CN107243629A - A kind of new type structure of hud nano-particle and preparation method thereof - Google Patents

A kind of new type structure of hud nano-particle and preparation method thereof Download PDF

Info

Publication number
CN107243629A
CN107243629A CN201710434566.9A CN201710434566A CN107243629A CN 107243629 A CN107243629 A CN 107243629A CN 201710434566 A CN201710434566 A CN 201710434566A CN 107243629 A CN107243629 A CN 107243629A
Authority
CN
China
Prior art keywords
solution
nanometer gold
gold bar
dna
adds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201710434566.9A
Other languages
Chinese (zh)
Other versions
CN107243629B (en
Inventor
石党委
翟逸
郭宝柱
赵秀敏
吴永坤
刘钦松
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SHANDONG BOAOKE BIOTECHNOLOGY CO Ltd
Original Assignee
SHANDONG BOAOKE BIOTECHNOLOGY CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SHANDONG BOAOKE BIOTECHNOLOGY CO Ltd filed Critical SHANDONG BOAOKE BIOTECHNOLOGY CO Ltd
Priority to CN201710434566.9A priority Critical patent/CN107243629B/en
Publication of CN107243629A publication Critical patent/CN107243629A/en
Application granted granted Critical
Publication of CN107243629B publication Critical patent/CN107243629B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05Metallic powder characterised by the size or surface area of the particles
    • B22F1/054Nanosized particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102Metallic powder coated with organic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

The invention discloses a kind of new type structure of hud nano-particle, preparation method is:(1) CTAB solution is added in container, adds HAuCl4Solution, 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 of the stable protections of sulfhydrylation DNA;(3) nanometer gold bar is centrifuged, be dissolved in CTAB solution, sequentially add SDS solution, silver nitrate solution, L AA solution, standing is produced.The nano-particle of the present invention, with extraordinary stability, the silver covering at core shell structure two ends is very thin, the connected single-stranded meeting major parts of DNA are 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

