CN104129753B - Noble metal nano particles carries out the method for three-dimensional assembling - Google Patents
Noble metal nano particles carries out the method for three-dimensional assembling Download PDFInfo
- Publication number
- CN104129753B CN104129753B CN201410341852.7A CN201410341852A CN104129753B CN 104129753 B CN104129753 B CN 104129753B CN 201410341852 A CN201410341852 A CN 201410341852A CN 104129753 B CN104129753 B CN 104129753B
- Authority
- CN
- China
- Prior art keywords
- noble metal
- nano particles
- metal nano
- time
- centrifugal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a kind of method of nanogold particle being carried out to phase transfer and three-dimensional assembling.The method, comprise the steps: after centrifugal for the aqueous solution of noble metal nano particles, the aqueous solution adding two (amino-ethyl acyl Methylethyl) octadecylamine in centrifugal gained precipitation carries out ultrasonic, the organic solution of gained dispersion liquid and two (amino-ethyl acyl Methylethyl) octadecylamine is mixed after vibration, leave standstill, complete described noble metal nano particles by aqueous phase to the transfer of oil phase.It is centrifugal the noble metal nano particles being transferred to oil phase to be carried out first time again, the organic solution adding two (amino-ethyl acyl Methylethyl) octadecylamine in centrifugal gained precipitation is carried out ultrasonic, stir after gained dispersion liquid is mixed with the organic solution of the silica spheres of sulfydryl modification again, carry out second time centrifugal, gained precipitation is the described noble metal nano particles after three-dimensional assembling, completes the three-dimensional assembling of described noble metal nano particles.Said method is simple to operate, and phase transfer equilibration time is short, repeatability and control better.
Description
The application is the applying date is on September 9th, 2013, application number is 201310406513.8, invention and created name is the divisional application that " method that noble metal nano particles carries out phase transfer and three-dimensional assembling " applies for.
Technical field
The present invention relates to a kind of method that noble metal nano particles carries out phase transfer and three-dimensional assembling.
Background technology
In recent years, the numerous application studies in material science of noble metal nano particles is peculiar optics, electricity and magnetic property have caused the great interest of people.The research work of early stage regulation and control nano material physical property is devoted to control the dielectric constant of the composition of nano particle, size, pattern and medium.In view of the significance of controllability in functional material of the coupling in the assembly of nano particle between particle and surface plasma body resonant vibration intensity, the assembling of nano particle becomes the focus of a research already.In numerous assemble methods, be a typical example with the 3D assembling of spherical colloid particle if silica is support.But, due to the silica spheres that the surface of great majority employing is at present water miscible amino head, it can only remove adsorbing metal nano particle by weak electrostatic force, therefore, the attach amount of metal nanoparticle on silica spheres is difficult to control, and effective assembling cannot realize.Silica spheres as amido modified in people such as ChungangWang attaches nanometer gold bar using the probe as immunoassays.(Wang, C.; Chen, Y.; Wang, T.; Ma, Z.; Su, Z.Monodispersed Gold Nanorod-Embedded Silica Particles as NovelRaman Labels for Biosensing.Advanced Functional Materials2008,18 (2), 355-361) silica spheres as sulfydryl modification is rolled into a ball for hydrophobic function, it attaches metal nanoparticle by strong chemical bond, but, nano particle due to major applications is water-soluble, dimension, the application of hydrophobic silica ball is subject to great restriction.Remove to attach ~ the nanogold particle of 3nm as the people such as Sarah L.Westcott utilize the silica spheres of sulfydryl modification, its amount of attaching is very little; (Westcott, Sarah L.; Oldenburg, Steven J.; Lee, T.Randall; Halas, Naomi J.Formation and Adsorption of Clusters of Gold Nanoparticles onto FunctionalizedSilica Nanoparticle Surfaces, Langmuir1998,14 (19), the multiple nano particle that 5396-5401.) difference forms by the people such as Zhenda Lu effectively attaches on the silica spheres of sulfydryl modification, obtains the assembly of several functions.(Lu, Zhenda; Gao, Chuanbo; Zhang, Qiao; Chi, Miaofang; Howe, Jane Y.; Yin, Yadong.Direct Assembly of Hydrophobic Nanoparticles to Multifunctional Structures, Nano Letters (2011), 11 (8), 3404-3412) in addition, the above-mentioned method mentioned only demonstrates the granule of below 10nm and attaches effect preferably, therefore significantly limit its range of application.
