CN107189314B - A kind of gold/polymer/gold three-layer nuclear shell nanometer dumbbell material and its preparation method and application - Google Patents
A kind of gold/polymer/gold three-layer nuclear shell nanometer dumbbell material and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of gold/polymer/gold three-layer nuclear shell nanometer dumbbell materials and its preparation method and application, feature is the core-shell nano material by gold nanorods kernel, polymeric shell layer positioned at gold nanorods surface and the gold nano cap composition positioned at gold nanorods both ends, wherein, kernel length is 100-400 nanometers, the polystyrene polyacrylic acid block copolymer layer that stick surface crust is 10 nanometers of thickness, the gold nano cap that stick both ends are partial size 80-130 nanometers, its gold/polymer/gold composite nano materials for using Seed inducement method to prepare, advantage is that have inside and outside two layers of noble metal gold nano grain, under the action of external exciting light, can intercouple effect between the surface local electromagnetic field that they are generated, generating, there is the SERS signal of very high strength to export.Preparation process of the present invention is simple, and the period is short, and yield is high, easy to spread and large-scale production.
Description
Technical field
The present invention relates to material engineering and field of nanometer technology, more particularly, to a kind of gold/polymer/Jin Sancenghekena
Rice dumbbell material and its preparation method and application.
Background technique
In past 20 years, due to the detection sensitivity with unimolecule rank, Surface enhanced Raman scattering (SERS)
Technology has been developed as life health care, the efficient analysis detection means in the fields such as environmental monitoring and food safety.Various
In SERS material, the advantage of noble metal nanometer material is that its surface plasma body resonant vibration (LSPR) can induce generation extremely strong
Local electromagnetic field shows excellent enhancing characteristic.In these noble metal nanometer materials, gold is with its preferable biocompatibility
Show one's talent with simple preparation process.Currently, people have been successfully prepared diversified gold nano-material, such as nanometer
Stick, nanocube, nanometer sheet and nanometer bipyramid etc..By changing the structure and pattern of these gold nano-materials, people can be with
It effectively adjusts its surface plasma bulk properties and obtains more excellent optical property.But due to wherein without containing between nanometer
Gap, individual gold nano grain, SERS signal are in general too weak to for Single Molecule Detection.Meanwhile SERS nano-probe
Efficiency and reliability be frequently subjected to the damage of dissociation of ligand or exchange.Therefore, it is necessary to utilize advanced nano-fabrication technique
The novel compound gold nano-material with molecular shield and nano gap is made, to obtain better SERS performance.
Summary of the invention
Gold/the polymerization for the SERS signal output with very high strength that technical problem to be solved by the invention is to provide a kind of
Object/gold three-layer nuclear shell nanometer dumbbell material and its preparation method and application.
The technical scheme of the invention to solve the technical problem is: a kind of gold/polymer/gold three-layer nuclear shell nanometer
Dumbbell material, the core-shell nano material by gold nanorods kernel, positioned at gold nanorods surface polymeric shell layer and be located at Jenner
The gold nano cap composition at rice stick both ends, wherein the length of the gold nanorods kernel is 100-400 nanometers, the polymer
The polystyrene polyacrylic acid block copolymer layer that shell is 10 nanometers of thickness, the partial size of the gold nano cap are received for 80-130
Rice.
