CN107057257A - Surface-enhanced Raman scattering substrate assembled by pH response type template, preparation method and method for detecting molecules by using substrate - Google Patents
Surface-enhanced Raman scattering substrate assembled by pH response type template, preparation method and method for detecting molecules by using substrate Download PDFInfo
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- CN107057257A CN107057257A CN201710260419.4A CN201710260419A CN107057257A CN 107057257 A CN107057257 A CN 107057257A CN 201710260419 A CN201710260419 A CN 201710260419A CN 107057257 A CN107057257 A CN 107057257A
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- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 53
- 239000000758 substrate Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000004044 response Effects 0.000 title claims abstract description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010931 gold Substances 0.000 claims abstract description 32
- 229910052737 gold Inorganic materials 0.000 claims abstract description 32
- 229910052709 silver Inorganic materials 0.000 claims abstract description 22
- 239000004332 silver Substances 0.000 claims abstract description 22
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 12
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 23
- 238000012360 testing method Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000001514 detection method Methods 0.000 claims description 20
- 239000002105 nanoparticle Substances 0.000 claims description 16
- 238000000429 assembly Methods 0.000 claims description 11
- 230000000712 assembly Effects 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 10
- FCMUPMSEVHVOSE-UHFFFAOYSA-N 2,3-bis(ethenyl)pyridine Chemical compound C=CC1=CC=CN=C1C=C FCMUPMSEVHVOSE-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000008236 heating water Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 230000008602 contraction Effects 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229920001059 synthetic polymer Polymers 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 229910021642 ultra pure water Inorganic materials 0.000 claims 1
- 239000012498 ultrapure water Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 1
- 235000013339 cereals Nutrition 0.000 description 12
- 239000002082 metal nanoparticle Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 2
- 230000005672 electromagnetic field Effects 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000011896 sensitive detection Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000209094 Oryza Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- NMWONDKHBZEDMY-UHFFFAOYSA-H [Au](Cl)(Cl)Cl.C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+].[Na+].[Na+] Chemical compound [Au](Cl)(Cl)Cl.C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+].[Na+].[Na+] NMWONDKHBZEDMY-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000916 dilatatory effect Effects 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XXQBGBUZLWZPKT-UHFFFAOYSA-N n-prop-2-enoylbuta-2,3-dienamide Chemical compound C=CC(=O)NC(=O)C=C=C XXQBGBUZLWZPKT-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- 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
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- C—CHEMISTRY; METALLURGY
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0831—Gold
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- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention relates to a surface-enhanced Raman scattering substrate assembled by a pH response type template, a preparation method and a method for detecting molecules by using the substrate. The template on the Raman scattering substrate is polydivinyl pyridine sensitive to pH, noble metal gold or silver particles are modified on the template, the template contracts and expands along with the adjustment of the pH value, and the gap between gold or silver nano particles in the substrate is dynamically adjusted, so that an adjustable hot spot is formed; the silver nano particles are 25-35 nm in size, and the size of the composite substrate is about 1 mu m. The substrate SERS 'hot spot' prepared by the method is adjustable, so that molecules to be detected effectively fall into the substrate 'hot spot' range. Selecting a pH sensitive polymer as a template, mixing the pH sensitive polymer with gold and silver nanoparticles and a molecule to be detected, and adjusting the pH value of the solution, so that the SERS hot point can be dynamically adjusted.
Description
Technical field
The present invention relates to SERS technology and the detection method of correlation, a kind of pH responses are specifically related to
Surface enhanced Raman scattering substrate, preparation method and the method using the substrate detection molecules of type template assemblies.
Background technology
SERS (SERS) technology is because with high detection sensitivity, using the teaching of the invention it is possible to provide what testing molecule enriched
Finger print information, has been acknowledged as a kind of advanced analysis and detection method.Noble metal gold, silver nano-particle is often used as SERS
Detect that the plasma resonance between substrate, its nano-particle can produce strong electromagnetic field, amplify the Raman signal of testing molecule.