Recently, a lot of scholar is devoted to water miscible nano particle to transfer to oil phase to obtaining oil-soluble nano particle from aqueous phase, then these methods adopt poisonous solvent as ionic liquid and lauryl mercaptan, in addition, the spherical particle that these methods can only shift below 18nm is main nano particle, and its equilibration time is also very long.As the water-soluble nano gold grain of below 18nm is successfully transferred in oil phase with the alkylamine of amphipathic different chain length by the people such as MatthiasKarg to some extent; (Karg, Matthias; Schelero, Natascha; Oppel, Claudia; Gradzielski, Michael; Hellweg, Thomas; Von Klitzing, Regine.Versatile Phase Transfer of GoldNanoparticles from Aqueous Media to Different Organic Media, Chemistry – A EuropeanJournal (2011), 17 (16), 4648-4654.) people such as Guor-Tzo Wei is that nanogold particle is transferred to oil phase from aqueous phase by medium with ionic liquid.(Wei, Guor-Tzo; Yang, Zusing; Lee, Chia-Ying; Yang, Hsiao-Yen; Wang, C.R.Chris.Aqueous-Organic Phase Transfer of Gold Nanoparticles and GoldNanorods Using an Ionic Liquid, Journal of the American Chemical Society (2004), 126 (16), 5036-5037.) therefore, be necessary to develop a kind of eurytopic, economic, phase transfer method easily.
Summary of the invention
The object of this invention is to provide a kind of method of nanogold particle being carried out to phase transfer and three-dimensional assembling.
The invention provides a kind of two (amino-ethyl acyl Methylethyl) octadecylamine and noble metal nano particles is being transferred to the application in oil phase by aqueous phase.
Present invention also offers a kind of two (amino-ethyl acyl Methylethyl) octadecylamine carries out in three-dimensional assembling application at noble metal nano particles.
In above-mentioned application, described noble metal is selected from least one in gold, platinum and silver;
In described aqueous phase, solvent is water;
In described oil phase, solvent is chloroform, carrene, toluene, acetone, DMF or chlorobenzene;
The particle diameter of described noble metal nano particles is 2-500nm;
The apparent form of described noble metal nano particles is nanometer gold bar, nanometer golden flower, nano gold spherical, nanometer star or nanometer sheet;
The length of described nanometer gold bar is 25-500nm, and diameter is 5-30nm;
The diameter of described nanometer golden flower is 30-100nm;
The diameter of described nano gold spherical is 2-40nm.
Method noble metal nano particles being transferred to oil phase by aqueous phase provided by the invention, comprises the steps:
After centrifugal for the aqueous solution of noble metal nano particles, the aqueous solution adding two (amino-ethyl acyl Methylethyl) octadecylamine in centrifugal gained precipitation carries out ultrasonic, the organic solution of gained dispersion liquid and two (amino-ethyl acyl Methylethyl) octadecylamine is mixed after vibration, leave standstill, complete described noble metal nano particles by aqueous phase to the transfer of oil phase;
Or,
The aqueous solution adding two (amino-ethyl acyl Methylethyl) octadecylamine in the aqueous solution of noble metal nano particles carries out ultrasonic disperse, the organic solution of gained dispersion liquid and two (amino-ethyl acyl Methylethyl) octadecylamine is mixed after vibration, leave standstill, complete described noble metal nano particles by aqueous phase to the transfer of oil phase.
In said method, described noble metal is selected from least one in gold, platinum and silver;
The apparent form of described noble metal nano particles is nanometer gold bar, nanometer golden flower, nano gold spherical, nanometer star or nanometer sheet;
The particle diameter of described noble metal nano particles is 2-500nm;
In the organic solution of described two (amino-ethyl acyl Methylethyl) octadecylamine, solvent is chloroform, carrene, toluene, acetone, DMF or chlorobenzene.
In described centrifugation step, centrifugal force is 400-10000g;
When described noble metal nano particles is nanometer gold bar, centrifugal force is specially 8000g;
When described noble metal nano particles is nanometer golden flower, centrifugal force is specially 7000g;
Centrifugal number of times is 2-5 time, is specially 3 times;
The at every turn centrifugal time is 7-20 minute, is specially 10 minutes;
The concentration of the aqueous solution of described two (amino-ethyl acyl Methylethyl) octadecylamine is 0.1-3mM, is specially 1mM;
Volumetric usage is identical with the volume of the aqueous solution of described noble metal nano particles;
In described ultrasonic step, power is 200-800W, is specially 600W;
Time is 20-60 second, is specially 30 seconds;
The mass percentage concentration of the organic solution of described two (amino-ethyl acyl Methylethyl) octadecylamine is 0.8-2.5%, is specially 1%;
Volumetric usage is identical with the volume of the aqueous solution of described noble metal nano particles;
In described vibrating step, the time is 20 seconds to 3 minutes, is specially 30 seconds;
In described stating step, the time is 20 seconds to 5 minutes, is specially 1 minute.