A kind of new type structure of hud nano-particle and preparation method thereof
Technical field
The present invention relates to a kind of new type structure of hud nano-particle and preparation method thereof, belong to nanobiology and nanometer medicine Thing field.
Background technology
Gold is extracted first as heavy metal material in B.C. 5th century, when gold is divided into less than 100nm sizes Golden nanometer particle becomes more precious when golden.Golden nanometer particle (gold nanoparticle) is the molecule for referring to gold, and its is straight Footpath is in 1~100nm, and golden nanometer particle has higher cloud density, dielectric property and catalytic action, with good biology Compatibility, can be combined, and do not influence its bioactivity with a variety of large biological molecules.Diameter Nano grade golden nanometer particle, Elementary cell is all the particle of microsize, and with the golden unexistent physical characteristic of many macroscopic views, such as optical effect, surface are imitated Should, small-size effect, Dielectric confinement effect, macro quanta tunnel effect and some other special effectses.Golden nanometer particle Special effects cause golden nanometer particle to be widely used in the research fields such as material, medical test, disease treatment.
Golden nanometer particle is deep to be had deep love for by researcher because of its excellent all manifold effect, and research is most sufficiently nanometer at present Gold goal and nanometer gold bar.Nanogold is bored as a kind of new golden nanometer particle, and early stage is not very due to its synthesis preparation method Maturation, therefore the property research of nanogold cone much also rests on theoretical research stage.Current researcher utilizes seed mediated growth method, By controlling the temperature factor in building-up 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 nano-particle.Stretching Nano-particle be optical research preferable nano-particle, its spectrum is adjusted by changing the draw ratio of particle.With nanogold Rod is compared, and the tip portion at two 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 first by it has been found that be the by-product that is synthesized as nanometer gold bar What thing was present, researcher shows that the surface plasma volume property of nanogold cone is higher than using the calculating research of FDTD scheduling theories and received The surface plasma volume property of the golden rod of rice.Theoretical calculation shows nanogold cone in necks such as surface plasma body resonant vibration, Raman enhancings Domain has great researching value, huge promotion will be played to the application in terms of bio-imaging, electrooptical device, treatment of cancer Effect.
What current Raman enhancing mechanism was generally accepted mainly has both of which:Physics enhancement mode and Chemical enhancement pattern. Physics enhancement mode is also known as surface plasma body resonant vibration model;Chemical enhancement pattern is mainly based upon technical face binding molecule The Raman enhancing of chemical property and molecule and the environment on surface.Physics strengthens both model and Chemical enhancement model and had any different, It is complementary to one another again simultaneously, typically in Raman enhancing, the two exists simultaneously.People under the enhanced mechanism guiding of research Raman, Synthesize the Nano sol of various forms, such as nanometer rods, nano wire, nano flower, triangle and square.Core-shell type nano structure Turn into study hotspot, gold and silver core shell structure is research and applies more core shell structures, and it combines the particle diameter of aurosol Uniformly, stably, good biocompatibility the characteristics of, while possess the high Raman enhancement effect of silver again, therefore silver nucleocapsid knot 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 bar-shaped 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 current method is prepared is by a thin layer of Silver covering, can exist on some follow-up bio-modifications influences.
The content of the invention
