CN102672197A - Method for preparing multipurpose isoionic gold nanoparticle film - Google Patents
Method for preparing multipurpose isoionic gold nanoparticle film Download PDFInfo
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- CN102672197A CN102672197A CN2012101708460A CN201210170846A CN102672197A CN 102672197 A CN102672197 A CN 102672197A CN 2012101708460 A CN2012101708460 A CN 2012101708460A CN 201210170846 A CN201210170846 A CN 201210170846A CN 102672197 A CN102672197 A CN 102672197A
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Abstract
The invention discloses a method for preparing a multipurpose isoionic gold nanoparticle film and belongs to the technical field of material chemistry. By using a gold nanoparticle modified by deoxyribonucleic acid (DNA), the gold nanoparticle is assembled layer by layer in the process of complimentary hybridization of the DNA, and the gold nanoparticle film is prepared; the gold nanoparticle film is represented through a scanning electron microscopy and an atomic force microscope, so that the surface of the prepared film is regular and homogeneous, and the thickness of the film is about 1 micrometer; and the prepared gold nanparticle film is subjected to mechanical property test, the hardness of the film can be tested greatly higher than that of the original gold nugget through a test performed by a nano indenter, and the Young modulus is 80.85 GPa. The gold nanoparticle film can be well applied to nano sensors and high-strength materials in the future.
Description
Technical field
A kind of preparation method of multiduty isoionic golden nanometer particle film belongs to material chemistry technical field.
Background technology
Golden nanometer particle is closely extensively receiving scientist's research interest decades with its excellent photoelectric character, and these character of golden nanometer particle are applied to fields such as optics, biology sensor, catalytic science and procedural assembling.Though the optics and the electronics character of golden nanometer particle and the film be made up of golden nanometer particle are studied and assess,, the engineering properties of golden nanometer particle film does not obtain excellent research.
Laminated assembling technology is that a kind of material with nanoscale designs to reach the universal method of control material internal structure.Since the nineties in last century, this technology is used for producing senior coating and composite widely.Nano material comprises that inorganic molecule bunch, nano particle and nucleic acid etc. can be as the multilayer films of the successful preparation layer assembly of element.Laminated assembling technology has the application of many practicalities.Such as being used to prepare super-hydrophobic interface, sensor, semipermeable membrane, the film of optical activity and response, medicine is carried, bionical coating etc., most application all is based on hypothesis layer assembly coating and has sufficiently high mechanical performance.Layer assembly compound for some material is studied.But, study also insufficient for golden nanometer particle.
Aspect engineering properties, dna molecular comes on the scene gradually.The DNA polymer can not only connect golden nanometer particle or other particles make up the block structure that designs, and they also demonstrate excellent mechanical performance in addition, mainly come from their double-stranded rigidity.The curvature of the inherence of DNA and elasticity have very big influence to its mechanical performance.The Young's modulus of DNA is similar to the value of plastics at 0.3-1 GPa.
Therefore, the engineering properties of preparation and research golden nanometer particle and DNA compound is quite necessary.Be similar to clay and polymer complex film, organic and inorganic compound demonstrates outstanding mechanical performance, and these character come from the high mechanical performance of these compounds.The compound of expection DNA-nano particle also has similar character.
The present invention at first utilizes DNA, adopts the natrium citricum reducing process to prepare the golden nanometer particle of dna modification.The DNA that is selected for use is the DNA of 12 bases, comprises complementary 12-C and 12-G.Nano particle is realized the layer assembly for nano particle through being modified at the complementary pairing effect of its surperficial nucleic acid.This process is different from traditional layer assembly method, and traditional method generally all is to assemble through the difference of the electric charge between two kinds of materials.Experimental result finds out that through ESEM and AFM the golden nanometer particle film of preparation is more even, and thickness is about 1 micron.Measure its hardness through nano-hardness tester and be greatly improved compared with original gold bullion, Young's modulus is at 80.85GPa.This kind golden nanometer particle film can have good application on the nano-sensor in future and high-strength material.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of high-intensity isoionic golden nanometer particle film, regular, the homogeneous in membrane structure surface of preparation, the thickness of film and have very high hardness and Young's modulus about 1 micron.