Noble metal nano particles provided by the invention carries out the method for three-dimensional assembling, comprises the steps:
1) according to aforementioned method provided by the invention, described noble metal nano particles is transferred to oil phase by aqueous phase;
2) by step 1) to carry out first time centrifugal for the gained noble metal nano particles that is transferred to oil phase, the organic solution adding two (amino-ethyl acyl Methylethyl) octadecylamine in centrifugal gained precipitation is carried out ultrasonic, stir after gained dispersion liquid is mixed with the organic solution of the silica spheres of sulfydryl modification again, carry out second time centrifugal, gained precipitation is the described noble metal nano particles after three-dimensional assembling, completes the three-dimensional assembling of described noble metal nano particles.
Step 2 described in said method) first time centrifugation step in, centrifugal force is 400-5000g;
Described noble metal nano particles be nanometer gold bar and nanometer golden flower time, centrifugal force is specially 3000g;
When described noble metal nano particles is nano gold spherical, centrifugal force is specially 4000g;
Centrifugal number of times is 2-5 time, is specially 2 times;
The at every turn centrifugal time is 3-15 minute, is specially 5 minutes;
In the organic solution of described two (the amino-ethyl acyl Methylethyl) organic solutions of octadecylamine and the silica spheres of sulfydryl modification, solvent is chloroform, carrene, toluene, acetone, DMF or chlorobenzene;
The concentration of the organic solution of described two (amino-ethyl acyl Methylethyl) octadecylamine is 0.01-2mM, is specially 0.05mM;
The volume that volumetric usage and described noble metal nano particles are transferred to oil phase gained solution is identical;
The silica spheres of described sulfydryl modification is rigging, and its diameter is 100-400nm, is specially 200nm;
In the organic solution of the silica spheres of described sulfydryl modification, in the silica spheres of sulfydryl modification and described organic solution, the amount ratio of organic solvent is 14mg:2mL;
The volume ratio that the organic solution of the silica spheres of described sulfydryl modification and noble metal nano particles are transferred to oil phase gained solution is 5-50 μ L:4mL, is specially 15 μ L:4mL;
In described ultrasonic step, power is 200-800W, is specially 600W;
Time is 20-60 second, is specially 20 seconds;
In described whipping step, rotating speed is 300-1200rpm, is specially 600rpm;
Time is 0.5-8 hour, is specially 3 hours;
In described second time centrifugation step, centrifugal force is 400-5000g;
Described noble metal nano particles be nanometer gold bar and nanometer golden flower time, centrifugal force is specially 3000g;
When described noble metal nano particles is nano gold spherical, centrifugal force is specially 4000g;
Centrifugal number of times is 2-5 time, is specially 2 times;
The at every turn centrifugal time is 2-10 minute, is specially 3 minutes.
The surfactant molecule C of the present invention's application " branch " shape, amphipathic, polyamino head
18n
3(two (amino-ethyl acyl Methylethyl) octadecylamine), as protective agent, the aqueous phase that nanogold particle is protected from the hydrophily protective agent by double-layer surface-active agent or individual layer at large-area oil-water interfaces place under vibration condition forwards the oil phase protected by monolayer surface activating agent to.
The method of three-dimensional assembling provided by the invention, silica spheres by sulfydryl modification is template, by silica spheres stirring reaction in oil phase of the dewatering nano gold grain after phase transfer and sulfydryl modification, by the generation of strong S-Au key, large nano particle is made also can be firmly adsorbed on the silica spheres of sulfydryl modification, form the 3D assembly of the nanogold particle of different morphologies, and its adsorption density reported much larger than current document.
Nanogold particle is carried out phase transfer compare with the method that 3D assembles with existing by the present invention, has following advantage:
For phase transfer: the more existing report of raw material environmental friendliness more; Operating process is simple, and phase transfer equilibration time is short; Reaction needed raw material is cheap and easy to get, reduces to produce to rise this; The size of the nanogold particle shifted is greater than the size that current document is reported, expands its range of application; Different morphologies can be shifted as spherical, bar-shaped, flower-shaped nanogold particle; Reproducible.
Assemble for 3D: easy and simple to handle, one-step method can realize the nanogold particle direct-assembling of large-sized different morphologies on the silica spheres of spherical template-sulfydryl modification; Better control: regulate nanogold particle attaching on the silica spheres of sulfydryl modification to measure the Nanoscale assemblies of different structure by the ratio both regulating.
Accompanying drawing explanation
Fig. 1 is the photo in embodiment 1,2,3 before and after nanogold particle phase transfer.
Fig. 2 (a) is the stereoscan photograph of nanometer gold bar before phase transfer in embodiment 1, Fig. 2 (b) is the stereoscan photograph of nanometer gold bar after phase transfer in embodiment 1, can find out, nanometer gold bar its pattern before and after phase transfer does not change substantially.