For above-mentioned prior art, the invention provides a kind of new type structure of hud nano-particle and preparation method thereof.This The new type structure of hud nano-particle of invention, profile is similar to the structure that nanogold is bored, common with extremely strong surface plasma Shake effect;Body structure surface covers one layer of silver-colored film, with the Raman enhancing effect that Nano silver grain is extremely strong;For ease of modification Gold and silver core shell structure, is easy to follow-up application study;For the nano-particle of special sex modification, the spy of 1-dimention nano particle is realized Different in nature end modification, is the head to head configuration (head-to-head) of excellent performance.The method of the present invention utilizes the DNA with sulfydryl The nanometer gold bar of single-stranded protection is as core, under certain environment, and silver bag is prepared using reducing agent L-AA reduction silver nitrate growths Golden core-shell nano, the core shell structure profile is bored similar to nanogold, and the core shell structure whole body is protected by the DNA ends of the naked leakage in part Shield, two ends silver nanoparticle layer covering is relatively thin, and most of naked leakage outside, can both play a protective role, base complementrity can be utilized again The preparation of special construction is realized in pairing, and core shell structure property is stable, is had in fields such as bio-light electronics, biological nano detections huge Big application value.
The present invention is achieved by the following technical solutions:
A kind of new type structure of hud nano-particle, is prepared by the following method and obtains:
(1) preparation of nanometer gold bar:At room temperature, by 10~15ml 0.1molL-1CTAB solution be added to reaction hold In device (20ml round-bottomed flasks), 50~80ul 50mmolL is added-1HAuCl4Solution, quick stirring 1 minute;Then It is rapidly added 0.6~1.0ml 10mmolL-1NaBH4Solution, quick stirring 1 minute, obtains crystal seed;
By 30~40ml 0.1molL-1CTAB solution be added in another reaction vessel (50ml round-bottomed flasks), fit When (being added while stirring, with well mixed) under speed stirring, 230~250ul 50mmolL is added-1HAuCl4Solution, Then 230~250ul 10mmolL is added-1Silver nitrate solution, add 150~180ul 0.1molL-1L- AA solution (ascorbic acid solution), now solution become colorless by light yellow, be eventually adding 90ul crystal seeds, stir 1 minute, stand 4 hours, solution colour was changed into taupe from colourless, and nanometer gold bar is made;
The NaBH4Solution, need to use to be placed in after preceding preparation, preparation in -20 DEG C of refrigerators and place 10 minutes, stand-by;
(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 is dissolved in 0.2% (mass percent) SDS solution, with hydrochloric acid conditioning solution pH to 3 ± 0.5, Add 5 × tbe buffer liquid so that its final concentration of 1 × TBE, then add 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, mix, stand 5 points Clock, obtains the nanometer gold bar of the stable protections of sulfhydrylation DNA;
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 (sulfhydrylation DNA sequence dna is 5 ' SH-AAA AAA AAA AAA AAA) of the invention, entrusts Shanghai Sheng Gong bioengineering limited company synthesizes, and is purified through HPLC, is to be dissolved in ultra-pure water before freeze-dried powder, use, standby;
(3) 8000~10000rpm of the nanometer gold bar centrifugations 10 stably protected sulfhydrylation DNA obtained above~ 20mins, to remove unnecessary discrete sulfhydrylation DNA in solution, is dissolved in 0.05M CTAB solution, and adding 1%SDS solution makes SDS final concentration of 0.05~0.1% (mass fraction), adding silver nitrate solution, (mol ratio of gold, silver is 1:0.8~1: 1.5), being eventually adding reducing agent L-AA solution, (silver and L-AA mol ratio are 1:12~1:18), mix, stand 3 hours, produce New type structure of hud nano-particle --- silver-colored gold-covered nano core-shell structure nanometer particle.
The new type structure of hud nano-particle of the present invention, with extraordinary stability, adds NaCl, concentration in the solution When reaching 1 mole every liter, still keep being stabilized, do not occur aggregate and precipitate, be easy to follow-up correlative study.Au-Ag nucleocapsid knots The transmission electron microscope of structure is as shown in Fig. 2 the silver covering at core shell structure two ends is very thin, therefore is connected as the nanometer gold bar of core The single-stranded meeting major parts of DNA are exposed outside, on the one hand as blocking group, make core shell structure property stable, on the other hand can profit With the base pairing principle of DNA double helical structure, the terminal modified one-dimensional of core shell structure two is realized.Different from general Jenner The nano-particles such as rice grain, gold and silver core shell structure, because its modification is non-directional, it is impossible to realize special sex modification, it is difficult to realize class It is similar to head to head (head-to-head) this structure.Researcher calculates research using FDTD scheduling theories and found, sharp receives Rice corpuscles surface electronic is concentrated, and surface plasma body resonant vibration effect is better than the slow blunt region of nano-particle.Head to head nanostructured It is the close structure of two nano-particle sharp parts, stronger nanoparticle surface plasma resonance can be realized.This hair Bright new type structure of hud nano-particle, research shows that nano-particle tip portion has higher surface plasma bulk effect, Therefore the directed modification of nano-particle has huge application value in fields such as bio-light electronics, biological nano detections.
