CN102921957A - Technological method for precious metal nano-particles based on modified collagen - Google Patents
Technological method for precious metal nano-particles based on modified collagen Download PDFInfo
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- CN102921957A CN102921957A CN2012104383263A CN201210438326A CN102921957A CN 102921957 A CN102921957 A CN 102921957A CN 2012104383263 A CN2012104383263 A CN 2012104383263A CN 201210438326 A CN201210438326 A CN 201210438326A CN 102921957 A CN102921957 A CN 102921957A
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Abstract
The invention discloses a technological method for precious metal nano-particles based on modified collagen. The technological method comprises modified collagen is dissolved in water, the solution concentration ranges from 0.1 wt% to 10 wt%, the solution is heated to 60 DEG C to 100 DEG C and stirred, a precious metal precursor is added in the modified collagen solution, and the mixture is reacted at a temperature in a range of 60 DEG C to 100 DEG C to obtain monometal nano-particles; and another precious metal precursor is added, and the mixture is reacted continuously at a temperature ranging from 60 DEG C to 100 DEG C to obtain duplex precious metal nano-particles. According to the method, the modified collagen serves as a template agent and a reducing agent for the growth of precious metal nano-particles, novel research fields of collagen are developed, and nano-particle sizes are controlled to be in a range of 1 nm to 30 nm by changing the concentration of the modified collagen solution.
Description
Technical field
The present invention relates to a kind of preparations of nanomaterials method, particularly a kind of process of the noble metal nano particles based on modified collagen albumen belongs to field of material preparation.
Background technology
The noble metal nano crystal can be bound large biological molecule such as albumen, enzyme, DNA and be widely used and become one of focus of research in biomarker and field of biological detection.Large biological molecule is owing to having good location and recognition capability is the mould material of desirable preparation noble metal nano crystal.Recent study shows peptide chain because its specific biological nature and typical three-dimensional spiral structure successfully are applied in the preparations of nanomaterials, as can successfully regulating and control the gold grain growth under aspartic acid, lysine, tyrosine and the trp residue room temperature.Collagen is rich in the amino acid such as glycine, proline, hydroxyproline, and its architectural feature is triple-helix structure, makes its molecular structure highly stable, and has reduced immunogenicity and good biocompatibility etc.Active group in the collagen peptide chain comprises suspended double bond, – NH
2, – SH is with – COOH easily by other biomolecule modification, is that a comparatively ideal natural macromolecular material is regulated and control nanoparticle growth.The people such as Yujing Sun utilize the collagen of Ι type to prepare the noble metal nano particles Web materials.The collagen of Ι type is in the pH of solution＜7 o'clock stabilizing agent and templates as the noble metal nano particles growth.This syntheti c route is compared with the present invention, is to introduce sodium borohydride as the reducing agent of precious metal ion.The present invention is that applying modified collagen is used as reducing agent and stabilizing agent is regulated and control Au, Ag, Pt and Au-Ag, the Ag-Pt nano particle increases.
Summary of the invention
The process that the purpose of this invention is to provide a kind of noble metal nano particles based on modified collagen albumen.
Realize that technical solution of the present invention is: a kind of process of the noble metal nano particles based on modified collagen albumen, noble metal nano particles comprises monometallic and duplex metal nano granule, if preparation monometallic nano particle step is 1 and 2, if preparation duplex metal nano granule step is 1,2,3, described method is:
Step 1, with the modified collagen protein dissolution in water, solution concentration is 0.1wt%～10wt%, heating is also stirred;
Step 2, add a kind of noble metal precursor body in the step 1, at 60～100 ℃ of lower reaction certain hours, obtain the monometallic nano-colloid;
Step 3, add another kind of noble metal precursor body in the step 2, at 60～100 ℃ of lower reaction certain hours that continue, namely get the bimetal nano colloid.
