CN110261367A - A kind of SERS substrate, preparation method, regulate and control SERS substrate hotspot architecture method and SERS substrate application - Google Patents
A kind of SERS substrate, preparation method, regulate and control SERS substrate hotspot architecture method and SERS substrate application Download PDFInfo
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Abstract
The invention belongs to spectrum analysis field more particularly to a kind of SERS substrate, preparation method, regulate and control SERS substrate hotspot architecture method and SERS substrate application.SERS substrate provided by the invention includes two parts: stretchable polymeric membrane, and the noble metal nano chain being embedded into stretchable polymeric membrane, and the noble metal nano chain is self-assembly of by noble metal nano particles.SERS substrate provided by the invention overcomes the shortcomings that existing SERS substrate lacks Modulatory character, and hotspot architecture can be by double regulation control.And the SERS substrate also has excellent selective penetrated property, can be directly used for analyzing the small-molecule substance in complicated food and biological sample, does not need to carry out complex sample cumbersome pre-separation.In addition, SERS substrate sensitivity, preferable homogeneity and stability also with higher provided by the invention, and easy to carry, can long-term preservation, be very suitable to on-site test, there is very big some commercial potential.
Description
Technical field
The invention belongs to spectrum analysis field more particularly to a kind of SERS substrate, preparation method, regulation SERS substrate heat
The application of the method and SERS substrate of point structure.
Background technique
Surface enhanced Raman spectroscopy (SERS) is since comprising unique finger print information, non-destructive and ultrasensitiveness are special
Point is widely used to the fields such as chemistry, biology and environmental analysis.The enhancing mechanism being widely recognized as in the field SERS is electricity
Magnetic field-enhanced (EM), produced by the near-field coupling as the local surface plasma in noble metal nano particles.Local electromagnetism
The size of field determines that this gap is usually less than 10nm by the gap size (gap) between metal nanoparticle, also by image
Referred to as " hot spot ".The result shows that gap be 1nm when electromagnetic field it is most strong, and be lower than 0.5nm when by occur electron tunneling effect cause
The violent decline of SERS signal.Therefore, design, building and the regulation of hotspot architecture be the most important research direction in the field SERS it
One.
The simplest method that " hot spot " is constructed will be received using difunctional bridging agents (linker) such as two mercaptan, DNA
Rice grain connects to realize, but the size of " hot spot " its spacing constructed in this way depends on the length of bridging agent,
And adjustability is poor.
In addition, 3D hot spot matrix can be createed by the volatilization of simple solvent, similar, the 2D film that liquid level is assembled into
The variation in gap can also be dynamically observed by the volatilization of solvent.But the disadvantages of this method is the tune of hot spot
Control is irreversible, uncontrollable, and hot spot generation process is very time-consuming.
In addition, being also by the combination of stimulus responsive polymers and metal nanoparticle is a kind of side for commonly constructing hot spot
Method, it chemically or physically (pH, temperature) stimulation can will be converted into optical signalling.By changing pH or temperature, it can be achieved that can
Inverse dynamic regulation hotspot architecture.But the regulation of hot spot is usually only carried out in point-to-point transmission, cannot achieve the regulation of continuous reversible.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of SERS substrate, preparation method, regulation SERS substrate hot spots
The application of the method and SERS substrate of structure, the hotspot architecture of SERS substrate provided by the invention can be realized simple, reversible, dynamic
State, continuous regulation.
The present invention provides a kind of SERS substrates, comprising:
Stretchable polymeric membrane；
With the noble metal nano chain being embedded into the stretchable polymeric membrane；
The noble metal nano chain is self-assembly of by noble metal nano particles.
Preferably, the stretchable polymeric membrane includes high molecular material and plasticizer；
The high molecular material includes polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, polyacrylamide, poly- third
One of olefin(e) acid and polyacrylate are a variety of.
Preferably, the noble metal nano chain is self-assembly of by 2~20 noble metal nano particles；
The length of the noble metal nano chain is 30~800nm.
Preferably, the noble metal nano particles include the golden contracted payment of spherical shape of spherical gold nano grain and/or core-shell structure
Nano particle；
The partial size of the noble metal nano particles is 10~50nm.
The present invention provides a kind of preparation methods of SERS substrate, comprising the following steps:
A) it induces the noble metal nano particles in the noble metal nano particles hydrosol to be self-assembly of noble metal nano chain, obtains
To the sol solutions containing noble metal nano chain；
B) sol solutions that step a) is obtained are mixed with the raw material for being used to prepare stretchable polymeric membrane, obtains into film liquid；
C) it is film-made described at film liquid, obtains SERS substrate.