Brief description of the drawings
Fig. 1:Core shell structure prepares simplified schematic diagram.
Fig. 2:Au-Ag core shell structures project electron microscope.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Involved instrument, reagent, material etc. in following embodiments, are existing in the prior art unless otherwise noted Conventional instrument, reagent, material etc., can be obtained by regular commercial sources.Involved experimental method in following embodiments, inspection Survey method etc., is existing normal experiment method in the prior art, detection method etc. unless otherwise noted.
Embodiment 1 prepares new type structure of hud nano-particle
Preparation process is as shown in figure 1, step is as follows:
(1) preparation of nanometer gold bar:At room temperature, by 10ml 0.1molL-1CTAB solution be added to container (20ml Round-bottomed flask) in, add 50ul 50mmolL-1HAuCl4Solution, quick stirring 1 minute;Then it is rapidly added 0.6ml 10mmolL-1NaBH4Solution, quick stirring 1 minute, obtains crystal seed;
By 30ml 0.1molL-1CTAB solution be added in another container (50ml round-bottomed flasks), appropriate speed is stirred Mix down and (add while stirring, with well mixed), add 234ul 50mmolL-1HAuCl4Solution, then adds 234ul 10mmolL-1Silver nitrate solution, add 150ul 0.1molL-1L-AA solution (ascorbic acid solution), this When solution become colorless by light yellow, be eventually adding 90ul crystal seeds, stir 1 minute, stand 4 hours, solution colour is by without discoloration For taupe, nanometer gold bar is made;
The NaBH4Solution, is prepared using preceding, is placed in -20 DEG C of refrigerators and places 10 minutes after preparation, stand-by;
(2) DNA modification of nanometer gold bar:At room temperature, the nanometer gold bar 8000rpm of above-mentioned preparation is centrifuged into 15min, reject Supernatant, is dissolved in 0.2% (mass percent) SDS solution, with hydrochloric acid conditioning solution pH to 3, adds 5 × tbe buffer liquid, 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 sulfhydrylation DNA and nanometer gold bar is 2000 to DNA:1), mix, stand 5 minutes, obtain the stable protections of sulfhydrylation DNA Nanometer gold bar;
Sulfhydrylation DNA used of the invention, sequence is 5 ' SH-AAA AAA AAA AAA AAA, the biological work of commission Shanghai life work Journey limited company synthesizes, and is purified through HPLC, is to be dissolved in ultra-pure water before freeze-dried powder, use, standby;
The synthesis of Shanghai Sheng Gong bioengineering limited company is entrusted, is purified through HPLC, is to be dissolved in before freeze-dried powder, use It is standby in ultra-pure water;
(3) the nanometer gold bar 8000rpm of the stable protections of sulfhydrylation DNA obtained above is centrifuged 15min to remove solution In unnecessary discrete dna, be dissolved in 0.05M CTAB solution, adding 1%SDS solution makes the (quality point of SDS final concentration of 0.05% Number), adding silver nitrate solution, (mol ratio of gold, silver is 1:1), being eventually adding reducing agent L-AA solution, (silver rubs with L-AA's You are than being 1:15), mix, stand 3 hours, produce new type structure of hud nano-particle --- silver-colored gold-covered nano nuclear shell structure nano Particle.
The new type structure of hud nano-particle of the present invention, with extraordinary stability, adds NaCl, concentration in the solution When reaching 1 mole every liter, still keep being stabilized, do not occur aggregate and precipitate, be easy to follow-up correlative study.Au-Ag nucleocapsid knots The transmission electron microscope of structure is as shown in Fig. 2 the silver covering at core shell structure two ends is very thin, therefore is connected as the nanometer gold bar of core The single-stranded meeting major parts of DNA are exposed outside, on the one hand as blocking group, make core shell structure property stable, on the other hand can profit With the base pairing principle of DNA double helical structure, the terminal modified one-dimensional of core shell structure two is realized.Different from general Jenner The nano-particles such as rice grain, gold and silver core shell structure, because its modification is non-directional, it is impossible to realize special sex modification, it is difficult to realize class It is similar to head to head (head-to-head) this structure.Researcher calculates research using FDTD scheduling theories and found, sharp receives Rice corpuscles surface electronic is concentrated, and surface plasma body resonant vibration effect is better than the slow blunt region of nano-particle.Head to head nanostructured It is the close structure of two nano-particle sharp parts, stronger nanoparticle surface plasma resonance can be realized.This hair Bright new type structure of hud nano-particle, research shows that nano-particle tip portion has higher surface plasma bulk effect, Therefore the directed modification of nano-particle has huge application value in fields such as bio-light electronics, biological nano detections.