Modified collagen albumen described in the step 1 is that collagen obtains through acid or alkali partial hydrolysis; Described heating-up temperature is 60～100 ℃.
Noble metal precursor body described in the step 2 and 3 is golden chloric acid or chloroaurate, silver salt, chloroplatinic acid or chloroplatinate, the mass ratio 1 * 10 of described noble metal precursor body total amount and modified collagen albumen
-5～5 * 10
-3, the reaction response time of described preparation monometallic nano particle is 2～6h; The total reaction time of described preparation duplex metal nano granule also is 2～6h.
The present invention compared with prior art, its remarkable advantage: ⑴ has introduced a kind of preparation method of simple novel noble metal nano particles, with the collagen of modification template and the reducing agent as the noble metal nano particles growth, the recent studies on field of developing collagen; ⑵ with the template of modified collagen albumen as the noble metal nano growth, and the degraded of modified collagen albumen does not affect the pattern of noble metal nano particles; ⑶ the concentration of modified collagen protein solution can be used to the size of nano particle.Change the spherical noble metal nano particles that modified collagen protein solution concentration can obtain the size homogeneous, size 1～30nm; Since in the collagen a plurality of amino acid sequences Au, Ag nano particle are had strong binding effect, noble metal or duplex metal nano granule colloidal stability are strong, for a new field has been opened up in the application of collagen in biomaterial.
Below in conjunction with the drawings and specific embodiments the present invention is described in further detail.
Description of drawings
The TEM photo of Fig. 1 embodiment of the invention 3 prepared gold nano grains.
The specific embodiment
The case study on implementation of gold, silver, Pt nanoparticle preparation
Embodiment 1:
Step 1 is dissolved in 0.1g modified collagen albumen (commercially available) in the 100mL deionized water, is heated to 80
oC also stirs;
Step 2 adds the chlorauric acid solution of 0.5mL 0.1wt% in the step 1,80
oReact 2h under the C, obtain the gold nano colloid.
Embodiment 2
Step 1 is dissolved in 2g modified collagen albumen in the 98mL deionized water, is heated to 60
oC also stirs;
Step 2 adds the golden sodium chlorate solution of 1mL 1wt% in the step 1,60
oReact 4h under the C, obtain the gold nano colloid.
Embodiment 3
Step 1 is dissolved in 10g modified collagen albumen in the 90mL deionized water, is heated to 80
oC also stirs;
Step 2 adds the liquor argenti nitratis ophthalmicus of 100 μ L 0.1wt% in the step 1,80
oReact 3h under the C, obtain nanoparticles, its TEM photo as shown in Figure 1.
Embodiment 4
Step 1 is dissolved in 2g modified collagen albumen in the 98mL deionized water, is heated to 100
oC also stirs;
Step 2 adds the silver acetate solution of 0.5mL 0.1wt% in the step 1,100
oReact 2h under the C, obtain nanoparticles.
Embodiment 5
Step 1 is dissolved in 2g modified collagen albumen in the 98mL deionized water, is heated to 80
oC also stirs;
Step 2 adds the platinum acid chloride solution of 0.5mL 0.1wt% in the step 1,80
oReact 2h under the C, obtain the platinum nano-colloid.
Embodiment 6
Step 1 is dissolved in 5g modified collagen albumen in the 95mL deionized water, is heated to 80
oC also stirs;
Step 2 adds the potassium chloroplatinate solution of 1mL 1wt% in the step 1,60
oReact 6h under the C, obtain the platinum nano-colloid.
The case study on implementation of Jin-Yin (Au-Ag) and silver-platinum (Ag-Pt) duplex metal nano granule
Embodiment 7
Step 1 is dissolved in 0.1g modified collagen albumen in the 100mL deionized water, is heated to 80
oC also stirs;
Step 2 adds the chlorauric acid solution of 0.2mL 0.1wt% in the step 1,80
oReact 1h under the C;
Step 3 adds the liquor argenti nitratis ophthalmicus of 0.3mL 0.1wt% in the step 2,80
oContinue reaction 1h under the C, obtain bimetallic Ag-Au nano-colloid.
