CN104162452A - Method utilizing recyclable template to prepare core-shell structural hybrid nano particles - Google Patents
Method utilizing recyclable template to prepare core-shell structural hybrid nano particles Download PDFInfo
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Abstract
The invention belongs to the technical field of nano materials, and specifically relates to a method utilizing a recyclable template to prepare core-shell structural hybrid nano particles. Amphiphilic segmented polymer poly(ethylene oxide)-b-poly(4-vinylpyridine) can carry out self-assembly in a selective solvent and generates core-shell structural micelles which are taken as the template in the method. Then the template is used to prepare a core-shell structural hybrid nano particle, which takes the Au nano particles as the core, and N,N-methylenebisacrylamide crosslinked polyisopropylacrylamide as the shell. The core-shell particle has very good temperature responsiveness, at the same time, a synergetic effect exists between the core and shell of the particle, and the volume of the hybrid particle can be increased or reduced by utilizing the photo-thermal effect of the core namely the Au nano particles.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to the method that the recyclable template of a kind of use is prepared the yolk-eggshell structure hybridization nano particle with photo-thermal effect and temperature-responsive.
Background technology
In recent years, the nano particle of preparing novel structure has become a kind of important means of obtaining specific function formed material
[1-5].In the nano material of numerous functionalization, the nano material with yolk-eggshell structure has been subject to paying close attention to widely
[6].Yolk-eggshell structure is (yolk) taking nano particle as core, at its peripheral shell (eggshell) that has one or more layers nanoscale, has the mobile a kind of multi-level nano-structure of certain space and core between core and shell
[7].The nucleocapsid of yolk-eggshell structure nano particle can be both organic or inorganic material, can be also hybrid material, and its internal cavities is equivalent to provide a micro-capsule reactor, adds the functional synergy of coker and shell, at medicine controlled releasing
[8,9], efficient catalytic
[10,11], efficient lithium ion battery
[12]show wide application prospect with aspects such as chemical sensors.
At present, the preparation method of yolk-eggshell structure nano particle is generally template
[13-16].Template is mainly divided into four steps: the first step, prepare the core of yolk-eggshell structure; Second step, modifies one deck template layer at the skin of core; The 3rd step, modifies one deck shell outward again at template layer, forms three-decker particle; The 4th step, calcines middle template layer or etch away, and finally obtains yolk-eggshell structure nano particle.Template has advantages of that preparation method is easier, structure designability strong and wide accommodation, but also has its general problem.First, the template that template is used can not reuse, and in the process of preparation, is to sacrifice template; Secondly, core and shell need to be prepared respectively by two steps.Therefore, the method can be brought the shortcoming that loss is larger in actual applications.
Bibliography:
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Summary of the invention
The object of the present invention is to provide a kind of step simply to there is the method for the yolk-eggshell structure hybridization nano particle of light thermal property with recyclable template preparation.
Yolk-eggshell structure hybridization nano particle prepared by the recyclable template of use provided by the present invention, its structure is taking Au nano particle as core, with N, the crosslinked PNIPAM (PNIPAM) of N-dimethylene bisacrylamide (MBA) is shell; Its preparation method concrete steps are as follows:
(1) there is the preparation of the yolk-eggshell structure hybridization nano particle of photo-thermal effect and temperature-responsive
block polymer Pluronic F-127-b-P4VP (PEO-b-P4VP) of 25 ~ 50mg and azodiisobutyronitrile (AIBN) are dissolved in 1～5ml methyl alcohol, drip deionized water until there is opalescence, obtain the micella particle solution of PEO-b-P4VP; Wherein:
The concentration of micella particle solution is 0.1～2mg/ml, and AIBN concentration is 0.1～0.5mg/ml;
the aqueous solution of chloraurate of preparation 0.1～0.5mg/ μ l is for subsequent use; According to the ratio of gold chloride and PEO-b-P4VP mol ratio 10～1:1, by step
the micella particle solution that preparation obtains and chlorauric acid solution are placed in flask and stir 6～24h;
Under 40～50 DEG C of conditions, in airtight flask, pass into argon gas 1～3h to remove the methyl alcohol in solution; Then in solution, add NIPAM and MBA, stir 3～12h, under argon shield condition, be warming up to 75～85 DEG C, polymerisation 1～3h, solution is by transparent change claret;
With hydrochloric acid solution regulator solution pH value to 1～4, stir 12～48h; Separate by the high speed centrifugation of 8000～20000rpm again, separate 0.5～2h, obtain template polymer PEO-b-P4VP supernatant and red solid yolk-eggshell structure hybridization nano particle.