Embodiment 2 prepares new type structure of hud nano-particle
Step is as follows:
(1) preparation of nanometer gold bar:At room temperature, by 15ml 0.1molL-1CTAB solution be added to reaction vessel In (20ml round-bottomed flasks), 80ul 50mmolL is added-1HAuCl4Solution, quick stirring 1 minute;Then it is rapid to add Enter 1.0ml 10mmolL-1NaBH4Solution, quick stirring 1 minute, obtains crystal seed;
By 40ml 0.1molL-1CTAB solution be added in another reaction vessel (50ml round-bottomed flasks), appropriate speed (added while stirring, with well mixed) under degree stirring, add 250ul 50mmolL-1HAuCl4Solution, is then added 250ul 10mmolL-1Silver nitrate solution, add 180ul 0.1molL-1L-AA solution (ascorbic acid is molten Liquid), now solution is become colorless by light yellow, is eventually adding 90ul crystal seeds, is stirred 1 minute, stands 4 hours, solution colour by It is colourless to be changed into taupe, nanometer gold bar is made;
The NaBH4Solution, need to use to be placed in after preceding preparation, preparation in -20 DEG C of refrigerators and place 10 minutes, stand-by;
(2) DNA modification of nanometer gold bar:At room temperature, the nanometer gold bar 10000rpm of above-mentioned preparation is centrifuged into 20mins, abandoned Except supernatant, it is dissolved in 0.2% (mass percent) SDS solution, with hydrochloric acid conditioning solution pH to 3, adds 5 × tbe buffer liquid, So that its final concentration of 1 × TBE, then adds 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, mix, stand 5 minutes, obtain the stable protections of sulfhydrylation DNA Nanometer gold bar;
(3) the nanometer gold bar 10000rpm by the stable protections of sulfhydrylation DNA obtained above centrifuges 20mins, molten to remove Unnecessary discrete sulfhydrylation DNA, is dissolved in 0.05M CTAB solution in liquid, and adding 1%SDS solution makes SDS final concentration of 0.1% (mass fraction), adding silver nitrate solution, (mol ratio of gold, silver is 1:1.5), be eventually adding reducing agent L-AA solution (silver with L-AA mol ratio is 1:18), mix, stand 3 hours, produce new type structure of hud nano-particle --- silver-colored gold-covered nano nucleocapsid Structure nano particle.
Embodiment 3 prepares new type structure of hud nano-particle
Step is as follows:
(1) preparation of nanometer gold bar:At room temperature, by 12ml 0.1molL-1CTAB solution be added to reaction vessel In (20ml round-bottomed flasks), 60ul 50mmolL is added-1HAuCl4Solution, quick stirring 1 minute;Then it is rapid to add Enter 0.8ml 10mmolL-1NaBH4Solution, quick stirring 1 minute, obtains crystal seed;
By 35ml 0.1molL-1CTAB solution be added in another reaction vessel (50ml round-bottomed flasks), appropriate speed (added while stirring, with well mixed) under degree stirring, add 240ul 50mmolL-1HAuCl4Solution, is then added 240ul 10mmolL-1Silver nitrate solution, add 170ul 0.1molL-1L-AA solution (ascorbic acid is molten Liquid), now solution is become colorless by light yellow, is eventually adding 90ul crystal seeds, is stirred 1 minute, stands 4 hours, solution colour by It is colourless to be changed into taupe, nanometer gold bar is made;
The NaBH4Solution, need to use to be placed in after preceding preparation, preparation in -20 DEG C of refrigerators and place 10 minutes, stand-by;
(3) DNA modification of nanometer gold bar:At room temperature, the nanometer gold bar 8000rpm of above-mentioned preparation is centrifuged into 20mins, abandoned Except supernatant, it is dissolved in 0.2% (mass percent) SDS solution, with hydrochloric acid conditioning solution pH to 3, adds 5 × tbe buffer liquid, So that its final concentration of 1 × TBE, then adds 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, mix, stand 5 minutes, obtain the stable protections of sulfhydrylation DNA Nanometer gold bar;
(3) the nanometer gold bar 8000rpm by the stable protections of sulfhydrylation DNA obtained above centrifuges 20mins, molten to remove Unnecessary discrete sulfhydrylation DNA, is dissolved in 0.05M CTAB solution in liquid, and adding 1%SDS solution makes SDS final concentration of 0.08% (mass fraction), adding silver nitrate solution, (mol ratio of gold, silver is 1:0.8), it is eventually adding reducing agent L-AA molten (silver and L-AA mol ratio are 1 to liquid:12), mixing, stand 3 hours, produce new type structure of hud nano-particle --- silver is covered with gold leaf Nano-core-shell structure nano-particle.

