CN107225235A - A kind of gold/silver/polymer/silver core-shell nano mushroom material with SERS activity and its preparation method and application - Google Patents
A kind of gold/silver/polymer/silver core-shell nano mushroom material with SERS activity and its preparation method and application Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- 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
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
Abstract
The invention discloses a kind of gold/silver/polymer/silver core-shell nano mushroom material with SERS activity and its preparation method and application, the core-shell nano mushroom material is by gold nano kernel, it is wrapped in the silver nanoparticle clad of gold nano core surface, it is wrapped in the polymeric outer layer of silver nanoparticle cover surface, the part of silver-colored shell four positioned at polymeric outer layer surface is constituted, wherein, gold nano kernel is the gold nano grain that particle diameter is 35~40 nanometers, silver nanoparticle clad is the silver nanoparticle layer that thickness is 2~10 nanometers, polymeric outer layer is the polystyrene polyacrylic acid block copolymer layer that thickness is 5~10 nanometers, silver-colored shell is the mushroom head silver nanoparticle layer that thickness is 90~130 nanometers；Advantage is that it uses Seed inducement method to prepare, with multilayer noble metal gold and silver nanometer layer, in the presence of external exciting light, and can intercouple effect between the surface local electromagnetic field that they are produced, and produces the SERS signal with very high strength and exports.
Description
Technical field
The present invention relates to material engineering and field of nanometer technology, more particularly, to a kind of gold/silver with SERS activity/gather
Compound/silver core-shell nano mushroom material and its preparation method and application.
Background technology
In past 20 years, due to the sensitivity with unimolecule rank, SERS (SERS) technology
Have been developed as the efficient analysis detection means in the fields such as life health care, environmental monitoring and food security.In various SERS materials
In material, the advantage of noble metal nanometer material is that its surface plasma body resonant vibration (LSPR) can be induced and produces extremely strong local electricity
Magnetic field, shows excellent enhancing characteristic.In these noble metal nanometer materials, gold is with its good chemical stability and biology
Compatibility and enjoy people to pay close attention to.Up to the present, people developed a variety of technologies of preparing synthesized nanometer rods, nanometer stand
Gold nano grains of pattern such as cube, nanometer sheet and nanometer sea urchin etc..By changing the structure and pattern of these gold nano-materials,
People can effectively adjust its surface plasma body resonant vibration characteristic.But, the SERS signal that single gold nano grain is sent
It is generally weaker, and be attached to the stability of the Raman molecular on gold nano grain surface and be frequently subjected to dissociation of ligand or the damage of exchange
Evil.Therefore, silver-colored shell is wrapped in outside gold nano grain to improve the stability of Raman molecular and the output intensity of Raman signal.
Meanwhile, extremely strong SERS signal output is further obtained, the gap built in nanostructured less than 10 nanometers is very must
Want.Therefore, the novel gold-silver composite material material with nano gap is made using advanced nano-fabrication technique, to obtain more
Good SERS performances are a popular research directions in current detection field.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of gold/silver/polymer/silver nucleocapsid with SERS activity and received
Rice mushroom material and its preparation method and application, there is the SERS signal of very high strength to export for it.
The present invention solve the technical scheme that is used of above-mentioned technical problem for：A kind of gold/silver/polymerization with SERS activity
Thing/silver core-shell nano mushroom material, it is characterised in that：The core-shell nano mushroom material by gold nano kernel, be wrapped in it is described
The silver nanoparticle clad of gold nano core surface, the polymeric outer layer for being wrapped in described silver nanoparticle cover surface, positioned at institute
The part of silver-colored shell four composition on the polymeric outer layer surface stated, wherein, described gold nano kernel is that particle diameter is 35~40 nanometers
Gold nano grain, described silver nanoparticle clad is silver nanoparticle that thickness is 2~10 nanometers layer, and described polymeric outer layer is
Thickness is 5~10 nanometers of polystyrene polyacrylic acid block copolymer layer, and described silver-colored shell is that thickness is 90~130 nanometers
Mushroom head silver nanoparticle layer.