Above-mentioned gold/polymer/gold three-layer nuclear shell nanometer dumbbell material core-shell nano material preparation method, including following step
It is rapid:
1) preparation of gold nanorods
A. sodium citrate and gold chloride mixed aqueous solution are configured, citric acid is added thereto when being vigorously stirred at room temperature
Sodium and the sodium borohydride solution of gold chloride mixed aqueous solution volume 3% restore to obtain gold seeds solution；
B. take above-mentioned gold seeds solution be added to 9 times of volumes of gold seeds solution methyl bromide ammonium and gold chloride mixing it is water-soluble
In liquid, then rapidly join gold seeds solution 50 × 10-3The aqueous ascorbic acid of times volume, reaction obtained the first reaction after 15 seconds
Liquid；The first reaction solution is taken to be added rapidly to the hexadecane trimethyl ammonium bromide and gold chloride mixing water of 9 times of volumes of the first reaction solution
In solution, then rapidly join the first reaction solution 50 × 10-3The aqueous ascorbic acid of times volume, reaction obtains second after 30 seconds anti-
Answer liquid；The second reaction solution is taken to be added to the hexadecane trimethyl ammonium bromide and gold chloride mixing water of the second 3-45 times of reaction solution volume
In solution, persistently stir 1 hour after stop stirring and it is 24 hours static, take supernatant liquor away, lower liquid be collected after centrifugation
Precipitating is to get gold nanorods；
2) gold/polymer core shell nanometer material preparation
Gold nanorods made from step 1) are taken to be added to embedding containing Raman molecular 2- thionaphthol and polystyrene polyacrylic acid
It in the dimethylformamide in water of section copolymer and is vigorously stirred to be placed in oil bath pan at 110 DEG C and heats 2 hours, later
It is slowly dropped to room temperature, precipitating is collected after centrifugation to get gold/polymer core shell nanometer material；
3) gold/polymer/gold three-layer nuclear shell nanometer dumbbell material preparation
By gold made from step 2)/polymer core shell nanometer material be dissolved in by gold chloride, hexadecane trimethyl ammonium bromide and
Sodium hydroxide is dissolved in mixed liquor made of water, and aqueous ascorbic acid is slowly added dropwise while stirring, and it is small to react 1 at room temperature
When, after reaction, precipitating, gold/polymer/gold three-layer nuclear shell nanometer dumbbell material is collected after centrifugation.
The preparation of step 1) gold nanorods specifically:
A. sodium citrate and 20 milliliters of gold chloride mixed aqueous solution are configured, are added thereto when being vigorously stirred at room temperature
0.6 milliliter of sodium borohydride solution restores to obtain gold seeds solution；
B. take 1 milliliter of above-mentioned gold seeds solution be added to 9 milliliters of hexadecane trimethyl ammonium bromides and gold chloride mixing it is water-soluble
In liquid, then rapidly joins after 50 microlitres of aqueous ascorbic acids react 15 seconds and obtain the first reaction solution；Take 1 milliliter of first reaction solution
It is added rapidly in 9 milliliters of hexadecane trimethyl ammonium bromides and gold chloride mixed aqueous solution, then rapidly joins 50 microlitres of Vitamin Cs
Aqueous acid, reaction obtained the second reaction solution after 30 seconds；1 milliliter of second reaction solution is taken to be added to 15-45 milliliters of hexadecane front threes
In base ammonium bromide and gold chloride mixed aqueous solution, persistently stir 1 hour after stop stirring and it is 24 hours static, it is clear to take upper layer away
Lower liquid is collected precipitating after twenty minutes with 10000 revs/min of centrifugations to get gold nanorods by liquid.
The concentration of sodium citrate is 0.00025 mM of every milli in the sodium citrate and gold chloride mixed aqueous solution
It rises, the concentration of gold chloride is 0.00025 mM every milliliter；The concentration of sodium borohydride is 0.1 in the sodium borohydride solution
MM every milliliter；Hexadecane trimethyl ammonium bromide in the hexadecane trimethyl ammonium bromide and gold chloride mixed aqueous solution
Concentration is 0.1 mM every milliliter, and the concentration of gold chloride is 0.00025 mM every milliliter；The aqueous ascorbic acid
The concentration of middle ascorbic acid is 0.1 mM every milliliter.
Step 2) gold/polymer core shell nanometer material preparation specifically: add whole gold nanorods made from step 1)
Enter to containing 0.05-0.1 milligrams of Raman molecular 2- thionaphthols and 0.5-1 milligrams of polystyrene polyacrylic acid block copolymers by
In the mixed liquor of 900-1800 microlitres of dimethylformamide and 200-400 microlitres of deionized water composition, and it is vigorously stirred and is placed on
It is heated 2 hours at 110 DEG C in oil bath pan, is slowly dropped to room temperature later, precipitating is collected after centrifugation to get gold/polyalcohol nucleocapsid
Nano material.
