CN107243629B - A kind of core-shell structure nanometer particle and preparation method thereof - Google Patents
A kind of core-shell structure nanometer particle and preparation method thereof Download PDFInfo
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- CN107243629B CN107243629B CN201710434566.9A CN201710434566A CN107243629B CN 107243629 B CN107243629 B CN 107243629B CN 201710434566 A CN201710434566 A CN 201710434566A CN 107243629 B CN107243629 B CN 107243629B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a kind of core-shell structure nanometer particles, the preparation method comprises the following steps: CTAB solution is added in container by (1), HAuCl is added4Solution adds NaBH4Solution obtains crystal seed；CTAB solution is added in another container, HAuCl is sequentially added4Nanometer gold bar is made in solution, silver nitrate solution, L-AA solution, crystal seed；(2) DNA modification of nanometer gold bar obtains the nanometer gold bar that sulfhydrylation DNA stablizes protection；(3) nanometer gold bar is centrifuged, is dissolved in CTAB solution, sequentially add SDS solution, silver nitrate solution, L-AA solution is stood to obtain the final product.Nanoparticle of the invention, with extraordinary stability, the silver covering at core-shell structure both ends is very thin, the connected single-stranded meeting major part of DNA is exposed outside, tip portion has higher surface plasma bulk effect, has huge application value in fields such as bio-light electronics, biological nano detections.
Description
Technical field
The present invention relates to a kind of core-shell structure nanometer particles and preparation method thereof, belong to nanobiology and Nano medication
Field.
Background technique
Gold is extracted as heavy metal material in B.C. 5th century for the first time, when gold is divided into lower than 100nm size
Become more precious when gold nanoparticle gold.Gold nanoparticle (gold nanoparticle) refers to the molecule of gold, straight
Diameter has biology well in 1~100nm, gold nanoparticle cloud density with higher, dielectric property and catalytic action
Compatibility, can be in conjunction with a variety of large biological molecules, and do not influence its bioactivity.Diameter Nano grade gold nanoparticle,
Basic unit is all the particle of microsize, has the unexistent physical characteristic of many macroscopic view gold, such as optical effect, surface effect
It answers, small-size effect, Dielectric confinement effect, macro quanta tunnel effect and some other special effects.Gold nanoparticle
Special effects make gold nanoparticle be widely used in the research fields such as material, medical test, disease treatment.
Gold nanoparticle is because of its excellent all manifold effect, and deep to be had deep love for by researcher, research is most adequately nanometer at present
Gold goal and nanometer gold bar.For nanogold cone as a kind of novel gold nanoparticle, early period is not very due to its synthesis preparation method
Maturation, therefore the property research of nanogold cone much also rests on theoretical research stage.Researcher utilizes seed mediated growth method at present,
By the temperature factor in control synthesis process, the extraordinary dispersed nano gold cone particle of homogeneity is obtained, has been nanogold
Quickly propelling for cone research is laid a good foundation.
The plasma model of metal nanoparticle depends on shape, size, composition and the local environment of nanoparticle.It stretches
Nanoparticle be optical research ideal nanoparticle, the draw ratio by changing particle adjusts its spectrum.With nanogold
Stick is compared, and the tip portion at both ends of nanogold cone has bigger curvature, and the field enhancing of tip portion is bigger, and nanogold cone is gathered around
There are the plasma properties for surmounting nanometer gold bar.Nanogold cone is for the first time by it has been found that be the by-product synthesized as nanometer gold bar
Existing for object, researcher is calculated using FDTD scheduling theory research shows that the surface plasma volume property that nanogold is bored is higher than and receives
The surface plasma volume property of the golden stick of rice.Theoretical calculation shows nanogold cone in necks such as surface plasma body resonant vibration, Raman enhancings
Domain has great researching value, will play huge promotion to the application of bio-imaging, electrooptical device, treatment of cancer etc.
Effect.
At present Raman enhancing mechanism generally accept there are mainly two types of mode: physics enhancement mode and Chemical enhancement mode.