Preferably, step a) is specifically included:
A1 the noble metal nano particles hydrosol is mixed with modified molecules), obtains the modified noble metal nano particles in surface
The hydrosol；
A2) to pass through step a1) processing the hydrosol carry out centrifugal concentrating, be then re-dispersed into dielectric constant be less than etc.
In the solvent of water, sol solutions are obtained；
A3 the ionic strength for) regulating and controlling the sol solutions, makes your gold the noble metal nano particles in sol solutions are self-assembly of
Belong to nano chain, obtains the sol solutions containing noble metal nano chain.
Preferably, step a1) in, the content of noble metal nano particles is 10 in the noble metal nano particles hydrosol-13
~10-8mol/L；The modified molecules include three sulfonate of triphenylphosphine, (to sulfonyl-phenyl) phenyl phosphonium salt and diphenyl three
One of methoxyl group phosphorus -3- sulfonate is a variety of；The modified molecules in the hydrosol final concentration of 10-9~10-2mol/
L；
Step a2) in, the volume ratio of the hydrosol and solvent is (5~20): 1；
Step a3) in, regulate and control the mode of the ionic strength are as follows: mix the sol solutions with salt；The salt includes sodium
One of halide, potassium halide, ammonium halide, sodium sulphate, potassium sulfate, ammonium sulfate, sodium nitrate, potassium nitrate and ammonium nitrate or
It is a variety of；The salt in sol solutions final concentration of 10-6~10-2mol/L。
Preferably, in step b), the raw material of the stretchable polymeric membrane includes high molecular material and plasticizer；
The high molecular material is being 5~20g/100mL at the content in film liquid；
The plasticizer accounts for 5~20wt% of the high molecular material quality.
The present invention provides a kind of methods of regulation SERS substrate hotspot architecture, comprising the following steps:
The SERS substrate described in above-mentioned technical proposal stretches.
The present invention provides the methods that the small-molecule substance in a kind of pair of mixed system carries out SERS detection, including following step
It is rapid:
Mixed system is added dropwise in the one side of SERS substrate described in above-mentioned technical proposal, after its drying, to the SERS
The another side of substrate carries out SERS detection, obtains the SERS testing result of small-molecule substance.
Compared with prior art, the present invention provides a kind of SERS substrate, preparation method, regulation SERS substrate hot spot knots
The application of the method and SERS substrate of structure.SERS substrate provided by the invention includes two parts: stretchable polymeric membrane, and insertion
To the noble metal nano chain in the stretchable polymeric membrane, the noble metal nano chain is by noble metal nano particles self assembly shape
At.SERS substrate provided by the invention overcomes the shortcomings that existing SERS substrate lacks Modulatory character, and hotspot architecture can be double
To regulation, specifically: on the one hand, the present invention can be realized by controlling the condition of noble metal nano particles self assembly to noble metal
The regulation of nanometer chain length；On the other hand, the present invention can make polymeric membrane generate deformation by dynamic mechanicals efforts, thus
Realization carries out accurate, continuous and reversible regulation to the gap for the noble metal nano chain being embedded.Moreover, because the present invention selects
Host material of the polymeric membrane as SERS substrate is selected, therefore can also make substrate that there is excellent selective penetrated property, that is, is allowed small
Molecule diffuses into " hot spot " region and macromolecular is blocked on region except hot spot, is based on the characteristic, provided by the invention
SERS substrate can be directly used for the small-molecule substance in analysis complicated food and biological sample (such as milk, serum, urine), no
It needs to carry out complex sample cumbersome pre-separation.In addition, can also protect testing molecule as host material using polymeric membrane
When carrying out SERS detection from the damage of laser, the detection accuracy of SERS substrate is improved.In addition, SERS provided by the invention
Substrate sensitivity also with higher, preferable homogeneity and stability, and easy to carry, can long-term preservation, be very suitable to existing
Field detecting has very big some commercial potential.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is ultraviolet-visible (UV-VIS) abosrption spectrogram for the nanogold that the embodiment of the present invention 2 provides；
Fig. 2 is transmission electron microscope (TEM) image for the nanogold that the embodiment of the present invention 2 provides；
Fig. 3 is the TEM figure for the gold nano chain that the embodiment of the present invention 5 provides；
Fig. 4 is the UV-VIS figure for the SERS substrate that the embodiment of the present invention 5 provides；
Fig. 5 is UV- of the SERS substrate of the offer of the embodiment of the present invention 6 in non-stretched, elongation strain 50% and after restoring
VIS figure；
Fig. 6 is the SERS substrate of the offer of the embodiment of the present invention 6 in differently strained lower detection same concentration (10-7Mol/L)
The SERS spectra figure of crystal violet；
Fig. 7 is the SERS substrate detection 10 that the embodiment of the present invention 7 provides-750 SERS spectra figures of the CV of mol/L；
Fig. 8 is the SERS spectra figure of the CV for the SERS substrate detection detection various concentration that the embodiment of the present invention 7 provides；
Fig. 9 is the CV that various concentration is detected after the SERS substrate that the embodiment of the present invention 7 provides stores 4 months at room temperature
SERS spectra figure；
Figure 10 is the offer of the embodiment of the present invention 8 to the detected SERS spectra figure of SERS backside of substrate progress；
Figure 11 is the offer of the embodiment of the present invention 9 to the detected SERS spectra figure of SERS backside of substrate progress.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The present invention provides a kind of SERS substrates, comprising:
Stretchable polymeric membrane；
With the noble metal nano chain being embedded into the stretchable polymeric membrane；
The noble metal nano chain is self-assembly of by noble metal nano particles.