Claims (6)

1. a kind of new type structure of hud nano-particle, it is characterised in that:It is prepared by the following method and obtains:
(1) preparation of nanometer gold bar:At room temperature, by 10~15ml 0.1molL-1CTAB solution be added to reaction vessel In, add 50~80ul 50mmolL-1HAuCl4Solution, is stirred 1 minute;Then add 0.6~1.0ml's 10mmol·L-1NaBH4Solution, stirs 1 minute, obtains crystal seed;
By 30~40ml 0.1molL-1CTAB solution be added in another reaction vessel, under stirring, add 230~ 250ul 50mmolL-1HAuCl4Solution, then adds 230~250ul 10mmolL-1Silver nitrate solution, then add Enter 150~180ul 0.1molL-1L-AA solution, be eventually adding 90ul crystal seeds, 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~ 20mins, reject supernatant is dissolved in 0.2%SDS solution, with hydrochloric acid conditioning solution pH to 3 ± 0.5, adds tbe buffer liquid, So that its final concentration of 1 × TBE, then adds 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 500~10000:1, mix, stand 5 minutes, obtain sulfhydrylation DNA steady Surely the nanometer gold bar protected;
(3) 8000~10000rpm of nanometer gold bar by the stable protections of sulfhydrylation DNA obtained above centrifuges 10~20mins, molten Solution is in 0.05M CTAB solution, and adding SDS solution makes SDS final concentration of 0.05~0.1%, adds silver nitrate solution, gold, The mol ratio of silver is 1:0.8~1:1.5, reducing agent L-AA solution is eventually adding, the silver-colored mol ratio with L-AA is 1:12~1:18, Mix, stand 3 hours, produce.
2. new type structure of hud nano-particle according to claim 1, it is characterised in that:The sequence of the sulfhydrylation DNA For 5 ' SH-AAA AAA AAA AAA AAA.
3. new type structure of hud nano-particle according to claim 1 or 2, it is characterised in that:Step is as follows:
(1) preparation of nanometer gold bar:At room temperature, by 10ml 0.1molL-1CTAB solution be added in container, add 50ul 50mmolL-1HAuCl4Solution, quick stirring 1 minute;Then it is rapidly added 0.6ml 10mmolL-1NaBH4 Solution, quick stirring 1 minute, obtains crystal seed;
By 30ml 0.1molL-1CTAB solution be added in another container, under stirring, add 234ul 50mmolL-1 HAuCl4Solution, then adds 234ul 10mmolL-1Silver nitrate solution, add 150ul 0.1molL-1's L-AA solution, is eventually adding 90ul crystal seeds, stirs 1 minute, stands 4 hours, and nanometer gold bar is made;
The NaBH4Solution, is prepared using preceding, is placed in -20 DEG C of refrigerators and places 10 minutes after preparation, stand-by;
(2) DNA modification of nanometer gold bar:At room temperature, the nanometer gold bar 8000rpm of above-mentioned preparation is centrifuged into 15min, reject supernatant Liquid, is dissolved in 0.2%SDS solution, with hydrochloric acid conditioning solution pH to 3, adds 5 × tbe buffer liquid so that its final concentration of 1 × TBE, then adds NaCl solution to the final concentration of 500mmolL of NaCl-1, sulfhydrylation DNA is eventually adding, sulfhydrylation DNA is with receiving The weight ratio of the golden rod of rice is 2000:1, mix, stand 5 minutes, obtain the nanometer gold bar of the stable protections of sulfhydrylation DNA;
(3) it is the nanometer gold bar 8000rpm centrifugations 15min of the stable protections of sulfhydrylation DNA obtained above is more in solution to remove Remaining discrete dna, is dissolved in 0.05M CTAB solution, and adding 1%SDS solution makes SDS final concentration of 0.05%, adds nitric acid Silver-colored solution, the mol ratio of gold, silver is 1:1, reducing agent L-AA solution is eventually adding, the silver-colored mol ratio with L-AA is 1:15, mix, 3 hours are stood, is produced.
4. a kind of preparation method of new type structure of hud nano-particle, it is characterised in that:Comprise the following steps:
(1) preparation of nanometer gold bar:At room temperature, by 10~15ml 0.1molL-1CTAB solution be added to reaction vessel In, add 50~80ul 50mmolL-1HAuCl4Solution, is stirred 1 minute;Then add 0.6~1.0ml's 10mmol·L-1NaBH4Solution, stirs 1 minute, obtains crystal seed;
By 30~40ml 0.1molL-1CTAB solution be added in another reaction vessel, under stirring, add 230~ 250ul 50mmolL-1HAuCl4Solution, then adds 230~250ul 10mmolL-1Silver nitrate solution, then add Enter 150~180ul 0.1molL-1L-AA solution, be eventually adding 90ul crystal seeds, 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~ 20mins, reject supernatant is dissolved in 0.2%SDS solution, with hydrochloric acid conditioning solution pH to 3 ± 0.5, adds tbe buffer liquid, So that its final concentration of 1 × TBE, then adds 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 500~10000:1, mix, stand 5 minutes, obtain sulfhydrylation DNA steady Surely the nanometer gold bar protected;
(3) 8000~10000rpm of nanometer gold bar by the stable protections of sulfhydrylation DNA obtained above centrifuges 10~20mins, molten Solution is in 0.05M CTAB solution, and adding SDS solution makes SDS final concentration of 0.05~0.1%, adds silver nitrate solution, gold, The mol ratio of silver is 1:0.8~1:1.5, reducing agent L-AA solution is eventually adding, the silver-colored mol ratio with L-AA is 1:12~1:18, Mix, stand 3 hours, produce.
5. the preparation method of new type structure of hud nano-particle according to claim 3, it is characterised in that:The sulfhydrylation DNA sequence is 5 ' SH-AAA AAA AAA AAA AAA.
6. the preparation method of the new type structure of hud nano-particle according to claim 4 or 5, it is characterised in that:Step is such as Under:
(1) preparation of nanometer gold bar:At room temperature, by 10ml 0.1molL-1CTAB solution be added in container, add 50ul 50mmolL-1HAuCl4Solution, quick stirring 1 minute;Then it is rapidly added 0.6ml 10mmolL-1NaBH4 Solution, quick stirring 1 minute, obtains crystal seed;
By 30ml 0.1molL-1CTAB solution be added in another container, under stirring, add 234ul 50mmolL-1 HAuCl4Solution, then adds 234ul 10mmolL-1Silver nitrate solution, add 150ul 0.1molL-1's L-AA solution, is eventually adding 90ul crystal seeds, stirs 1 minute, stands 4 hours, and nanometer gold bar is made;
The NaBH4Solution, is prepared using preceding, is placed in -20 DEG C of refrigerators and places 10 minutes after preparation, stand-by;
(2) DNA modification of nanometer gold bar:At room temperature, the nanometer gold bar 8000rpm of above-mentioned preparation is centrifuged into 15min, reject supernatant Liquid, is dissolved in 0.2%SDS solution, with hydrochloric acid conditioning solution pH to 3, adds 5 × tbe buffer liquid so that its final concentration of 1 × TBE, then adds NaCl solution to the final concentration of 500mmolL of NaCl-1, sulfhydrylation DNA is eventually adding, sulfhydrylation DNA is with receiving The weight ratio of the golden rod of rice is 2000:1, mix, stand 5 minutes, obtain the nanometer gold bar of the stable protections of sulfhydrylation DNA;
(3) it is the nanometer gold bar 8000rpm centrifugations 15min of the stable protections of sulfhydrylation DNA obtained above is more in solution to remove Remaining discrete dna, is dissolved in 0.05M CTAB solution, and adding 1%SDS solution makes SDS final concentration of 0.05%, adds nitric acid Silver-colored solution, the mol ratio of gold, silver is 1:1, reducing agent L-AA solution is eventually adding, the silver-colored mol ratio with L-AA is 1:15, mix, 3 hours are stood, is produced.
CN201710434566.9A 2017-06-09 2017-06-09 A kind of core-shell structure nanometer particle and preparation method thereof Active CN107243629B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710434566.9A CN107243629B (en) 2017-06-09 2017-06-09 A kind of core-shell structure nanometer particle and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710434566.9A CN107243629B (en) 2017-06-09 2017-06-09 A kind of core-shell structure nanometer particle and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107243629A true CN107243629A (en) 2017-10-13
CN107243629B CN107243629B (en) 2019-01-22