Physics enhancement mode is also known as surface plasma body resonant vibration model；Chemical enhancement mode is mainly based upon technical face binding molecule
The enhancing of the Raman of chemical property and molecule and the environment on surface.Physics enhancing both model and Chemical enhancement model are had any different,
It is complementary to one another again simultaneously, generally in Raman enhancing, the two is existed simultaneously.People research Raman enhancing mechanism guidance under,
Synthesize the Nano sol of various forms, such as nanometer rods, nano wire, nano flower, triangle and square.Core-shell type nano structure
Research hotspot is had become, gold and silver core-shell structure is research and applies more core-shell structure, it combines the partial size of aurosol
Uniformly, the characteristics of stabilization, good biocompatibility, while possessing the high Raman enhancement effect of silver again, therefore the nucleocapsid knot that silver is covered with gold leaf
Structure has very big researching value.
What silver-colored gold filled core-shell structure research was hotter at present is concentrated mainly on spherical and rodlike core-shell structure, similar to nanometer
Golden taper and starlike core-shell structure are relatively fewer.The gold and silver core-shell structure surface that method prepares at present is by a thin layer of
Silver covering, can exist on subsequent some bio-modifications influences.
Summary of the invention
For the above-mentioned prior art, the present invention provides a kind of core-shell structure nanometer particles and preparation method thereof.The present invention
Core-shell structure nanometer particle, shape be similar to nanogold cone structure, have extremely strong surface plasma body resonant vibration effect；Knot
Structure surface covers one layer of silver-colored film, has the extremely strong Raman reinforcing effect of Nano silver grain；For the gold and silver nucleocapsid convenient for modification
Structure is convenient for subsequent application study；For the nanoparticle of special sex modification, the specific end of 1-dimention nano particle is realized
Modification, for the head to head configuration (head-to-head) haveing excellent performance.Method of the invention utilizes the single-stranded protection of the DNA with sulfydryl
Nanometer gold bar as core, under certain environment, received using reducing agent L-AA reduction silver nitrate growth preparation silver nucleocapsid covered with gold leaf
Rice corpuscles, the core-shell structure shape are bored similar to nanogold, and the core-shell structure whole body is protected by the end DNA of the naked leakage in part, both ends
The covering of silver nanoparticle layer is relatively thin, and most of naked leakage outside, can not only play a protective role, but also can use base pair complementarity realization
The preparation of special construction, core-shell structure property are stablized, and have huge application in fields such as bio-light electronics, biological nano detections
Value.
The present invention is achieved by the following technical solutions:
A kind of core-shell structure nanometer particle is prepared by the following method to obtain:
(1) preparation of nanometer gold bar: at room temperature, by the 0.1molL of 10~15ml-1CTAB solution be added to reaction hold
In device (20ml round-bottomed flask), the 50mmolL of 50~80ul is added-1HAuCl4Solution quickly stirs 1 minute；Then
It is rapidly added the 10mmolL of 0.6~1.0ml-1NaBH4Solution, quickly stirring 1 minute, obtains crystal seed；
By the 0.1molL of 30~40ml-1CTAB solution be added in another reaction vessel (50ml round-bottomed flask), fit
When (being added while stirring, to be uniformly mixed) under speed stirring, the 50mmolL of 230~250ul is added-1HAuCl4Solution,
Then the 10mmolL of 230~250ul is added-1Silver nitrate solution, add the 0.1molL of 150~180ul-1L-
AA solution (ascorbic acid solution), solution is become colorless by light yellow at this time, is eventually adding 90ul crystal seed, is stirred 1 minute, is stood
4 hours, solution colour became taupe from colourless, and nanometer gold bar is made；
The NaBH4Solution need to use preceding preparation, and preparation, which is placed in -20 DEG C of refrigerators, places 10 minutes, for use；
(2) DNA modification of nanometer gold bar: at room temperature, 8000~10000rpm of nanometer gold bar of above-mentioned preparation is centrifuged 10
~20mins, reject supernatant are dissolved in 0.2% (mass percent) SDS solution, with hydrochloric acid conditioning solution pH to 3 ± 0.5,
5 × tbe buffer liquid is added, so that its final concentration of 1 × TBE, is then added NaCl solution to the final concentration of 500mmol of NaCl
L-1, it is eventually adding sulfhydrylation DNA, the weight ratio of sulfhydrylation DNA and nanometer gold bar is 500~10000:1, is mixed, and stands 5 points
Clock obtains the nanometer gold bar that sulfhydrylation DNA stablizes protection；
The sequence of the sulfhydrylation DNA is that (5 ' ends are sulfydryl to 5 ' SH-AAA AAA AAA AAA AAA, and nucleotide sequence is such as
Shown in SEQ ID NO.1)；
Sulfhydrylation DNA used in the present invention (sulfhydrylation DNA sequence dna is 5 ' SH-AAA AAA AAA AAA AAA), entrusts Shanghai
The synthesis of Sheng Gong bioengineering limited liability company, purifies through HPLC, is freeze-dried powder, is dissolved in ultrapure water before use, spare；
(3) by sulfhydrylation DNA obtained above stablize protection 8000~10000rpm of nanometer gold bar centrifugation 10~
20mins is dissolved in 0.05M CTAB solution with removing extra discrete sulfhydrylation DNA in solution, and 1%SDS solution, which is added, to be made
SDS final concentration of 0.05~0.1% (mass fraction), add silver nitrate solution (molar ratio of gold, silver is in 1:0.8~1:
1.5), be eventually adding reducing agent L-AA solution (silver is 1:12~1:18 with the molar ratio of L-AA), mix, stand 3 hours to get
Core-shell structure nanometer particle --- silver-colored gold-covered nano core-shell structure nanometer particle.