SERS substrate provided by the invention includes stretchable polymeric membrane and noble metal nano chain.Wherein, described stretchable
Polymeric membrane preferably includes high molecular material and plasticizer；The high molecular material is preferably that hydrophilic polymer includes but unlimited
In polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyethylene oxide (PEO), polyacrylamide, polyacrylic acid and poly- third
One of olefin(e) acid ester is a variety of；The weight average molecular weight of the hydrophilic polymer is preferably 50000~2000000, specifically may be used
For 50000,100000,130000,200000,300000,360000,400000,500000,800000,1000000,
1300000,1500000 or 2000000；The plasticizer includes but is not limited to low molecular poly；The low molecular weight
Polyethylene glycol preferably includes polyethylene glycol 200 and/or polyethylene glycol 400；The plasticizer preferably accounts for the high molecular material matter
Amount 5~20wt%, concretely 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%,
13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt% or 20wt%；The stretchable polymeric membrane
Thickness is preferably 100~500 μm, concretely 100 μm, 125 μm, 150 μm, 175 μm, 200 μm, 225 μm, 250 μm, 275 μm,
300 μm, 325 μm, 350 μm, 375 μm, 400 μm, 425 μm, 450 μm, 475 μm or 500 μm.
In the present invention, the noble metal nano chain is embedded into the stretchable polymeric membrane, by noble metal nano
Grain is self-assembly of.Wherein, the noble metal nano particles preferably include spherical gold nano grain (Au NPs) and/or nucleocapsid knot
The golden contracted payment nano particle (Ag@Au NPs) of the spherical shape of structure；The partial size of the noble metal nano particles is preferably 10~50nm, specifically
It can be 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm or 50nm；The main chain of the noble metal nano chain is preferred
It is self-assembly of by 2~20 noble metal nano particles, concretely 2,3,4,5,6,7,8,9,10
A, 11,12,13,14,15,16,17,18,19 or 20；The length of the noble metal nano chain
Preferably 30~800nm, concretely 30nm, 50nm, 80nm, 100nm, 120nm, 150nm, 170nm, 200nm, 230nm,
250nm, 270nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm or
800nm。
The present invention also provides a kind of preparation methods of SERS substrate, comprising the following steps:
A) it induces the noble metal nano particles in the noble metal nano particles hydrosol to be self-assembly of noble metal nano chain, obtains
To the sol solutions containing noble metal nano chain；
B) sol solutions that step a) is obtained are mixed with the raw material for being used to prepare stretchable polymeric membrane, obtains into film liquid；
C) it is film-made described at film liquid, obtains SERS substrate.
In preparation method provided by the invention, prepare the noble metal nano particles hydrosol first.Wherein, the noble metal
The content of noble metal nano particles is preferably 10 in the nano particle hydrosol-13~10-8Mol/L, concretely 10-13mol/L、
10-12mol/L、10-11mol/L、1.09×10-11mol/L、10-10mol/L、10-9mol/L、1.6×10-9Mol/L or 10- 8mol/L；The specific choice and partial size of the noble metal nano particles hereinbefore by the agency of, details are not described herein.The present invention
The source of the noble metal nano particles hydrosol is not particularly limited, those skilled in the art can prepare according to known method
It obtains, details are not described herein.
In preparation method provided by the invention, after obtaining the noble metal nano particles hydrosol, noble metal nano is induced
Noble metal nano particles in the grain hydrosol are self-assembly of noble metal nano chain, obtain the colloidal sol containing noble metal nano chain
Liquid, the process specifically includes the following steps:
A1 the noble metal nano particles hydrosol is mixed with modified molecules), obtains the modified noble metal nano particles in surface
The hydrosol；
A2) to pass through step a1) processing the hydrosol carry out centrifugal concentrating, be then re-dispersed into dielectric constant be less than etc.