Fig. 2 (c) is the stereoscan photograph of nanometer golden flower before phase transfer in embodiment 2, Fig. 2 (d) is the stereoscan photograph of nanometer golden flower after phase transfer in embodiment 2, can find out, nanometer golden flower its pattern before and after phase transfer does not change substantially.
Fig. 2 (e) is the stereoscan photograph of nano gold spherical before phase transfer in embodiment 3, Fig. 2 (f) is the stereoscan photograph of nano gold spherical after phase transfer in embodiment 2, can find out, nano gold spherical its pattern before and after phase transfer does not change substantially.
Fig. 3 (a) is the electromicroscopic photograph of nanometer gold bar 3D assembling on the silica spheres of sulfydryl modification in embodiment 4.
Fig. 3 (b) is the electromicroscopic photograph of nanometer golden flower 3D assembling on the silica spheres of sulfydryl modification in embodiment 5.
Fig. 3 (c) is the electromicroscopic photograph of nano gold spherical 3D assembling on the silica spheres of sulfydryl modification in embodiment 6.
All scales in Fig. 2 are 1 μm.
All scales in Fig. 3 are 2 μm.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described raw material all can obtain from open commercial sources if no special instructions.
In the present invention, the method that nanometer gold bar and original solution thereof can provide according to following document is prepared and obtains: Sau, TapanK.; Murphy, Catherine J.Seeded High Yield Synthesis of Short Au Nanorods in AqueousSolution, Langmuir (2004), 20 (15), 6414-6420:
Be specially:
(1) first gold seeds is prepared: by the 10mM NaBH just prepared
4(0.6mL) 0.1M CTAB (7.5mL) and 0.01M HAuCl is added
4(0.25mL) in mixed aqueous solution, vigorous stirring 2min, then by it in 25 DEG C of standing 2h.
(2) growth of rod: by 0.10M CTAB (4.75mL), 0.01M HAuCl
43H
2o (0.200mL), 0.01M AgNO
3(0.030mL) join successively in flask, stirred and evenly mixed, then 0.10M AA (0.032mL) is added in mixed solution, finally, seed solution (0.01mL) is added in above-mentioned mixed solution, after stirring 10s, obtains in 25 DEG C of standing 12h.
The length of gained nanometer gold bar is 25-500nm, and diameter is 5-30nm;
Nanometer golden flower can be prepared by the following method and obtain:
1) the gold seeds solution (gold seeds solution concentration is 0.24mM) being 20nm by the particle diameter of 50 μ L natrium citricum protections joins 4mL by C18N3 and HAuCl
4in the mixed aqueous solution of composition, wherein, the concentration of C18N3 is 0.6mM, HAuCl
4concentration be 0.25mM, in this mixed solution, then add the ascorbic acid AA of 10 μ L0.1M, shake this mixed solution gently, then room temperature leave standstill carries out reduction reaction 12h;
2) by step 1) react complete mixed solution centrifugal 5min under 5000rpm, draw supernatant liquor, precipitation ultra-pure water disperses again, this process repeats 3 times, finally the gold nano grain obtained is dispersed in 1mL ultra-pure water, drip on the copper mesh of silicon chip and carbon film covering, drying at room temperature, obtains nanometer golden flower again.Whole course of reaction is carried out (20-25 DEG C) in room temperature.
Gained nanometer golden flower is carried out scanning nuclear microprobe sign, and known, the surperficial branch density of gained nanometer golden flower is high, and particle diameter is 100nm, and the mode of appearance of surperficial branch is feeler type, and the particle diameter of core is 20nm, and surperficial branch is mono-crystalline structures; And this nanometer golden flower has better monodispersity, and rough surface.
The method that nano gold spherical can provide according to following document is prepared and obtains: Ji, Xiaohui; Song, Xiangning; Li, Jun; Bai, Yubai; Yang, Wensheng; Peng, Xiaogang.Size Control of Gold Nanocrystals inCitrate Reduction:The Third Role of Citrate, Journal of the American Chemical Society (2007), 129 (45), 13939-13948;
The diameter of gained nano gold spherical is 2-40nm.
The method that the silica spheres of sulfydryl modification can provide according to following document is prepared and obtains: Kim, J.-H.; Kim, J.-S.; Choi, H.; Lee, S.-M.; Jun, B.-H.; Yu, K.-N.; Kuk, E.; Kim, Y.-K.; Jeong, D.H.; Cho, M.-H.; Lee, Y.-S.Nanoparticle Probes with Surface Enhanced Raman Spectroscopic Tagsfor Cellular Cancer Targeting, Analytical Chemistry (2006), 78 (19), 6967-6973.