Research shows that gap relationships of the enhancing of this signal often between noble metal nano particles are close：On the one hand, noble metal is worked as
When nano-particle gap is less than 10nm, the electromagnetic field that its plasma resonance is produced drastically is strengthened, and forms effective SERS focuses；Separately
On the one hand, this SERS focus has its effective range, and only when testing molecule falls in this hotspot range, the Raman signal of generation is
It can largely improve, reach highly sensitive detection.
In existing research, most of detection is all to mix the noble metal gold, silver nano-particle of synthesis with testing molecule,
Then progress SERS detections on silicon chip are added drop-wise to, this method is simple, but after gold, silver Nano sol is added dropwise on silicon chip,
Gap each other is not regulated and controled, i.e., gap is uneven, and the hotspot's distribution scope of formation is big, and testing molecule falls into focus
Probability it is small, the sensitivity of detection and homogeneity all it is difficult to ensure that.Some studies the synthesis for being directed to SERS substrates, right
Noble metal nano particles are assembled, can be by the clearance control of noble metal nano particles in below 10nm, but requirement of experiment
It is higher, it is difficult to be widely used.
The content of the invention
The technical problem to be solved in the present invention is to overcome that existing SERS substrates " focus " are uneven and molecule is difficult to fall into heat
Point effective range technical deficiency the problems such as there is provided a kind of SRES " focus is adjustable ", testing molecule is effectively dropped into base
Surface enhanced Raman scattering substrate, preparation method and the utilization substrate inspection of pH response type template assemblies in the range of bottom " focus "
The method for surveying molecule.
To achieve these goals, the technical solution adopted in the present invention is：A kind of surface of pH response types template assemblies
Strengthening the template on Raman scattering substrate, its Raman scattering substrate is modified in the poly- divinyl pyridine sensitive to pH, template
Have noble metal gold or a silver particles, template produced with pH value regulation shrink with expansion, while golden or silver-colored in dynamic regulation substrate is received
Rice corpuscles gap, so as to form adjustable focus；Nano silver grain size is 25~35nm, and the size of composite substrate is about 1 μm.
A kind of method for the surface enhanced Raman scattering substrate for preparing pH response type template assemblies, first with initiator and
Crosslinking agent synthetic polymer template, recycles reduction of sodium citrate agent synthesis gold or Nano silver grain, and regulation polymer template is molten
The pH value of liquid is acidity, and gold, silver nano-particle is mixed, produces the adjustable surface enhanced Raman scattering substrate of focus.
Preferably, the preparation method of polymer template is：50mL pure water is added in 250mL three-necked flask, water
Bath is heated to 80 DEG C, is passed through the polymer monomer that 0.55g is added after nitrogen purification, 30min -- divinyl pyridine and 0.04g's
After crosslinking agent -- methylene diacrylamine, mixing 10min, 0.050g potassium peroxydisulfate is rapidly joined as initiator, gathered
Reaction is closed to start；Solution turned cloudy after 5~15min is reacted, 80 DEG C of reaction constant temperature continues 1h；Then stirring is cooled to room temperature, is
Removal some of which oligomer and unconverted monomer, the polymer solution of gained is carried out with 5000r/min rotating speed
Centrifugation, the time is 10min, rear to use second distillation water washing 3 times, each ultrasound 10min, by the poly- divinyl pyridine of gained point
It is dispersed in stand-by in 50mL ultra-pure waters.It is milky when polymer template shrinks, to be colorless and transparent during expansion.
Preferably, the preparation method of gold or Nano silver grain is：By 99mL redistilled water, the chlorine that 1mL concentration is 1%
Auric acid or silver nitrate, are added sequentially in 250mL three-necked flask, magnetic agitation, and heating water bath is rapidly added matter to after seething with excitement
The sodium citrate solution 1mL that amount fraction is 1% is as reducing agent, obtained gold or Nano silver grain；With secondary water supersound washing 3
It is secondary, it is dispersed in stand-by in 10mL distilled water.Sodium citrate is again simultaneously stabilizer, gold, silver nano-particle is stablized and deposits
Preserving for a long time.Obtained aurosol is claret, and silver sol is celadon.