In the solvent of Yu Shui (dielectric constant of water is 80.4), sol solutions are obtained；
A3 the ionic strength for) regulating and controlling the sol solutions, makes your gold the noble metal nano particles in sol solutions are self-assembly of
Belong to nano chain, obtains the sol solutions containing noble metal nano chain.
In the preparation step of the above-mentioned sol solutions containing noble metal nano chain provided by the invention, step a1) in, it is described
Modified molecules include but is not limited to three sulfonate of triphenylphosphine, (to sulfonyl-phenyl) phenyl phosphonium salt and diphenyl trimethoxy
One of phosphorus -3- sulfonate is a variety of, concretely three sulfonate sodiums of triphenylphosphine, (to sulfonyl-phenyl) Phenylphosphine sodium
Salt, diphenyl trimethoxy phosphorus -3- sulfonate sodium, three sulfonic acid potassium salts of triphenylphosphine, (to sulfonyl-phenyl) Phenylphosphine sylvite, two
Phenyl trimethoxy phosphorus -3- sulfonic acid potassium salt, three sulfonic acid ammonium salts of triphenylphosphine, (to sulfonyl-phenyl) Phenylphosphine ammonium salt and diphenyl
One of trimethoxy phosphorus -3- sulfonic acid ammonium salt is a variety of；Final concentration of the modified molecules in the hydrosol is preferably 10-9~
10-2Mol/L, concretely 10-9mol/L、10-8mol/L、10-7mol/L、10-6mol/L、10-5mol/L、10-4mol/L、10- 3Mol/L or 10-2mol/L；The mixing preferably carries out under agitation, and the time of the stirring is preferably 12~for 24 hours, tool
Body can be 12h, 14h, 16h, 18h, 20h, 22h or for 24 hours.In the present invention, by using modified molecules to noble metal nano
Grain carries out surface and is modified, and noble metal nano particles can be made to be wrapped up by the molecule with stronger binding ability, to promote nano particle
Subsequent progress chain type self assembly.
In the preparation step of the above-mentioned sol solutions containing noble metal nano chain provided by the invention, step a2) in, it is described
The dielectric constant of solvent is preferably 1~50；The solvent preferably includes water and/or dielectric constant is less than the organic solvent of water；Institute
Stating organic solvent includes but is not limited to one of hexamethylene, isopropanol, ethyl alcohol, acetonitrile and methanol or a variety of；Water is described molten
The volume content of agent is preferably 0~50%, and concretely 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%
Or 50%；The volume ratio of the hydrosol and solvent is preferably (5~20): 1, concretely 5:1,10:1,15:1 or 20:1.
In the preparation step of the above-mentioned sol solutions containing noble metal nano chain provided by the invention, step a3) in, regulation
The mode of the ionic strength is preferred are as follows: mixes the sol solutions with salt.Wherein, the salt includes but is not limited to sodium halogenation
One of object, potassium halide, ammonium halide, sodium sulphate, potassium sulfate, ammonium sulfate, sodium nitrate, potassium nitrate and ammonium nitrate are more
Kind；Final concentration of the salt in sol solutions is preferably 10-6~10-2Mol/L, concretely 10-6mol/L、10-5mol/L、10-4mol/L、10-3Mol/L or 10-2mol/L。
In preparation method provided by the invention, after obtaining the sol solutions containing noble metal nano chain, by the sol solutions
It is mixed with the raw material for being used to prepare stretchable polymeric membrane, obtains into film liquid.Wherein, the raw material of the stretchable polymeric membrane is excellent
Choosing includes high molecular material and plasticizer；The high molecular material and the plasticizer are specifically chosen hereinbefore by the agency of,
Details are not described herein；The high molecular material is being preferably 5~20g/100mL at the content in film liquid, concretely 5g/
100mL、6g/100mL、7g/100mL、8g/100mL、9g/100mL、10g/100mL、11g/100mL、12g/100mL、13g/
100mL, 14g/100mL, 15g/100mL, 16g/100mL, 17g/100mL, 18g/100mL, 19g/100mL or 20g/100mL；
The plasticizer preferably accounts for 5~20wt% of the high molecular material quality, concretely 5wt%, 6wt%, 7wt%,
8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%,
19wt% or 20wt%.
In preparation method provided by the invention, after obtaining into film liquid, it is film-made described at film liquid.Wherein, the film
Specific steps preferably include: be applied to described on substrate at film liquid, later drying and forming-film, finally by the film after drying from lining
It is removed on bottom.In the present invention, the temperature of the drying is preferably 15~50 DEG C, concretely 15 DEG C, 20 DEG C, 25 DEG C of (rooms
Temperature), 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C or 50 DEG C.After film, SERS substrate provided by the invention is obtained.