Be specially:
Tetraethoxysilane (1.8mL) is dropwise added under agitation in the mixed solution of ammoniacal liquor (3mL) and absolute ethyl alcohol (40mL), this mixed solution is stirred 24h under 25 DEG C of conditions.By mixed solution centrifuge washing 3 times under 5000g, the condition of 8min/ time, in 40 DEG C of baking ovens, place 3h make it dry, be the silica spheres of gained.Taking 0.2g silica spheres is dissolved in 3mL ethanol, adds 50 μ L MPTMS and 50 μ L ammoniacal liquor successively, this mixed solution is stirred 12h under 25 DEG C of conditions to it.By this mixture centrifuge washing 3 times under 5000g, the condition of 8min/ time, in 60 DEG C of baking ovens, place 3h make it dry, be the silica spheres of sulfydryl modification;
The silica bulb diameter of gained sulfydryl modification is 200nm;
Surfactant amphiphile, amphiphilic molecule two (amino-ethyl acyl Methylethyl) octadecylamine (C
18n
3) can provide according to following document method preparation and obtain: Wang, W.; Lu, W.S.; Jiang, L.Influence of pH on the AggregationMorphology of a Novel Surfactant with Single Hydrocarbon Chain and Multi-AmineHeadgroups, J.Phys.Chem.B (2008), 112,1409-1413.
Embodiment 1, utilize surfactant two (amino-ethyl acyl Methylethyl) octadecylamine (C
18n
3) by nanometer gold bar phase transfer
By nanometer gold bar original solution (4mL) centrifuge washing three times under centrifugal force is 8000g, the condition of 10min/ time, to go out CTAB unnecessary in preparation process, in centrifugal product, add the C that 4mL concentration is 1mM
18n
3the aqueous solution, by its ultrasonic 30s under the condition of 600W.By solution obtained above and 1%C
18n
3chloroformic solution mixing, vibration 30s, leaves standstill 1 minute, completes phase transfer, nanometer gold bar transfer to lower floor from the aqueous phase on upper strata chloroform mutually, as shown in Fig. 1 (a).
The pattern of nanometer gold bar in aqueous phase and oil phase, respectively as shown in Fig. 2 (a), 2 (b), can see that its pattern does not almost become before and after phase transfer.
Embodiment 2, utilize surfactant two (amino-ethyl acyl Methylethyl) octadecylamine (C
18n
3) by nanometer golden flower phase transfer
According to the step of embodiment 1, only the nanometer gold bar in embodiment 1 is replaced with nanometer golden flower, centrifugal force replaces with 7000g, completes the phase transfer of nanometer golden flower.
As shown in Fig. 1 (b).The pattern of nanometer golden flower in aqueous phase and oil phase, respectively as shown in Fig. 2 (c), 2 (d), can see that its pattern does not almost become before and after phase transfer.
Embodiment 3, utilize surfactant two (amino-ethyl acyl Methylethyl) octadecylamine (C
18n
3) by nano gold spherical phase transfer
Be 1%C by nano gold spherical original solution (4mL) and mass percentage concentration
18n
3chloroformic solution mixing, vibration 30s, leaves standstill 1 minute, completes phase transfer, nano gold spherical transfer to lower floor from the aqueous phase on upper strata chloroform mutually, as shown in Fig. 1 (c).
The pattern of nano gold spherical in aqueous phase and oil phase, respectively as shown in Fig. 2 (e), 2 (f), can see that its pattern does not almost become before and after phase transfer.
Embodiment 4, by nanometer gold bar with the silica spheres of sulfydryl modification for template carries out 3D assembling, step is as follows:
The chloroformic solution (4mL) of nanometer gold bar phase transfer obtained, with centrifuge washing twice under 3000g, the condition of 5min/ time, adds 0.05mM C to centrifugal product
18n
3chloroformic solution (2mL), by its ultrasonic 20s under the condition of 600W.The chloroformic solution (15 μ L) of the silica spheres of sulfydryl modification is added, to stir 3h under the condition of 600r/min to gained solution.By this mixture with centrifuge washing twice under 3000g, the condition of 3min/ time, the centrifugal product of gained is the 3D assembly of nanometer gold bar, as shown in Fig. 3 (a).
Wherein, the chloroformic solution of the silica spheres of sulfydryl modification is joined by the silica spheres of the sulfydryl modification of 14mg in 2mL chloroform to dissolve to disperse to obtain.
Embodiment 5, by nanometer golden flower with the silica spheres of sulfydryl modification for template carries out 3D assembling, step is as follows:
The chloroformic solution (4mL) of nanometer golden flower phase transfer obtained, with centrifuge washing twice under 3000g, the condition of 5min/ time, adds 0.05mM C to centrifugal product
18n
3chloroformic solution (2mL), by its ultrasonic 20s under the condition of 600W.The chloroformic solution (15 μ L) of the silica spheres of sulfydryl modification is added, to stir 3h under the condition of 600r/min to gained solution.By this mixture with centrifuge washing twice under 3000g, the condition of 3min/ time, the centrifugal product of gained is the 3D assembly of nanometer golden flower, and nanometer golden flower successfully attaches on the silica spheres of sulfydryl modification, as shown in Fig. 3 (b).