Embodiment 8
Step 1 is dissolved in 2g modified collagen albumen in the 98mL deionized water, is heated to 60
oC also stirs;
Step 2 adds the golden sodium chlorate solution of 0.5mL 1wt% in the step 1,60
oReact 3h under the C;
Step 3 adds the liquor argenti nitratis ophthalmicus of 0.5mL 0.1wt% in the step 2,60
oContinue reaction 3h under the C, obtain bimetallic Ag-Au nano-colloid.
Embodiment 9
Step 1 is dissolved in 10g modified collagen albumen in the 90mL deionized water, is heated to 80
oC also stirs;
Step 2 adds the chlorauric acid solution of 50 μ L 0.1wt% in the step 1,80
oReact 2h under the C;
Step 3 adds the liquor argenti nitratis ophthalmicus of 50 μ L 0.1wt% in the step 2,80
oContinue reaction 2h under the C, obtain bimetallic Ag-Au nano-colloid.
Embodiment 10
Step 1 is dissolved in 2g modified collagen albumen in the 98mL deionized water, is heated to 100
oC also stirs;
Step 2 adds the silver acetate solution of 0.5mL 0.1wt% in the step 1,100
oReact 1h under the C;
Step 3 adds the sodium chloraurate solution of 0.5mL 0.1wt% in the step 2,100
oContinue reaction 1h under the C, obtain bimetallic Ag-Au nano-colloid.
Embodiment 11
Step 1 is dissolved in 4g modified collagen albumen in the 96mL deionized water, is heated to 80
oC also stirs;
Step 2 adds the platinum acid chloride solution of 0.5mL 0.1wt% in the step 1,80
oReact 1.5h under the C;
Step 3 adds the liquor argenti nitratis ophthalmicus of 0.5mL 0.1wt% in the step 2,80
oContinue reaction 1.5h under the C, obtain bimetallic Ag-Pt nano-colloid.
Embodiment 12
Step 1 is dissolved in 5g modified collagen albumen in the 95mL deionized water, is heated to 80
oC also stirs;
Step 2 adds the potassium chloroplatinate solution of 0.5mL 1wt% in the step 1,60
oReact 3h under the C;
Step 3 adds the silver acetate solution of 0.5mL 1wt% in the step 2,60
oContinue reaction 3h under the C; Obtain bimetallic Ag-Pt nano-colloid.
Claims (5)
1. the process based on the noble metal nano particles of modified collagen albumen is characterized in that described noble metal nano particles comprises monometallic and duplex metal nano granule, and described monometallic nanometer grain preparation method comprises the steps:
Step 1, with the modified collagen protein dissolution in water, solution concentration is 0.1wt%～10wt%, heating is also stirred;
Step 2, add a kind of noble metal precursor body in the step 1,60～100 ℃ of lower reactions, obtain monometallic nano particle colloid;
Described duplex metal nano granule is by adding another kind of noble metal precursor body in the product of step 2, react 60～100 ℃ of lower continuation, namely getting the duplex metal nano granule colloid.
2. the process of the noble metal nano particles based on modified collagen albumen according to claim 1 is characterized in that the modified collagen albumen described in the step 1 is that collagen obtains through acid or alkali partial hydrolysis; Described heating-up temperature is 60～100 ℃.
3. the process of the noble metal nano particles based on modified collagen albumen according to claim 1 is characterized in that described noble metal precursor body is golden chloric acid or chloroaurate, silver salt, chloroplatinic acid or chloroplatinate.
4. the process of the noble metal nano particles based on modified collagen albumen according to claim 1 is characterized in that the mass ratio 1 * 10 of described noble metal precursor body total amount and modified collagen albumen
-5～5 * 10
-3
5. the process of the noble metal nano particles based on modified collagen albumen according to claim 1, the reaction time that it is characterized in that preparing single noble metal nano particles is 2～6h; The total reaction time of the two noble metal nano particles of preparation is 2～6h.