The shortcomings that lacking Modulatory character the present invention overcomes existing SERS substrate, by the way that noble metal nano chain (MNCs) is embedding
Enter into stretchable polymeric membrane, obtains a kind of SERS substrate of energy double regulation control hotspot architecture.It is provided by the invention
SERS substrate and preparation method thereof includes at least following advantages:
1) preparation method is very simple, is suitble to industrialization.
2) on the one hand hotspot architecture can be realized by double regulation control by controlling the condition of noble metal nano particles self assembly
Static state regulation to noble metal nano chain length；On the other hand essence can be carried out by the gap of the noble metal nano chain of mechanical force pair
Really, continuous and reversible dynamic regulation.
3) regulation of nano gap simply uses very much, and simple mechanical stretching can be realized；And since mechanical force has
There is vector property, therefore regulates and controls more for controllability.
4) there is excellent selective penetrated property, i.e. permission small molecule enters hot spot region, and macromolecular is trapped in outside hot spot, because
This SERS substrate can be directly used for the small molecule object in analysis complicated food and biological sample (such as milk, serum, urine)
Matter does not need to carry out complex sample cumbersome pre-separation, is highly suitable for the early diagnosis and food safety detection of disease.
5) using polymeric membrane as host material, the package assembly of stable noble metal nano chain can be played the role of, tested
The result shows that: SERS substrate provided by the invention has good stability, and still has preferable detection effect after saving 4 months.
And polymeric membrane can also protect testing molecule, from the damage of laser, to improve the accuracy of detection when carrying out SERS detection.
6) in addition, it is SERS substrate provided by the invention sensitivity also with higher, excellent reproducibility, preferable uniform
Property, and it is easy to carry, can long-term preservation, be very suitable to on-site test, there is very big some commercial potential.
The present invention also provides a kind of methods of regulation SERS substrate hotspot architecture, comprising the following steps: to above-mentioned technology
SERS substrate described in scheme is stretched.
In regulation method provided by the invention, the SERS substrate is stretched by using mechanicals efforts, it can
The gap for being embedded in noble metal nano chain in the substrate is set to change, to realize the regulation to SERS substrate hotspot architecture.
Regulation method provided by the invention is regulated and controled by hotspot architecture of the mechanical force to SERS substrate, include at least with
Lower advantage:
1) regulation to SERS substrate hotspot architecture can be realized by simple mechanical force, it is easy to operate.
2) since mechanical force has vector property, the controllability of this method is stronger.
It is including following the present invention also provides the method that the small-molecule substance in a kind of pair of mixed system carries out SERS detection
Step:
Mixed system is added dropwise in the one side (front) of SERS substrate described in above-mentioned technical proposal, after its drying, to institute
The another side (back side) for stating SERS substrate carries out SERS detection, obtains the SERS testing result of small-molecule substance.
In detection method provided by the invention, since the host material of SERS substrate is polymeric membrane, base can be assigned
The excellent selective penetrated property in bottom.When the front in SERS substrate is added dropwise in mixed system, the macromolecular substances in mixed system are such as
Protein etc. can not penetrate into the upper surface in substrate and being trapped within substrate, and small-molecule substance then easily enters hot spot
Region, after the mixed system drying for being added drop-wise to SERS substrate surface, being detected by the back side to SERS substrate can be obtained
To the SERS testing result of small-molecule substance, and do not occur any fluorescence interference.
Detection method provided by the invention does not need to carry out complex sample cumbersome pre-separation, can to complicated food and
Small-molecule substance in biological sample (such as milk, serum, urine) is directly detected, and the early stage for being highly suitable for disease examines
Disconnected and food safety detection.
For the sake of becoming apparent from, it is described in detail below by following embodiment.
Embodiment 1
Golden contracted payment nano particle (Ag@Au NPs) colloidal sol is prepared, specific steps include:
The water of 99mL is added in three-necked flask, then the silver nitrate solution 0.5mL of 0.2M is added thereto, is heated with stirring to
The sodium citrate solution 4mL that 1wt% is added after boiling continues to keep boiling 30min, stops heating, and naturally cool to room
Temperature obtains silver nano-grain (Ag NPs) colloidal sol.
The Ag NPs colloidal sol of 10mL is taken, is added the 1wt%'s of 0.2M hydroxylamine hydrochloride solution 0.5mL sum under stirring conditions
Chlorauric acid solution 0.568mL continues to stir 30min, golden contracted payment nano particle (Ag@Au NPs) colloidal sol is obtained, in the colloidal sol
Ag@Au NPs partial size be about 40nm, content is 1.09 × 10-11mol/L。
Embodiment 2
Gold nano grain (Au NPs) colloidal sol is prepared, specific steps include:
The water of 99mL is added in three-necked flask, then the chlorauric acid solution 1mL of 1wt% is added thereto, is heated with stirring to
The sodium citrate solution 5mL that 1wt% is added after boiling continues to keep boiling 30min, stops heating, and naturally cool to
Room temperature obtains gold nano grain (Au NPs) colloidal sol, and the Au NPs partial size in the colloidal sol is about 15nm, and content is 1.6 × 10- 9mol/L。
Au NPs manufactured in the present embodiment is detected, as a result as depicted in figs. 1 and 2, Fig. 1 is the embodiment of the present invention 2
Ultraviolet-visible (UV-VIS) abosrption spectrogram of the nanogold of offer, Fig. 2 are the nanogold that embodiment 2 provides in the present invention
Transmission electron microscope (TEM) image.
Embodiment 3
SERS substrate is prepared, specific steps include:
1) Ag@Au NPs colloidal sol 100mL prepared by Example 1 is added 10-2M (to sulfonyl-phenyl) Phenylphosphine di-potassium
Solution (BSPP) 1mL, gentle agitation 12h obtains the modified Ag@Au NPs colloidal sol in surface.
2) the modified Ag@Au NPs colloidal sol 100mL in surface is taken, is dispersed in the water of 10mL, adds again after centrifugal concentrating
Enter the ionic strength of 30 μ L of 1M sodium chloride solution regulation colloidal sol, so that nano-particles self assemble forms nano chain, the nano chain
Main chain be about made of 15~20 nano particles.
3) polyvinyl alcohol that weight average molecular weight is 130000 is added in the nano chain colloidal sol (about 10mL) prepared to step 2)
(PVA) 0.8g adds 0.064g polyethylene glycol 200 as plasticizer, stirs evenly, obtain into film liquid.
4) sheet glass having a size of 2.5cm × 7.5cm is taken.
5) it will be applied at film liquid on sheet glass, and be placed in drying and forming-film in 40 DEG C of baking ovens, obtain with a thickness of 300 ± 50 μm
SERS substrate.
Embodiment 4
SERS substrate is prepared, specific steps include:
1) Example 2 prepares gold nano grain (Au NPs) colloidal sol 100mL, is added 10-5The diphenyl trimethoxy of M
Phosphorus -3- sulfonate sodium solution 2mL, gentle agitation for 24 hours, obtain the modified Au NPs colloidal sol in surface.
2) the modified Au NPs colloidal sol 20mL in surface is taken, is dispersed in 2mL ethyl alcohol again after centrifugal concentrating, 0.1M is added
5 μ L of sodium chloride solution regulates and controls the ionic strength of colloidal sol, so that nano-particles self assemble forms gold nano chain, the gold nano chain
Main chain is about made of 3~6 nano particles.
3) the polyethylene pyrrole that weight average molecular weight is 360000 is added in the gold nano chain colloidal sol (about 2mL) prepared to step 2)
Pyrrolidone (PVP) 0.3g, adds 0.04g polyethylene glycol 400 as plasticizer, stirs evenly, obtain into film liquid.
4) the PDMS substrate having a size of 0.6cm × 2cm is prepared.
5) it will be applied at film liquid on PDMS substrate, and be placed in room temperature and spontaneously dry film forming, obtain with a thickness of 200 ± 50 μm
SERS substrate.
Embodiment 5
SERS substrate is prepared, specific steps include:
1) Example 2 prepares gold nano grain (Au NPs) colloidal sol 100mL, is added 10-4Three sulphurs of triphenylphosphine of M
Sour trisodium salt (TPTSS) 1mL, gentle agitation for 24 hours, obtain the modified Au NPs colloidal sol in surface.
2) the modified Au NPs colloidal sol 100mL in surface is taken, is dispersed in 10mL ethyl alcohol and water 1:1 again after centrifugal concentrating
The ionic strength of 50 μ L of 0.5M sodium chloride solution regulation colloidal sol is added in the in the mixed solvent of (volume ratio), so that nano particle is certainly
Assembling forms gold nano chain.Transmission electron microscope observation is carried out to gold nano chain manufactured in the present embodiment, as a result such as Fig. 3 institute
Show, Fig. 3 is the TEM figure for the gold nano chain that the embodiment of the present invention 5 provides.As seen in Figure 3, the main chain of the gold nano chain
It is made of 13 nano particles.
3) polyethylene that weight average molecular weight is 1300000 is added in the gold nano chain colloidal sol (about 10mL) prepared to step 2)
Pyrrolidones (PVP) 2g, adds 0.32g polyethylene glycol 400 as plasticizer, stirs evenly, obtain into film liquid.
4) the PDMS substrate having a size of 0.6cm × 2cm is prepared.
5) it will be applied at film liquid on PDMS substrate, and be placed in room temperature and spontaneously dry film forming, obtain with a thickness of 400 ± 50 μm
SERS substrate.UV-VIS is carried out to the SERS substrate of step 5) preparation, as a result as shown in figure 4, Fig. 4 is the embodiment of the present invention 5
The UV-VIS of the SERS substrate of offer schemes.
Embodiment 6
The hot spot of SERS substrate regulates and controls:
SERS substrate prepared by Example 5, by its Uniform Tension to its optical property of certain strain detecting (UV-
VIS variation), as a result as shown in figure 5, Fig. 5 is that the SERS substrate that the embodiment of the present invention 6 provides is in non-stretched, elongation strain
50% and restore after UV-VIS figure.As seen in Figure 5, coupled plasma peak position is moved when being stretched to 50% strain
Dynamic, when stress release, coupled plasma peak position can be restored to initial value.
Molecule to be detected is instilled in SERS substrate prepared by embodiment 5, then by its Uniform Tension to certain strain,
SERS spectra of the testing molecule under certain strain is detected, as a result as shown in fig. 6, Fig. 6 is the SERS that the embodiment of the present invention 6 provides
Substrate is in differently strained lower detection same concentration (10-7Mol/L the SERS spectra figure of crystal violet (CV)), in Fig. 6, from bottom to top
Strain is gradually increased, respectively 0%, 4.5%, 9.1%, 13.6%, 18.2%, 22.7%, 27.3%, 31.8%, 36.4%,
40.9%, 45.5%.As seen in Figure 6, the intensity of SERS first increases reduces again, shows the controllable of SERS hot spot
Property.
Embodiment 7
The performance evaluation of SERS substrate:
1) homogeneity:
SERS substrate prepared by Example 5, takes the 10 of 2 μ L-7The crystal violet of mol/L drips the one side in SERS substrate, so
50 point measurements are randomly selected on a large scale in this face afterwards and obtain 50 SERS spectras, and count every in 1619cm-1That locates is strong
Degree, as a result as shown in fig. 7, Fig. 7 is the SERS substrate detection 10 that the embodiment of the present invention 7 provides-7The 50 of the crystal violet (CV) of mol/L
SERS spectra figure.The strength difference of this 50 spectrum is smaller as can be known from Fig. 7, in 1619cm-1The relative standard deviation of signal
(RSD) it is 12.7%, is much smaller than 20%, this shows that the SERS substrate has preferable homogeneity.
2) sensitivity:
The freshly prepared SERS substrate of Example 5, takes the crystal violet 10 of 2 μ L various concentrations-7Mol/L, 10-8Mol/L,
10-9Mol/L, 10-10Mol/L is dripped respectively in SERS substrate, then in its SERS spectra of this planar survey, as shown in figure 8, Fig. 8
It is the SERS spectra figure of the crystal violet (CV) for the SERS substrate detection detection various concentration that the embodiment of the present invention 7 provides.From Fig. 8
Know minimum detectable CV to 10-10Mol/L, the SERS substrate sensitivity with higher.
3) stability:
The freshly prepared SERS substrate of Example 5, by it, (25 DEG C) are stored 4 months at room temperature, then take 2 μ L not
With the crystal violet 10 of concentration-7Mol/L, 10-8Mol/L, 10-9Mol/L, 10-10Mol/L is dripped respectively in SERS substrate, then herein
Its SERS spectra of planar survey, as shown in figure 9, Fig. 9 is that the SERS substrate that the embodiment of the present invention 7 provides stores 4 months at room temperature
The SERS spectra figure of the crystal violet (CV) of various concentration is detected afterwards.Even if the SERS after having stored as can be known from Fig. 94 months
The still detectable CV to 10 of substrate-10Mol/L, therefore the SERS substrate has preferable stability.
Embodiment 8
The method for detecting serum small molecular substance:
The SERS substrate for taking above-described embodiment 5 to prepare, test serum stoste is directly dripped in the front of SERS substrate, to it
SERS substrate is overturn after drying, SERS substrate viscous (substrate front surface is contacted with sheet glass) on the glass sheet is then placed in Raman
In detection platform, SERS backside of substrate is detected, the results are shown in Figure 10, and Figure 10 is pair that the embodiment of the present invention 8 provides
SERS backside of substrate carries out detected SERS spectra figure, wherein 725,745cm-1Belong to hypoxanthic ring around absorbing
Dynamic peak.As it can be seen that detection method provided in this embodiment does not need to carry out any pretreatment to serum stoste, so that it may detect bleeding
Small molecule hypoxanthine in clear.
