CN102049226A - Method for preparing TMV template-based nano-gold material - Google Patents

Method for preparing TMV template-based nano-gold material Download PDF

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CN102049226A
CN102049226A CN2010105459843A CN201010545984A CN102049226A CN 102049226 A CN102049226 A CN 102049226A CN 2010105459843 A CN2010105459843 A CN 2010105459843A CN 201010545984 A CN201010545984 A CN 201010545984A CN 102049226 A CN102049226 A CN 102049226A
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tmv
template
gold
solution
mosaic virus
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CN102049226B (en
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刘楠
姜兴益
李中皓
张洪非
侯宏卫
唐纲岭
陈再根
陈欢
李雪
胡清源
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Zhengzhou Tobacco Research Institute of CNTC
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Zhengzhou Tobacco Research Institute of CNTC
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Abstract

The invention discloses a method for preparing a tobacco mosaic virus (TMV) template-based nano-gold material. In the method, soluble sulfite and soluble thiocyanate react with chloroauric acid so as to obtain a gold-containing complexing ion [Au(SCN)2<->] which can be strongly combined with a TMV template and can improve the growth density of nano-gold on TMV; and gold is reduced into free gold by a reducing agent in situ, so that the TMV template-based nano-gold material with high growth density is formed.

Description

A kind of nm of gold preparation methods based on the tobacco mosaic virus (TMV) template
Technical field
The present invention relates to a kind of nm of gold preparation methods, belong to organic and inorganic composite functional material preparing technical field based on the tobacco mosaic virus (TMV) template.
Background technology
Virus can become desirable template (R. Tsukamoto, M. Muraoka, M. Seki, H. Tabata, the I. Yamashita. Synthesis of CoPt and FePt that constructs new material 3Nanowires Using the Central Channel of Tobacco Mosaic Virus as a Biotemplate [J]. Chem. Mater., 2007,19:2389.).Except can be on nanometer and molecular level carrying out the microcosmic assembling to material, virus capsid protein also has the space binding site that rule distributes, can be so that be the material ordering that template is constructed with it, and these all can be to the performance generation active influence of material.Tobacco mosaic virus (TMV) (TMV) is a kind of template that is used to construct low-dimensional materials, and this virus has nano tubular structure, and pipe range is 300 nm, and bore is 4 nm, and external diameter is 18 nm.There is the various active group on the inside and outside surface of TMV, by changing reaction condition, different material is combined on the inside and outside surface of TMV nanotube, thereby obtains having the new material of difference in functionality
The preparation nanocrystalline, line that with TMV is that template is carried out, be important application (the R. J. Tseng of TMV template in the material field, C. Tsai, L. Ma, J. Ouyang, C. S. Ozkan, Y. Yang. Digital memory device based on tobacco mosaic virus conjugated with nanoparticles [J]. Nature Nanotechnology, 2006,1:72..M.?Knez,?M.?Sumser,?A.?M.?Bittner,?C.?Wege,?H.?Jeske,?T.?P.?Martin,?K.?Kern.?Spatially?selective?nucleation?of?metal?clusters?on?the?tobacco?mosaic?virus?[J].?Adv.?Funct.?Mater.,?2004,?14:?116.。E.?Dujardin,?C.?Peet,?G.?Stubbs,?J.?N.?Culver,?S.?Mann.?Organization?of?metallic?nanoparticles?using?tobacco?mosaic?virus?templates?[J].?Nano?Lett.,?2003,?3:?413.)。At present, realized the growth of multiple noble metal nanocrystalline, line in the TMV nanotube surface.Current research concentrates in the growth based on nanocrystalline, the line of TMV template, and the research that relates to material property is very rare.Oxidation has significant catalytic action to gold nanocrystals to CO, and the TMV template can play well stable, peptizaiton to nanocrystalline, and therefore the gold nanocrystals based on the TMV template growth has the potentiality that obtain application in CO catalytic oxidation field.But from current research, often can not obtain good template coverage rate based on the gold nanocrystals of TMV template growth, promptly gold nanocrystals stand density on the TMV template is not high, as shown in Figure 1, and the raising that this can restricted T MV-nm of gold material catalytic performance.