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| CN103170641A (en) * | 2013-03-19 | 2013-06-26 | 燕山大学 | Method of preparing platinum nano particles by using cotton bollworm karyotype polyhedrin |
| CN104001933A (en) * | 2014-05-12 | 2014-08-27 | 燕山大学 | Method for preparing gold nanowire by means of cotton bollworm karyotype polyhedrin extractive |
| CN104722776A (en) * | 2015-04-09 | 2015-06-24 | 中南大学 | Synthesis process of silver nano clusters |
| CN104739657A (en) * | 2015-03-20 | 2015-07-01 | 中国科学院过程工程研究所 | Collagen gel containing nanogold, and prepetition method and application thereof |
| CN104985193A (en) * | 2015-07-24 | 2015-10-21 | 天津大学 | Alloy nano-particle preparation method based on protein reduction method |
| CN107363254A (en) * | 2017-06-16 | 2017-11-21 | 江苏大学 | A kind of application of golden platinum nanometer rod composite material and its photo-thermal antibacterial |
| CN110976908A (en) * | 2019-12-27 | 2020-04-10 | 海南医学院 | Gold-platinum bimetallic nano-particles and preparation method thereof |
| CN114774698A (en) * | 2022-04-02 | 2022-07-22 | 西北工业大学 | Method for extracting noble metal simple substance by using protein assembly |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103170641B (en) * | 2013-03-19 | 2014-12-24 | 燕山大学 | Method of preparing platinum nano particles by using cotton bollworm karyotype polyhedrin |
| CN103170641A (en) * | 2013-03-19 | 2013-06-26 | 燕山大学 | Method of preparing platinum nano particles by using cotton bollworm karyotype polyhedrin |
| CN104001933B (en) * | 2014-05-12 | 2016-03-02 | 燕山大学 | Bollworm polyhedrosis protein extract is utilized to prepare the method for nanowires of gold |
| CN104001933A (en) * | 2014-05-12 | 2014-08-27 | 燕山大学 | Method for preparing gold nanowire by means of cotton bollworm karyotype polyhedrin extractive |
| CN104739657A (en) * | 2015-03-20 | 2015-07-01 | 中国科学院过程工程研究所 | Collagen gel containing nanogold, and prepetition method and application thereof |
| CN104739657B (en) * | 2015-03-20 | 2017-11-14 | 中国科学院过程工程研究所 | A kind of collagen gel containing nanogold and its production and use |
| CN104722776A (en) * | 2015-04-09 | 2015-06-24 | 中南大学 | Synthesis process of silver nano clusters |
| CN104722776B (en) * | 2015-04-09 | 2018-03-06 | 中南大学 | A kind of silver receives the synthesis technique of cluster |
| CN104985193A (en) * | 2015-07-24 | 2015-10-21 | 天津大学 | Alloy nano-particle preparation method based on protein reduction method |
| CN107363254A (en) * | 2017-06-16 | 2017-11-21 | 江苏大学 | A kind of application of golden platinum nanometer rod composite material and its photo-thermal antibacterial |
| CN110976908A (en) * | 2019-12-27 | 2020-04-10 | 海南医学院 | Gold-platinum bimetallic nano-particles and preparation method thereof |
| CN110976908B (en) * | 2019-12-27 | 2023-02-24 | 海南医学院 | Gold-platinum bimetallic nano-particles and preparation method thereof |
| CN114774698A (en) * | 2022-04-02 | 2022-07-22 | 西北工业大学 | Method for extracting noble metal simple substance by using protein assembly |
| CN114774698B (en) * | 2022-04-02 | 2023-10-20 | 西北工业大学 | Method for extracting precious metal simple substance by utilizing protein assembly |
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Application publication date: 20130213 |