CN107189314A - 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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Abstract
The invention discloses a kind of gold/polymer/gold three-layer nuclear shell nanometer dumbbell material 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 two ends, wherein, kernel length is 100 400 nanometers, rod surface crust is the polystyrene polyacrylic acid block copolymer layer of 10 nanometers of thickness, rod two ends are the gold nano cap of 80 130 nanometers of particle diameter, it uses gold/polymer/gold composite nano materials prepared by Seed inducement method, advantage is that have inside and outside two layers of noble metal gold nano grain, in the presence of external exciting light, can intercouple effect between the surface local electromagnetic field that they are produced, the SERS signal with very high strength is produced to export.Preparation technology of the present invention is simple, and the cycle is short, and yield is high, it is easy to promotes and mass produces.
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 technology
In past 20 years, due to the detection sensitivity with unimolecule rank, SERS（SERS）
Technology has been developed as life health care, the efficient analysis detection means in the field such as environmental monitoring and food security.Various
In SERS materials, the advantage of noble metal nanometer material is its surface plasma body resonant vibration（LSPR）Generation can be induced 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 technology.At present, people have been successfully prepared diversified gold nano-material, such as nanometer
Rod, nanocube, nanometer sheet and nanometer bipyramid etc..By changing the structure and pattern of these gold nano-materials, people can be with
Effectively adjust its surface plasma bulk properties and obtain more excellent optical property.But, due to not containing wherein between nanometer
Gap, single gold nano grain, its SERS signal is in general too weak to be used for Single Molecule Detection.Meanwhile, SERS nano-probes
Efficiency and reliability be frequently subjected to the infringement 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 more preferable SERS performances.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of gold/polymerization of the SERS signal output with very high strength
Thing/gold three-layer nuclear shell nanometer dumbbell material and its preparation method and application.
The present invention solve the technical scheme that is used of above-mentioned technical problem for：A kind of gold/polymer/gold three-layer nuclear shell nanometer
Dumbbell material, the core-shell nano material is by gold nanorods kernel, the polymeric shell layer positioned at gold nanorods surface and positioned at Jenner
The gold nano cap composition at rice rod two ends, wherein the length of described gold nanorods kernel is 100-400 nanometers, described polymerization
Thing shell is the polystyrene polyacrylic acid block copolymer layer of 10 nanometers of thickness, and the particle diameter of described gold nano cap is 80-
130 nanometers.
The preparation method of above-mentioned gold/polymer/gold three-layer nuclear shell nanometer dumbbell material core-shell nano material, including following step
Suddenly：
1）The preparation of gold nanorods
A. configuration sodium citrate and gold chloride mixed aqueous solution, added thereto when being stirred vigorously at room temperature sodium citrate and
The sodium borohydride solution reduction of gold chloride mixed aqueous solution volume 3% obtains gold seeds solution；
B. above-mentioned gold seeds solution is taken to be added to the methyl bromide ammonium and gold chloride mixed aqueous solution of 9 times of volumes of gold seeds solution
In, then the aqueous ascorbic acid of 50 times of volumes of gold seeds solution is rapidly joined, reaction obtains the first reaction solution after 15 seconds；Take
One reaction solution is added rapidly in the hexadecane trimethyl ammonium bromide and gold chloride mixed aqueous solution of 9 times of volumes of the first reaction solution,
The aqueous ascorbic acid of first 50 times of volumes of reaction solution is rapidly joined again, and reaction obtains the second reaction solution after 30 seconds；Take second
Reaction solution is added in the hexadecane trimethyl ammonium bromide and gold chloride mixed aqueous solution of the second 3-45 times of reaction solution volume, is continued
Stirring stops stirring and static 24 hours after 1 hour, take supernatant liquor away, lower floor's liquid collected after centrifugation is precipitated, gold is produced
Nanometer rods；
2）The preparation of gold/polymer core shell nanometer material
Take step 1）Obtained gold nanorods are added to common containing Raman molecular 2- thionaphthols and polystyrene polyacrylic acid block
Be placed in the dimethylformamide in water of polymers and after being stirred vigorously in oil bath pan at 110 DEG C heat 2 hours, afterwards slowly
Room temperature is down to, collected after centrifugation precipitation produces gold/polymer core shell nanometer material；
3）The preparation of gold/polymer/gold three-layer nuclear shell nanometer dumbbell material
By step 2）Obtained gold/polymer core shell nanometer material is dissolved in by gold chloride, hexadecane trimethyl ammonium bromide and hydrogen-oxygen
Change sodium to be dissolved in the mixed liquor that water is made, aqueous ascorbic acid is slowly added dropwise while stirring, at room temperature reaction 1 hour, instead
After should terminating, collected after centrifugation precipitation, gold/polymer/gold three-layer nuclear shell nanometer dumbbell material.
Step 1）The preparation of gold nanorods is specially：
A. 20 milliliters of configuration sodium citrate and gold chloride mixed aqueous solution, add 0.6 thereto when being stirred vigorously at room temperature
Milliliter sodium borohydride solution reduction obtains gold seeds solution；
B. above-mentioned 1 milliliter of gold seeds solution is taken to be added in 9 milliliters of hexadecane trimethyl ammonium bromides and gold chloride mixed aqueous solution,
Rapidly join again after 50 microlitres of aqueous ascorbic acids react 15 seconds and obtain 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 obtains 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, stop stirring after persistently stirring 1 hour and static 24 hours, take supernatant liquor away, will
Lower floor's liquid is collected after being centrifuged 20 minutes with 10000 revs/min to be precipitated, and produces gold nanorods.
The concentration of sodium citrate is 0.00025 mM per milli in described sodium citrate and gold chloride mixed aqueous solution
Rise, the concentration of gold chloride is 0.00025 mM every milliliter；The concentration of sodium borohydride is 0.1 in described sodium borohydride solution
MM every milliliter；Hexadecane trimethyl ammonium bromide in described 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；Described aqueous ascorbic acid
The concentration of middle ascorbic acid is 0.1 mM every milliliter.
Step 2）The preparation of gold/polymer core shell nanometer material is specially：By step 1）Obtained whole gold nanorods add
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 placed in after being stirred vigorously
In being heated 2 hours at 110 DEG C in oil bath pan, room temperature is slowly dropped to afterwards, and collected after centrifugation precipitation produces gold/polyalcohol nucleocapsid
Nano material.
Step 3）The preparation of gold/polymer/gold three-layer nuclear shell nanometer dumbbell material is specially：By step 2）It 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 the 5-15 milliliter mixed liquors that water is made, and 2-6 milliliters of Vitamin C sour waters are slowly added dropwise while stirring
Solution, reacts 1 hour at room temperature, after reaction terminates, collected after centrifugation precipitation, produces gold/polymer/gold three-layer nuclear shell nanometer
Dumbbell material.
The concentration of ascorbic acid is 1 milligram every milliliter in described aqueous ascorbic acid.
Step 1）-3）Middle centrifugal speed is 5000-15000 revs/min, and centrifugation time is 5-30 minutes.
The application of above-mentioned gold/polymer/gold three-layer nuclear shell nanometer dumbbell material, described core-shell nano dumbbell material is increasing
The purposes of strong SERS signal output facet.
Compared with prior art, the advantage of the invention is that：Present invention firstly discloses it is a kind of with SERS activity gold/
Polymer/gold three-layer nuclear shell nanometer dumbbell material, the core-shell nano material is by gold nanorods kernel, positioned at gold nanorods surface
Polymeric shell layer and the gold nano cap composition positioned at gold nanorods two ends, with novel three-layer nuclear shell structure and novel dumbbell
Shape structure, wherein amphipathic block copolymer, particularly polystyrene acrylic acid block copolymer are due to good saturating
Photosensitiveness, the output without influenceing SERS signal.It can be adsorbed in addition, it forms exposed hydrophilic functional group after clad
Gold ion simultaneously forms the gold nano cap for being located at gold nanorods two ends in the presence of reducing agent, by very thin polymer shell,
The plasmon coupling of inside and outside layer gold will cause strong electromagnetic hotspot, causes the extreme of SERS signal and strengthens.
Gold/polymer/gold composite nano materials that the present invention is prepared using Seed inducement method, its gold nanorods kernel two ends
Two gold nano caps have been coated, in the presence of external exciting light, the surface local that gold nanorods and gold nano cap are produced respectively
The effect of intercoupling more by force can occur between electromagnetic field, hot spot region is produced so that this core-shell nano dumbbell material has
The SERS signal output of very high strength.Preparation technology of the present invention is simple, and the cycle is short, and yield is high, it is easy to promotes and mass produces.
Brief description of the drawings
Fig. 1 is the transmitted electron of the gold/polymer/gold three-layer nuclear shell nanometer dumbbell material prepared in the embodiment of the present invention 1
Microphotograph；
Fig. 2 is the high magnification transmission electricity of the gold/polymer/gold three-layer nuclear shell nanometer dumbbell material prepared in the embodiment of the present invention 1
Sub- microphotograph；
Fig. 3 is the Raman detection using the gold/polymer prepared in the embodiment of the present invention 1/gold three-layer nuclear shell nanometer dumbbell material
As a result；
Fig. 4 is the transmission electron microscopy of the gold/polymer/gold three-layer nuclear shell nanometer dumbbell material prepared in the embodiment of the present invention 2
Mirror photo；
Fig. 5 is the Raman detection using the gold/polymer prepared in the embodiment of the present invention 2/gold three-layer nuclear shell nanometer dumbbell material
As a result；
Fig. 6 is the transmission electron microscopy of the gold/polymer/gold three-layer nuclear shell nanometer dumbbell material prepared in the embodiment of the present invention 3
Mirror photo；
Fig. 7 is the Raman detection using the gold/polymer prepared in the embodiment of the present invention 3/gold three-layer nuclear shell nanometer dumbbell material
As a result.
Embodiment
The present invention is described in further detail below in conjunction with accompanying drawing embodiment.
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.Unless otherwise specified, embodiment
In the conventional meanses that are well known to those skilled in the art of used technological means, raw materials used is commercial goods.Embodiment
The middle Raman spectrum detector BWS415 used is purchased from Bi Da Imtech of the U.S.（B&W Tek Inc.）.
Embodiment 1
The preparation method of gold/polymer with SERS activity/gold three-layer nuclear shell nanometer dumbbell material comprises the following steps：
1st, the preparation of gold nanorods
A. 20 milliliters of configuration sodium citrate and gold chloride mixed aqueous solution, add 0.6 thereto when being stirred vigorously at room temperature
Milliliter sodium borohydride solution reduction obtains gold seeds solution；Configure hexadecane trimethyl ammonium bromide and gold chloride mixed aqueous solution；
The concentration of sodium citrate is 0.00025 mM every milliliter wherein in sodium citrate and gold chloride mixed aqueous solution, gold chloride
Concentration is 0.00025 mM every milliliter；The concentration of sodium borohydride is 0.1 mM every milliliter in sodium borohydride solution；16
The concentration of hexadecane trimethyl ammonium bromide is 0.1 mM every milliliter in alkane trimethylammonium bromide and gold chloride mixed aqueous solution,
The concentration of gold chloride is 0.00025 mM every milliliter；
B. above-mentioned 1 milliliter of gold seeds solution is taken to be added in 9 milliliters of hexadecane trimethyl ammonium bromides and gold chloride mixed aqueous solution,
Rapidly join again after 50 microlitres of aqueous ascorbic acids react 15 seconds and obtain 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 obtains 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, stop stirring after persistently stirring 1 hour and static 24 hours, take supernatant liquor away, will
Lower floor's liquid is collected after being centrifuged 20 minutes with 10000 revs/min to be precipitated, and produces gold nanorods；Wherein in aqueous ascorbic acid
The concentration of ascorbic acid is 0.1 mM every milliliter.
2nd, whole gold nanorods made from above-mentioned steps are taken to be added to containing 0.1 milligram of Raman molecular 2- thionaphthol and 1 milli
The dimethylformamide of gram polystyrene polyacrylic acid block copolymer（1800 microlitres）And deionized water（400 microlitres）Mixing is molten
It is placed in liquid and after being stirred vigorously in oil bath pan, in being heated 2 hours at 110 DEG C, room temperature is slowly dropped to afterwards, with 10000 revs/min
Zhongli's heart collects precipitation after 20 minutes, produce gold/polymer core shell nanometer material；
3rd, take made from above-mentioned steps whole gold/polymer core shell nanometer materials be dissolved in by 0.3 milligram of gold chloride, 15 milligram 16
Alkane trimethylammonium bromide and 2.4 milligrams of sodium hydroxides are dissolved in 15 milliliters of mixed liquors that water is made, and 6 millis are slowly added dropwise while stirring
Rise the aqueous solution of ascorbic acid（Concentration is 1 milligram every milliliter）, at room temperature react 1 hour, reaction terminate after, with 10000 turns/
Minute centrifugation collects precipitation after 20 minutes, produces 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 the gold nano cap composition positioned at gold nanorods two ends, wherein, kernel is the gold nanorods of 400 nanometers of length, and rod surface is
The polystyrene polyacrylic acid block copolymer layer of 10 nanometers of thickness, rod two ends are the gold nano cap of 80-100 nanometers of particle diameter.
Fig. 1 shows that what is prepared in the present embodiment has gold/polymer/gold three-layer nuclear shell nanometer dumbbell material of SERS activity
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 what is prepared in the present embodiment has gold/polymer/gold three-layer nuclear shell nanometer dumbbell material of SERS activity
The high magnification transmission electron microscope photo of material, figure it is seen that prepared gold nanorods are almost transparent poly- by one layer
Compound shell is wrapped up.
Fig. 3 is the gold/polymer/gold three-layer nuclear shell nanometer dumbbell with SERS activity prepared using the above method
Material Raman spectrogram.From figure 3, it can be seen that the SERS active materials have good SERS signal enhancement effect, its
1074 cm-1The Raman signal intensity at place reaches 40000.
Embodiment 2
The preparation method of gold/polymer with SERS activity/gold three-layer nuclear shell nanometer dumbbell material comprises the following steps：
1st, the preparation of gold nanorods
A. 20 milliliters of configuration sodium citrate and gold chloride mixed aqueous solution, add 0.6 thereto when being stirred vigorously at room temperature
Milliliter sodium borohydride solution reduction obtains gold seeds solution；Configure hexadecane trimethyl ammonium bromide and gold chloride mixed aqueous solution；
The concentration of sodium citrate is 0.00025 mM every milliliter wherein in sodium citrate and gold chloride mixed aqueous solution, gold chloride
Concentration is 0.00025 mM every milliliter；The concentration of sodium borohydride is 0.1 mM every milliliter in sodium borohydride solution；16
The concentration of hexadecane trimethyl ammonium bromide is 0.1 mM every milliliter in alkane trimethylammonium bromide and gold chloride mixed aqueous solution,
The concentration of gold chloride is 0.00025 mM every milliliter；
B. above-mentioned 1 milliliter of gold seeds solution is taken to be added in 9 milliliters of hexadecane trimethyl ammonium bromides and gold chloride mixed aqueous solution,
Rapidly join again after 50 microlitres of aqueous ascorbic acids react 15 seconds and obtain 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 obtains the second reaction solution after 30 seconds；3 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, stop stirring after persistently stirring 1 hour and static 24 hours, take supernatant liquor away, will
Lower floor's liquid is collected after being centrifuged 30 minutes with 5000 revs/min to be precipitated, and produces gold nanorods；Wherein aqueous ascorbic acid moderate resistance
The concentration of bad hematic acid is 0.1 mM every milliliter.
2nd, take made from above-mentioned steps whole gold nanorods be added to containing 0.075 milligram of Raman molecular 2- thionaphthol and
The dimethylformamide of 0.75 milligram of polystyrene polyacrylic acid block copolymer（1350 microlitres）And deionized water（300 microlitres）
It is placed in mixed solution and after being stirred vigorously in oil bath pan in being heated 2 hours at 110 DEG C, room temperature is slowly dropped to afterwards, with 5000
Rev/min centrifugation 30 minutes after collect precipitation, produce gold/polymer core shell nanometer material；
3rd, take made from above-mentioned steps whole gold/polymer core shell nanometer materials be dissolved in by 0.25 milligram of gold chloride, 10 milligram ten
Six alkane trimethylammonium bromides and 1.6 milligrams of sodium hydroxides are dissolved in 10 milliliters of mixed liquors that water is made, and 4 are slowly added dropwise while stirring
The aqueous solution of milliliter ascorbic acid（Concentration is 1 milligram every milliliter）, react 1 hour at room temperature, after reaction terminates, with 5000
Rev/min centrifugation collects precipitation after 30 minutes, produces 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 the gold nano cap composition positioned at gold nanorods two ends, wherein, kernel is the gold nanorods of 300 nanometers of length, and rod surface is
The polystyrene polyacrylic acid block copolymer layer of 10 nanometers of thickness, rod two ends are the gold nano cap of 110-130 nanometers of particle diameter.
Fig. 4 shows that what is prepared in the present embodiment has gold/polymer/gold three-layer nuclear shell nanometer dumbbell material of SERS activity
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 the gold/polymer/gold three-layer nuclear shell nanometer dumbbell with SERS activity prepared using the above method
Material Raman spectrogram.From fig. 5, it can be seen that the SERS active materials have good SERS signal enhancement effect, its
1074 cm-1The Raman signal intensity at place reaches 30000.
Embodiment 3
The preparation method of gold/polymer with SERS activity/gold three-layer nuclear shell nanometer dumbbell material comprises the following steps：
1st, the preparation of gold nanorods
A. 20 milliliters of configuration sodium citrate and gold chloride mixed aqueous solution, add 0.6 thereto when being stirred vigorously at room temperature
Milliliter sodium borohydride solution reduction obtains gold seeds solution；Configure hexadecane trimethyl ammonium bromide and gold chloride mixed aqueous solution；
The concentration of sodium citrate is 0.00025 mM every milliliter wherein in sodium citrate and gold chloride mixed aqueous solution, gold chloride
Concentration is 0.00025 mM every milliliter；The concentration of sodium borohydride is 0.1 mM every milliliter in sodium borohydride solution；16
The concentration of hexadecane trimethyl ammonium bromide is 0.1 mM every milliliter in alkane trimethylammonium bromide and gold chloride mixed aqueous solution,
The concentration of gold chloride is 0.00025 mM every milliliter；
B. above-mentioned 1 milliliter of gold seeds solution is taken to be added in 9 milliliters of hexadecane trimethyl ammonium bromides and gold chloride mixed aqueous solution,
Rapidly join again after 50 microlitres of aqueous ascorbic acids react 15 seconds and obtain 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 obtains the second reaction solution after 30 seconds；5 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, stop stirring after persistently stirring 1 hour and static 24 hours, take supernatant liquor away, will
Lower floor's liquid is collected after being centrifuged 5 minutes with 15000 revs/min to be precipitated, and produces gold nanorods；Wherein aqueous ascorbic acid moderate resistance
The concentration of bad hematic acid is 0.1 mM every milliliter.
2nd, whole gold nanorods made from above-mentioned steps are taken to be added to containing 0.05 milligram of Raman molecular 2- thionaphthol and 0.5
The dimethylformamide of milligram polystyrene polyacrylic acid block copolymer（1800 microlitres）And deionized water（400 microlitres）Mixing
Be placed in solution and after being stirred vigorously in oil bath pan at 110 DEG C heat 2 hours, room temperature is slowly dropped to afterwards, with 15000 turns/
Minute centrifugation collects precipitation after 5 minutes, produces gold/polymer core shell nanometer material；
3rd, take made from above-mentioned steps whole gold/polymer core shell nanometer materials be dissolved in by 0.2 milligram of gold chloride, 5 milligram 16
In 5 milliliters of mixed liquors of alkane trimethylammonium bromide and 0.8 milligram of sodium hydroxide composition, be slowly added dropwise while stirring 2 milliliters it is anti-bad
The aqueous solution of hematic acid（Concentration is 1 milligram every milliliter）, at room temperature react 1 hour, reaction terminate after, with 15000 revs/min from
The heart collects precipitation after 5 minutes, produce 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 the gold nano cap composition positioned at gold nanorods two ends, wherein, kernel is the Silver nanorod of 100 nanometers of length, and rod surface is
The polystyrene polyacrylic acid block copolymer layer of 10 nanometers of thickness, rod two ends are the gold nano cap of 90-100 nanometers of particle diameter.
Fig. 6 shows that what is prepared in the present embodiment has gold/polymer/gold three-layer nuclear shell nanometer dumbbell material of SERS activity
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 the gold/polymer/gold three-layer nuclear shell nanometer dumbbell with SERS activity prepared using the above method
Material Raman spectrogram.From figure 7 it can be seen that the SERS active materials have good SERS signal enhancement effect, its
1074 cm-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, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (9)
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
Rod kernel, the polymeric shell layer positioned at gold nanorods surface and the gold nano cap positioned at gold nanorods two ends are constituted, wherein described
The length of gold nanorods kernel be 100-400 nanometer, described polymeric shell layer is poly- for the polystyrene of 10 nanometers of thickness
Acrylic block copolymers layer, the particle diameter of described gold nano cap is 80-130 nanometers.
2. a kind of preparation method of gold/polymer/gold three-layer nuclear shell nanometer dumbbell material described in claim 1, its feature exists
In comprising the following steps：
1）The preparation of gold nanorods
A. configuration sodium citrate and gold chloride mixed aqueous solution, added thereto when being stirred vigorously at room temperature sodium citrate and
The sodium borohydride solution reduction of gold chloride mixed aqueous solution volume 3% obtains gold seeds solution；
B. above-mentioned gold seeds solution is taken to be added to the methyl bromide ammonium and gold chloride mixed aqueous solution of 9 times of volumes of gold seeds solution
In, then the aqueous ascorbic acid of 50 times of volumes of gold seeds solution is rapidly joined, reaction obtains the first reaction solution after 15 seconds；Take
One reaction solution is added rapidly in the hexadecane trimethyl ammonium bromide and gold chloride mixed aqueous solution of 9 times of volumes of the first reaction solution,
The aqueous ascorbic acid of first 50 times of volumes of reaction solution is rapidly joined again, and reaction obtains the second reaction solution after 30 seconds；Take second
Reaction solution is added in the hexadecane trimethyl ammonium bromide and gold chloride mixed aqueous solution of the second 3-45 times of reaction solution volume, is continued
Stirring stops stirring and static 24 hours after 1 hour, take supernatant liquor away, lower floor's liquid collected after centrifugation is precipitated, gold is produced
Nanometer rods；
2）The preparation of gold/polymer core shell nanometer material
By step 1）Obtained gold nanorods are added to common containing Raman molecular 2- thionaphthols and polystyrene polyacrylic acid block
Be placed in the dimethylformamide in water of polymers and after being stirred vigorously in oil bath pan at 110 DEG C heat 2 hours, afterwards slowly
Room temperature is down to, collected after centrifugation precipitation produces gold/polymer core shell nanometer material；
3）The preparation of gold/polymer/gold three-layer nuclear shell nanometer dumbbell material
By step 2）Obtained gold/polymer core shell nanometer material is dissolved in by gold chloride, hexadecane trimethyl ammonium bromide and hydrogen-oxygen
Change sodium to be dissolved in the mixed liquor that water is made, aqueous ascorbic acid is slowly added dropwise while stirring, at room temperature reaction 1 hour, instead
After should terminating, collected after centrifugation precipitation, gold/polymer/gold three-layer nuclear shell nanometer dumbbell material.
3. a kind of preparation method of gold/polymer according to claim 2/gold three-layer nuclear shell nanometer dumbbell material, it is special
Levy and be step 1）The preparation of gold nanorods is specially：
A. 20 milliliters of configuration sodium citrate and gold chloride mixed aqueous solution, add 0.6 thereto when being stirred vigorously at room temperature
Milliliter sodium borohydride solution reduction obtains gold seeds solution；
B. above-mentioned 1 milliliter of gold seeds solution is taken to be added to 9 milliliters of hexadecane trimethyl ammonium bromides and gold chloride mixed aqueous solution
In, then rapidly join after 50 microlitres of aqueous ascorbic acids react 15 seconds and obtain the first reaction solution；Take 1 milliliter of first reaction solution fast
Speed is added in 9 milliliters of hexadecane trimethyl ammonium bromides and gold chloride mixed aqueous solution, then rapidly joins 50 microlitres of ascorbic acid
The aqueous solution, reaction obtains the second reaction solution after 30 seconds；1 milliliter of second reaction solution is taken to be added to 15-45 milliliters of cetrimoniums
In ammonium bromide and gold chloride mixed aqueous solution, stop stirring after persistently stirring 1 hour and static 24 hours, take supernatant liquor away,
Collect and precipitate after lower floor's liquid is centrifuged 20 minutes with 10000 revs/min, produce gold nanorods.
4. a kind of preparation method of gold/polymer according to claim 3/gold three-layer nuclear shell nanometer dumbbell material, it is special
Levy and be：The concentration of sodium citrate is 0.00025 mM every milliliter in described sodium citrate and gold chloride mixed aqueous solution,
The concentration of gold chloride is 0.00025 mM every milliliter；The concentration of sodium borohydride is 0.1 mmoles in described sodium borohydride solution
You have every milliliter；The concentration of hexadecane trimethyl ammonium bromide in described hexadecane trimethyl ammonium bromide and gold chloride mixed aqueous solution
For 0.1 mM every milliliter, the concentration of gold chloride is 0.00025 mM every milliliter；Described aqueous ascorbic acid moderate resistance
The concentration of bad hematic acid is 0.1 mM every milliliter.
5. a kind of preparation method of gold/polymer according to claim 4/gold three-layer nuclear shell nanometer dumbbell material, it is special
Levy and be step 2）The preparation of gold/polymer core shell nanometer material is specially：Take step 1）Obtained whole gold nanorods are added
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 placed in after being stirred vigorously
In being heated 2 hours at 110 DEG C in oil bath pan, room temperature is slowly dropped to afterwards, and collected after centrifugation precipitation produces gold/polyalcohol nucleocapsid
Nano material.
6. a kind of preparation method of gold/polymer according to claim 5/gold three-layer nuclear shell nanometer dumbbell material, it is special
Levy and be step 3）The preparation of gold/polymer/gold three-layer nuclear shell nanometer dumbbell material is specially：By step 2）Obtained 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
Milligram sodium hydroxide is dissolved in the 5-15 milliliter mixed liquors that water is made, and 2-6 milliliters of ascorbic acid is slowly added dropwise while stirring water-soluble
Liquid, reacts 1 hour at room temperature, after reaction terminates, collected after centrifugation precipitation, produces gold/polymer/gold three-layer nuclear shell nanometer mute
Bell material.
7. a kind of preparation method of gold/polymer according to claim 6/gold three-layer nuclear shell nanometer dumbbell material, it is special
Levy and be：The concentration of ascorbic acid is 1 milligram every milliliter in described aqueous ascorbic acid.
8. a kind of preparation of gold/polymer/gold three-layer nuclear shell nanometer dumbbell material according to any one of claim 2-7
Method, it is characterised in that：Step 1）-3）Middle centrifugal speed is 5000-15000 revs/min, and centrifugation time is 5-30 minutes.
9. a kind of application of gold/polymer/gold three-layer nuclear shell nanometer dumbbell material any one of claim 1-8, its
It is characterised by：Purposes of the described core-shell nano dumbbell material in enhancing SERS signal output facet.
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| CN109676153A (en) * | 2019-01-28 | 2019-04-26 | 武汉科技大学 | A kind of method that can prepare simultaneously porous gold nano grain Yu hexagon gold-nano-piece |
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| CN113777034A (en) * | 2021-08-20 | 2021-12-10 | 嘉兴学院 | Gold nanometer bipyramid array substrate and preparation method and application thereof |
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| CN113777034B (en) * | 2021-08-20 | 2024-04-19 | 嘉兴学院 | Gold nano bipyramid array substrate and preparation method and application thereof |
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