Core-shell structure nanometer particle of the invention has extraordinary stability, NaCl is added in the solution, concentration reaches
It at 1 mole every liter, still keeps being stabilized, aggregate and precipitate does not occur, be convenient for subsequent correlative study.Au-Ag core-shell structure
Transmission electron microscope is as shown in Fig. 2, the silver covering at core-shell structure both ends is very thin, therefore the connected DNA of nanometer gold bar as core
Single-stranded meeting major part is exposed outside, is on the one hand used as blocking group, stablizes core-shell structure property, on the other hand can use
The base pairing principle of DNA double helical structure realizes the terminal modified one-dimensional of core-shell structure two.Different from general gold nano
The nanoparticles such as particle, gold and silver core-shell structure can not achieve special sex modification, it is difficult to realize similar because its modification is non-directional
(head-to-head) this structure in head to head.Researcher calculates the nanometer the study found that sharp using FDTD scheduling theory
Particle surface electron concentration, what surface plasma body resonant vibration effect was better than nanoparticle delays blunt region.Head to head nanostructure is
The close structure of two nanoparticle sharp parts can be realized stronger nanoparticle surface plasma resonance.The present invention
Core-shell structure nanometer particle therefore received research shows that nanoparticle tip portion has higher surface plasma bulk effect
The directed modification of rice corpuscles has huge application value in fields such as bio-light electronics, biological nano detections.
Detailed description of the invention
Fig. 1: core-shell structure prepares simplified schematic diagram.
Fig. 2: Au-Ag core-shell structure projects electron microscope.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.
Instrument involved in following embodiments, reagent, material etc. are unless otherwise noted existing in the prior art
Conventional instrument, reagent, material etc., can be obtained by regular commercial sources.Experimental method involved in following embodiments, inspection
Survey method etc. is unless otherwise noted existing routine experiment method in the prior art, detection method etc..
Embodiment 1 prepares core-shell structure nanometer particle
Preparation process is as shown in Figure 1, steps are as follows:
(1) preparation of nanometer gold bar: at room temperature, by the 0.1molL of 10ml-1CTAB solution be added to container (20ml
Round-bottomed flask) in, add the 50mmolL of 50ul-1HAuCl4Solution quickly stirs 1 minute；Then it is rapidly added
The 10mmolL of 0.6ml-1NaBH4Solution, quickly stirring 1 minute, obtains crystal seed；
By the 0.1molL of 30ml-1CTAB solution be added in another container (50ml round-bottomed flask), appropriate speed is stirred
It mixes down and (is added while stirring, to be uniformly mixed), the 50mmolL of 234ul is added-1HAuCl4Then 234ul is added in solution
10mmolL-1Silver nitrate solution, add the 0.1molL of 150ul-1L-AA solution (ascorbic acid solution), this
When solution become colorless by light yellow, be eventually adding 90ul crystal seed, stir 1 minute, stand 4 hours, solution colour is by no discoloration
For taupe, nanometer gold bar is made；
The NaBH4Solution, using preceding preparation, preparation, which is placed in -20 DEG C of refrigerators, places 10 minutes, for use；
(2) DNA modification of nanometer gold bar: at room temperature, the nanometer gold bar 8000rpm of above-mentioned preparation is centrifuged 15min, reject
Supernatant is dissolved in 0.2% (mass percent) SDS solution, with hydrochloric acid conditioning solution pH to 3,5 × tbe buffer liquid is added, makes
Its final concentration of 1 × TBE is obtained, NaCl solution is then added to the final concentration of 500mmolL of NaCl-1, it is eventually adding sulfhydrylation
DNA (weight ratio of sulfhydrylation DNA and nanometer gold bar is 2000:1), mixes, stands 5 minutes, obtain sulfhydrylation DNA and stablize protection
Nanometer gold bar；
Sulfhydrylation DNA used in the present invention, 5 ' SH-AAA AAA AAA AAA AAA of sequence, the raw work biology work in commission Shanghai
The synthesis of journey limited liability company, purifies through HPLC, is freeze-dried powder, is dissolved in ultrapure water before use, spare；
The synthesis of Shanghai Sheng Gong bioengineering limited liability company is entrusted, is purified through HPLC, is freeze-dried powder, is dissolved in front of use
It is spare in ultrapure water；
(3) sulfhydrylation DNA obtained above is stablized into the nanometer gold bar 8000rpm centrifugation 15min of protection to remove solution