(2) use the template polymer PEO-b-P4VP reclaiming to repeat to prepare the yolk-eggshell structure hybridization nano particle with photo-thermal effect and temperature-responsive
First the AIBN methanol solution that, compound concentration is 1～10mg/ml is for subsequent use; Separate the extremely neutrality of pH value that obtains PEO-b-P4VP supernatant with sodium hydroxide solution regulating step (1), again form micella particle solution; And then adding appropriate AIBN methanol solution, to make AIBN concentration be 0.1～0.5mg/ml; Obtain in step (1)
micella particle solution;
In repeating step (1)
operation, again obtain template polymer PEO-b-P4VP supernatant and red solid yolk-eggshell structure hybridization nano particle.
In the present invention, recirculation step (2) operation, can constantly reclaim template polymer, in order to prepare yolk-eggshell structure hybridization nano particle.
In the present invention, azodiisobutyronitrile is both as the initator of NIPAM and MBA copolymerization, again as the reducing agent of gold chloride.
In the present invention, this yolk-eggshell structure nano particle has temperature-responsive, when temperature is during higher than 32 DEG C of the lower critical solution temperatures (LCST) of PNIPAM, and the yolk-eggshell structure nano particle generation volume contraction in the aqueous solution, when temperature is during lower than 32 DEG C, particle volume is expanded again.
Compared with existing preparation method, the invention has the advantages that:
solved the ubiquitous template of template and can not reclaim and reusable shortcoming, this method by regulator solution pH value more centrifugal way just can reclaim easily template;
shortened preparation process, utilize AIBN as the initator of NIPAM and MBA copolymerization again as the feature of the reducing agent of gold chloride, the step of preparing respectively core and shell in general template is reduced to " step " and forms core and shell;
the yolk-eggshell structure hybridization nano particle of preparation has good light thermal property, there is good catalysis and medicine carrying controlled release application prospect, give this particle temperature response with the shell of the crosslinked PNIPAM of MBA, and the Au nanometer core that the particle diameter of preparation is about 45nm has photo-thermal effect, temperature rise under the radiation of visible light that particle solution is 532nm at wavelength, its PNIPAM cross-linked network shell shrinks and produces synergy.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of yolk-eggshell structure hybridization nano particle.
Fig. 2 is the dynamic light scattering phenogram of yolk-eggshell structure hybridization nano particle.
Fig. 3 is the X x ray diffration pattern x of yolk-eggshell structure hybridization nano particle.
Fig. 4 separates the template polymer PEO-b-P4VP aqueous solution photo reclaiming and the yolk-eggshell structure hybridization nano particle solid photo obtaining.
Fig. 5 uses the template polymer PEO-b-P4VP reclaiming to repeat to prepare the transmission electron microscope picture of yolk-eggshell structure hybridization nano particle, and shell is dyeed with ruthenium tetroxide.
Fig. 6 uses the template polymer PEO-b-P4VP reclaiming to repeat to prepare the dynamic light scattering phenogram of yolk-eggshell structure hybridization nano particle.
Fig. 7 is the dynamic light scattering phenogram of the temperature-responsive of yolk-eggshell structure hybridization nano particle.
Fig. 8 is the dynamic light scattering phenogram of the photo-thermal effect of yolk-eggshell structure hybridization nano particle.
Detailed description of the invention
Embodiment 1
There is the preparation of the yolk-eggshell structure hybridization nano particle of photo-thermal effect and temperature-responsive.