Embodiment 6, by nano gold spherical with the silica spheres of sulfydryl modification for template carries out 3D assembling, step is as follows:
The chloroformic solution (4mL) of nano gold spherical phase transfer obtained, with centrifuge washing twice under 4000g, the condition of 5min/ time, adds 0.05mM C to centrifugal product
18n
3chloroformic solution (2mL), by its ultrasonic 20s under the condition of 600W.The chloroformic solution (15 μ L) of the silica spheres of sulfydryl modification is added, to stir 3h under the condition of 600r/min to gained solution.By this mixture with centrifuge washing twice under 4000g, the condition of 3min/ time, the centrifugal product of gained is the 3D assembly of nano gold spherical, and as shown in Fig. 3 (b), nano gold spherical attaches to high-density on the silica spheres of sulfydryl modification.
Claims (5)
1. noble metal nano particles carries out a method for three-dimensional assembling, comprises the steps:
1) as follows described noble metal nano particles is transferred to oil phase by aqueous phase:
After centrifugal for the aqueous solution of noble metal nano particles, the aqueous solution adding two (amino-ethyl acyl Methylethyl) octadecylamine in centrifugal gained precipitation carries out ultrasonic, the organic solution of gained dispersion liquid and two (amino-ethyl acyl Methylethyl) octadecylamine is mixed after vibration, leave standstill, complete described noble metal nano particles by aqueous phase to the transfer of oil phase;
Or,
The aqueous solution adding two (amino-ethyl acyl Methylethyl) octadecylamine in the aqueous solution of noble metal nano particles carries out ultrasonic disperse, the organic solution of gained dispersion liquid and two (amino-ethyl acyl Methylethyl) octadecylamine is mixed after vibration, leave standstill, complete described noble metal nano particles by aqueous phase to the transfer of oil phase;
2) by step 1) to carry out first time centrifugal for the gained noble metal nano particles that is transferred to oil phase, the organic solution adding two (amino-ethyl acyl Methylethyl) octadecylamine in centrifugal gained precipitation is carried out ultrasonic, stir after gained dispersion liquid is mixed with the organic solution of the silica spheres of sulfydryl modification again, carry out second time centrifugal, gained precipitation is the described noble metal nano particles after three-dimensional assembling, completes the three-dimensional assembling of described noble metal nano particles;
Described step 2) first time centrifugation step in, centrifugal force is 400-5000g;
Centrifugal number of times is 2-5 time;
The at every turn centrifugal time is 3-15 minute;
In the organic solution of described two (the amino-ethyl acyl Methylethyl) organic solutions of octadecylamine and the silica spheres of sulfydryl modification, solvent is chloroform, carrene, toluene, acetone, DMF or chlorobenzene;
The concentration of the organic solution of described two (amino-ethyl acyl Methylethyl) octadecylamine is 0.01-2mM;
The volume that volumetric usage and described noble metal nano particles are transferred to oil phase gained solution is identical;
The diameter of the silica spheres of described sulfydryl modification is 100-400nm;
In the organic solution of the silica spheres of described sulfydryl modification, in the silica spheres of sulfydryl modification and described organic solution, the amount ratio of organic solvent is 14mg:2mL;
The volume ratio that the organic solution of the silica spheres of described sulfydryl modification and noble metal nano particles are transferred to oil phase gained solution is 5-50 μ L:4mL;
In described ultrasonic step, power is 200-800W;
Time is 20-60 second;
In described whipping step, rotating speed is 300-1200rpm;
Time is 0.5-8 hour;
In described second time centrifugation step, centrifugal force is 400-5000g;
Centrifugal number of times is 2-5 time;
The at every turn centrifugal time is 2-10 minute.
2. method according to claim 1, is characterized in that: described step 2) first time centrifugation step in,
Described noble metal nano particles be nanometer gold bar and nanometer golden flower time, centrifugal force is 3000g;
When described noble metal nano particles is nano gold spherical, centrifugal force is 4000g;
Centrifugal number of times is 2 times;
The at every turn centrifugal time is 5 minutes;
The concentration of the organic solution of described two (amino-ethyl acyl Methylethyl) octadecylamine is 0.05mM;
The volume that volumetric usage and described noble metal nano particles are transferred to oil phase gained solution is identical;
The diameter of the silica spheres of described sulfydryl modification is 200nm;
The volume ratio that the organic solution of the silica spheres of described sulfydryl modification and noble metal nano particles are transferred to oil phase gained solution is 15 μ L:4mL;
In described ultrasonic step, power is 600W;
Time is 20 seconds;
In described whipping step, rotating speed is 600rpm;
Time is 3 hours;
In described second time centrifugation step,
Described noble metal nano particles be nanometer gold bar and nanometer golden flower time, centrifugal force is 3000g;
When described noble metal nano particles is nano gold spherical, centrifugal force is 4000g;
Centrifugal number of times is 2 times;
The at every turn centrifugal time is 3 minutes.