The preparation method of the above-mentioned gold/silver/polymer/silver core-shell nano mushroom material with SERS activity, its feature
It is：Comprise the following steps：
Step one：The preparation of gold nano kernel：Aqueous solution of chloraurate is heated to 90~120 degrees Celsius, temperature stabilization is treated
Back is stirred vigorously side and adds sodium citrate aqueous solution, after reaction terminates for 15~25 minutes, collected after centrifugation precipitation, produces Jenner
Rice kernel, its particle diameter is 35~40 nanometers；
Step 2：The preparation of gold/galactic nucleus shell nanometer material：Gold nano kernel made from step one is taken, side is acute at room temperature
Strong stirring side rapidly joins the aqueous solution as made from 4- dredges yl benzoic acid and sodium hydroxide is dissolved in water, stands 1.5~2.5 hours
Afterwards, hydrazine hydrate aqueous solution and silver nitrate aqueous solution are gradually added when being stirred vigorously, after reaction terminates for 11~13 hours, after centrifugation
Precipitation is collected, gold/galactic nucleus shell nanometer material is produced；
Step 3：The preparation of gold/silver/polymer core shell nanometer material：By gold made from step 2/galactic nucleus shell nanometer material
After centrifugal concentrating, it is added to containing the Palmitoyl-sn-Glycero -3- Ethylphosphocholines (sodium salt) of molecule 2- bis- and polystyrene
In the mixed solution being made up of dimethylformamide and deionized water of polyacrylic acid block copolymer, and be stirred vigorously after
Heated 1.5~2.5 hours under 100~120 degrees Celsius, room temperature is slowly dropped to afterwards, collected after centrifugation precipitation produces gold/silver/and gathered
Compound core-shell nano material；
Step 4：The preparation of gold/silver/polymer/silver core-shell nano mushroom material：By gold/silver/polymerization made from step 3
Thing core-shell nano material is dissolved in silver nitrate and sodium citrate are dissolved in the mixed solution that water is made, and is delayed while stirring at room temperature
Slow that aqueous ascorbic acid is added dropwise, after reaction terminates for 1 hour, collected after centrifugation precipitation produces gold/silver/polymer/silver nucleocapsid and received
Rice mushroom material.
Described step one is specially：50~100 milliliters of concentration is heated for the aqueous solution of chloraurate of 10 mg/mls
To 90~120 degrees Celsius, treat that temperature stabilization back is stirred vigorously side and adds 0.75~1.5 milliliter of concentration for 10 mg/mls
Sodium citrate aqueous solution, reaction terminate within 15~25 minutes after, collected after centrifugation precipitation, produce gold nano kernel.
Described step two is specially：Whole gold nano kernels made from step one are taken, at room temperature when being stirred vigorously
The concentration for rapidly joining 8~24 microlitres is that the 4- of 0.00057 mM/milliliter dredges the yl benzoic acid aqueous solution and 8~24 microlitres
Concentration is the sodium hydrate aqueous solution of 0.25 mM/milliliter, after standing 1.5~2.5 hours, is gradually added when being stirred vigorously
10~30 microlitres of concentration is that the hydrazine hydrate aqueous solution and 10~30 microlitres of concentration of 0.01 mM/milliliter are 0.01 mmoles
The silver nitrate aqueous solution of that/milliliter, after reaction terminates for 11~13 hours, collected after centrifugation precipitation produces gold/silver-colored core-shell nano material
Material.
Described step three is specially：After whole gold/galactic nucleus shell nanometer material centrifugal concentratings made from step 2, add
To contain 0.05~0.1 milligram of the Palmitoyl-sn-Glycero -3- Ethylphosphocholines (sodium salt) of molecule 2- bis- and 0.5~1 milli
Gram polystyrene polyacrylic acid block copolymer by 900~1800 microlitres of dimethylformamide and 200~400 microlitres
Deionized water composition mixed solution in, and be stirred vigorously after under 100~120 degrees Celsius heat 1.5~2.5 hours, afterwards
Room temperature is slowly dropped to, collected after centrifugation precipitation produces gold/silver/polymer core shell nanometer material.