Step 3) gold/polymer/gold three-layer nuclear shell nanometer dumbbell material preparation specifically: step 2) is made all
Gold/polymer core shell nanometer material is dissolved in by 0.2-0.3 milligrams of gold chlorides, 5-15 milligrams of hexadecane trimethyl ammonium bromides and 0.8-
2.4 milligrams of sodium hydroxides are dissolved in 5-15 made of water milliliters of mixed liquor, and 2-6 milliliters of Vitamin C sour waters are slowly added dropwise while stirring
Solution reacts 1 hour at room temperature, after reaction, precipitating is collected after centrifugation to get gold/polymer/gold three-layer nuclear shell nanometer
Dumbbell material.
The concentration of ascorbic acid is 1 milligram every milliliter in the aqueous ascorbic acid.
Step 1) -3) in centrifugal speed be 5000-15000 revs/min, centrifugation time be 5-30 minutes.
The application of above-mentioned gold/polymer/gold three-layer nuclear shell nanometer dumbbell material, the core-shell nano dumbbell material are increasing
The purposes of strong SERS signal output facet.
Compared with the prior art, the advantages of the present invention are as follows: present invention firstly discloses one kind with the active gold of SERS/
Polymer/gold three-layer nuclear shell nanometer dumbbell material, the core-shell nano material by gold nanorods kernel, positioned at gold nanorods surface
Polymeric shell layer and gold nano cap positioned at gold nanorods both ends form, with novel three-layer nuclear shell structure and novel dumbbell
Shape structure, wherein amphiphilic block copolymer, especially polystyrene acrylic acid block copolymer is due to good
Photosensitiveness, the output without influencing SERS signal.In addition, exposed hydrophilic functional group can be adsorbed after it forms clad
Gold ion simultaneously forms the gold nano cap for being located at gold nanorods both ends under the action of reducing agent, by very thin polymer shell,
The plasmon coupling of inside and outside layer gold will cause strong electromagnetic hotspot, and the extreme of SERS signal is caused to enhance.
The present invention uses gold/polymer/gold composite nano materials of Seed inducement method preparation, gold nanorods kernel both ends
Two gold nano caps have been coated, under the action of external exciting light, surface local that gold nanorods and gold nano cap generate respectively
The effect of intercoupling more by force can occur between electromagnetic field, hot spot region is generated, so that this core-shell nano dumbbell material has
The SERS signal of very high strength exports.Preparation process of the present invention is simple, and the period is short, and yield is high, easy to spread and large-scale production.
Detailed description of the invention
Fig. 1 is the gold/polymer/gold three-layer nuclear shell nanometer dumbbell material transmitted electron prepared in the embodiment of the present invention 1
Microscope photo；
Fig. 2 is saturating for the gold/polymer/gold three-layer nuclear shell nanometer dumbbell material high magnification prepared in the embodiment of the present invention 1
Penetrate electron micrograph；
Fig. 3 is to utilize the gold/polymer prepared in the embodiment of the present invention 1/gold three-layer nuclear shell nanometer dumbbell material Raman
Testing result；
Fig. 4 is the gold/polymer/gold three-layer nuclear shell nanometer dumbbell material transmitted electron prepared in the embodiment of the present invention 2
Microscope photo；
Fig. 5 is to utilize the gold/polymer prepared in the embodiment of the present invention 2/gold three-layer nuclear shell nanometer dumbbell material Raman
Testing result；
Fig. 6 is the gold/polymer/gold three-layer nuclear shell nanometer dumbbell material transmitted electron prepared in the embodiment of the present invention 3
Microscope photo；
Fig. 7 is to utilize the gold/polymer prepared in the embodiment of the present invention 3/gold three-layer nuclear shell nanometer dumbbell material Raman
Testing result.