Technical scheme of the present invention: a kind of preparation method of multiduty isoionic golden nanometer particle film; Synthesizing of the golden nanometer particle of dna modification; Golden nanometer particle is through DNA hybridization layer assembly film forming; The golden nanometer particle of preparing and the sign of film, and the mensuration of the mechanical performance of the golden nanometer particle film of preparing;
Processing step is:
(1) golden nanometer particle of dna modification is synthetic:
The Milli-Q ultra-pure water of a, 1.9mL, the HAuCl of 0.1mL concentration 5mM
4Solution joins in the reaction vial 37.0 ℃ of mixings;
The DNA of the 12-C sequence of the 50 μ M of b1,20 μ L joins in a step a gained mixed system, 37.0 ℃ of stirring and evenly mixing 15min;
The DNA of the 12-G sequence of the 50 μ M of b2,20 μ L joins in another part step a gained mixed system, 37.0 ℃ of stirring and evenly mixing 15min;
C, respectively in b1, b2 gained dna solution, under stirring condition, respectively add the citric acid three sodium solution of the mass and size mark 1% new preparation of 40 μ L fast;
D, this mixed system are subsequently at 37.0 ℃ of stirring reaction 12h; Solution colour is from the faint yellow redness that becomes; The solution of gold nanoparticles of the 12-C dna modification that obtains respectively after the reaction and the solution of gold nanoparticles of 12-G dna modification, 4 ℃ of preservations are to carry out next step experiment;
Said 12-C sequence DNA is: 5 '-CCCCCCCCCCCC-3 ',
Said 12-G sequence DNA is: 5 '-GGGGGGGGGGGG-3 ';
(2) golden nanometer particle is hybridized the layer assembly film forming through DNA:
The sheet glass of a slice cleaning is immersed in the poly dimethyl two propylene ammonium chloride PDDA solution of mass and size mark 1%, reacts 5 min, takes out, and cleans 2 min, air blow drying with ultra-pure water; Then, sheet glass is immersed in the solution of gold nanoparticles of 12-C dna modification and go, react 15 min, make golden nanometer particle be adsorbed onto sheet glass and get on; Reaction finishes to clean 2 min, air blow drying with ultra-pure water; Immerse in the solution of gold nanoparticles of 12-G dna modification again and go, react 15 min, make golden nanometer particle carry out layer assembly through the nucleic acid hybridization effect, reaction finishes to clean 2 min, air blow drying with ultra-pure water; Replace said process then, control the thickness of golden nanometer particle film through the cycle-index of control assembling;
The solution of gold nanoparticles of soaking a 12-C dna modification is as coating one deck, and the solution of gold nanoparticles of soaking a 12-G dna modification again is as the coating second layer, and the rest may be inferred;
The thickness of control golden nanometer particle film is coating 180-220 layer;
(3) golden nanometer particle of preparing and the sign of film:
Adopt transmission electron microscope, ESEM and AFM that the golden nanometer particle film of preparing is characterized;
(4) engineering properties of the golden nanometer particle film of preparation characterizes
Adopt nano-hardness tester that the hardness of the golden nanometer particle film of preparation is measured with the parameter of its Young's modulus associated mechanical character;
Beneficial effect of the present invention: the present invention utilizes the golden nanometer particle of dna modification, and the complementary crossover process through DNA realizes the layer assembly to golden nanometer particle, preparation golden nanometer particle film.Characterize regular, the homogeneous in membrane structure surface that draws preparation through ESEM and AFM, the thickness of film is about 1 micron.Mechanical performance through to the golden nanometer particle film for preparing is measured, and measures its hardness through nano-hardness tester and is greatly improved compared with original gold bullion, and Young's modulus is at 80.85GPa.This kind golden nanometer particle film can have good application on the nano-sensor in future and high-strength material.
Description of drawings
The auxiliary trisodium citrate reduction of Fig. 1 12-C and 12-G DNA gold chloride synthesizes the TEM figure of golden nanometer particle.(a), the TEM of 12-C-DNA gold nano-particles modified figure; (b), the TEM of 12-G-DNA gold nano-particles modified figure.
The sem photograph of the golden nanometer particle film of Fig. 2 preparation.(a) being sem photograph under the low power, (b) is the sem photograph under the high power.
The AFM figure of the golden nanometer particle film of Fig. 3 preparation.AFM figure behind 200 layers of the golden nanometer particle films of preparation.