Family

ID=60018017

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710434566.9A Active CN107243629B (en) 2017-06-09 2017-06-09 A kind of core-shell structure nanometer particle and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107243629B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107916263A (en) * 2017-11-10 2018-04-17 刁晓荃 The preservation particulate and long-term preservation method of inhereditary material
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
CN108145176A (en) * 2018-01-10 2018-06-12 云南大学 A kind of autoreduction preparation method of gold nano ball-bar polymer
CN110625138A (en) * 2019-10-30 2019-12-31 中山大学 DNA-oriented gold-silver bimetallic nanoparticle and preparation method and application thereof
CN111408732A (en) * 2020-04-23 2020-07-14 江南大学 Method for synthesizing chiral nano material by utilizing DNA induction and chiral light auxiliary growth

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102382815A (en) * 2011-09-15 2012-03-21 王利兵 Binary plasma nanoparticle site singularity self-assembly method
CN102825261A (en) * 2012-09-29 2012-12-19 江南大学 Binary plasma nanoparticle site specificity self-assembling method
CN102908633A (en) * 2012-07-31 2013-02-06 南京大学 Multifunctional gold and silver core-shell nanoparticles and preparation method
WO2013069732A1 (en) * 2011-11-08 2013-05-16 財団法人神奈川科学技術アカデミー Magnetic nanoparticles
CN103776772A (en) * 2014-02-14 2014-05-07 国家纳米科学中心 Method for detecting DNA (deoxyribonucleic acid) on basis of gold nanocone accumulated circular dichroism signal
CN104985176A (en) * 2015-06-11 2015-10-21 江南大学 Preparation method of silver-wrapped gold nanorod dimer with controllable chiral signals
CN106729710A (en) * 2016-12-20 2017-05-31 上海纳米技术及应用国家工程研究中心有限公司 A kind of thermochemotherapy Integral rice grain and preparation and application