By 25 mg block polymer PEO
113-b-P4VP
64(under be designated as the degree of polymerization) and 10mgAIBN are placed in sample bottle, after interpolation 5ml methyl alcohol, add magneton and stir 6 h, at room temperature drip 10ml deionized water in sample bottle with the speed of 1 ml/h, solution occurs that opalescence forms micella particle, then it is for subsequent use to be settled to 50 ml by deionized water.The aqueous solution of chloraurate of preparing 0.1 mg/ μ l is for subsequent use.According to the ratio of gold chloride and PEO-b-P4VP mol ratio 2:1, get respectively the PEO-b-P4VP micellar solution of 5ml and 2 μ l chlorauric acid solutions and be placed in flask and stir 12 h.Under 45 oC conditions, in airtight flask, lead to argon gas 1h.Then in solution, add 8mgNIPAM and 1mg MBA, stir 3h, be warming up to 76oC reaction 1.5h under argon shield condition, solution is by transparent change claret.By hydrochloric acid solution regulator solution pH value to 3, stir 24 h.Separate and obtain template polymer PEO-b-P4VP supernatant and red solid yolk-eggshell structure hybridization nano particle by the 15000rpm high speed centrifugation of 1h again.
Transmission electron microscope characterizes (Fig. 1) and shows that the nano particle making is monodisperse status, and size, compared with homogeneous, exists in Au nano particle periphery the material that one deck contrast is lower, with the crosslinked PNIPAM shell of MBA.Meanwhile, between Au nano particle and PNIPAM, exist certain space, therefore formed taking PNIPAM network structure as shell, Au nano particle is the yolk-eggshell structure hybridization nano particle of core.Dynamic light scattering characterizes (Fig. 2) and shows that its hydrodynamic radius <Rh> is 81 nm, and PDI is 0.19.X-ray diffraction spectrum (Fig. 3) shows, the Au nano particle in hybrid particle has good crystal formation.
Use the template polymer PEO-b-P4VP reclaiming to repeat to prepare the yolk-eggshell structure hybridization nano particle with photo-thermal effect and temperature-responsive.
Compound concentration is that the AIBN methanol solution of 5mg/ml is for subsequent use.Regulate in embodiment 1 and separate the pH value that obtains PEO-b-P4VP supernatant to neutrality with sodium hydroxide solution, then add 20 μ lABIN methanol solutions and 2 μ l concentration are the aqueous solution of chloraurate of 0.1 mg/ μ l.Repeat part operation in embodiment 1, under 45 oC conditions, in airtight flask, lead to argon gas 1h.Then in solution, add 8mg NIPAM and 1mg MBA, stir 3h, be warming up to 76oC reaction 1.5h under argon shield condition, solution is by transparent change claret.By hydrochloric acid solution regulator solution pH value to 3, stir 24 h.Separate and again obtain template polymer PEO-b-P4VP supernatant and red solid yolk-eggshell structure hybridization nano particle by the 15000rpm high speed centrifugation of 1h again.
Fig. 4 shows, can be separated and be obtained red solid yolk-eggshell structure hybridization nano particle by high speed centrifugation.Transmission electron microscope characterizes (Fig. 5) and shows to utilize recovery template polymer again to prepare yolk-eggshell structure hybridization nano particle.Dynamic light scattering characterizes (Fig. 6) and shows that its hydrodynamic radius <Rh> is 87 nm, and PDI is 0.209.
Embodiment 2
There is the preparation of the yolk-eggshell structure hybridization nano particle of photo-thermal effect and temperature-responsive.
By 50mg block polymer PEO
113-b-P4VP
64(under be designated as the degree of polymerization) and 20mg AIBN are placed in sample bottle, after adding 5ml methyl alcohol, add magneton stirring 24h, at room temperature drip 10ml deionized water in sample bottle with the speed of 1 ml/h, solution occurs that opalescence forms micella particle, then it is for subsequent use to be settled to 50 ml by deionized water.The aqueous solution of chloraurate of preparing 0.4 mg/ μ l is for subsequent use.According to the ratio of gold chloride and PEO-b-P4VP mol ratio 4:1, get respectively the PEO-b-P4VP micellar solution of 5ml and 2 μ l chlorauric acid solutions and be placed in flask and stir 24 h.Under 45 oC conditions, in airtight flask, lead to argon gas 2h.Then in solution, add 20mg NIPAM and 3mg MBA, stir 6h, be warming up to 76oC reaction 2h under argon shield condition, solution is by transparent change claret.By hydrochloric acid solution regulator solution pH value to 3, stir 36 h.Separate and obtain template polymer PEO-b-P4VP supernatant and red solid yolk-eggshell structure hybridization nano particle by the 10000rpm high speed centrifugation of 1.5h again.