In extra discrete dna, be dissolved in 0.05M CTAB solution, 1%SDS solution, which is added, makes (the quality point of SDS final concentration of 0.05%
Number), silver nitrate solution (molar ratio of gold, silver is in 1:1) is added, being eventually adding reducing agent L-AA solution, (silver rubs with L-AA's
You are than being 1:15), mix, stand 3 hours to get core-shell structure nanometer particle --- silver-colored gold-covered nano nuclear shell structure nano grain
Son.
Core-shell structure nanometer particle of the invention has extraordinary stability, NaCl is added in the solution, concentration reaches
It at 1 mole every liter, still keeps being stabilized, aggregate and precipitate does not occur, be convenient for subsequent correlative study.Au-Ag core-shell structure
Transmission electron microscope is as shown in Fig. 2, the silver covering at core-shell structure both ends is very thin, therefore the connected DNA of nanometer gold bar as core
Single-stranded meeting major part is exposed outside, is on the one hand used as blocking group, stablizes core-shell structure property, on the other hand can use
The base pairing principle of DNA double helical structure realizes the terminal modified one-dimensional of core-shell structure two.Different from general gold nano
The nanoparticles such as particle, gold and silver core-shell structure can not achieve special sex modification, it is difficult to realize similar because its modification is non-directional
(head-to-head) this structure in head to head.Researcher calculates the nanometer the study found that sharp using FDTD scheduling theory
Particle surface electron concentration, what surface plasma body resonant vibration effect was better than nanoparticle delays blunt region.Head to head nanostructure is
The close structure of two nanoparticle sharp parts can be realized stronger nanoparticle surface plasma resonance.The present invention
Core-shell structure nanometer particle therefore received research shows that nanoparticle tip portion has higher surface plasma bulk effect
The directed modification of rice corpuscles has huge application value in fields such as bio-light electronics, biological nano detections.
Embodiment 2 prepares core-shell structure nanometer particle
Steps are as follows:
(1) preparation of nanometer gold bar: at room temperature, by the 0.1molL of 15ml-1CTAB solution be added to reaction vessel
In (20ml round-bottomed flask), the 50mmolL of 80ul is added-1HAuCl4Solution quickly stirs 1 minute；Then add rapidly
Enter the 10mmolL of 1.0ml-1NaBH4Solution, quickly stirring 1 minute, obtains crystal seed；
By the 0.1molL of 40ml-1CTAB solution be added in another reaction vessel (50ml round-bottomed flask), appropriate speed
It (is added while stirring, to be uniformly mixed) under degree stirring, the 50mmolL of 250ul is added-1HAuCl4Then solution is added
The 10mmolL of 250ul-1Silver nitrate solution, add the 0.1molL of 180ul-1L-AA solution (ascorbic acid is molten
Liquid), solution is become colorless by light yellow at this time, is eventually adding 90ul crystal seed, is stirred 1 minute, stand 4 hours, solution colour by
It is colourless to become taupe, nanometer gold bar is made；
The NaBH4Solution need to use preceding preparation, and preparation, which is placed in -20 DEG C of refrigerators, places 10 minutes, for use；
(2) DNA modification of nanometer gold bar: at room temperature, the nanometer gold bar 10000rpm of above-mentioned preparation is centrifuged 20mins, is abandoned
It except supernatant, is dissolved in 0.2% (mass percent) SDS solution, with hydrochloric acid conditioning solution pH to 3,5 × tbe buffer liquid is added,
So that its final concentration of 1 × TBE, is then added NaCl solution to the final concentration of 500mmolL of NaCl-1, it is eventually adding sulfhydrylation
The weight ratio of DNA, sulfhydrylation DNA and nanometer gold bar is 10000:1, is mixed, and stands 5 minutes, obtains sulfhydrylation DNA and stablizes protection
Nanometer gold bar；
(3) the sulfhydrylation DNA obtained above nanometer gold bar 10000rpm for stablizing protection is centrifuged 20mins, it is molten to remove
Extra discrete sulfhydrylation DNA, is dissolved in 0.05M CTAB solution in liquid, and 1%SDS solution, which is added, makes SDS final concentration of 0.1%
(mass fraction) adds silver nitrate solution (molar ratio of gold, silver is in 1:1.5), be eventually adding reducing agent L-AA solution (silver with
The molar ratio of L-AA is 1:18), mix, stand 3 hours to get core-shell structure nanometer particle --- silver-colored gold-covered nano core-shell structure
Nanoparticle.