3. method according to claim 2, is characterized in that: described step 1) in, noble metal is selected from least one in gold, platinum and silver;
The apparent form of described noble metal nano particles is nanometer gold bar, nanometer golden flower, nano gold spherical, nanometer star or nanometer sheet;
The particle diameter of described noble metal nano particles is 2-500nm;
In the organic solution of described two (amino-ethyl acyl Methylethyl) octadecylamine, solvent is chloroform, carrene, toluene, acetone, DMF or chlorobenzene.
4., according to described method arbitrary in claim 1-3, it is characterized in that: described step 1) in centrifugation step, centrifugal force is 400-10000g;
Centrifugal number of times is 2-5 time;
The at every turn centrifugal time is 7-20 minute;
The concentration of the aqueous solution of described two (amino-ethyl acyl Methylethyl) octadecylamine is 0.1-3mM;
Volumetric usage is identical with the volume of the aqueous solution of described noble metal nano particles;
In described ultrasonic step, power is 200-800W;
Time is 20-60 second;
The mass percentage concentration of the organic solution of described two (amino-ethyl acyl Methylethyl) octadecylamine is 0.8-2.5%;
Volumetric usage is identical with the volume of the aqueous solution of described noble metal nano particles;
In described vibrating step, the time is 20 seconds to 3 minutes;
In described stating step, the time is 20 seconds to 5 minutes.
5. method according to claim 4, is characterized in that: described step 1) in centrifugation step, when described noble metal nano particles is nanometer gold bar, centrifugal force is 8000g;
When described noble metal nano particles is nanometer golden flower, centrifugal force is 7000g;
Centrifugal number of times is 3 times;
The at every turn centrifugal time is 10 minutes;
The concentration of the aqueous solution of described two (amino-ethyl acyl Methylethyl) octadecylamine is 1mM;
In described ultrasonic step, power is 600W;
Time is 30 seconds;
The mass percentage concentration of the organic solution of described two (amino-ethyl acyl Methylethyl) octadecylamine is 1%;
In described vibrating step, the time is 30 seconds;
In described stating step, the time is 1 minute.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310406513.8A CN103496666B (en) | 2013-09-09 | 2013-09-09 | Method for phase transferring and three-dimensional assembling of precious metal nano-particles |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310406513.8A Division CN103496666B (en) | 2013-09-09 | 2013-09-09 | Method for phase transferring and three-dimensional assembling of precious metal nano-particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104129753A CN104129753A (en) | 2014-11-05 |
| CN104129753B true CN104129753B (en) | 2015-09-16 |
Family
ID=49861960
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310406513.8A Expired - Fee Related CN103496666B (en) | 2013-09-09 | 2013-09-09 | Method for phase transferring and three-dimensional assembling of precious metal nano-particles |
| CN201410341852.7A Expired - Fee Related CN104129753B (en) | 2013-09-09 | 2013-09-09 | Noble metal nano particles carries out the method for three-dimensional assembling |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310406513.8A Expired - Fee Related CN103496666B (en) | 2013-09-09 | 2013-09-09 | Method for phase transferring and three-dimensional assembling of precious metal nano-particles |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN103496666B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602544A (en) * | 2015-12-24 | 2016-05-25 | 北京北达聚邦科技有限公司 | Preparation method for converting aqueous phase quantum dots into oil phase quantum dots |
| CN106935871B (en) * | 2015-12-31 | 2019-07-09 | 中国科学院化学研究所 | A kind of mesoporous PtAu nano material of hollow ball-shape and the preparation method and application thereof |
| CN106270498B (en) * | 2016-08-24 | 2018-09-18 | 浙江大学 | A method of phase transfer is carried out to noble metal nano particles |
| TWI698507B (en) * | 2018-12-06 | 2020-07-11 | 財團法人工業技術研究院 | Modified metal nanoplate and conductive paste comprising the same |
| CN113500200B (en) * | 2021-06-24 | 2022-05-17 | 北京航空航天大学 | Surface modification method for gold nanorod water-phase-oil-phase conversion by using seed growth method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051687A (en) * | 2009-11-03 | 2011-05-11 | 中国科学院化学研究所 | Method for preparing gold crystals by adopting surface active agent molecule C18N3 |
| CN102233434A (en) * | 2011-06-16 | 2011-11-09 | 中国科学院化学研究所 | Method for preparing nano/micron gold hierarchical structure material |