The engineering properties figure of the golden nanometer particle film of Fig. 4 preparation.(a) graph of a relation of modulus and depth of cup,
(b) graph of a relation of hardness and depth of cup, (c) contact area and the graph of a relation that contacts the degree of depth, (d) the contact degree of depth and the graph of a relation that contacts the power that applies.
The specific embodiment
(1) golden nanometer particle of dna modification is synthetic
The preparation of aqueous solution of chloraurate: the gold chloride of 1g once is dissolved in the solution that is made into 5mM in the distilled water of 500mL.The preparation of nano Au particle is through the preparation of trisodium citrate reduction gold chloride.12-C DNA used in the present invention, 12-G DNA give birth to worker's bioengineering Co., Ltd available from Chinese Shanghai, and carry out purifying through efficient liquid phase.All glass apparatus all pass through chloroazotic acid and soak, and ultra-pure water cleans, and dries subsequent use.
Synthesizing of the golden nanometer particle of dna modification:
The Milli-Q ultra-pure water of a, 1.9mL, the HAuCl of 0.1mL
4Solution (concentration 5mM) joins in the reaction vial, 37.0 ℃ of mixings;
The DNA of the 12-C sequence of the 50 μ M of b1,20 μ L joins in a step a gained mixed system, 37.0 ℃ of stirring and evenly mixing 15min;
The DNA of the 12-G sequence of the 50 μ M of b2,20 μ L joins in another part step a gained mixed system, 37.0 ℃ of stirring and evenly mixing 15min;
C, respectively in b1, b2 gained dna solution, under stirring condition, respectively add the citric acid three sodium solution of the mass and size mark 1% new preparation of 40 μ L fast;
D, this mixed system are subsequently at 37.0 ℃ of stirring reaction 12h; Solution colour is from the faint yellow redness that becomes; The solution of gold nanoparticles of the 12-C dna modification that obtains respectively after the reaction and the solution of gold nanoparticles of 12-G dna modification, 4 ℃ of preservations are to carry out next step experiment;
The golden nanometer particle that is synthesized is seen Fig. 1, and synthetic golden nanometer particle is the golden nanometer particle of uniform ball property, the regular shape of synthetic golden nanometer particle, uniform particle diameter.
(2) golden nanometer particle is hybridized the layer assembly film forming through DNA:
Concrete scheme is: the sheet glass of a slice cleaning is immersed in 1% (mass and size mark) poly dimethyl, two propylene ammonium chloride (PDDA) solution, reacts 5 minutes, takes out, and cleans 2 minutes air blow drying with ultra-pure water.Then, glass is immersed in the solution of gold nanoparticles of 12-C dna modification and go, reacted 15 minutes, make golden nanometer particle be adsorbed onto glass and get on.Reaction finishes to clean 2 minutes air blow drying with ultra-pure water.In the solution of gold nanoparticles that immerses the 12-G dna modification, go, reacted 15 minutes, make golden nanometer particle carry out layer assembly through the nucleic acid hybridization effect, reaction finishes to clean 2 minutes air blow drying with ultra-pure water.Replace said process then, control the thickness of golden nanometer particle film through the cycle-index of control assembling.
(3) golden nanometer particle of preparing and the sign of film:
The sign of the transmission electron microscope of golden nanometer particle is following:
The golden nanometer particle sample drop of getting 8 μ L is added on the copper mesh of carbon film support, under infrared lamp, carries out drying.Transmission electron microscope adopts the Electronic Speculum of JEOL JEM-2100 model, and its accelerating potential is 200 kV.(Fig. 1)
The ESEM of golden nanometer particle film characterizes:
Get the golden nanometer particle film for preparing, bond on the surface sweeping Electronic Speculum objective table, observe through conducting resinl.Used ESEM model is FEI Nova NanoLab.(Fig. 2)
AFM characterizes: at first at the bottom of the silicon wafer-based, prepare the golden nanometer particle film, the method above is the same in the method for preparation on glass.Used ESEM model is NanoScope IIIa.(Fig. 3)
(4) engineering properties of the golden nanometer particle film of preparation characterizes
The model of used nano-hardness tester is Nanoinstruments NanoIndenter II, adopts the indenter of Berkovich shape, and the calculating of hardness and Young's modulus is from the mean value of 5 points of zones of different on the film.(Fig. 4).
Claims (1)
1. the preparation method of a multiduty isoionic golden nanometer particle film; It is characterized in that: the golden nanometer particle of dna modification synthetic; Golden nanometer particle is through DNA hybridization layer assembly film forming; The golden nanometer particle of preparing and the sign of film, and the mensuration of the mechanical performance of the golden nanometer particle film of preparing;
Processing step is:
(1) golden nanometer particle of dna modification is synthetic:
The Milli-Q ultra-pure water of a, 1.9mL, the HAuCl of 0.1mL concentration 5mM
4Solution joins in the reaction vial 37.0 ℃ of mixings;
The DNA of the 12-C sequence of the 50 μ M of b1,20 μ L joins in a step a gained mixed system, 37.0 ℃ of stirring and evenly mixing 15min;
The DNA of the 12-G sequence of the 50 μ M of b2,20 μ L joins in another part step a gained mixed system, 37.0 ℃ of stirring and evenly mixing 15min;
C, respectively in b1, b2 gained dna solution, under stirring condition, respectively add the citric acid three sodium solution of the mass and size mark 1% new preparation of 40 μ L fast;
D, this mixed system are subsequently at 37.0 ℃ of stirring reaction 12h; Solution colour is from the faint yellow redness that becomes; The solution of gold nanoparticles of the 12-C dna modification that obtains respectively after the reaction and the solution of gold nanoparticles of 12-G dna modification, 4 ℃ of preservations are to carry out next step experiment;
Said 12-C sequence DNA is: 5 '-CCCCCCCCCCCC-3 ',
Said 12-G sequence DNA is: 5 '-GGGGGGGGGGGG-3 ';
(2) golden nanometer particle is hybridized the layer assembly film forming through DNA:
The sheet glass of a slice cleaning is immersed in the poly dimethyl two propylene ammonium chloride PDDA solution of mass and size mark 1%, reacts 5 min, takes out, and cleans 2 min, air blow drying with ultra-pure water; Then, sheet glass is immersed in the solution of gold nanoparticles of 12-C dna modification and go, react 15 min, make golden nanometer particle be adsorbed onto sheet glass and get on; Reaction finishes to clean 2 min, air blow drying with ultra-pure water; Immerse in the solution of gold nanoparticles of 12-G dna modification again and go, react 15 min, make golden nanometer particle carry out layer assembly through the nucleic acid hybridization effect, reaction finishes to clean 2 min, air blow drying with ultra-pure water; Replace said process then, control the thickness of golden nanometer particle film through the cycle-index of control assembling;
The solution of gold nanoparticles of soaking a 12-C dna modification is as coating one deck, and the solution of gold nanoparticles of soaking a 12-G dna modification again is as the coating second layer, and the rest may be inferred;
The thickness of control golden nanometer particle film is coating 180-220 layer;
(3) golden nanometer particle of preparing and the sign of film:
Adopt transmission electron microscope, ESEM and AFM that the golden nanometer particle film of preparing is characterized;
(4) engineering properties of the golden nanometer particle film of preparation characterizes
Adopt nano-hardness tester that the hardness of the golden nanometer particle film of preparation is measured with the parameter of its Young's modulus associated mechanical character.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104399974A (en) * | 2014-12-16 | 2015-03-11 | 天津工业大学 | Continuous control method for gold nanometer particle aggregate microstructure |
| CN105478747A (en) * | 2015-12-10 | 2016-04-13 | 济南大学 | Fusiform gold nano particle with remarkable near-infrared light absorbability and manufacturing method thereof |
| CN105710389A (en) * | 2016-04-20 | 2016-06-29 | 中南大学 | Technology for enhancing fluorescence and improving anti-oxidant activity of DNA-Ag NCs |
| CN106966357A (en) * | 2017-03-27 | 2017-07-21 | 大连理工大学 | A kind of preparation method of golden nanometer particle pair |
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| CN105710389A (en) * | 2016-04-20 | 2016-06-29 | 中南大学 | Technology for enhancing fluorescence and improving anti-oxidant activity of DNA-Ag NCs |
| CN105710389B (en) * | 2016-04-20 | 2018-12-25 | 中南大学 | A kind of fluorescence enhancing silver nanoclusters and the technique for improving its antioxidant activity |
| CN106966357A (en) * | 2017-03-27 | 2017-07-21 | 大连理工大学 | A kind of preparation method of golden nanometer particle pair |
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