Preferably, the preparation method of surface enhanced Raman scattering substrate is：0.5mL polymer template is taken, 0.1mol/ is used
L salt acid for adjusting pH value takes 0.5mL gold or silver nanoparticle colloidal sol to be added in polymer template solution, filled to acid (being about 3)
Divide mixing.Finally add certain density testing molecule crystal violet, magnetic agitation 5min.Conventionally, by mixed liquor
It is added drop-wise on silicon chip, detects testing molecule SERS signal.
A kind of method of the surface enhanced Raman scattering substrate detection molecules of utilization pH response type template assemblies, by polymer
Template, gold or silver nanoparticle colloidal sol are mixed with testing molecule under sour environment, and it is alkalescence then to adjust the pH value of mixed solution, with
The contraction of template, gold or Nano silver grain gap reduce, and testing molecule is locked between gold or Nano silver grain by effective,
It is set to be in SERS hotspot ranges, detection signal measuring obtains the SERS spectrograms of the testing molecule.
Surface enhanced Raman scattering substrate, preparation method and the utilization substrate inspection of the pH response type template assemblies of the present invention
The method for surveying molecule, its principles of science, which is analyzed, is：
First, selection divinyl pyridine is as monomer, and methylene diacrylamine is as crosslinking agent, and potassium peroxydisulfate is as drawing
Send out agent, polymerize obtained poly- divinyl pyridine as template, this polymer in acid medium because amino is positively charged, phase
Repulsion is produced between mutually, therefore polymer is swelling state, when gradually adjusting solution to alkalescence, the proton of amino is gradually dissociated,
The positive charge of polymer belt is reduced to last not charged, and repulsion constantly reduces, therefore polymer is gradually received by original swelling state
Contracting, volume-diminished.
2nd, the selected monomer of polymer template, crosslinking agent and initiator, the signal produced in SERS detections are weaker,
Influence will not be produced on the detection of testing molecule or is disturbed.
3rd, gold, silver Nano sol is obtained using reduction of sodium citrate gold chloride or silver nitrate, preparation method is simple, fits
Preferably preserve for a long time.When SERS is detected, Nano silver grain is mixed with polymer template, by adjusting the pH value of solution, not only
Nano silver grain gap can effectively be regulated and controled, dynamic SERS focuses are formed, meanwhile, testing molecule can be locked effectively
It is in the range of SERS, to produce strong SERS signal, reach highly sensitive detection between gold, silver nano-particle.
Relative to prior art, beneficial effects of the present invention performance is as follows：
1), in conventional art synthesis SERS substrates, gold, silver nano-particle gap can not effectively be adjusted, obtained SERS
Focus is uneven, and the SERS signal of generation is unstable, influences the sensitivity of detection.And existing SERS substrates are realized to gold, silver
The assemble method of nano-particle is all relatively complicated, most of all quickly to form " focus ", and substrate prepared by the present invention
SERS " focus is adjustable " method is simple, and polymer sensitive selection pH is as template, with gold, silver nano-particle and to be measured point
Son mixing, adjusts the pH value of solution, you can dynamic regulation SERS focuses.
2), the method for preparation method of the invention and detection molecules is simple, with wide market application foreground.
Brief description of the drawings
With reference to embodiments with accompanying drawing to the present invention pH response type template assemblies surface enhanced Raman scattering substrate,
Preparation method and make and being discussed further using the method for the substrate detection molecules.
Fig. 1 prepares and testing molecule is carried out the signal of Raman spectrum method for detecting surface reinforcement for the substrate of the present invention
Figure.As seen in Figure 1, gel template is mixed with noble metal nano particles and testing molecule in the expanded state, after
The pH value of solution is adjusted, gel template is shunk, not only reduce the noble metal nano particles gap wherein modified, the SERS of formation
Focus increases；Meanwhile, testing molecule is locked in the hotspot range that noble metal nano particles are formed, SERS detection sensitivities
Improve.
The optical photograph and polymer molecule of polymer template synthesized in the SERS substrates for the present invention Fig. 2 are with molten
Molecule structure change when liquid pH value changes and the contraction that produces and dilating principle schematic diagram.As seen in Figure 2, polymer
Added in template after HCl, make protonated amino positively charged, repulsion is produced each other, template is swelling state, shows nothing
Color transparence；When the pH of regulation solution alkalescence, proton is neutralized, and the repulsion of molecule each other reduces, and template is gradually tapered up,
It is rendered as milky.This dilation process has good invertibity.