Specific embodiment
The present invention will be described in further detail below with reference to the embodiments of the drawings.
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..Unless otherwise specified, embodiment
Used in the conventional means that are well known to those skilled in the art of technological means, raw materials used is commercial goods.Embodiment
Used in Raman spectrum detector BWS415 be purchased from U.S. Bi Da Imtech (B&W Tek Inc.).
Embodiment 1
With the active gold/polymer of SERS/gold three-layer nuclear shell nanometer dumbbell material preparation method the following steps are included:
1, the preparation of gold nanorods
A. sodium citrate and 20 milliliters of gold chloride mixed aqueous solution are configured, are added thereto when being vigorously stirred at room temperature
0.6 milliliter of sodium borohydride solution restores to obtain gold seeds solution；It configures hexadecane trimethyl ammonium bromide and gold chloride mixing is water-soluble
Liquid；Wherein the concentration of sodium citrate is 0.00025 mM every milliliter in sodium citrate and gold chloride mixed aqueous solution, gold chloride
Concentration be 0.00025 mM every milliliter；The concentration of sodium borohydride is 0.1 mM every milliliter in sodium borohydride solution；Ten
The concentration of hexadecane trimethyl ammonium bromide is 0.1 mM of every milli in six alkane trimethylammonium bromides and gold chloride mixed aqueous solution
It rises, the concentration of gold chloride is 0.00025 mM every milliliter；
B. take 1 milliliter of above-mentioned gold seeds solution be added to 9 milliliters of hexadecane trimethyl ammonium bromides and gold chloride mixing it is water-soluble
In liquid, then rapidly joins after 50 microlitres of aqueous ascorbic acids react 15 seconds and obtain the first reaction solution；Take 1 milliliter of first reaction solution
It is added rapidly in 9 milliliters of hexadecane trimethyl ammonium bromides and gold chloride mixed aqueous solution, then rapidly joins 50 microlitres of Vitamin Cs
Aqueous acid, reaction obtained the second reaction solution after 30 seconds；1 milliliter of second reaction solution is taken to be added to 15-45 milliliters of hexadecane front threes
In base ammonium bromide and gold chloride mixed aqueous solution, persistently stir 1 hour after stop stirring and it is 24 hours static, it is clear to take upper layer away
Lower liquid is collected precipitating after twenty minutes with 10000 revs/min of centrifugations to get gold nanorods by liquid；Wherein ascorbic acid is water-soluble
The concentration of ascorbic acid is 0.1 mM every milliliter in liquid.
2, whole gold nanorods made from above-mentioned steps is taken to be added to containing 0.1 milligram of Raman molecular 2- thionaphthol and 1 milli
The dimethylformamide (1800 microlitres) of gram polystyrene polyacrylic acid block copolymer and (400 microlitres) mixing of deionized water are molten
It in liquid and is vigorously stirred and is placed in oil bath pan, heated 2 hours at 110 DEG C, be slowly dropped to room temperature, later with 10000 revs/min
Zhongli's heart collects precipitating after twenty minutes to get gold/polymer core shell nanometer material；
3, the gold of whole made from above-mentioned steps/polymer core shell nanometer material is taken to be dissolved in by 0.3 milligram of gold chloride, 15 milligrams
Hexadecane trimethyl ammonium bromide and 2.4 milligrams of sodium hydroxides are dissolved in 15 milliliters of mixed liquors made of water, are slowly dripped while stirring
Add the aqueous solution (concentration is 1 milligram every milliliter) of 6 milliliters of ascorbic acid, at room temperature reaction 1 hour, after reaction, with
10000 revs/min of centrifugations collect precipitating after twenty minutes to get gold/polymer/gold three-layer nuclear shell nanometer dumbbell material.
The core-shell nano material prepared in the present embodiment is by gold nanorods kernel, the polymer shell positioned at gold nanorods surface
Layer and gold nano cap positioned at gold nanorods both ends form, wherein kernel is 400 nanometers of length of gold nanorods, and stick surface is
10 nanometers of thickness of polystyrene polyacrylic acid block copolymer layer, the gold nano cap that stick both ends are partial size 80-100 nanometers.
Fig. 1 shows that is prepared in the present embodiment has the active gold/polymer of SERS/gold three-layer nuclear shell nanometer dumbbell material
The transmission electron microscope photo of material, it will be seen from figure 1 that prepared nano material is dumbbell shaped three-layer nuclear shell structure.
Fig. 2 shows that is prepared in the present embodiment has the active gold/polymer of SERS/gold three-layer nuclear shell nanometer dumbbell material
The high magnification transmission electron microscope photo of material, figure it is seen that prepared gold nanorods are almost transparent poly- by one layer
Close object shell package.
Fig. 3 is to be prepared using the above method with the active gold/polymer of SERS/gold three-layer nuclear shell nanometer dumbbell
Material Raman spectrogram.From figure 3, it can be seen that the SERS active material has good SERS signal enhancement effect,
1074cm-1The Raman signal intensity at place reaches 40000.
Embodiment 2
With the active gold/polymer of SERS/gold three-layer nuclear shell nanometer dumbbell material preparation method the following steps are included:
1, the preparation of gold nanorods
A. sodium citrate and 20 milliliters of gold chloride mixed aqueous solution are configured, are added thereto when being vigorously stirred at room temperature
0.6 milliliter of sodium borohydride solution restores to obtain gold seeds solution；It configures hexadecane trimethyl ammonium bromide and gold chloride mixing is water-soluble
Liquid；Wherein the concentration of sodium citrate is 0.00025 mM every milliliter in sodium citrate and gold chloride mixed aqueous solution, gold chloride
Concentration be 0.00025 mM every milliliter；The concentration of sodium borohydride is 0.1 mM every milliliter in sodium borohydride solution；Ten
The concentration of hexadecane trimethyl ammonium bromide is 0.1 mM of every milli in six alkane trimethylammonium bromides and gold chloride mixed aqueous solution
It rises, the concentration of gold chloride is 0.00025 mM every milliliter；
B. take 1 milliliter of above-mentioned gold seeds solution be added to 9 milliliters of hexadecane trimethyl ammonium bromides and gold chloride mixing it is water-soluble
In liquid, then rapidly joins after 50 microlitres of aqueous ascorbic acids react 15 seconds and obtain the first reaction solution；Take 1 milliliter of first reaction solution
It is added rapidly in 9 milliliters of hexadecane trimethyl ammonium bromides and gold chloride mixed aqueous solution, then rapidly joins 50 microlitres of Vitamin Cs
Aqueous acid, reaction obtained the second reaction solution after 30 seconds；3 milliliter of second reaction solution is taken to be added to 15-45 milliliters of hexadecane front threes
In base ammonium bromide and gold chloride mixed aqueous solution, persistently stir 1 hour after stop stirring and it is 24 hours static, it is clear to take upper layer away
Liquid collects precipitating to get gold nanorods after being centrifuged lower liquid 30 minutes with 5000 revs/min；Wherein ascorbic acid is water-soluble
The concentration of ascorbic acid is 0.1 mM every milliliter in liquid.
2, take whole gold nanorods made from above-mentioned steps be added to containing 0.075 milligram of Raman molecular 2- thionaphthol and
The dimethylformamide (1350 microlitres) and deionized water (300 microlitres) of 0.75 milligram of polystyrene polyacrylic acid block copolymer
It in mixed solution and is vigorously stirred to be placed in oil bath pan and is heated 2 hours at 110 DEG C, be slowly dropped to room temperature, later with 5000
Rev/min centrifugation 30 minutes after collect precipitating to get gold/polymer core shell nanometer material；
3, the gold of whole made from above-mentioned steps/polymer core shell nanometer material is taken to be dissolved in by 0.25 milligram of gold chloride, 10 millis
Gram hexadecane trimethyl ammonium bromide and 1.6 milligrams of sodium hydroxides are dissolved in 10 milliliters of mixed liquors made of water, while stirring slowly
The aqueous solution (concentration is 1 milligram every milliliter) of 4 milliliters of ascorbic acid is added dropwise, at room temperature reaction 1 hour, after reaction, with
5000 revs/min centrifugation 30 minutes after collect precipitating to get gold/polymer/gold three-layer nuclear shell nanometer dumbbell material.
The core-shell nano material prepared in the present embodiment is by gold nanorods kernel, the polymer shell positioned at gold nanorods surface
Layer and gold nano cap positioned at gold nanorods both ends form, wherein kernel is 300 nanometers of length of gold nanorods, and stick surface is
10 nanometers of thickness of polystyrene polyacrylic acid block copolymer layer, the gold nano cap that stick both ends are partial size 110-130 nanometers.
Fig. 4 shows that is prepared in the present embodiment has the active gold/polymer of SERS/gold three-layer nuclear shell nanometer dumbbell material
The transmission electron microscope photo of material, from fig. 4, it can be seen that prepared nano material is dumbbell shaped three-layer nuclear shell structure.
Fig. 5 is to be prepared using the above method with the active gold/polymer of SERS/gold three-layer nuclear shell nanometer dumbbell
Material Raman spectrogram.From fig. 5, it can be seen that the SERS active material has good SERS signal enhancement effect,
1074cm-1The Raman signal intensity at place reaches 30000.
Embodiment 3
With the active gold/polymer of SERS/gold three-layer nuclear shell nanometer dumbbell material preparation method the following steps are included:
1, the preparation of gold nanorods
A. sodium citrate and 20 milliliters of gold chloride mixed aqueous solution are configured, are added thereto when being vigorously stirred at room temperature
0.6 milliliter of sodium borohydride solution restores to obtain gold seeds solution；It configures hexadecane trimethyl ammonium bromide and gold chloride mixing is water-soluble
Liquid；Wherein the concentration of sodium citrate is 0.00025 mM every milliliter in sodium citrate and gold chloride mixed aqueous solution, gold chloride
Concentration be 0.00025 mM every milliliter；The concentration of sodium borohydride is 0.1 mM every milliliter in sodium borohydride solution；Ten
The concentration of hexadecane trimethyl ammonium bromide is 0.1 mM of every milli in six alkane trimethylammonium bromides and gold chloride mixed aqueous solution
It rises, the concentration of gold chloride is 0.00025 mM every milliliter；
B. take 1 milliliter of above-mentioned gold seeds solution be added to 9 milliliters of hexadecane trimethyl ammonium bromides and gold chloride mixing it is water-soluble
In liquid, then rapidly joins after 50 microlitres of aqueous ascorbic acids react 15 seconds and obtain the first reaction solution；Take 1 milliliter of first reaction solution
It is added rapidly in 9 milliliters of hexadecane trimethyl ammonium bromides and gold chloride mixed aqueous solution, then rapidly joins 50 microlitres of Vitamin Cs
Aqueous acid, reaction obtained the second reaction solution after 30 seconds；5 milliliter of second reaction solution is taken to be added to 15-45 milliliters of hexadecane front threes
In base ammonium bromide and gold chloride mixed aqueous solution, persistently stir 1 hour after stop stirring and it is 24 hours static, it is clear to take upper layer away
Lower liquid is collected precipitating after five minutes with 15000 revs/min of centrifugations to get gold nanorods by liquid；Wherein ascorbic acid is water-soluble
The concentration of ascorbic acid is 0.1 mM every milliliter in liquid.
2, whole gold nanorods made from above-mentioned steps is taken to be added to containing 0.05 milligram of Raman molecular 2- thionaphthol and 0.5
The dimethylformamide (1800 microlitres) of milligram polystyrene polyacrylic acid block copolymer and (400 microlitres) of deionized water mixing
In solution and be vigorously stirred to be placed in oil bath pan and heated 2 hours at 110 DEG C, be slowly dropped to room temperature later, with 15000 turns/
Minute centrifugation collects precipitating after five minutes to get gold/polymer core shell nanometer material；
3, the gold of whole made from above-mentioned steps/polymer core shell nanometer material is taken to be dissolved in by 0.2 milligram of gold chloride, 5 milligrams
In 5 milliliters of mixed liquors of hexadecane trimethyl ammonium bromide and 0.8 milligram of sodium hydroxide composition, 2 milliliters are slowly added dropwise while stirring
The aqueous solution (concentration is 1 milligram every milliliter) of ascorbic acid, reacts 1 hour, at room temperature after reaction, with 15000 revs/min
Zhongli's heart collects precipitating after five minutes to get gold/polymer/gold three-layer nuclear shell nanometer dumbbell material.
The core-shell nano material prepared in the present embodiment is by gold nanorods kernel, the polymer shell positioned at gold nanorods surface
Layer and gold nano cap positioned at gold nanorods both ends form, wherein kernel is 100 nanometers of length of Silver nanorod, and stick surface is
10 nanometers of thickness of polystyrene polyacrylic acid block copolymer layer, the gold nano cap that stick both ends are partial size 90-100 nanometers.
Fig. 6 shows that is prepared in the present embodiment has the active gold/polymer of SERS/gold three-layer nuclear shell nanometer dumbbell material
The transmission electron microscope photo of material, from fig. 6, it can be seen that prepared nano material is dumbbell shaped three-layer nuclear shell structure.
Fig. 7 is to be prepared using the above method with the active gold/polymer of SERS/gold three-layer nuclear shell nanometer dumbbell
Material Raman spectrogram.From figure 7 it can be seen that the SERS active material has good SERS signal enhancement effect,
1074cm-1The Raman signal intensity at place reaches 22000.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (4)
1. a kind of gold/polymer/gold three-layer nuclear shell nanometer dumbbell material, it is characterised in that: the core-shell nano material is by gold nano
Stick kernel, the polymeric shell layer positioned at gold nanorods surface and the composition of the gold nano cap positioned at gold nanorods both ends, wherein described
The length of gold nanorods kernel be 100-400 nanometer, the polymeric shell layer is 10 nanometers of thickness of polystyrene poly- third
Olefin(e) acid block copolymer layer, the partial size of the gold nano cap are 80-130 nanometers.
2. a kind of gold/polymer described in claim 1/gold three-layer nuclear shell nanometer dumbbell material preparation method, feature exist
In the following steps are included:
1) preparation of gold nanorods
A. sodium citrate and 20 milliliters of gold chloride mixed aqueous solution are configured, are added 0.6 thereto when being vigorously stirred at room temperature
Milliliter sodium borohydride solution restores to obtain gold seeds solution；
B. 1 milliliter of above-mentioned gold seeds solution is taken to be added in 9 milliliters of hexadecane trimethyl ammonium bromides and gold chloride mixed aqueous solution,
It is rapidly joined after 50 microlitres of aqueous ascorbic acids react 15 seconds again and obtains the first reaction solution；Take 1 milliliter of first reaction solution quick
It is added in 9 milliliters of hexadecane trimethyl ammonium bromides and gold chloride mixed aqueous solution, then rapidly joins 50 microlitres of Vitamin C sour waters
Solution, reaction obtained the second reaction solution after 30 seconds；1 milliliter of second reaction solution is taken to be added to 15-45 milliliters of cetrimonium bromines
Change in ammonium and gold chloride mixed aqueous solution, stops stirring and 24 hours static after persistently stirring 1 hour, take supernatant liquor away, it will