Described step four is specially：1~2 milliliter made from step 3 of gold/silver/polymer core shell nanometer material is molten
In 9~18 milliliters of the mixed solution that water is made is dissolved in by 2~4 milligrams of silver nitrate and 6~12 milligrams of sodium citrate, in
The concentration for being slowly added dropwise 2~4 milliliters while stirring at room temperature is the aqueous ascorbic acid of 2 mg/mls, reacts 1 hour and ties
Shu Hou, collected after centrifugation precipitation, produces gold/silver/polymer/silver core-shell nano mushroom material.
The centrifugal speed of centrifugal treating in collected after centrifugation precipitation process of the described step one into described step four
For 5000~15000 revs/min, centrifugation time is 5~30 minutes；Gold/galactic nucleus shell nanometer material in described step three from
The centrifugal speed of centrifugal treating is 5000~15000 revs/min in heart concentration process, and centrifugation time is 5~30 minutes.
The application of the above-mentioned gold/silver/polymer/silver core-shell nano mushroom material with SERS activity, it is characterised in that：
Purposes of the described gold/silver/polymer/silver core-shell nano mushroom material in enhancing SERS signal output facet.
Compared with prior art, the advantage of the invention is that：
1) present invention firstly discloses a kind of gold/silver/polymer/silver core-shell nano mushroom material with SERS activity,
The core-shell nano mushroom material by gold nano kernel, be wrapped in the silver nanoparticle clad of gold nano core surface, be wrapped in Yin Na
The polymeric outer layer of rice cover surface, the part of silver-colored shell four composition positioned at polymeric outer layer surface, with novel multilayer
Core shell structure and the mushroom-shaped structure of novelty (a large amount of nano gaps for having between nucleocapsid and the curvature of mushroom-shaped structure compared with
Big tip location can produce substantial amounts of SERS focuses in the presence of external exciting light), wherein amphipathic block copolymerization
Thing, particularly polystyrene acrylic acid block copolymer are due to good translucency, without the output of influence SERS signal.
2) present invention prepares gold/silver/polymer/silver core-shell nano mushroom material using Seed inducement method, with close phase
The silver-colored shell of golden core even and inside and outside two layers of silver nanoparticle layer at a distance of only 10 rans, in the presence of external exciting light, they
Can intercouple effect between the surface local electromagnetic field of generation, produce hot spot region so that and the gold/silver/polymer/
The SERS signal that silver-colored core-shell nano mushroom material has very high strength is exported.
3) present invention is prepared using Seed inducement method, and preparation technology is simple, and the cycle is short, and yield is high, it is easy to promoted and big rule
Mould is produced.
Brief description of the drawings
Fig. 1 is the transmission electron microscope photo of the gold nano kernel prepared in the embodiment of the present invention one；
Fig. 2 is the transmission electron microscope photo of the gold/galactic nucleus shell nanometer material prepared in the embodiment of the present invention one；
The transmission electron microscope of gold/silver/polymer core shell nanometer materials of the Fig. 3 to be prepared in the embodiment of the present invention one shines
Piece；
Fig. 4 is the transmitted electron of the gold/silver/polymer/silver core-shell nano mushroom material prepared in the embodiment of the present invention one
Microphotograph；
Fig. 5 is the Raman using the gold/silver prepared in the embodiment of the present invention one/polymer/silver core-shell nano mushroom material
Testing result；
Fig. 6 is the transmitted electron of the gold/silver/polymer/silver core-shell nano mushroom material prepared in the embodiment of the present invention two
Microphotograph；
Fig. 7 is the Raman using the gold/silver prepared in the embodiment of the present invention two/polymer/silver core-shell nano mushroom material
Testing result；
Fig. 8 is the transmitted electron of the gold/silver/polymer/silver core-shell nano mushroom material prepared in the embodiment of the present invention three
Microphotograph；
Fig. 9 is the Raman using the gold/silver prepared in the embodiment of the present invention three/polymer/silver core-shell nano mushroom material
Testing 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 one：
A kind of preparation for gold/silver/polymer/silver core-shell nano mushroom material with SERS activity that the present embodiment is proposed
Method, it comprises the following steps：
Step one：50 milliliters of concentration is heated to 100 degrees Celsius for the aqueous solution of chloraurate of 10 mg/mls, temperature is treated
The stable back of degree is stirred vigorously side and adds sodium citrate aqueous solution of 0.75 milliliter of the concentration for 10 mg/mls, reacts 20 points
After clock terminates, collect and precipitate after being centrifuged 20 minutes with 10000 revs/min, produce gold nano kernel.
