CN104625045B - Extra small golden nanometer particle and synthetic method thereof - Google Patents
Extra small golden nanometer particle and synthetic method thereof Download PDFInfo
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- CN104625045B CN104625045B CN201510039356.0A CN201510039356A CN104625045B CN 104625045 B CN104625045 B CN 104625045B CN 201510039356 A CN201510039356 A CN 201510039356A CN 104625045 B CN104625045 B CN 104625045B
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Abstract
The invention discloses a kind of extra small golden nanometer particle and synthetic method thereof, belong to Polymer Synthesizing field and metal nanoparticle synthesis field；Described extra small golden nanometer particle includes the Amphipathilic block polymer being wrapped in outer layer and is positioned at the gold particle at center.The invention also discloses the synthetic method of described extra small golden nanometer particle, first pass through the Invertible ideal synthesis Amphipathilic block polymer containing reproducibility aniline monomer, it is directly dissolved in again in water, is eventually adding aqueous solution of chloraurate, be formed in situ described extra small golden nanometer particle.The inventive method has the advantages that synthetic method is simple, reaction condition is gentle, and obtained extra small gold nanometer particle grain size is homogeneous and does not assembles, and has temperature-sensing property.Solving extra small gold nanometer particle grain size heterogeneity and the easy technical problem that gathering etc. occurs in prior art, can be applied to Polymer Synthesizing field, the synthetic method as a kind of general extra small golden nanometer particle is used.
Description
Technical field
The present invention belongs to Polymer Synthesizing field and metal nanoparticle synthesis field, is specifically related to a kind of extra small golden nanometer particle
And synthetic method.
Background technology
Golden nanometer particle due to itself exclusive characteristic have been subjected to the highest concern, particularly grain size between 1～
The extra small golden nanometer particle of 3nm, its gold grain bigger relative to size or other catalyst have more in some organic reaction
High catalysis activity.So the synthetic method of extra small golden nanometer particle has become the problem that researchers are paid attention to.
Have some methods synthesizing extra small golden nanometer particle in recent years.Proposing for the first time such as Schmid utilizes hydrogen phosphide stably to surpass
The method of little golden nanometer particle, concrete synthetic method is that diborane reduction triphenylphosphine auric chloride obtains particle diameter in toluene is 1.4nm
Gold grain.But the condition that this method needs is the harshest, and diborane gas used has the strongest toxicity.Later
Someone improves the method, with triphenylphosphine as stabilizer, obtains the gold of 1.5nm under mild conditions with sodium borohydride reduction
Nanoparticle.1994, Brust and Schiffrin was found that one method more easily, and they utilize lauryl mercaptan
The stable gold grain presoma obtained through sodium borohydride reduction, synthesize in this way obtain size uniformity, particle diameter is less than 5nm
Golden nanometer particle.This method has become the main stream approach synthesizing extra small gold grain.
Other complexant is utilized in succession to be in the news out to the method stablizing extra small golden nanometer particle in recent years.Adenosine triphosphatase,
The Novel Ligands such as linear polymer, dendritic occurs in the research in the most more forward position.It addition, there is people to utilize imidazoles
The ionic liquid of salt successfully synthesizes extra small golden nanometer particle.
Although prior art provides the method for the extra small golden nanometer particle of many synthesis, but, it is extra small that current main stream approach synthesizes
Gold particle there is also size heterogeneity, the shortcoming easily assembling, being difficult to functionalization.It is difficult to prepare chi as made reducing agent with sodium citrate
Very little homogeneous extra small gold particle, and gold particle is easily assembled.Also there is reported in literature directly to make complexant with polymer with steady simultaneously
Determining agent, one-step synthesis gold particle under conditions of without adding other reducing agents, such as polyvinyl pyrrolidone, polyvinyl alcohol.But
It is to there is not yet report and utilize this base polymer to produce the example of extra small gold particle.Therefore, a kind of more convenient, general surpassing is needed badly
Little golden nanometer particle synthetic method.
Summary of the invention
The present invention proposes a kind of golden nanometer particle with ultra-small grain size, and it has the following characteristics that (1) golden nanometer particle is former
Position synthesis is also wrapped in by one layer of amphipathic nature polyalcohol；(2) particle diameter of this extra small golden nanometer particle is 1.7 ± 0.5nm；(3)
This extra small golden nanometer particle granule can be assembled with long term storage and not.
The extra small golden nanometer particle of the present invention, including being wrapped in the Amphipathilic block polymer of outer layer and being positioned at the gold particle at center.
The particle diameter of described extra small golden nanometer particle is 1.7 ± 0.5nm.The structural representation of the extra small golden nanometer particle of the present invention, such as Fig. 1
Shown in (a).