Use the template polymer PEO-b-P4VP reclaiming to repeat to prepare the yolk-eggshell structure hybridization nano particle with photo-thermal effect and temperature-responsive.
Compound concentration is that the AIBN methanol solution of 5mg/ml is for subsequent use.Regulate in embodiment 1 and separate the pH value that obtains PEO-b-P4VP supernatant to neutrality with sodium hydroxide solution, then add 40 μ l ABIN methanol solutions and 2 μ l concentration are the aqueous solution of chloraurate of 0.4 mg/ μ l.Repeat part operation in embodiment 2, under 45 oC conditions, in airtight flask, lead to argon gas 2h.Then in solution, add 20mg NIPAM and 3mg MBA, stir 6h, be warming up to 76oC reaction 2h under argon shield condition, solution is by transparent change claret.By hydrochloric acid solution regulator solution pH value to 3, stir 36 h.Separate and again obtain template polymer PEO-b-P4VP supernatant and red solid yolk-eggshell structure hybridization nano particle by the 10000rpm high speed centrifugation of 1.5h again.
Embodiment 3
There is the preparation of the yolk-eggshell structure hybridization nano particle of photo-thermal effect and temperature-responsive.
By 25 mg block polymer PEO
113-b-P4VP
64(under be designated as the degree of polymerization) and 8mg AIBN are placed in sample bottle, after adding 5ml methyl alcohol, add magneton stirring 12h, at room temperature drip 10ml deionized water in sample bottle with the speed of 1 ml/h, solution occurs that opalescence forms micella particle, then it is for subsequent use to be settled to 50 ml by deionized water.The aqueous solution of chloraurate of preparation 0.1mg/ μ l is for subsequent use.According to the ratio of gold chloride and PEO-b-P4VP mol ratio 1:1, get respectively the PEO-b-P4VP micellar solution of 5ml and 1 μ l chlorauric acid solution and be placed in flask and stir 12 h.Under 45 oC conditions, in airtight flask, lead to argon gas 1.5h.Then in solution, add 8mg NIPAM and 1mg MBA, stir 6h, be warming up to 76oC reaction 1h under argon shield condition, solution is by transparent change claret.By hydrochloric acid solution regulator solution pH value to 3, stir 12 h.Separate and obtain template polymer PEO-b-P4VP supernatant and red solid yolk-eggshell structure hybridization nano particle by the 20000rpm high speed centrifugation of 1h again.
Use the template polymer PEO-b-P4VP reclaiming to repeat to prepare the yolk-eggshell structure hybridization nano particle with photo-thermal effect and temperature-responsive.
Compound concentration is that the AIBN methanol solution of 5mg/ml is for subsequent use.Regulate in embodiment 3 and separate the pH value that obtains PEO-b-P4VP supernatant to neutrality with sodium hydroxide solution, then add 16 μ l ABIN methanol solutions and 1 μ l concentration is the aqueous solution of chloraurate of 0.1 mg/ μ l.Repeat part operation in embodiment 3, under 45 oC conditions, in airtight flask, lead to argon gas 1.5h.Then in solution, add 8mg NIPAM and 1mg MBA, stir 6h, be warming up to 76oC reaction 1h under argon shield condition, solution is by transparent change claret.By hydrochloric acid solution regulator solution pH value to 3, stir 12 h.Separate and again obtain template polymer PEO-b-P4VP supernatant and red solid yolk-eggshell structure hybridization nano particle by the 20000rpm high speed centrifugation of 1h again.
The Thermo-sensitive test of yolk-eggshell structure hybridization nano particle.
Characterize the response of yolk-eggshell structure hybridization nano particle in the aqueous solution under condition of different temperatures with dynamic light scattering and change, test condition rises to 50 oC from room temperature and is down to room temperature again.
Fig. 7 demonstration, the hydrodynamic radius <Rh> of this particle is 87nm at ambient temperature, PDI is 0.106; When solution is warming up to 50 oC, hydrodynamic radius <Rh> is 67 nm, and PDI is 0.125; While being cooled to room temperature again, hydrodynamic radius <Rh> is 87 nm, and PDI is 0.13.Visible, in the time being warming up to 50 oC higher than lower critical solution temperature 32 oC of PNIPAM, the hydrodynamic radius of yolk-eggshell structure hybridization nano particle has reduced approximately 20 nm, and is down to room temperature when temperature, and hydrodynamic radius can return to again before intensification.Therefore, this yolk-eggshell structure hybridization nano particle has Thermo-sensitive.
The photo-thermal effect test of yolk-eggshell structure hybridization nano particle.
Use the visible light source that wavelength is 532nm to irradiate the yolk-eggshell structure hybridization nano particle aqueous solution, after 20min, solution temperature rises to 49 oC by 27 oC, use dynamic light scattering respectively to its sign, result shows that (Fig. 8) its hydrodynamic radius <Rh> is respectively 88.9nm and 70.9nm, <Rh> has reduced 18nm, therefore, this yolk-eggshell structure hybridization nano particle has good photo-thermal effect.
Claims (1)
1. prepare the method for yolk-eggshell structure hybridization nano particle by recyclable template for one kind, this hybridized nanometer particle structure is taking Au nano particle as core, with N, and the crosslinked PNIPAM (PNIPAM) of N-dimethylene bisacrylamide (MBA) is shell; The concrete steps that it is characterized in that preparation method are as follows:
(1) there is the preparation of the yolk-eggshell structure hybridization nano particle of photo-thermal effect and temperature-responsive
block polymer Pluronic F-127-b-P4VP PEO-b-P4VP of 25 ~ 50mg and azodiisobutyronitrile AIBN are dissolved in 1～5ml methyl alcohol, drip deionized water until there is opalescence, obtain the micella particle solution of PEO-b-P4VP; Wherein:
The concentration of micella particle solution is 0.1～2mg/ml, and AIBN concentration is 0.1～0.5mg/ml;
the aqueous solution of chloraurate of preparation 0.1～0.5mg/ μ l is for subsequent use; According to the ratio of gold chloride and PEO-b-P4VP mol ratio 10～1:1, respectively by step
the micella particle solution that preparation obtains and chlorauric acid solution are placed in flask and stir 6～24h;
Under 40～50 DEG C of conditions, in airtight flask, pass into argon gas 1～3h to remove the methyl alcohol in solution; Then in solution, add NIPAM and MBA, stir 3～12h, under argon shield condition, be warming up to 75～85 DEG C, polymerisation 1～3h, solution is by transparent change claret;
With hydrochloric acid solution regulator solution pH value to 1～4, stir 12～48h; Separate by the high speed centrifugation of 8000～20000rpm again, separate 0.5～2h, obtain template polymer PEO-b-P4VP supernatant and red solid yolk-eggshell structure hybridization nano particle;
(2) use the template polymer PEO-b-P4VP reclaiming to repeat to prepare the yolk-eggshell structure hybridization nano particle with photo-thermal effect and temperature-responsive
First the AIBN methanol solution that, compound concentration is 1～10mg/ml is for subsequent use; Separate the extremely neutrality of pH value that obtains PEO-b-P4VP supernatant with sodium hydroxide solution regulating step (1), again form micella particle solution; And then adding appropriate AIBN methanol solution, to make AIBN concentration be 0.1～0.5mg/ml; Obtain in step (1)
micella particle solution;
In repeating step (1)
operation, again obtain template polymer PEO-b-P4VP supernatant and red solid yolk-eggshell structure hybridization nano particle.
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| CN104480699B (en) * | 2014-12-15 | 2016-06-08 | 中国科学技术大学 | Light-operated switch controls preparation method and the light-operated switch of element |
| CN106861756A (en) * | 2017-03-06 | 2017-06-20 | 华北科技学院 | A kind of Au Pt bimetal nanos composite micelle and preparation method and application |
| CN106861756B (en) * | 2017-03-06 | 2019-08-02 | 华北科技学院 | A kind of Au-Pt bimetal nano composite micelle and preparation method and application |
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