Step 2：Whole gold nano kernels made from step one are taken, 8 microlitres are rapidly joined when being stirred vigorously at room temperature
Concentration be that to dredge the yl benzoic acid aqueous solution and 8 microlitres of concentration be 0.25 mM/milliliter by the 4- of 0.00057 mM/milliliter
Sodium hydrate aqueous solution, after standing 2 hours, it is 0.01 mM/milli that 10 microlitres of concentration is gradually added when being stirred vigorously
The hydrazine hydrate aqueous solution risen and the silver nitrate aqueous solution that 10 microlitres of concentration is 0.01 mM/milliliter, reaction terminate for 12 hours
Afterwards, collect and precipitate after being centrifuged 20 minutes with 10000 revs/min, produce gold/galactic nucleus shell nanometer material.
Step 3：Whole gold/galactic nucleus shell nanometer material made from step 2 is dense with 10000 revs/min of centrifugations 20 minutes
After contracting, it is added to containing 0.05 milligram of the Palmitoyl-sn-Glycero -3- Ethylphosphocholines (sodium salt) of molecule 2- bis- and 0.5 milli
Gram polystyrene polyacrylic acid block copolymer by 900 microlitres of dimethylformamide and 200 microlitres of deionized water group
Into mixed solution in, and be stirred vigorously after under 110 degrees Celsius heat 2 hours, room temperature is slowly dropped to afterwards, with 10000 turns/
Minute centrifugation collects precipitation after 20 minutes, produces gold/silver/polymer core shell nanometer material.
Step 4：1 milliliter made from step 3 of gold/silver/polymer core shell nanometer material is dissolved in by 2 milligrams of nitric acid
Silver and 6 milligrams of sodium citrate are dissolved in 9 milliliters of the mixed solution that water is made, and 2 millis are slowly added dropwise while stirring at room temperature
The concentration risen is the aqueous ascorbic acid of 2 mg/mls, after reaction terminates for 1 hour, is centrifuged 20 minutes with 10000 revs/min
Precipitation is collected afterwards, produces gold/silver/polymer/silver core-shell nano mushroom material.
What the present embodiment was prepared has gold/silver/polymer/silver core-shell nano mushroom material of SERS activity by Jenner
Rice kernel, be wrapped in the silver nanoparticle clad of gold nano core surface, be wrapped in silver nanoparticle cover surface polymeric outer layer,
The part of silver-colored shell four positioned at polymeric outer layer surface is constituted, wherein, gold nano kernel is the gold nano that particle diameter is 36 nanometers
Grain, silver nanoparticle clad is the silver nanoparticle layer that thickness is 5.5 nanometers, and polymeric outer layer is the polystyrene that thickness is 8.5 nanometers
Polyacrylic acid block copolymer layer, silver-colored shell is the mushroom head silver nanoparticle layer that thickness is 125 nanometers.
Gold/silver/polymer/silver core-shell nano mushroom the material for having SERS active that the present embodiment is prepared can be applied
In enhancing SERS signal output facet.
Fig. 1 shows the transmission electron microscope photo of the gold nano kernel prepared in the present embodiment.
Fig. 2 shows the transmission electron microscope photo of the gold/galactic nucleus shell nanometer material prepared in the present embodiment.From figure
As can be seen that prepared gold/galactic nucleus shell nanometer material is core shell structure in 2.
The transmission electron microscope that Fig. 3 shows the gold/silver/polymer core shell nanometer material prepared in the present embodiment shines
Piece.From figure 3, it can be seen that prepared gold/silver/polymer core shell nanometer material is three-layer nuclear shell structure.
Fig. 4 shows the transmitted electron of the gold/silver/polymer/silver core-shell nano mushroom material prepared in the present embodiment
Microphotograph.Figure 4, it is seen that prepared gold/silver/polymer/silver core-shell nano mushroom material is four layers of nucleocapsid
Structure.
Fig. 5 gives the Raman inspection using the gold/silver prepared in the present embodiment/polymer/silver core-shell nano mushroom material
Light-metering spectrogram.From figure 5 it can be seen that gold/the silver/polymer/silver core-shell nano mushroom material has good SERS signal
Enhancement effect, it is in 1078cm-1The Raman signal intensity at place reaches 6500.Abscissa is Raman shift (Raman in Fig. 5
Shift), ordinate is intensity (Intensity).
Embodiment two：
A kind of preparation for gold/silver/polymer/silver core-shell nano mushroom material with SERS activity that the present embodiment is proposed
Method, it comprises the following steps：
Step one：75 milliliters of concentration is heated to 100 degrees Celsius for the aqueous solution of chloraurate of 10 mg/mls, temperature is treated
The stable back of degree is stirred vigorously side and adds sodium citrate aqueous solution of 1.125 milliliters of the concentration for 10 mg/mls, reacts 20 points
After clock terminates, collected within 30 minutes and precipitated with 5000 revs/min of centrifugations, produce gold nano kernel.
Step 2：Whole gold nano kernels made from step one are taken, 16 are rapidly joined when being stirred vigorously at room temperature micro-
The concentration risen is that the thin yl benzoic acid aqueous solution of 4- and 16 microlitres of concentration of 0.00057 mM/milliliter are 0.25 mM/milli
The sodium hydrate aqueous solution risen, after standing 2 hours, gradually added when being stirred vigorously 20 microlitres of concentration for 0.01 mM/
The hydrazine hydrate aqueous solution and 20 microlitres of concentration of milliliter are the silver nitrate aqueous solution of 0.01 mM/milliliter, react 12 hours and tie
Shu Hou, is collected and precipitated, produce gold/galactic nucleus shell nanometer material for 30 minutes with 5000 revs/min of centrifugations.
Step 3：Whole gold/galactic nucleus shell nanometer materials made from step 2 are concentrated for 30 minutes with 5000 revs/min of centrifugations
Afterwards, it is added to containing 0.075 milligram of the Palmitoyl-sn-Glycero -3- Ethylphosphocholines (sodium salt) of molecule 2- bis- and 0.75 milli
Gram polystyrene polyacrylic acid block copolymer by 1350 microlitres of dimethylformamide and 300 microlitres of deionized water group
Into mixed solution in, and be stirred vigorously after under 110 degrees Celsius heat 2 hours, room temperature is slowly dropped to afterwards, with 5000 turns/
Minute centrifugation collects precipitation in 30 minutes, produces gold/silver/polymer core shell nanometer material.
Step 4：1.5 milliliters made from step 3 of gold/silver/polymer core shell nanometer material is dissolved in by 3 milligrams of nitre
Sour silver and 9 milligrams of sodium citrate are dissolved in 13.5 milliliters of the mixed solution that water is made, slow while stirring at room temperature to drip
Plus 3 milliliters of concentration is the aqueous ascorbic acid of 2 mg/mls, after reaction terminates for 1 hour, with 5000 revs/min of centrifugations 30
Minute collects precipitation, produces gold/silver/polymer/silver core-shell nano mushroom material.
What the present embodiment was prepared has gold/silver/polymer/silver core-shell nano mushroom material of SERS activity by Jenner
Rice kernel, be wrapped in the silver nanoparticle clad of gold nano core surface, be wrapped in silver nanoparticle cover surface polymeric outer layer,
The part of silver-colored shell four positioned at polymeric outer layer surface is constituted, wherein, gold nano kernel is the gold nano that particle diameter is 40 nanometers
Grain, silver nanoparticle clad is the silver nanoparticle layer that thickness is 4.5 nanometers, and polymeric outer layer is the polystyrene that thickness is 8.5 nanometers
Polyacrylic acid block copolymer layer, silver-colored shell is the mushroom head silver nanoparticle layer that thickness is 105 nanometers.
Gold/silver/polymer/silver core-shell nano mushroom the material for having SERS active that the present embodiment is prepared can be applied
In enhancing SERS signal output facet.
Fig. 6 shows the transmitted electron of the gold/silver/polymer/silver core-shell nano mushroom material prepared in the present embodiment
Microphotograph.From fig. 6 it can be seen that prepared gold/silver/polymer/silver core-shell nano mushroom material is four layers of nucleocapsid
Structure.
Fig. 7 gives the Raman inspection using the gold/silver prepared in the present embodiment/polymer/silver core-shell nano mushroom material
Light-metering spectrogram.It can be seen from figure 7 that gold/the silver/polymer/silver core-shell nano mushroom material has good SERS signal
Enhancement effect, it is in 1078cm-1The Raman signal intensity at place reaches 6000.Abscissa is Raman shift (Raman in Fig. 7
Shift), ordinate is intensity (Intensity).
Embodiment three：
A kind of preparation for gold/silver/polymer/silver core-shell nano mushroom material with SERS activity that the present embodiment is proposed
Method, it comprises the following steps：
Step one：100 milliliters of concentration is heated to 100 degrees Celsius for the aqueous solution of chloraurate of 10 mg/mls, temperature is treated
The stable back of degree is stirred vigorously side and adds sodium citrate aqueous solution of 1.5 milliliters of the concentration for 10 mg/mls, reacts 20 minutes
After end, collect and precipitate after being centrifuged 5 minutes with 15000 revs/min, produce gold nano kernel.
Step 2：Whole gold nano kernels made from step one are taken, 24 are rapidly joined when being stirred vigorously at room temperature micro-
The concentration risen is that the thin yl benzoic acid aqueous solution of 4- and 24 microlitres of concentration of 0.00057 mM/milliliter are 0.25 mM/milli
The sodium hydrate aqueous solution risen, after standing 2 hours, gradually added when being stirred vigorously 30 microlitres of concentration for 0.01 mM/
The hydrazine hydrate aqueous solution and 30 microlitres of concentration of milliliter are the silver nitrate aqueous solution of 0.01 mM/milliliter, react 12 hours and tie
Shu Hou, is collected after being centrifuged 5 minutes with 15000 revs/min and precipitated, produce gold/galactic nucleus shell nanometer material.
Step 3：Whole gold/galactic nucleus shell nanometer materials made from step 2 are concentrated for 5 minutes with 15000 revs/min of centrifugations
Afterwards, it is added to containing 0.1 milligram of the Palmitoyl-sn-Glycero -3- Ethylphosphocholines (sodium salt) of molecule 2- bis- and 1 milligram
Polystyrene polyacrylic acid block copolymer is made up of 1800 microlitres of dimethylformamide and 400 microlitres of deionized water
In mixed solution, and it is stirred vigorously after being heated 2 hours under 110 degrees Celsius, room temperature is slowly dropped to afterwards, with 15000 revs/min
Centrifugation collects precipitation after 5 minutes, produces gold/silver/polymer core shell nanometer material.
Step 4：2 milliliters made from step 3 of gold/silver/polymer core shell nanometer material is dissolved in by 4 milligrams of nitric acid
Silver and 12 milligrams of sodium citrate are dissolved in 18 milliliters of the mixed solution that water is made, and are slowly added dropwise 4 while stirring at room temperature
The concentration of milliliter is the aqueous ascorbic acid of 2 mg/mls, after reaction terminates for 1 hour, and 5 points are centrifuged with 15000 revs/min
Precipitation is collected after clock, gold/silver/polymer/silver core-shell nano mushroom material is produced.
What the present embodiment was prepared has gold/silver/polymer/silver core-shell nano mushroom material of SERS activity by Jenner
Rice kernel, be wrapped in the silver nanoparticle clad of gold nano core surface, be wrapped in silver nanoparticle cover surface polymeric outer layer,
The part of silver-colored shell four positioned at polymeric outer layer surface is constituted, wherein, gold nano kernel is the gold nano that particle diameter is 35 nanometers
Grain, silver nanoparticle clad is the silver nanoparticle layer that thickness is 2 nanometers, and polymeric outer layer is the polystyrene poly- third that thickness is 10 nanometers
Olefin(e) acid block copolymer layer, silver-colored shell is the mushroom head silver nanoparticle layer that thickness is 104 nanometers.
Gold/silver/polymer/silver core-shell nano mushroom the material for having SERS active that the present embodiment is prepared can be applied
In enhancing SERS signal output facet.
Fig. 8 shows the transmitted electron of the gold/silver/polymer/silver core-shell nano mushroom material prepared in the present embodiment
Microphotograph.As can be seen from Figure 8, prepared gold/silver/polymer/silver core-shell nano mushroom material is four layers of nucleocapsid
Structure.
Fig. 9 gives the Raman inspection using the gold/silver prepared in the present embodiment/polymer/silver core-shell nano mushroom material
Light-metering spectrogram.It can be seen in figure 9 that gold/the silver/polymer/silver core-shell nano mushroom material has good SERS signal
Enhancement effect, it is in 1078cm-1The Raman signal intensity at place reaches 5000.Abscissa is Raman shift (Raman in Fig. 9
Shift), ordinate is intensity (Intensity).
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 (8)
1. a kind of gold/silver/polymer/silver core-shell nano mushroom material with SERS activity, it is characterised in that：The core-shell nano
Mushroom material by gold nano kernel, be wrapped in the silver nanoparticle clad of described gold nano core surface, be wrapped in described silver
The polymeric outer layer of nanometer cover surface, the part of silver-colored shell four composition positioned at described polymeric outer layer surface, wherein, institute
The gold nano kernel stated is the gold nano grain that particle diameter is 35~40 nanometers, and described silver nanoparticle clad is that thickness is 2~10
The silver nanoparticle layer of nanometer, described polymeric outer layer is the polystyrene polyacrylic acid block copolymer that thickness is 5~10 nanometers
Layer, described silver-colored shell is the mushroom head silver nanoparticle layer that thickness is 90~130 nanometers.
2. a kind of preparation of the gold/silver/polymer/silver core-shell nano mushroom material with SERS activity described in claim 1
Method, it is characterised in that：Comprise the following steps：
Step one：The preparation of gold nano kernel：Aqueous solution of chloraurate is heated to 90~120 degrees Celsius, temperature stabilization back is treated
It is stirred vigorously side and adds sodium citrate aqueous solution, after reaction terminates for 15~25 minutes, collected after centrifugation precipitation is produced in gold nano
Core, its particle diameter is 35~40 nanometers；
Step 2：The preparation of gold/galactic nucleus shell nanometer material：Gold nano kernel made from step one is taken, side is acutely stirred at room temperature
Mix side and rapidly join the aqueous solution as made from 4- dredges yl benzoic acid and sodium hydroxide is dissolved in water, after standing 1.5~2.5 hours, side
It is stirred vigorously side and gradually adds hydrazine hydrate aqueous solution and silver nitrate aqueous solution, after reaction terminates for 11~13 hours, collected after centrifugation
Precipitation, produces gold/galactic nucleus shell nanometer material；
Step 3：The preparation of gold/silver/polymer core shell nanometer material：By gold made from step 2/galactic nucleus shell nanometer material centrifugation
After concentration, it is added to containing the Palmitoyl-sn-Glycero -3- Ethylphosphocholines (sodium salt) of molecule 2- bis- and polystyrene poly- third
In the mixed solution being made up of dimethylformamide and deionized water of olefin(e) acid block copolymer, and be stirred vigorously after 100~
Heated 1.5~2.5 hours under 120 degrees Celsius, room temperature is slowly dropped to afterwards, collected after centrifugation precipitation produces gold/silver/polymer
Core-shell nano material；
Step 4：The preparation of gold/silver/polymer/silver core-shell nano mushroom material：By gold/silver/polymer core made from step 3
Shell nanometer material is dissolved in silver nitrate and sodium citrate are dissolved in the mixed solution that water is made, slow while stirring at room temperature to drip
Plus aqueous ascorbic acid, after reaction terminates for 1 hour, collected after centrifugation precipitation produces gold/silver/polymer/silver core-shell nano mushroom
Mushroom material.
3. a kind of gold/silver/polymer/silver core-shell nano mushroom material with SERS activity according to claim 2
Preparation method, it is characterised in that：Described step one is specially：By chlorine gold of 50~100 milliliters of the concentration for 10 mg/mls
Aqueous acid is heated to 90~120 degrees Celsius, treats that the concentration that temperature stabilization back is stirred vigorously 0.75~1.5 milliliter of side addition is
The sodium citrate aqueous solution of 10 mg/mls, after reaction terminates for 15~25 minutes, collected after centrifugation precipitation is produced in gold nano
Core.
4. a kind of gold/silver/polymer/silver core-shell nano mushroom material with SERS activity according to claim 3
Preparation method, it is characterised in that：Described step two is specially：Whole gold nano kernels made from step one are taken, at room temperature
Rapidly joined when being stirred vigorously 8~24 microlitres of concentration for the 4- of 0.00057 mM/milliliter dredge the yl benzoic acid aqueous solution and
8~24 microlitres of concentration is the sodium hydrate aqueous solution of 0.25 mM/milliliter, and after standing 1.5~2.5 hours, side is acutely stirred
Mix side and gradually add hydrazine hydrate aqueous solution and 10~30 microlitre of concentration of 10~30 microlitres of the concentration for 0.01 mM/milliliter
For the silver nitrate aqueous solution of 0.01 mM/milliliter, after reaction terminates for 11~13 hours, collected after centrifugation precipitation produces gold/silver
Core-shell nano material.
5. a kind of gold/silver/polymer/silver core-shell nano mushroom material with SERS activity according to claim 4
Preparation method, it is characterised in that：Described step three is specially：By whole gold/galactic nucleus shell nanometer material made from step 2 from
After heart concentration, it is added to containing 0.05~0.1 milligram of the Palmitoyl-sn-Glycero -3- Ethylphosphocholine (sodium of molecule 2- bis-
Salt) and 0.5~1 milligram of polystyrene polyacrylic acid block copolymer by 900~1800 microlitres dimethylformamide and
In the mixed solution of 200~400 microlitres of deionized water composition, and it is stirred vigorously after heating 1.5 under 100~120 degrees Celsius
~2.5 hours, room temperature is slowly dropped to afterwards, and collected after centrifugation precipitation produces gold/silver/polymer core shell nanometer material.
6. a kind of gold/silver/polymer/silver core-shell nano mushroom material with SERS activity according to claim 5
Preparation method, it is characterised in that：Described step four is specially：By 1~2 milliliter made from step 3 of gold/silver/polymer core
Shell nanometer material is dissolved in is dissolved in 9~18 milliliters that water is made by 2~4 milligrams of silver nitrate and 6~12 milligrams of sodium citrate
In mixed solution, 2~4 milliliters of concentration is slowly added dropwise while stirring at room temperature water-soluble for the ascorbic acid of 2 mg/mls
Liquid, after reaction terminates for 1 hour, collected after centrifugation precipitation produces gold/silver/polymer/silver core-shell nano mushroom material.
7. a kind of gold/silver/polymer/silver core-shell nano with SERS activity according to any one of claim 2 to 6
The preparation method of mushroom material, it is characterised in that：Collected after centrifugation of the described step one into described step four was precipitated
The centrifugal speed of centrifugal treating is 5000~15000 revs/min in journey, and centrifugation time is 5~30 minutes；In described step three
Gold/galactic nucleus shell nanometer material centrifugal concentrating during centrifugal treating centrifugal speed be 5000~15000 revs/min, centrifugation
Time is 5~30 minutes.
8. gold/silver/polymer/silver core-shell nano the mushroom with SERS activity any one of a kind of claim 1 to 7
The application of material, it is characterised in that：Described gold/silver/polymer/silver core-shell nano mushroom material is in enhancing SERS signal output
The purposes of aspect.
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