CN102310201A - Surface phosphonic acid functionalized Au nano particle preparing method - Google Patents
Surface phosphonic acid functionalized Au nano particle preparing method Download PDFInfo
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- CN102310201A CN102310201A CN201110306591A CN201110306591A CN102310201A CN 102310201 A CN102310201 A CN 102310201A CN 201110306591 A CN201110306591 A CN 201110306591A CN 201110306591 A CN201110306591 A CN 201110306591A CN 102310201 A CN102310201 A CN 102310201A
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Abstract
The invention discloses a surface phosphonic acid functionalized Au nano particle (AuNPs) preparing method. Olefin organic phosphonic acid is used as a reducing agent to be added into a HAuCl4 water solution and heated at the temperature of 80-120 DEG C under a stirring condition for reaction, and surface phosphonated spherical Au nano particles with uniform size and regular shapes are obtained. The surfaces of the prepared AuNPs are wrapped by oxidization products of the reduction agent and then are decorated with phosphonic acid base groups, so the colloid stability of AuNPs is effectively improved, the phenomenon of agglomeration is avoided, and the phosphonic acid functionalized AuNPs with good monodispersity and uniform particle size are prepared. The preparing method disclosed by the invention has a clear and reliable mechanism and is simple and feasible, and the obtained AuNPs have excellent colloid stability in water and wide application prospects in the material science and biomedicine fields of nano devices, fuel batteries, bio-mimetic enzyme sensors and the like.
Description
Technical field
The present invention relates to a kind of preparation method of functionalization golden nanometer particle, relate in particular to a kind of golden nanometer particle preparation method of finishing phosphonyl group.
Background technology
Golden nanometer particle (AuNPs) promptly refers to the molecule of gold, and its diameter has high electron density, dielectric property and catalytic action at 1～100 nm, can combine with multiple large biological molecule, and not influence its biologically active.By HAuCl
4Can prepare the nm of gold of various different-grain diameters easily through reducing process, its color takes on a red color to purple according to diameter.AuNPs has caused various fields researchers' such as optics, biology, catalysis, sensor and medical treatment interest owing to its unique physics, chemical property.The AuNPs of stably dispersing has very high using value at biological field in the aqueous solution.
A lot of different methods that prepare AuNPs are arranged at present, and wherein the wet chemistry reducing process is a kind of very tradition and the method for popularizing that is used to prepare the stable AuNPs of aqueous dispersion.Because AuNPs is very easy to reunite and sedimentation in aqueous environment, so thereby can use some protective agents to cover its surface usually reaches stable purpose.The polymer that contains corresponding functional group as mercaptan, hydrogen phosphide, amine, carboxylate, biomolecule and some has been widely used in stablizes AuNPs, mainly is based on the Coulomb repulsion effect strong between the functional group of dissociating or the hydrophily of functional group's oneself height.Than-NH
2With-the COOH group ,-PO
3H
2Because the binary acid of himself essence has wideer pH response range, thereby makes the AuNPs of phosphonic acidsization in very wide pH scope, all have the Coulomb repulsion effect.Therefore, all show outstanding colloidal stability in the aqueous solution of the AuNPs of phosphonic acids functionalization in very wide pH scope.
The present invention is intended to utilize chemical reduction method to prepare functionalization AuNPs; Make AuNPs finishing phosphonyl group; Through Coulomb repulsion between the phosphonyl group and the outstanding hydrophily of phosphonyl group self; Effectively improve the colloidal stability of AuNPs in the aqueous solution, prepare the AuNPs of the phosphonic acids functionalization of monodispersed, uniform particle diameter.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of golden nanometer particle (AuNPs) of surperficial phosphonic acids functionalization; To overcome AuNPs is prone to reunion, sedimentation in the aqueous solution defective; Can make single AuNPs of dispersion of the regular surperficial phosphonic acids functionalization of uniform particle diameter, shape, to satisfy the requirement of relevant field development.
The technical scheme that the present invention adopted is following:
A kind of preparation method of golden nanometer particle of surperficial phosphonic acids functionalization is characterized in that, a certain amount of olefines organic phospho acid reducing agent is joined HAuCl
4In the aqueous solution, 80 ~ 120 ℃ of reacting by heating under the stirring condition obtain the golden nanometer particle of surperficial phosphonic acidsization.
The inventive method utilizes the olefines organic phospho acid as reducing agent, adopts " one kettle way " with HAuCl
4Be reduced into uniform particle diameter, the regular monodisperse spherical AuNPs of shape.In the preparation process,, thereby on the AuNPs surface, modify phosphonyl group because the oxidation product of reducing agent is coated on the AuNPs surface.