Embodiment 3 prepares core-shell structure nanometer particle
Steps are as follows:
(1) preparation of nanometer gold bar: at room temperature, by the 0.1molL of 12ml-1CTAB solution be added to reaction vessel
In (20ml round-bottomed flask), the 50mmolL of 60ul is added-1HAuCl4Solution quickly stirs 1 minute；Then add rapidly
Enter the 10mmolL of 0.8ml-1NaBH4Solution, quickly stirring 1 minute, obtains crystal seed；
By the 0.1molL of 35ml-1CTAB solution be added in another reaction vessel (50ml round-bottomed flask), appropriate speed
It (is added while stirring, to be uniformly mixed) under degree stirring, the 50mmolL of 240ul is added-1HAuCl4Then solution is added
The 10mmolL of 240ul-1Silver nitrate solution, add the 0.1molL of 170ul-1L-AA solution (ascorbic acid is molten
Liquid), solution is become colorless by light yellow at this time, is eventually adding 90ul crystal seed, is stirred 1 minute, stand 4 hours, solution colour by
It is colourless to become taupe, nanometer gold bar is made；
The NaBH4Solution need to use preceding preparation, and preparation, which is placed in -20 DEG C of refrigerators, places 10 minutes, for use；
(3) DNA modification of nanometer gold bar: at room temperature, the nanometer gold bar 8000rpm of above-mentioned preparation is centrifuged 20mins, is abandoned
It except supernatant, is dissolved in 0.2% (mass percent) SDS solution, with hydrochloric acid conditioning solution pH to 3,5 × tbe buffer liquid is added,
So that its final concentration of 1 × TBE, is then added NaCl solution to the final concentration of 500mmolL of NaCl-1, it is eventually adding sulfhydrylation
The weight ratio of DNA, sulfhydrylation DNA and nanometer gold bar is 5000:1, is mixed, and stands 5 minutes, obtains sulfhydrylation DNA and stablizes protection
Nanometer gold bar；
(3) the sulfhydrylation DNA obtained above nanometer gold bar 8000rpm for stablizing protection is centrifuged 20mins, it is molten to remove
Extra discrete sulfhydrylation DNA, is dissolved in 0.05M CTAB solution in liquid, and 1%SDS solution, which is added, keeps SDS final concentration of
0.08% (mass fraction) adds silver nitrate solution (molar ratio of gold, silver is in 1:0.8), it is molten to be eventually adding reducing agent L-AA
Liquid (molar ratio of silver and L-AA are 1:12), mixes, stands 3 hours to get core-shell structure nanometer particle --- silver-colored gold-covered nano
Core-shell structure nanometer particle.