| CN103273080A (en) * | 2013-05-30 | 2013-09-04 | 中国科学院化学研究所 | Nanometer golden flower and preparation method and application of nanometer golden flower |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100485011C (en) * | 2006-12-22 | 2009-05-06 | 华中师范大学 | Preparation method for water-soluble quantum point under condition of phase transition |
| CN102728831B (en) * | 2012-06-19 | 2015-04-29 | 中国科学院化学研究所 | Method for dispersing, purifying and/or assembling nano gold rods |
-
2013
- 2013-09-09 CN CN201310406513.8A patent/CN103496666B/en not_active Expired - Fee Related
- 2013-09-09 CN CN201410341852.7A patent/CN104129753B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051687A (en) * | 2009-11-03 | 2011-05-11 | 中国科学院化学研究所 | Method for preparing gold crystals by adopting surface active agent molecule C18N3 |
| CN102233434A (en) * | 2011-06-16 | 2011-11-09 | 中国科学院化学研究所 | Method for preparing nano/micron gold hierarchical structure material |
| CN103273080A (en) * | 2013-05-30 | 2013-09-04 | 中国科学院化学研究所 | Nanometer golden flower and preparation method and application of nanometer golden flower |
Non-Patent Citations (3)
| Title |
|---|
| Fabrication of color changeable polystyrene spheres decorated by gold nanoparticles and their label-free biosensing;Xia Y, Lu W, Jiang L.;《Nanotechnology》;20100125;第21卷(第8期);第085501页 * |
| Polystyrene spheres coated with gold nanoparticles for detection of DNA;Li S, Xia Y, Zhang J, et al.;《Electrophoresis》;20100830;第31卷(第18期);第3090-3096页 * |
| Surfactants possessing multiple polar heads. A perspective on their unique aggregation behavior and applications;Bhattacharya S, Samanta S K.;《The Journal of Physical Chemistry Letters》;20110405;第2卷(第8期);第914-920页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104129753A (en) | 2014-11-05 |
| CN103496666B (en) | 2015-04-29 |
| CN103496666A (en) | 2014-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104129753B (en) | Noble metal nano particles carries out the method for three-dimensional assembling | |
| Martin et al. | Charged gold nanoparticles in non-polar solvents: 10-min synthesis and 2D self-assembly | |
| Das et al. | Nanofluids: science and technology | |
| Yuan et al. | Synthesis of highly fluorescent metal (Ag, Au, Pt, and Cu) nanoclusters by electrostatically induced reversible phase transfer | |
| Zheng et al. | One-step one-phase synthesis of monodisperse noble-metallic nanoparticles and their colloidal crystals | |
| Guerrero-Martínez et al. | Nanostars shine bright for you: colloidal synthesis, properties and applications of branched metallic nanoparticles | |
| Fang et al. | Gold mesostructures with tailored surface topography and their self-assembly arrays for surface-enhanced Raman spectroscopy | |
| Bakshi et al. | Dependence of crystal growth of gold nanoparticles on the capping behavior of surfactant at ambient conditions | |
| US20080234394A1 (en) | System for forming janus particles | |
| CN104308172B (en) | A kind of method preparing the micro-nano metal of hollow cubic | |
| CN103406549B (en) | A kind of shape flower shape gold nano grain in full bloom and preparation method thereof | |
| Mitamura et al. | Fabrication and self-assembly of hydrophobic gold nanorods | |
| CN105598442B (en) | One-dimensional chain Au-Ag core-shell nanostructure, self-assembly preparation method thereof and SERS application | |
| Aguirre et al. | CTAB mediated reshaping of metallodielectric nanoparticles | |
| Ortiz et al. | Controlling the growth kinetics of nanocrystals via galvanic replacement: synthesis of Au tetrapods and star-shaped decahedra | |
| CN103231069A (en) | Preparation method for hollow nano metal | |
| Premkumar et al. | Shape-tailoring and catalytic function of anisotropic gold nanostructures | |
| Ma et al. | Interfacial nanodroplets guided construction of hierarchical Au, Au-Pt and Au-Pd particles as excellent catalysts | |
| Wang et al. | A rapid phase transfer method for nanoparticles using alkylamine stabilizers | |
| Wilson et al. | Separation of dendrimer-encapsulated Au and Ag nanoparticles by selective extraction | |
| Cai et al. | Insight into the fabrication and perspective of dendritic Ag nanostructures | |
| Li et al. | Gold/oil nanofluids stabilized by a gemini surfactant and their catalytic property | |
| CN103990814A (en) | Preparing method of gold nanoparticles | |
| Baral et al. | Synthesis of gold nanosheets with controlled morphology by combining a natural amino acid with high-frequency ultrasound | |
| CN103521778A (en) | Self-assembly preparation of one-dimensional nano-structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150916 Termination date: 20200909 |