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102382815A (en) * 2011-09-15 2012-03-21 王利兵 Binary plasma nanoparticle site singularity self-assembly method
WO2013069732A1 (en) * 2011-11-08 2013-05-16 財団法人神奈川科学技術アカデミー Magnetic nanoparticles
CN102908633A (en) * 2012-07-31 2013-02-06 南京大学 Multifunctional gold and silver core-shell nanoparticles and preparation method
CN102825261A (en) * 2012-09-29 2012-12-19 江南大学 Binary plasma nanoparticle site specificity self-assembling method
CN103776772A (en) * 2014-02-14 2014-05-07 国家纳米科学中心 Method for detecting DNA (deoxyribonucleic acid) on basis of gold nanocone accumulated circular dichroism signal
CN104985176A (en) * 2015-06-11 2015-10-21 江南大学 Preparation method of silver-wrapped gold nanorod dimer with controllable chiral signals
CN106729710A (en) * 2016-12-20 2017-05-31 上海纳米技术及应用国家工程研究中心有限公司 A kind of thermochemotherapy Integral rice grain and preparation and application

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107916263A (en) * 2017-11-10 2018-04-17 刁晓荃 The preservation particulate and long-term preservation method of inhereditary material
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
CN108145176A (en) * 2018-01-10 2018-06-12 云南大学 A kind of autoreduction preparation method of gold nano ball-bar polymer
CN110625138A (en) * 2019-10-30 2019-12-31 中山大学 DNA-oriented gold-silver bimetallic nanoparticle and preparation method and application thereof
CN110625138B (en) * 2019-10-30 2022-07-22 中山大学 DNA-oriented gold-silver bimetallic nanoparticle and preparation method and application thereof
CN111408732A (en) * 2020-04-23 2020-07-14 江南大学 Method for synthesizing chiral nano material by utilizing DNA induction and chiral light auxiliary growth

Also Published As

Publication number Publication date
CN107243629B (en) 2019-01-22

Similar Documents

Publication Publication Date Title
CN107243629B (en) A kind of core-shell structure nanometer particle and preparation method thereof
Zhan et al. A study of mesoporous silica-encapsulated gold nanorods as enhanced light scattering probes for cancer cell imaging
Ratto et al. Size and shape control in the overgrowth of gold nanorods
Zhang et al. Synthesis of size-tunable chitosan encapsulated gold–silver nanoflowers and their application in SERS imaging of living cells
CN105036070B (en) Gold nanorod-silicon dioxide core-shell structure nanometer material, preparation method and application
CN107849726A (en) The bicone template of single dispersing noble metal nano crystal is combined to
CN105832699B (en) A kind of Fe3O4@SiO2The preparation method and application of yolk-eggshell structure hollow complex microsphere
Liu et al. Plasmonic property and stability of core-shell Au@ SiO 2 nanostructures
US20170219572A1 (en) Lspr-based high sensitivity aptamer sensor using intercalation agent
CN107418554B (en) A kind of gold nanorods and upper conversion nano crystalline substance composite nano materials and preparation method thereof
CN108723385A (en) A kind of monocrystalline silver nanoparticle ball aqueous phase preparation method
CN113770372B (en) Preparation method of gold nanoparticle aggregate material
CN109596822A (en) A kind of gold core silver shell nanocomposite and preparation method thereof
CN109128210A (en) A kind of dumbbell shaped gold nano bipyramid/argentum nano composite material and preparation method thereof
CN104384523B (en) Preparing method of three-dimensional chiral silver nanometer material
Liu et al. Aptamer-modified selenium nanoparticles for dark-field microscopy imaging of nucleolin
CN103923656A (en) Preparation method of gadolinium oxide-coated ferroferric oxide magnetic fluorescent nano hollow spheres
CN106887295A (en) A kind of structure and preparation method of magnetic honeysuckle flower nano particle
Yang et al. The early life of gold nanorods: temporal separation of anisotropic and isotropic growth modes
CN105149613A (en) Preparation method for flaky silver nanometer materials
Xu et al. Synthesis and characterisation of a pH-sensitive magnetic nanocomposite for controlled delivery of doxorubicin
CN111718705A (en) One-dimensional core-shell structure nano material with optimized metal fluorescence enhancement effect and preparation method thereof
CN106141172B (en) Three-dimensional " photo frame and photograph " structure nano gold material, its synthetic method and application
Zeng et al. Up-down conversion luminescence and drug-loading capability of novel MoO3-x based carriers
Nafisah et al. Synthesis of gold nanorices on ITO substrate using silver seed-mediated growth method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant