CN103084210A - Method for preparing gelatin protein and gold nanoparticle composite thin film and application of gelatin protein and gold nanoparticle composite thin film - Google Patents

Method for preparing gelatin protein and gold nanoparticle composite thin film and application of gelatin protein and gold nanoparticle composite thin film Download PDF

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CN103084210A
CN103084210A CN2013100166002A CN201310016600A CN103084210A CN 103084210 A CN103084210 A CN 103084210A CN 2013100166002 A CN2013100166002 A CN 2013100166002A CN 201310016600 A CN201310016600 A CN 201310016600A CN 103084210 A CN103084210 A CN 103084210A
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gelatin
thin film
solution
nano wire
film
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彭新生
史力
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention discloses a method for preparing a gelatin protein and gold nanoparticle composite thin film and an application of the gelatin protein and gold nanoparticle composite thin film. By the method for preparing the gelatin protein and gold nanoparticle composite thin film, the gelatin protein and gold nanoparticle composite thin film is prepared by depositing gelatin on a Cu(OH)2 nano wire serving as a filtering layer by a filtering method, performing glue-connection and removing the Cu(OH)2 nano wire and then adsorbing and reducing chloroauric acid radical ions according to a reducing characteristic of the gelatin under the action of charge adsorption of the gelatin. The sizes of gold nanoparticles in the gelatin protein thin film can be controlled by controlling the pH value of a chloroauric acid solution and the reaction time of the gelatin protein thin film in the chloroauric acid solution. The method is simple and feasible; the gelatin protein and gold nanoparticle composite thin film can be used as a catalyst and the catalytic conversion efficiency of ortho-nitroaniline is extremely high; and the gelatin protein and gold nanoparticle composite thin film has the advantages of high repetitiveness and convenience in operation.

Description

The preparation method and its usage of gelatin protein gold nano grain laminated film
Technical field
The present invention relates to the thin film technology method, relate in particular to a kind of preparation method and its usage of gelatin protein gold nano grain laminated film.
Technical background
The biomineralization method is the natural process in the mimic biology body, utilizes organic matter to modulate the method for the inorganic matter of growth one fixed structure.Utilizing the biomineralization method to prepare nano particle is a relatively new interdisciplinary research field, relates to the association areas such as material, chemistry, biology and medical science.In numerous organic substrates, protein has caused special concern because of its three-D space structure, unique performance.Gelatin can be used as the good template of preparation nano particle, again because of its good biocompatibility, makes to can be applicable to biomedical sector after simply modifying.Utilize at present gelatin for the synthetic nanostructured of template is all the granular system that disperses in all reports, also there is no the report of respective films material, but film but has and more easily operates and the advantage such as recycling.The present invention utilizes on the basis that superfine nanowire prepares the porous protein film existing, by regulating the surface charge properties of albuminous membranae, reach the purpose of the metal ion of adsorbable oppositely charged through charge interaction, obtain metal/protein laminated film by solution reduction at last.The gelatin gold nano grain laminated film of the present invention's preparation has the ortho-nitraniline catalytic efficiency high, simple to operate, repeats catalysis utilization rate high.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method and its usage of gelatin protein gold nano grain laminated film is provided.
The preparation method's of gelatin protein gold nano grain laminated film step is as follows:
1) the 4mM copper nitrate aqueous solution of equal volume mixes under magnetic agitation with the 1.4mM monoethanolamine aqueous solution, places 2-3 days, generates Cu (OH) 2Nano wire solution, 20mlCu (OH) 2The nano wire solution filter is to form the thick hydrophilic mesoporous film of nanoscale on the Merlon porous lamina membranacea of 200 nm at pore size;
2) with 4.9ml Cu (OH) 2Nano wire solution and 0.1ml mass fraction are 1% gelatin solution mix and blend 5-6 minute, obtain gelatin and Cu (OH) 2Nano wire composite solution, and being filled on the thick hydrophilic mesoporous film of nanoscale is used 3ml, and mass percent is 2.5% glutaraldehyde solution glue connection 2-3 hour, obtains gelatin Cu (OH) 2The nano wire laminated film is with gelatin Cu (OH) 2The nano wire laminated film takes off from Merlon porous lamina membranacea, removes Cu (OH) with the watery hydrochloric acid of pH=2 2Nano wire obtains unsupported gelatin film;
3) unsupported gelatin film is put into the pH value and be reaction in the chlorauric acid solution of 2-4 1-7 days, and with washed with de-ionized water 2-3 time, obtain gelatin protein gold nano grain laminated film.
Gelatin protein gold nano grain laminated film is used for the catalysis of ortho-nitraniline.
The present invention is by controlling pH value size and the reaction time of gelatin protein film in chlorauric acid solution of chlorauric acid solution, in the gelatin protein film, the gold nano grain size can regulate and control, this method is simple, gelatin protein gold nano grain laminated film can be as catalyst, the catalyzed conversion that is used for ortho-nitraniline, maximum efficient is up to 1.99 mol O-nitroaniline/ (mol AuMin), and gelatin protein gold nano grain laminated film have advantages of that recycling rate of waterused is high and easy to operate.
Description of drawings
Fig. 1 is in the situation that chlorauric acid solution pH value is 4, and gelatin film reacts the TEM figure of 7 days in chlorauric acid solution;
Fig. 2 is in the situation that chlorauric acid solution pH value is 3, and gelatin film reacts the TEM figure of 1 day in chlorauric acid solution;
Fig. 3 is that gelatin film reacts the SEM sectional drawing of 7 days in chlorauric acid solution in the situation that chlorauric acid solution pH value is 2;
Fig. 4 is to be that 3 times reactions gelatin protein gold nano grain laminated film of 1 day is to the UV-vis picture of the catalytic process of ortho-nitraniline in chlorauric acid solution pH value.
The specific embodiment
Further illustrate the present invention below in conjunction with example.
Embodiment 1
1) the 4mM copper nitrate aqueous solution of equal volume mixes under magnetic agitation with the 1.4mM monoethanolamine aqueous solution, places 2 days, generates Cu (OH) 2Nano wire solution, 20mlCu (OH) 2The nano wire solution filter is to form the thick hydrophilic mesoporous film of nanoscale on the Merlon porous lamina membranacea of 200 nm at pore size;
2) with 4.9ml Cu (OH) 2Nano wire solution and 0.1ml mass fraction are 1% gelatin solution mix and blend 5 minutes, obtain gelatin and Cu (OH) 2Nano wire composite solution, and being filled on the thick hydrophilic mesoporous film of nanoscale is used 3ml, and mass percent is 2.5% glutaraldehyde solution glue connection 2 hours, obtains gelatin Cu (OH) 2The nano wire laminated film is with gelatin Cu (OH) 2The nano wire laminated film takes off from Merlon porous lamina membranacea, removes Cu (OH) with the watery hydrochloric acid of pH=2 2Nano wire obtains unsupported gelatin film;
3) unsupported gelatin film being put into the pH value is reaction 7 days in 2 chlorauric acid solution, and with washed with de-ionized water 2 times, obtains gelatin protein gold nano grain laminated film;
4) the gelatin protein gold nano grain laminated film that obtains is used for the catalyzed conversion of ortho-nitraniline, and efficient is up to 0.72 mol O-nitroaniline/ (mol AuMin).
Embodiment 2
1) the 4mM copper nitrate aqueous solution of equal volume mixes under magnetic agitation with the 1.4mM monoethanolamine aqueous solution, places 3 days, generates Cu (OH) 2Nano wire solution, 20mlCu (OH) 2The nano wire solution filter is to form the thick hydrophilic mesoporous film of nanoscale on the Merlon porous lamina membranacea of 200 nm at pore size;
2) with 4.9ml Cu (OH) 2Nano wire solution and 0.1ml mass fraction are 1% gelatin solution mix and blend 6 minutes, obtain gelatin and Cu (OH) 2Nano wire composite solution, and being filled on the thick hydrophilic mesoporous film of nanoscale is used 3ml, and mass percent is 2.5% glutaraldehyde solution glue connection 3 hours, obtains gelatin Cu (OH) 2The nano wire laminated film is with gelatin Cu (OH) 2The nano wire laminated film takes off from Merlon porous lamina membranacea, removes Cu (OH) with the watery hydrochloric acid of pH=2 2Nano wire obtains unsupported gelatin film;
3) unsupported gelatin film being put into the pH value is reaction 7 days in 4 chlorauric acid solution, and with washed with de-ionized water 3 times, obtains gelatin protein gold nano grain laminated film;
4) the gelatin protein gold nano grain laminated film that obtains is used for the catalyzed conversion of ortho-nitraniline, and efficient is up to 1.31 mol O-nitroaniline/ (mol AuMin).
Embodiment 3
1) the 4mM copper nitrate aqueous solution of equal volume mixes under magnetic agitation with the 1.4mM monoethanolamine aqueous solution, places 3 days, generates Cu (OH) 2Nano wire solution, 20mlCu (OH) 2The nano wire solution filter is to form the thick hydrophilic mesoporous film of nanoscale on the Merlon porous lamina membranacea of 200 nm at pore size;
2) with 4.9ml Cu (OH) 2Nano wire solution and 0.1ml mass fraction are 1% gelatin solution mix and blend 6 minutes, obtain gelatin and Cu (OH) 2Nano wire composite solution, and being filled on the thick hydrophilic mesoporous film of nanoscale is used 3ml, and mass percent is 2.5% glutaraldehyde solution glue connection 3 hours, obtains gelatin Cu (OH) 2The nano wire laminated film is with gelatin Cu (OH) 2The nano wire laminated film takes off from Merlon porous lamina membranacea, removes Cu (OH) with the watery hydrochloric acid of pH=2 2Nano wire obtains unsupported gelatin film;
3) unsupported gelatin film being put into the pH value is reaction 1 day in 3 chlorauric acid solution, and with washed with de-ionized water 3 times, obtains gelatin protein gold nano grain laminated film;
4) the gelatin protein gold nano grain laminated film that obtains is used for the catalyzed conversion of ortho-nitraniline, and efficient is up to 1.99 mol O-nitroaniline/ (mol AuMin).

Claims (2)

1. the preparation method of a gelatin protein gold nano grain laminated film is characterized in that its step is as follows:
1) the 4mM copper nitrate aqueous solution of equal volume mixes under magnetic agitation with the 1.4mM monoethanolamine aqueous solution, places 2-3 days, generates Cu (OH) 2Nano wire solution, 20mlCu (OH) 2The nano wire solution filter is to form the thick hydrophilic mesoporous film of nanoscale on the Merlon porous lamina membranacea of 200 nm at pore size;
2) with 4.9ml Cu (OH) 2Nano wire solution and 0.1ml mass fraction are 1% gelatin solution mix and blend 5-6 minute, obtain gelatin and Cu (OH) 2Nano wire composite solution, and being filled on the thick hydrophilic mesoporous film of nanoscale is used 3ml, and mass percent is 2.5% glutaraldehyde solution glue connection 2-3 hour, obtains gelatin Cu (OH) 2The nano wire laminated film is with gelatin Cu (OH) 2The nano wire laminated film takes off from Merlon porous lamina membranacea, removes Cu (OH) with the watery hydrochloric acid of pH=2 2Nano wire obtains unsupported gelatin film;
3) unsupported gelatin film is put into the pH value and be reaction in the chlorauric acid solution of 2-4 1-7 days, and with washed with de-ionized water 2-3 time, obtain gelatin protein gold nano grain laminated film.
2. the purposes of the gelatin protein gold nano grain laminated film of method preparation as claimed in claim 1, is characterized in that the catalysis for ortho-nitraniline.
CN2013100166002A 2013-01-17 2013-01-17 Method for preparing gelatin protein and gold nanoparticle composite thin film and application of gelatin protein and gold nanoparticle composite thin film Pending CN103084210A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103223299A (en) * 2013-05-17 2013-07-31 厦门大学 Macromolecular negative-charge ultrafiltration membrane and preparation method thereof
CN103977709A (en) * 2014-04-30 2014-08-13 宁波欧琳厨具有限公司 Modification method of hollow fiber ultrafilter membrane by employing gelatin protein and hydroxide nanowire
CN104497017A (en) * 2014-12-11 2015-04-08 浙江大学 Method for growing metal-organic framework seeds in gelatin layer
CN104588677A (en) * 2014-12-04 2015-05-06 华南理工大学 Method for synthesizing shewanella halitios into god nanoparticles and application of gold nanoparticles
CN105107388A (en) * 2015-07-24 2015-12-02 天津大学 Nanoparticle-embedded amyloid protein fiber filter membrane and method used for pollutant degradation
CN108261929A (en) * 2016-12-29 2018-07-10 湖南尔康明胶有限公司 A kind of preparation method of gelatin film

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CN101918119A (en) * 2007-07-11 2010-12-15 独立行政法人物质·材料研究机构 Flexible and autonomous protein nanofilm, method of producing the same and application thereof
CN102815666A (en) * 2012-05-17 2012-12-12 浙江大学 Preparation method and application of nano-particle film and porous film

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Publication number Priority date Publication date Assignee Title
CN101918119A (en) * 2007-07-11 2010-12-15 独立行政法人物质·材料研究机构 Flexible and autonomous protein nanofilm, method of producing the same and application thereof
CN102815666A (en) * 2012-05-17 2012-12-12 浙江大学 Preparation method and application of nano-particle film and porous film

Non-Patent Citations (1)

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Title
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103223299A (en) * 2013-05-17 2013-07-31 厦门大学 Macromolecular negative-charge ultrafiltration membrane and preparation method thereof
CN103977709A (en) * 2014-04-30 2014-08-13 宁波欧琳厨具有限公司 Modification method of hollow fiber ultrafilter membrane by employing gelatin protein and hydroxide nanowire
CN104588677A (en) * 2014-12-04 2015-05-06 华南理工大学 Method for synthesizing shewanella halitios into god nanoparticles and application of gold nanoparticles
CN104497017A (en) * 2014-12-11 2015-04-08 浙江大学 Method for growing metal-organic framework seeds in gelatin layer
CN104497017B (en) * 2014-12-11 2016-08-24 浙江大学 A kind of method growing Metal-organic frame seed in gelatin layer
CN105107388A (en) * 2015-07-24 2015-12-02 天津大学 Nanoparticle-embedded amyloid protein fiber filter membrane and method used for pollutant degradation
CN108261929A (en) * 2016-12-29 2018-07-10 湖南尔康明胶有限公司 A kind of preparation method of gelatin film

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Application publication date: 20130508