Summary of the invention
The purpose of this invention is to provide a kind of nm of gold preparation methods, to improve the stand density of nm of gold on the TMV template based on the tobacco mosaic virus (TMV) template.
In order to realize above purpose, the technical solution adopted in the present invention is: a kind of nm of gold preparation methods based on the tobacco mosaic virus (TMV) template, and its step is as follows:
1) preparation of solution
A makes suspension with tobacco mosaic virus (TMV)-TMV, ie in solution A, and solution A carried out ultrasonic processing, the processing time is 0 ~ 10 min;
B is mixed with mixed solution with solubility sulphite, solubility rhodanate, gold chloride, and concentration is respectively 0.05 ~ 0.1 M, 0.1 ~ 0.2 M, 0.01 ~ 0.05 M, leaves standstill ie in solution B then;
2) solution A is mixed with solution B and stir, add the reducing agent natrium citricum again, adding back concentration is 0.1 ~ 0.2 M, and in 40-60 ℃ of heat tracing processing, product is repeatedly washed, purifies with centrifugation method with deionized water then, obtain dark brown granule shape product, promptly based on the nm of gold material of tobacco mosaic virus (TMV) template.
The concentration of the suspension of TMV described in the step 1) a is 0.10 ~ 0.15mg/mL.
Carry out ultrasonic processing after the configuration of suspension described in the step 1) a, the processing time is 0 ~ 10 min.
Step 2) described heat tracing processing time is 60-90 minute.
Described solubility sulphite is potassium sulfite or sodium sulfite.
Described solubility rhodanate is potassium rhodanide or sodium sulfocyanate.
Nm of gold preparation methods based on the tobacco mosaic virus (TMV) template of the present invention adopts SO 3 2-With Au 3+Be reduced to Au +, SCN -Can with Au +Complexing comparatively stably is Au(SCN) 2 -, the functional group on this ion pair TMV surface has extremely strong combination, therefore adds SO in reaction system 3 2-, SCN -, just can hope and improve nm of gold growing environment on the TMV template, improve the stand density of nm of gold, adopt reducing agent with Au at last +In-situ reducing is the free state gold, forms the TMV-nm of gold material of high stand density.
Description of drawings
The nm of gold TEM photo based on the TMV template growth that Fig. 1 reports for document (Adv. Funct. Mater., 2004,14:116.);
Fig. 2 is the TEM photo based on the nm of gold material of tobacco mosaic virus (TMV) template of the present invention preparation.
The specific embodiment
Embodiment 1
The nm of gold preparation methods based on the tobacco mosaic virus (TMV) template of present embodiment, step is as follows:
1) preparation of solution
A makes the suspension that concentration is 0.10 mg/mL, ie in solution A with tobacco mosaic virus (TMV)-TMV;
B is with Na 2SO 3, NaSCN, gold chloride be dissolved in and make mixed solution, wherein Na in the deionized water 2SO 3, NaSCN, gold chloride concentration be respectively 0.05 M, 0.1 M, 0.01 M, mixed solution is left standstill more than 30 min ie in solution B;
2) solution A is mixed with solution B and stir more than 30 minutes, the natrium citricum that adds 0.1 M again, and in 40 ℃ of heat tracings processing 90 minutes, product is repeatedly washed, purifies with centrifugation method with deionized water then, obtain dark brown granule shape product, this product is scattered in the deionized water once more, promptly obtains containing the suspension of target product.For the ease of carrying out transmissioning electric mirror test, can earlier product be scattered in the deionized water, form the suspension that contains product, then again the trace suspension drop is tested to copper mesh.