Described olefines organic phospho acid is styryl phosphonic acids, vinylphosphonic acid, propylene phosphonic acids or isopropylene and phosphonic acid sodium.
Described HAuCl
4The pH of the aqueous solution is 3 ~ 12.
Described HAuCl
4Be 1:0.5 ~ 7 with the amount of substance ratio of olefines organic phospho acid.
The described reaction time is 10 ~ 120 min, preferred 10 min～20 min.
The preparation method of the golden nanometer particle of surperficial phosphonic acids functionalization of the present invention utilizes the olefines organic phospho acid as reducing agent, with HAuCl
4Be reduced into big or small homogeneous, the regular spherical AuNPs of shape.Prepared AuNPs finishing phosphonyl group; Through Coulomb repulsion between the phosphonyl group and the outstanding hydrophily of phosphonyl group self; Effectively raise the colloidal stability of AuNPs; Avoided the appearance of agglomeration, prepared that monodispersity is good, the AuNPs of the phosphonic acids functionalization of uniform particle diameter.It is clear and definite, reliable that the inventive method prepares process mechanism, and the preparation method is simple, and the product that obtains shows as outstanding colloidal stability in water.The AuNPs of the surperficial phosphonic acids functionalization that the inventive method makes has high electron density, dielectric property and catalytic action; Can combine with multiple large biological molecule; And do not influence its biologically active; Can be applied to the fields, forward position such as structure of bioelectrochemistry, electro-catalysis, ZrP material and bionical film, and wide application prospect arranged in material science such as nano-device, fuel cell, biosimulation enzyme sensor and biomedicine field.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not exceeded with the specific embodiment, but is limited claim.
Description of drawings
Fig. 1 is HAuCl
4With the ratio of the amount of substance of isopropylene and phosphonic acid sodium be the variation relation figure of the ultraviolet absorptivity of the AuNPs for preparing under the condition of 1:3 with the reaction time.
As can be seen from Figure 1, at HAuCl
4With preceding 3 min of isopropylene and phosphonic acid sodium reaction, the ultraviolet absorptivity of the AuNPs of generation increases rapidly along with the increase in reaction time, and isopropylene and phosphonic acid sodium reduction HAuCl is described
4Reaction very fast.After the reaction time arrived 10 min, the ultraviolet absorptivity of AuNPs was along with the increase in reaction time remains unchanged basically, and this shows that reaction carried out basically fully.Reduction to a certain degree takes place in the ultraviolet absorptivity of AuNPs on the contrary after 20 min, and the AuNPs of generation under the condition that continues heating a small amount of reunion possibly take place.Therefore recommend to select HAuCl
4With the reaction time of isopropylene and phosphonic acid sodium be 10 min～20 min.
Fig. 2 a to Fig. 2 d is HAuCl
4Be respectively 1:0.5 (a), 1:1 (b), 1:2 (c), 1:3 (d) with the ratio of the amount of substance of isopropylene and phosphonic acid sodium, the reaction time is the TEM collection of illustrative plates of the AuNPs of preparation under the 10 min reaction conditions.
From figure, obviously see, utilize isopropylene and phosphonic acid sodium as reducing agent, with HAuCl
4Big or small homogeneous, the regular spherical AuNPs of shape have been reduced into.This is to coat because the AuNPs surface is reduced the oxidation product of agent; Make its finishing phosphonyl group; Through Coulomb repulsion between the phosphonyl group and the outstanding hydrophily of phosphonyl group self, effectively raise the monodispersity of AuNPs, avoided the appearance of agglomeration.And along with HAuCl
4Constantly increase with the ratio of the amount of substance of isopropylene and phosphonic acid sodium, the particle diameter of AuNPs has taken place to diminish earlier and has afterwards become big variation.Visible by figure, HAuCl
4With the ratio of the amount of substance of isopropylene and phosphonic acid sodium be that the particle diameter of the AuNPs for preparing under the 1:1 condition is minimum.
Fig. 3 is HAuCl
4Be respectively 1:0.5 (a), 1:1 (b), 1:2 (c), 1:3 (d) with the ratio of the amount of substance of isopropylene and phosphonic acid sodium, the reaction time is the UV-vis collection of illustrative plates of the AuNPs of preparation under the 10 min reaction conditions.