Lower liquid collects precipitating after twenty minutes with 10000 revs/min of centrifugations to get gold nanorods；Wherein the sodium citrate and
The concentration of sodium citrate is 0.00025 mM every milliliter in gold chloride mixed aqueous solution, and the concentration of gold chloride is 0.00025 milli
Mole every milliliter；The concentration of sodium borohydride is 0.1 mM every milliliter in the sodium borohydride solution；The hexadecane three
The concentration of hexadecane trimethyl ammonium bromide is 0.1 mM every milliliter in methyl bromide ammonium and gold chloride mixed aqueous solution, chlorine gold
The concentration of acid is 0.00025 mM every milliliter；The concentration of ascorbic acid is 0.1 mM in the aqueous ascorbic acid
Every milliliter；
2) gold/polymer core shell nanometer material preparation
Gold nanorods made from step 1) are added to total containing Raman molecular 2- thionaphthol and polystyrene polyacrylic acid block
It in the dimethylformamide in water of polymers and is vigorously stirred to be placed in oil bath pan at 110 DEG C and heats 2 hours, later slowly
It is down to room temperature, precipitating is collected after centrifugation to get gold/polymer core shell nanometer material；Specifically: it takes all golden made from step 1)
Nanometer rods are added to total containing 0.05-0.1 milligrams of Raman molecular 2- thionaphthols and 0.5-1 milligrams of polystyrene polyacrylic acid blocks
In the mixed liquor of polymers being made of 900-1800 microlitres of dimethylformamide and 200-400 microlitres of deionized water, and acutely stir
It mixes to be placed in oil bath pan and be heated 2 hours at 110 DEG C, be slowly dropped to room temperature later, precipitating is collected after centrifugation to get golden/poly-
Close object core-shell nano material；
3) gold/polymer/gold three-layer nuclear shell nanometer dumbbell material preparation
Gold made from step 2)/polymer core shell nanometer material is dissolved in by gold chloride, hexadecane trimethyl ammonium bromide and hydrogen-oxygen
Change sodium to be dissolved in mixed liquor made of water, aqueous ascorbic acid is slowly added dropwise while stirring, at room temperature reaction 1 hour, instead
After answering, it is collected after centrifugation precipitating, gold/polymer/gold three-layer nuclear shell nanometer dumbbell material, specifically: step 2) is made
Whole gold/polymer core shell nanometer material be dissolved in by 0.2-0.3 milligrams of gold chlorides, 5-15 milligrams of hexadecane trimethyl ammonium bromides and
0.8-2.4 milligrams of sodium hydroxides are dissolved in 5-15 made of water milliliters of mixed liquor, and 2-6 milliliters of Vitamin Cs are slowly added dropwise while stirring
Aqueous acid reacts 1 hour at room temperature, after reaction, precipitating is collected after centrifugation to get gold/polymer/gold three-layer nuclear shell
Nanometer dumbbell material, wherein the concentration of ascorbic acid is 1 milligram every milliliter in the aqueous ascorbic acid.
3. a kind of gold/polymer according to claim 2/gold three-layer nuclear shell nanometer dumbbell material preparation method, special
Sign is: step 1) -3) in centrifugal speed be 5000-15000 revs/min, centrifugation time be 5-30 minutes.
4. a kind of application of gold/polymer of any of claims 1-3/gold three-layer nuclear shell nanometer dumbbell material,
Be characterized in that: the core-shell nano dumbbell material is for enhancing SERS signal output.
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| CN105562682A (en) * | 2016-01-15 | 2016-05-11 | 湖南大学 | Graphene-wrapped gold nanorod composite nanomaterial and preparation method thereof |
| CN106345999A (en) * | 2016-09-22 | 2017-01-25 | 安徽师范大学 | Preparation method of nanocomposite with two ends of gold rods coated with titanium dioxide |
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| CN105562682A (en) * | 2016-01-15 | 2016-05-11 | 湖南大学 | Graphene-wrapped gold nanorod composite nanomaterial and preparation method thereof |
| CN106345999A (en) * | 2016-09-22 | 2017-01-25 | 安徽师范大学 | Preparation method of nanocomposite with two ends of gold rods coated with titanium dioxide |
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