In a detailed description of the invention, the extra small golden nanometer particle of the present invention, including the Amphipathilic block polymer being wrapped in outer layer
And it is positioned at the gold particle at center；Its particle diameter is 1.7 ± 0.5nm.Wherein, the following formula I of described Amphipathilic block polymer
Shown in:
Wherein, m=50～200.
The present invention proposes the novel method for synthesizing of a kind of extra small golden nanometer particle, and the method belongs to the synthetic method proposed first,
First pass through reversible addion-fragmentation chain transfer polymerization (RAFT) synthesis to obtain containing three thioesters containing reproducibility aniline monomer and hydrophobic end
Amphipathilic block polymer, then this polymer is directly dissolved in water, finally quantitative aqueous solution of chloraurate is joined molten
Have in the solution of above-mentioned polymer, form described extra small golden nanometer particle through in-situ reducing.The inventive method building-up process, such as figure
Shown in 1 (b).Synthesize the extra small nanoparticle obtained according to the inventive method, its particle diameter is in the range of 1.7 ± 0.5nm.
The synthetic method of extra small golden nanometer particle proposed by the invention, comprises the following steps:
(1) monomer is polymerized synthesis hydrophilic long-chain by reversible addion-fragmentation chain transfer (RAFT), then in described hydrophilic length
The chain end of chain connects reproducibility monomer poly-N-phenylethylenediamine Methacrylamide, obtains hydrophobic end and contains the amphiphilic of three thioesters
Property block polymer.In this step, RAFT polymerization in monomer be NIPA, methacrylic acid polyoxyl 40 stearate,
Methacrylic acid or styrene sulfonic acid.
(2) by soluble in water for described Amphipathilic block polymer, stir one hour in ice bath, add aqueous solution of chloraurate；
Stir three hours, by the part of reproducibility aniline in Amphipathilic block polymer and gold chloride generation redox reaction, former
Position prepares described extra small golden nanometer particle.Preferably, described extra small golden nanometer particle removes free amphipathic block through dialysis again
Polymer and gold ion, remake dried.
In the present invention, described hydrophilic long-chain is poly-N-isopropyl acrylamide, polymethylacrylic acid polyoxyl 40 stearate, poly-methyl-prop
Olefin(e) acid, polystyrolsulfon acid.
In a detailed description of the invention, as a example by the hydrophilic long-chain synthesizing poly-N-isopropyl acrylamide, synthetic method of the present invention
Process is as follows:
(1) first with NIPA as monomer, it is polymerized synthesis hydrophilic long-chain poly-N-isopropyl acryloyl by RAFT
Amine, then connects poly-N-phenylethylenediamine Methacrylamide at its chain end, obtains hydrophobic end and contain the amphipathic of three thioesters
Block polymer.Shown in the following formula II of reaction scheme:
(2) dissolve a polymer in water, and stir after one hour in ice bath, add quantitative aqueous solution of chloraurate.Stirring
After three hours, free polymer and ion are removed in dialysis, are dried and i.e. prepare the extra small golden nanometer particle of temperature sensitive type.
According to the extra small golden nanometer particle of the method synthesis, including being wrapped in the Amphipathilic block polymer of outer layer and being positioned at center
Gold particle.The particle diameter of described extra small golden nanometer particle is 1.7 ± 0.5nm.Wherein, described Amphipathilic block polymer is following
Shown in formula (I '):
Wherein, the degree of polymerization of poly-N-isopropyl acrylamide is about 180, the degree of polymerization of poly-N-phenylethylenediamine Methacrylamide
It is about 4.
In the synthetic method of the extra small golden nanometer particle of the present invention, described Amphipathilic block polymer concentration in water is more than
0.06mg/ml。
In the synthetic method of the extra small golden nanometer particle of the present invention, reproducibility monomer N-phenylethylenediamine Methacrylamide and gold chloride
Mol ratio be 1:1.75.
The extra small golden nanometer particle obtained prepared according to the methods of the invention, including the Amphipathilic block polymer and the position that are wrapped in outer layer
Gold particle in center.The particle diameter of described extra small golden nanometer particle is 1.7 ± 0.5nm.
The extra small golden nanometer particle obtained prepared according to the methods of the invention, it has Thermo-sensitive, its temperature sensitive temperature range be 30 DEG C～
38℃。
The extra small golden nanometer particle obtained prepared according to the methods of the invention, the hydrophilic polymer that gold particle outer layer covers is permissible
For poly-N-isopropyl acrylamide, polymethylacrylic acid polyoxyl 40 stearate, polymethylacrylic acid or polystyrolsulfon acid.This parent
It is grafted poly-N-phenylethylenediamine Methacrylamide on waterborne polymeric, forms the hydrophobic end containing three thioesters, become amphipathic
Block polymer.
The Advantageous Effects of the present invention includes:
The synthetic method of the extra small golden nanometer particle of the present invention is simple, reaction condition is gentle, preparation-obtained extra small according to the present invention
Gold nanometer particle grain size is homogeneous and does not assembles, and has temperature-sensing property.
Accompanying drawing explanation
Fig. 1 (a) show the structural representation of the extra small golden nanometer particle of the present invention.
Fig. 1 (b) show the process of the present invention extra small golden nanometer particle preparation method.
Fig. 2 show the nuclear magnetic spectrum of poly-N-isopropyl acrylamide (PNIPAM) polymer；
Fig. 3 show the nuclear magnetic spectrum of Amphipathilic block polymer；
Fig. 4 show the uv-spectrogram of the extra small golden nanometer particle of PNIPAM-b-PNPEDMA Polymer-supported；
Fig. 5 show the TEM figure of the extra small golden nanometer particle of PNIPAM-b-PNPEDMA Polymer-supported.
Detailed description of the invention
In conjunction with specific examples below and accompanying drawing, the present invention is described in further detail, and the protection content of the present invention is not limited to
In following example.Under the spirit and scope without departing substantially from inventive concept, those skilled in the art it is conceivable that change and advantage
All it is included in the present invention, and with appending claims as protection domain.Implement the process of the present invention, condition, examination
Agent, experimental technique etc., outside the lower content mentioned specially, be universal knowledege and the common knowledge of this area, the present invention
Content is not particularly limited.
The synthetic method of the extra small golden nanometer particle of the present invention, comprises the steps:
(1) first with NIPA as monomer, it is polymerized with RAFT, synthesis hydrophilic long-chain poly-N-isopropyl acryloyl
Amine, then connects poly-N-phenylethylenediamine Methacrylamide at chain end, obtains hydrophobic end and contains the amphipathic embedding of three thioesters
Section polymer (poly-N-isopropyl acrylamide-b-poly-N-phenylethylenediamine Methacrylamide, PNIPAM-b-PNPEDMA).
Wherein, described step (1) is i.e. the synthesis of amphipathic pair of block polymer, the reaction scheme of its synthesis path such as formula II
Shown in:
Specifically, step (1) comprises the following steps:
The synthesis of (a) PNIPAM
By NIPA (1g), AIBN (0.72mg), RAFT reagent (16mg) (structural formula:),
DMF (1.5ml) joins in reaction tube, removes after oxygen 60 DEG C of tube sealing reactions 5 hours.Reaction precipitates after terminating in ether,
THF dissolves.Obtaining poly-N-isopropyl acrylamide (PNIPAM) polymer, the nuclear-magnetism result display degree of polymerization is 180.See Fig. 2.
The synthesis of (b) PNIPAM-b-PNPEDMA
By the PNIPAM (180mg) of synthesis, AIBN (0.15mg), NPEDMA (90mg), Isosorbide-5-Nitrae-dioxane (1.4ml) in step 1
Join in reaction tube, remove after oxygen 60 DEG C of tube sealing reactions 6 hours.Reaction precipitates after terminating in ether, and THF dissolves.
Obtain Amphipathilic block polymer, i.e. poly-N-isopropyl acrylamide-b-poly-N-phenylethylenediamine Methacrylamide
(PNIPAM-b-PNPEDMA), the nuclear-magnetism result display degree of polymerization is 4.See Fig. 3.
(2) dissolve a polymer in water, and stir after one hour in ice bath, quantitative aqueous solution of chloraurate join dissolved with
In the solution of above-mentioned PNIPAM-b-PNPEDMA.Wherein, the consumption of gold chloride is above-mentioned block polymer PNIPAM-b-PNPEDMA
1.75 times of middle N-phenylethylenediamine Methacrylamide mole.Free polymer and ion are removed in dialysis, are dried and can make
Obtain the extra small golden nanometer particle of temperature sensitive type.
Specifically, the process of step (2) is as follows:
Block polymer PNIPAM-b-PNPEDMA (5mg) is dissolved in 1ml deionized water, stirs 1 hour under ice bath.
80 μ l aqueous solution of chloraurate (0.02M) disposably join in the reactant liquor containing block polymer.Reaction 3 is stirred in ice bath
After hour, free polymer and ion are removed in dialysis, are drying to obtain the extra small Jenner of PNIPAM-b-PNPEDMA Polymer-supported
Rice corpuscles.Ultraviolet test result such as Fig. 4.TEM test result such as Fig. 5.