Can see from the UV-vis collection of illustrative plates of the AuNPs of different proportion preparation, be all to can be observed the characteristic absorption peak that comes from AuNPs about 520 nm at wavelength.And work as HAuCl
4With the ratio of the amount of substance of isopropylene and phosphonic acid sodium when 1:0.5 increases to 1:1, the blue shift of 3 nm has taken place in the uv absorption wavelength, shows that the particle diameter of AuNPs has reduced.And work as HAuCl
4When continuing to increase with the ratio of the amount of substance of isopropylene and phosphonic acid sodium, red shift has to a certain degree but taken place in the uv absorption wavelength, and particle diameter of this explanation AuNPs is increasing gradually.
The specific embodiment
Embodiment 1
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, using NaOH solution regulator solution pH is 12.In 120 ℃ of oil bath devices, constantly stir; Backflow is heated to boiling; Add 158 uL, 0.1 M isopropylene and phosphonic acid sodium solution then fast, continue backflow heated and stirred 10 ~ 20 min, solution is by the colourless peony that becomes; When color no longer changes, stop heating, obtain the AuNPs of the phosphonic acidsization of dispersion stabilization.
Embodiment 2
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, using NaOH solution regulator solution pH is 12.In 120 ℃ of oil bath devices, constantly stir; Backflow is heated to boiling; Add 316 uL, 0.1 M isopropylene and phosphonic acid sodium solution then fast, continue backflow heated and stirred 10 ~ 20 min, solution is by the colourless peony that becomes; When color no longer changes, stop heating, obtain the AuNPs of the phosphonic acidsization of dispersion stabilization.
Embodiment 3
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, using NaOH solution regulator solution pH is 12.In 120 ℃ of oil bath devices, constantly stir; Backflow is heated to boiling; Add 632 uL, 0.1 M isopropylene and phosphonic acid sodium solution then fast, continue backflow heated and stirred 10 ~ 20 min, solution is by the colourless peony that becomes; When color no longer changes, stop heating, obtain the AuNPs of the phosphonic acidsization of dispersion stabilization.
Embodiment 4
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, using NaOH solution regulator solution pH is 12.In 120 ℃ of oil bath devices, constantly stir; Backflow is heated to boiling; Add 947 uL, 0.1 M isopropylene and phosphonic acid sodium solution then fast, continue backflow heated and stirred 10 ~ 20 min, solution is by the colourless peony that becomes; When color no longer changes, stop heating, obtain the AuNPs of the phosphonic acidsization of dispersion stabilization.
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, using NaOH solution regulator solution pH is 3.In 120 ℃ of oil bath devices, constantly stir; Backflow is heated to boiling; Add 158 uL, 0.1 M styryl phosphonic acids solution then fast, continue backflow heated and stirred 10 ~ 20 min, solution is by the colourless peony that becomes; When color no longer changes, stop heating, obtain the AuNPs of the phosphonic acidsization of dispersion stabilization.
Embodiment 6
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, using NaOH solution regulator solution pH is 6.In 100 ℃ of oil bath devices, constantly stir; Backflow is heated to boiling; Add 316 uL, 0.1 M styryl phosphonic acids solution then fast, continue backflow heated and stirred 10 ~ 20 min, solution is by the colourless peony that becomes; When color no longer changes, stop heating, obtain the AuNPs of the phosphonic acidsization of dispersion stabilization.
Embodiment 7
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, using NaOH solution regulator solution pH is 9.In 100 ℃ of oil bath devices, constantly stir, reflux and be heated to boiling, add 632 uL, 0.1 M styryl phosphonic acids solution then fast; Continue the backflow heated and stirred; Solution stops heating by the colourless peony that becomes when color no longer changes, obtain the AuNPs of the phosphonic acidsization of dispersion stabilization.
Embodiment 8
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, using NaOH solution regulator solution pH is 12.In 80 ℃ of oil bath devices, constantly stir, the heating that refluxes adds 947 uL, 0.1 M styryl phosphonic acids solution then fast; Continue backflow heated and stirred 10 ~ 20 min; Solution stops heating by the colourless peony that becomes when color no longer changes, obtain the AuNPs of the phosphonic acidsization of dispersion stabilization.
Embodiment 9
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, using NaOH solution regulator solution pH is 12.In 120 ℃ of oil bath devices, constantly stir; Backflow is heated to boiling; Add 158 uL, 0.1 M vinylphosphonic acid solution then fast, continue backflow heated and stirred 10 ~ 20 min, solution is by the colourless peony that becomes; When color no longer changes, stop heating, obtain the AuNPs of the phosphonic acidsization of dispersion stabilization.