Claims (6)
1. a kind of core-shell structure nanometer particle, it is characterised in that: be prepared by the following method to obtain:
(1) preparation of nanometer gold bar: at room temperature, by the 0.1molL of 10~15ml-1CTAB solution be added to reaction vessel
In, add the 50mmolL of 50~80ul-1HAuCl4Solution stirs 1 minute；Then it is added 0.6~1.0ml's
10mmol·L-1NaBH4Solution stirs 1 minute, obtains crystal seed；
By the 0.1molL of 30~40ml-1CTAB solution be added in another reaction vessel, under stirring, be added 230~
The 50mmolL of 250ul-1HAuCl4Then the 10mmolL of 230~250ul is added in solution-1Silver nitrate solution, then plus
Enter the 0.1molL of 150~180ul-1L-AA solution, be eventually adding 90ul crystal seed, stir 1 minute, stand 4 hours, be made
Nanometer gold bar；
(2) DNA modification of nanometer gold bar: at room temperature, by 8000~10000rpm of nanometer gold bar of above-mentioned preparation centrifugation 10~
20min, reject supernatant are dissolved in 0.2%SDS solution, with hydrochloric acid conditioning solution pH to 3 ± 0.5, tbe buffer liquid are added, makes
Its final concentration of 1 × TBE is obtained, NaCl solution is then added to the final concentration of 500mmolL of NaCl-1, it is eventually adding sulfhydrylation
The weight ratio of DNA, sulfhydrylation DNA and nanometer gold bar is 500~10000:1, is mixed, and stands 5 minutes, it is steady to obtain sulfhydrylation DNA
Surely the nanometer gold bar protected；
(3) the sulfhydrylation DNA obtained above 8000~10000rpm of nanometer gold bar for stablizing protection is centrifuged 10~20min, it is molten
For solution in 0.05M CTAB solution, SDS solution, which is added, makes SDS final concentration of 0.05~0.1%, adds silver nitrate solution, gold,
The molar ratio of silver is eventually adding reducing agent L-AA solution in 1:0.8~1:1.5, and the silver-colored molar ratio with L-AA is 1:12~1:18,
Mix, stand 3 hours to get.
2. core-shell structure nanometer particle according to claim 1, it is characterised in that: the sequence of the sulfhydrylation DNA is 5 '
SH-AAA AAA AAA AAA AAA。
3. core-shell structure nanometer particle according to claim 1 or 2, it is characterised in that: steps are as follows:
(1) preparation of nanometer gold bar: at room temperature, by the 0.1molL of 10ml-1CTAB solution be added in container, add
The 50mmolL of 50ul-1HAuCl4Solution quickly stirs 1 minute；Then it is rapidly added the 10mmolL of 0.6ml-1NaBH4
Solution, quickly stirring 1 minute, obtains crystal seed；
By the 0.1molL of 30ml-1CTAB solution be added in another container, under stirring, the 50mmolL of 234ul is added-1
HAuCl4Then the 10mmolL of 234ul is added in solution-1Silver nitrate solution, add the 0.1molL of 150ul-1's
L-AA solution is eventually adding 90ul crystal seed, stirs 1 minute, stands 4 hours, and nanometer gold bar is made；
The NaBH4Solution, using preceding preparation, preparation, which is placed in -20 DEG C of refrigerators, places 10 minutes, for use；
(2) DNA modification of nanometer gold bar: at room temperature, the nanometer gold bar 8000rpm of above-mentioned preparation is centrifuged 15min, reject supernatant
Liquid is dissolved in 0.2%SDS solution, and with hydrochloric acid conditioning solution pH to 3,5 × tbe buffer liquid is added so that its final concentration of 1 ×
Then NaCl solution is added to the final concentration of 500mmolL of NaCl in TBE-1, be eventually adding sulfhydrylation DNA, sulfhydrylation DNA with receive
The weight ratio of the golden stick of rice is 2000:1, mixes, stands 5 minutes, obtains the nanometer gold bar that sulfhydrylation DNA stablizes protection；
(3) the nanometer gold bar 8000rpm centrifugation 15min for sulfhydrylation DNA obtained above being stablized protection is more in solution to remove
Remaining discrete dna is dissolved in 0.05M CTAB solution, and 1%SDS solution, which is added, makes SDS final concentration of 0.05%, adds nitric acid
Silver-colored solution, the molar ratio of gold, silver are eventually adding reducing agent L-AA solution in 1:1, and the silver-colored molar ratio with L-AA is 1:15, mix,
Stand 3 hours to get.