Embodiment 9
The method for detecting antibiotic in milk system:
The SERS substrate for taking above-described embodiment 5 to prepare, the milk of the sulfamethazine to be measured containing 0.01ppm is former
Liquid directly drips in the front of SERS substrate, overturns SERS substrate after its drying, then that SERS substrate is viscous on the glass sheet
(substrate front surface is contacted with sheet glass) is placed in Raman detection platform, detects to SERS backside of substrate, as a result such as Figure 11 institute
Show, Figure 11 is the offer of the embodiment of the present invention 9 to the detected SERS spectra figure of SERS backside of substrate progress, wherein 1098,
1587cm-1It is respectively belonging to the C-N stretching vibration of sulfadimidine and the stretching vibration of contraposition disubstituted benzenes ring.As it can be seen that this
The detection method that embodiment provides does not need to carry out any pretreatment to milk, so that it may detect that the sulfanilamide (SN) diformazan in milk is phonetic
Pyridine.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of SERS substrate, comprising:
Stretchable polymeric membrane；
With the noble metal nano chain being embedded into the stretchable polymeric membrane；
The noble metal nano chain is self-assembly of by noble metal nano particles.
2. SERS substrate according to claim 1, which is characterized in that the stretchable polymeric membrane includes high molecular material
And plasticizer；
The high molecular material includes polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, polyacrylamide, polyacrylic acid
With one of polyacrylate or a variety of.
3. SERS substrate according to claim 1, which is characterized in that the noble metal nano chain is by 2~20 noble metals
Nano-particles self assemble is formed；
The length of the noble metal nano chain is 30~800nm.
4. SERS substrate according to claim 1, which is characterized in that the noble metal nano particles include spherical gold nano
The golden contracted payment nano particle of the spherical shape of particle and/or core-shell structure；
The partial size of the noble metal nano particles is 10~50nm.
5. a kind of preparation method of SERS substrate, comprising the following steps:
A) it induces the noble metal nano particles in the noble metal nano particles hydrosol to be self-assembly of noble metal nano chain, is contained
There are the sol solutions of noble metal nano chain；
B) sol solutions that step a) is obtained are mixed with the raw material for being used to prepare stretchable polymeric membrane, obtains into film liquid；
C) it is film-made described at film liquid, obtains SERS substrate.
6. preparation method according to claim 5, which is characterized in that step a) is specifically included:
A1 the noble metal nano particles hydrosol is mixed with modified molecules), obtains the water-soluble of the modified noble metal nano particles in surface
Glue；
A2 centrifugal concentrating) is carried out to the hydrosol by step a1) processing, is then re-dispersed into dielectric constant less than or equal to water
Solvent in, obtain sol solutions；
A3 the ionic strength for) regulating and controlling the sol solutions, makes the noble metal nano particles in sol solutions be self-assembly of noble metal and receives
Rice chain, obtains the sol solutions containing noble metal nano chain.
7. preparation method according to claim 6, which is characterized in that step a1) in, the noble metal nano particles are water-soluble
The content of noble metal nano particles is 10 in glue-13~10-8mol/L；The modified molecules include three sulfonate of triphenylphosphine,
One of (to sulfonyl-phenyl) phenyl phosphonium salt and diphenyl trimethoxy phosphorus -3- sulfonate are a variety of；The modified molecules exist
Final concentration of 10 in the hydrosol-9~10-2mol/L；
Step a2) in, the volume ratio of the hydrosol and solvent is (5~20): 1；
Step a3) in, regulate and control the mode of the ionic strength are as follows: mix the sol solutions with salt；The salt includes sodium halogenation
One of object, potassium halide, ammonium halide, sodium sulphate, potassium sulfate, ammonium sulfate, sodium nitrate, potassium nitrate and ammonium nitrate are more
Kind；The salt in sol solutions final concentration of 10-6~10-2mol/L。
8. preparation method according to claim 5, which is characterized in that in step b), the original of the stretchable polymeric membrane
Material includes high molecular material and plasticizer；
The high molecular material is being 5~20g/100mL at the content in film liquid；
The plasticizer accounts for 5~20wt% of the high molecular material quality.
9. a method of regulation SERS substrate hotspot architecture, comprising the following steps:
SERS substrates described in any item to Claims 1 to 4 stretch.
10. the method that the small-molecule substance in a kind of pair of mixed system carries out SERS detection, comprising the following steps:
Mixed system is added dropwise in the one side of the described in any item SERS substrates of Claims 1 to 4, after its drying, to described
The another side of SERS substrate carries out SERS detection, obtains the SERS testing result of small-molecule substance.
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| CN111590085A (en) * | 2020-06-01 | 2020-08-28 | 中国农业科学院农业质量标准与检测技术研究所 | Au-Ag nano-chain composite SERS substrate and preparation method and application thereof |
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