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, using NaOH solution regulator solution pH is 12.In 120 ℃ of oil bath devices, constantly stir; Backflow is heated to boiling; Add 316 uL, 0.1 M vinylphosphonic acid solution then fast, continue backflow heated and stirred 10 ~ 20 min, solution is by the colourless peony that becomes; When color no longer changes, stop heating, obtain the AuNPs of the phosphonic acidsization of dispersion stabilization.
Embodiment 11
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, using NaOH solution regulator solution pH is 12.In 120 ℃ of oil bath devices, constantly stir; Backflow is heated to boiling; Add 632 uL, 0.1 M propylene phosphonic acids solution then fast, continue backflow heated and stirred 10 ~ 20 min, solution is by the colourless peony that becomes; When color no longer changes, stop heating, obtain the AuNPs of the phosphonic acidsization of dispersion stabilization.
Embodiment 12
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, using NaOH solution regulator solution pH is 12.In 120 ℃ of oil bath devices, constantly stir; Backflow is heated to boiling; Add 947 uL, 0.1 M propylene phosphonic acids solution then fast, continue backflow heated and stirred 10 ~ 20 min, solution is by the colourless peony that becomes; When color no longer changes, stop heating, obtain the AuNPs of the phosphonic acidsization of dispersion stabilization.
Claims (5)
1. the preparation method of the golden nanometer particle of a surperficial phosphonic acids functionalization is characterized in that, a certain amount of olefines organic phospho acid reducing agent is joined HAuCl
4In the aqueous solution, 80 ~ 120 ℃ of reacting by heating under the stirring condition obtain the golden nanometer particle of surperficial phosphonic acidsization.
2. the preparation method of the golden nanometer particle of surperficial phosphonic acids functionalization according to claim 1 is characterized in that described olefines organic phospho acid is styryl phosphonic acids, vinylphosphonic acid, propylene phosphonic acids or isopropylene and phosphonic acid sodium.
3. the preparation method of the golden nanometer particle of surperficial phosphonic acids functionalization according to claim 1 is characterized in that, described HAuCl
4Be 1:0.5 ~ 7 with the amount of substance ratio of olefines organic phospho acid.
4. the preparation method of the golden nanometer particle of surperficial phosphonic acids functionalization according to claim 1 is characterized in that, described HAuCl
4The pH scope of the aqueous solution is 3 ~ 12.
5. the preparation method of the golden nanometer particle of surperficial phosphonic acids functionalization according to claim 1 is characterized in that, the described reaction time is 10 ~ 120 min.
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| CN104127875A (en) * | 2014-03-11 | 2014-11-05 | 常州碳宇纳米科技有限公司 | Gene carrier of small size gold nanoparticle vesicle structure and preparation method thereof |
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| JP2005015846A (en) * | 2003-06-26 | 2005-01-20 | National Institute Of Advanced Industrial & Technology | Surface modified gold nanoparticle and its production method |
| KR20090087591A (en) * | 2008-02-13 | 2009-08-18 | 성균관대학교산학협력단 | Surface modification method of gold nano particle, and stabilization method of gold nano particles by surface modification |
| CN101987364A (en) * | 2010-09-14 | 2011-03-23 | 江南大学 | Method for preparing functional gold nanoparticles with high stability |
| CN102000833A (en) * | 2010-12-14 | 2011-04-06 | 天津大学 | Submicron Au particles and preparation method thereof |
| US20110198113A1 (en) * | 2010-02-13 | 2011-08-18 | Aculon, Inc. | Electroconductive inks made with metallic nanoparticles |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005015846A (en) * | 2003-06-26 | 2005-01-20 | National Institute Of Advanced Industrial & Technology | Surface modified gold nanoparticle and its production method |
| KR20090087591A (en) * | 2008-02-13 | 2009-08-18 | 성균관대학교산학협력단 | Surface modification method of gold nano particle, and stabilization method of gold nano particles by surface modification |
| US20110198113A1 (en) * | 2010-02-13 | 2011-08-18 | Aculon, Inc. | Electroconductive inks made with metallic nanoparticles |
| CN101987364A (en) * | 2010-09-14 | 2011-03-23 | 江南大学 | Method for preparing functional gold nanoparticles with high stability |
| CN102000833A (en) * | 2010-12-14 | 2011-04-06 | 天津大学 | Submicron Au particles and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104127875A (en) * | 2014-03-11 | 2014-11-05 | 常州碳宇纳米科技有限公司 | Gene carrier of small size gold nanoparticle vesicle structure and preparation method thereof |
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