediate dielectric layer is 10-50nm, institute
The thickness stating shell is 15-25nm.
The multi-layer core-shell nanostructured of gold-organosilicon-gold the most according to claim 7, its feature exists
Have in, the multi-layer core-shell nanostructured of described gold-organosilicon-gold and present bimodal ultraviolet-visible-near-infrared
Spectral Extinction, one of them peak is in the near infrared region of 700-900nm scope, and another peak is in
The visible region of 550-650nm scope.
10. according to the multi-layer core-shell nanostructured of the gold-organosilicon-gold according to any one of claim 7-9
Application in surface enhanced raman spectroscopy.
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| CN104551008B (en) * | 2015-01-16 | 2016-08-17 | 吉林大学 | A kind of preparation method of the adjustable gold nanoshell of spectrum |
| CN105108171B (en) * | 2015-09-24 | 2017-07-18 | 厦门大学 | A kind of preparation method of the nano particle of strong Raman signal |
| CN107186210B (en) * | 2017-05-17 | 2019-01-22 | 宁波大学 | A kind of gold/silver/polymer/silver nanometer sheet core-shell material and preparation method thereof |
| CN107282918B (en) * | 2017-05-17 | 2019-01-22 | 宁波大学 | A kind of Silver nanorod/polymer/silver nanometer sheet core-shell nano material and its preparation method and application |
| CN107460462B (en) * | 2017-08-17 | 2019-03-19 | 西安工业大学 | The preparation method of silver nano-grain compacted zone on silicon wafer |
| CN109557067B (en) * | 2017-09-26 | 2021-07-20 | 中国科学院烟台海岸带研究所 | Gold nanoparticle with nuclear-satellite structure and preparation method thereof |
| CN110470828B (en) * | 2019-07-30 | 2023-11-10 | 山东第一医科大学(山东省医学科学院) | Preparation method and detection method of cerebral apoplexy marker immunosensor |
| CN111421134B (en) * | 2020-04-04 | 2021-05-18 | 华中科技大学 | Micron gold cage shell structure material with broadband absorption characteristic and preparation thereof |
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