Embodiment 2
The nm of gold preparation methods based on the tobacco mosaic virus (TMV) template of present embodiment, step is as follows:
1) preparation of solution
A makes the suspension that concentration is 0.10 mg/mL, ie in solution A with tobacco mosaic virus (TMV)-TMV;
B is with Na 2SO 3, NaSCN, gold chloride be dissolved in and make mixed solution, wherein Na in the deionized water 2SO 3, NaSCN, gold chloride concentration be respectively 0.1 M, 0.2 M, 0.05 M, mixed solution is left standstill more than 30 min ie in solution B;
2) solution A is mixed with solution B and stir more than 30 minutes, the natrium citricum that adds 0.15 M again, and in 60 ℃ of heat tracings processing 60 minutes, product is repeatedly washed, purifies with centrifugation method with deionized water then, obtain dark brown granule shape product, this product is scattered in the deionized water once more, promptly obtains containing the suspension of target product.
Embodiment 3
The nm of gold preparation methods based on the tobacco mosaic virus (TMV) template of present embodiment, step is as follows:
1) preparation of solution
A makes the suspension that concentration is 0.15 mg/mL with tobacco mosaic virus (TMV)-TMV, with ultrasonic processing 10 min of this suspension, ie in solution A;
B is with Na 2SO 3, NaSCN, gold chloride be dissolved in and make mixed solution, wherein Na in the deionized water 2SO 3, NaSCN, gold chloride concentration be respectively 0.1 M, 0.2 M, 0.05 M, mixed solution is left standstill more than 30 min ie in solution B;
2) solution A is mixed with solution B and stir more than 30 minutes, the natrium citricum that adds 0.1 M again, and in 50 ℃ of heat tracings processing 75 minutes, product is repeatedly washed, purifies with centrifugation method with deionized water then, obtain dark brown granule shape product, this product is scattered in the deionized water once more, promptly obtains containing the suspension of target product.
Embodiment 4
The nm of gold preparation methods based on the tobacco mosaic virus (TMV) template of present embodiment, step is as follows:
1) preparation of solution
A makes the suspension that concentration is 0.12 mg/mL with tobacco mosaic virus (TMV)-TMV, with the ultrasonic processing of this suspension 5 minutes, ie in solution A;
B is with K 2SO 3, KSCN, gold chloride be dissolved in and make mixed solution, wherein K in the deionized water 2SO 3, KSCN, gold chloride concentration be respectively 0.08 M, 0.15 M, 0.03 M, mixed solution is left standstill more than the 30min ie in solution B;
2) solution A is mixed with solution B and stir more than 30 minutes, the natrium citricum that adds 0.2 M again, and in 40 ℃ of heat tracings processing 90 minutes, product is repeatedly washed, purifies with centrifugation method with deionized water then, obtain dark brown granule shape product, this product is scattered in the deionized water once more, promptly obtains containing the suspension of target product.
Embodiment 5
The nm of gold preparation methods based on the tobacco mosaic virus (TMV) template of present embodiment, step is as follows:
1) preparation of solution
A makes the suspension that concentration is 0.15 mg/mL with tobacco mosaic virus (TMV)-TMV, with ultrasonic processing 10 min of this suspension, ie in solution A;
B is with K 2SO 3, KSCN, gold chloride be dissolved in and make mixed solution, wherein K in the deionized water 2SO 3, KSCN, gold chloride concentration be respectively 0.1 M, 0.2 M, 0.05 M, mixed solution is left standstill more than 30 min ie in solution B;
2) solution A is mixed with solution B and stir more than 30 minutes, the natrium citricum that adds 0.1 M again, and in 60 ℃ of heat tracings processing 60 minutes, product is repeatedly washed, purifies with centrifugation method with deionized water then, obtain dark brown granule shape product, this product is scattered in the deionized water once more, promptly obtains containing the suspension of target product.

Claims (6)

1. nm of gold preparation methods based on the tobacco mosaic virus (TMV) template, it is characterized in that: its step is as follows:
1) preparation of solution
A makes suspension with tobacco mosaic virus (TMV)-TMV, ie in solution A, and solution A carried out ultrasonic processing, the processing time is 0 ~ 10 min;
B is mixed with mixed solution with solubility sulphite, solubility rhodanate, gold chloride, and concentration is respectively 0.05 ~ 0.1 M, 0.1 ~ 0.2 M, 0.01 ~ 0.05 M, leaves standstill ie in solution B then;
2) solution A is mixed with solution B and stir, add the reducing agent natrium citricum again, adding back concentration is 0.1 ~ 0.2 M, and in 40-60 ℃ of heat tracing processing, product is repeatedly washed, purifies with centrifugation method with deionized water then, obtain dark brown granule shape product, promptly based on the nm of gold material of tobacco mosaic virus (TMV) template.
2. the nm of gold preparation methods based on the tobacco mosaic virus (TMV) template according to claim 1 is characterized in that: the concentration of the suspension of TMV described in the step 1) a is 0.10 ~ 0.15mg/mL.
3. the nm of gold preparation methods based on the tobacco mosaic virus (TMV) template according to claim 1 is characterized in that: carry out ultrasonic processing after the configuration of suspension described in the step 1) a, the processing time is 0 ~ 10 min.
4. the nm of gold preparation methods based on the tobacco mosaic virus (TMV) template according to claim 1 is characterized in that: step 2) the described heat tracing processing time is 60-90 minute.
5. according to each described nm of gold preparation methods based on the tobacco mosaic virus (TMV) template of claim 1-4, it is characterized in that: described solubility sulphite is potassium sulfite or sodium sulfite.
6. according to each described nm of gold preparation methods based on the tobacco mosaic virus (TMV) template of claim 1-4, it is characterized in that: described solubility rhodanate is potassium rhodanide or sodium sulfocyanate.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103207160A (en) * 2013-04-11 2013-07-17 福建医科大学 Rapid determination method for thiocyanate with nanogold as coloring probe
CN103706800A (en) * 2014-01-16 2014-04-09 国家烟草质量监督检验中心 Method for growing nanogold on gene-modified tobacco mosaic virus nuclecapsid protein template
CN105327354A (en) * 2015-10-23 2016-02-17 中国科学院理化技术研究所 Preparation method of tobacco mosaic virus nanowire composite material with functionalized surface
CN105367630A (en) * 2014-08-11 2016-03-02 中国科学院苏州纳米技术与纳米仿生研究所 Method for preparing two-dimensional nanometer structure from tobacco mosaic virus capsid protein mutant

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CN101491835A (en) * 2009-02-27 2009-07-29 江南大学 Preparation method of heparin modified gold nano-particles
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US7569340B2 (en) * 2005-08-31 2009-08-04 Northwestern University Nanoarrays of single virus particles, methods and instrumentation for the fabrication and use thereof
CN101081435A (en) * 2007-06-28 2007-12-05 同济大学 Bionics method for preparation of precious metal simple substance nanometer material
CN101491835A (en) * 2009-02-27 2009-07-29 江南大学 Preparation method of heparin modified gold nano-particles

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103207160A (en) * 2013-04-11 2013-07-17 福建医科大学 Rapid determination method for thiocyanate with nanogold as coloring probe
CN103207160B (en) * 2013-04-11 2014-12-10 福建医科大学 Rapid determination method for thiocyanate with nanogold as coloring probe
CN103706800A (en) * 2014-01-16 2014-04-09 国家烟草质量监督检验中心 Method for growing nanogold on gene-modified tobacco mosaic virus nuclecapsid protein template
CN105367630A (en) * 2014-08-11 2016-03-02 中国科学院苏州纳米技术与纳米仿生研究所 Method for preparing two-dimensional nanometer structure from tobacco mosaic virus capsid protein mutant
CN105327354A (en) * 2015-10-23 2016-02-17 中国科学院理化技术研究所 Preparation method of tobacco mosaic virus nanowire composite material with functionalized surface
CN105327354B (en) * 2015-10-23 2018-03-27 中国科学院理化技术研究所 Preparation method of tobacco mosaic virus nanowire composite material with functionalized surface

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