4. a kind of preparation method of core-shell structure nanometer particle, it is characterised in that: the following steps are included:
(1) preparation of nanometer gold bar: at room temperature, by the 0.1molL of 10~15ml-1CTAB solution be added to reaction vessel
In, add the 50mmolL of 50~80ul-1HAuCl4Solution stirs 1 minute；Then it is added 0.6~1.0ml's
10mmol·L-1NaBH4Solution stirs 1 minute, obtains crystal seed；
By the 0.1molL of 30~40ml-1CTAB solution be added in another reaction vessel, under stirring, be added 230~
The 50mmolL of 250ul-1HAuCl4Then the 10mmolL of 230~250ul is added in solution-1Silver nitrate solution, then plus
Enter the 0.1molL of 150~180ul-1L-AA solution, be eventually adding 90ul crystal seed, stir 1 minute, stand 4 hours, be made
Nanometer gold bar；
(2) DNA modification of nanometer gold bar: at room temperature, by 8000~10000rpm of nanometer gold bar of above-mentioned preparation centrifugation 10~
20min, reject supernatant are dissolved in 0.2%SDS solution, with hydrochloric acid conditioning solution pH to 3 ± 0.5, tbe buffer liquid are added, makes
Its final concentration of 1 × TBE is obtained, NaCl solution is then added to the final concentration of 500mmolL of NaCl-1, it is eventually adding sulfhydrylation
The weight ratio of DNA, sulfhydrylation DNA and nanometer gold bar is 500~10000:1, is mixed, and stands 5 minutes, it is steady to obtain sulfhydrylation DNA
Surely the nanometer gold bar protected；
(3) the sulfhydrylation DNA obtained above 8000~10000rpm of nanometer gold bar for stablizing protection is centrifuged 10~20min, it is molten
For solution in 0.05M CTAB solution, SDS solution, which is added, makes SDS final concentration of 0.05~0.1%, adds silver nitrate solution, gold,
The molar ratio of silver is eventually adding reducing agent L-AA solution in 1:0.8~1:1.5, and the silver-colored molar ratio with L-AA is 1:12~1:18,
Mix, stand 3 hours to get.
5. the preparation method of core-shell structure nanometer particle according to claim 3, it is characterised in that: the sulfhydrylation DNA
Sequence be 5 ' SH-AAA AAA AAA AAA AAA.
6. the preparation method of core-shell structure nanometer particle according to claim 4 or 5, it is characterised in that: steps are as follows:
(1) preparation of nanometer gold bar: at room temperature, by the 0.1molL of 10ml-1CTAB solution be added in container, add
The 50mmolL of 50ul-1HAuCl4Solution quickly stirs 1 minute；Then it is rapidly added the 10mmolL of 0.6ml-1NaBH4
Solution, quickly stirring 1 minute, obtains crystal seed；
By the 0.1molL of 30ml-1CTAB solution be added in another container, under stirring, the 50mmolL of 234ul is added-1
HAuCl4Then the 10mmolL of 234ul is added in solution-1Silver nitrate solution, add the 0.1molL of 150ul-1's
L-AA solution is eventually adding 90ul crystal seed, stirs 1 minute, stands 4 hours, and nanometer gold bar is made；
The NaBH4Solution, using preceding preparation, preparation, which is placed in -20 DEG C of refrigerators, places 10 minutes, for use；
(2) DNA modification of nanometer gold bar: at room temperature, the nanometer gold bar 8000rpm of above-mentioned preparation is centrifuged 15min, reject supernatant
Liquid is dissolved in 0.2%SDS solution, and with hydrochloric acid conditioning solution pH to 3,5 × tbe buffer liquid is added so that its final concentration of 1 ×
Then NaCl solution is added to the final concentration of 500mmolL of NaCl in TBE-1, be eventually adding sulfhydrylation DNA, sulfhydrylation DNA with receive
The weight ratio of the golden stick of rice is 2000:1, mixes, stands 5 minutes, obtains the nanometer gold bar that sulfhydrylation DNA stablizes protection；
(3) the nanometer gold bar 8000rpm centrifugation 15min for sulfhydrylation DNA obtained above being stablized protection is more in solution to remove
Remaining discrete dna is dissolved in 0.05M CTAB solution, and 1%SDS solution, which is added, makes SDS final concentration of 0.05%, adds nitric acid
Silver-colored solution, the molar ratio of gold, silver are eventually adding reducing agent L-AA solution in 1:1, and the silver-colored molar ratio with L-AA is 1:15, mix,
Stand 3 hours to get.
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| CN108048906A (en) * | 2017-12-08 | 2018-05-18 | 中山大学 | A kind of DNA is oriented to gold nano-crystal and preparation method and application |
| CN108145176B (en) * | 2018-01-10 | 2019-05-31 | 云南大学 | A kind of autoreduction preparation method of gold nano ball-bar polymer |
| CN110625138B (en) * | 2019-10-30 | 2022-07-22 | 中山大学 | DNA-oriented gold-silver bimetallic nanoparticle and preparation method and application thereof |
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