Claims (8)
1. an extra small golden nanometer particle, it is characterised in that described extra small golden nanometer particle includes being wrapped in the amphipathic embedding of outer layer
Section polymer and be positioned at the gold particle at center；The particle diameter of described extra small golden nanometer particle is 1.7 ± 0.5nm；
Wherein, described Amphipathilic block polymer is as shown in following formula I:
Wherein, m=50～200.
2. the synthetic method of an extra small golden nanometer particle, it is characterised in that described method includes following:
(1) monomer is polymerized synthesis hydrophilic long-chain by reversible addion-fragmentation chain transfer, then at the last-in-chain(LIC) of described hydrophilic long-chain
Reproducibility monomer poly-N-phenylethylenediamine Methacrylamide in termination, obtains the amphipathic block that hydrophobic end contains three thioesters and gathers
Compound；
(2) by soluble in water for described Amphipathilic block polymer, stir one hour in ice bath, add aqueous solution of chloraurate；
Stir three hours, by the redox reaction of reproducibility aniline in Amphipathilic block polymer Yu gold chloride, prepare institute in situ
State extra small golden nanometer particle；
Wherein, described hydrophilic long-chain be poly-N-isopropyl acrylamide, polymethylacrylic acid polyoxyl 40 stearate, polymethylacrylic acid,
Polystyrolsulfon acid.
3. synthetic method as claimed in claim 2, it is characterised in that the reaction of described reversible addion-fragmentation chain transfer polymerization
Middle use dodecyl trithio ester as chain transfer agents, its structure as shown below:
4. synthetic method as claimed in claim 2, it is characterised in that when described hydrophilic long-chain is poly-N-isopropyl acrylamide,
Shown in the following formula II of reaction scheme of step (1):
5. the synthetic method as described in any one of claim 2-4, it is characterised in that described Amphipathilic block polymer is at water
In concentration more than 0.06mg/ml.
6. the synthetic method as described in any one of claim 2-4, it is characterised in that reproducibility monomer N-phenylethylenediamine first
Base acrylamide is 1:1.75 with the mol ratio of gold chloride.
7. the extra small golden nanometer particle prepared according to method described in any one of claim 2-4, it is characterised in that described
Extra small golden nanometer particle includes the Amphipathilic block polymer being wrapped in outer layer and is positioned at the gold particle at center；Described extra small gold nano
The particle diameter of particle is 1.7 ± 0.5nm.
8. according to the extra small golden nanometer particle described in claim 1 or 7, it is characterised in that described extra small golden nanometer particle has
Thermo-sensitive, its temperature sensitive temperature range is 30 DEG C～38 DEG C.
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| CN107936259A (en) * | 2017-10-26 | 2018-04-20 | 江南大学 | It is a kind of star-type polymer and preparation method thereof to be crosslinked with the temperature response type core of load gold nano particle |
| CN111303746A (en) * | 2020-03-31 | 2020-06-19 | 武汉中科先进技术研究院有限公司 | Antifogging coating and preparation method and application thereof |
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| CN106632774B (en) * | 2016-12-05 | 2019-10-11 | 上海大学 | Poplar bundles alcoxyl ether polymer, its modification gold nano microballoon and preparation method thereof |
| CN110441508B (en) * | 2019-05-06 | 2020-11-24 | 华南理工大学 | Test strip for rapidly detecting acrylamide in food based on nanogold composite coating |
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| CN101457024B (en) * | 2009-01-07 | 2011-09-07 | 东南大学 | Method for producing wood-plastic composite material and produced wood-plastic composite material |
| CN102962471B (en) * | 2012-11-13 | 2014-10-01 | 武汉理工大学 | Glucose responsive gold nanoparticle and preparation method and application thereof |
| CN102942832B (en) * | 2012-12-11 | 2014-10-01 | 青岛大学 | Preparation method of block macromolecule-nanometer metallic-film composite conductive material |
| CN103146115A (en) * | 2013-01-24 | 2013-06-12 | 厦门大学 | Polyhedral oligomeric silasesquioxane (POSS)-based load metal nanoparticle and preparation method thereof |
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| CN107936259A (en) * | 2017-10-26 | 2018-04-20 | 江南大学 | It is a kind of star-type polymer and preparation method thereof to be crosslinked with the temperature response type core of load gold nano particle |
| CN111303746A (en) * | 2020-03-31 | 2020-06-19 | 武汉中科先进技术研究院有限公司 | Antifogging coating and preparation method and application thereof |
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