Formed in the SERS substrates that Fig. 3 is prepared for the present invention after polymer (A), Nano silver grain (B) and its mixing
The TEM figures of compound substrate (C), and its corresponding UV-visible spectrum (D) of difference.As seen in Figure 3, Yin Na
Rice corpuscles is modified in gel template, and the obvious red shift of silver-colored absworption peak, illustrates Nano silver grain in the composite substrate of formation
Gap shrinks.
Embodiment
Embodiment 1
Step 1: the preparation method of polymer template is：
50mL pure water is added in 250mL three-necked flask, heating water bath is passed through nitrogen purification, 30min to 80 DEG C
0.55g polymer monomer -- divinyl pyridine and 0.04g crosslinking agent -- methylene diacrylamine, mixing are added afterwards
After 10min, 0.050g potassium peroxydisulfate is rapidly joined as initiator, polymerisation starts.React solution after 5~15min
Become cloudy, 80 DEG C of reaction constant temperature continues 1h.Then stirring is cooled to room temperature, in order to remove some of which oligomer and unpolymerized
Monomer, the polymer solution of gained is centrifuged with 5000r/min rotating speed, the time is 10min, after use redistilled water
Washing 3 times, each ultrasound 10min, the poly- divinyl pyridine of gained is dispersed in stand-by in 50mL ultra-pure waters.
Step 2: the preparation method of Nano silver grain is：
99mL redistilled water, the silver nitrate that 1mL concentration is 1% are added sequentially in 250mL three-necked flask,
Magnetic agitation, heating water bath to seethe with excitement after, be rapidly added mass fraction be 1% sodium citrate solution 1mL as reducing agent, obtain
The Nano silver grain size about 35nm arrived.With secondary water supersound washing 3 times, it is dispersed in stand-by in 10mL distilled water, obtains
The silver sol arrived is celadon.
Step 3: the preparation of surface enhanced Raman scattering substrate and SERS detections：
0.5mL polymer template is taken, with 0.1mol/L salt acid for adjusting pH value to acid (being about 3), 0.5mL silver is taken
Nano sol is added in polymer template solution, is sufficiently mixed.Finally add certain density testing molecule crystal violet, magnetic
Power stirs 5min.Conventionally, mixed liquor is added drop-wise on silicon chip, detects testing molecule SERS signal.
Embodiment 2
Step 1: the preparation method of polymer template is：
50mL pure water is added in 250mL three-necked flask, heating water bath is passed through nitrogen purification, 30min to 80 DEG C
0.55g polymer monomer -- divinyl pyridine and 0.04g crosslinking agent -- methylene diacrylamine, mixing are added afterwards
After 10min, 0.050g potassium peroxydisulfate is rapidly joined as initiator, polymerisation starts.React solution after 5~15min
Become cloudy, 80 DEG C of reaction constant temperature continues 1h.Then stirring is cooled to room temperature, in order to remove some of which oligomer and unpolymerized
Monomer, the polymer solution of gained is centrifuged with 5000r/min rotating speed, the time is 10min, after use redistilled water
Washing 3 times, each ultrasound 10min, the poly- divinyl pyridine of gained is dispersed in stand-by in 50mL ultra-pure waters.
Step 2: the preparation method of golden nanometer particle is：
99mL redistilled water, the gold chloride that 1mL concentration is 1% are added sequentially in 250mL three-necked flask,
Magnetic agitation, heating water bath to seethe with excitement after, be rapidly added mass fraction be 1% sodium citrate solution 1mL as reducing agent, obtain
The golden nanometer particle size about 40nm arrived.With secondary water supersound washing 3 times, it is dispersed in stand-by in 10mL distilled water, obtains
The aurosol arrived is claret.
Step 3: the preparation of surface enhanced Raman scattering substrate and SERS detections：
0.5mL polymer template is taken, with 0.1mol/L salt acid for adjusting pH value to acid (being about 3), 0.5mL gold is taken
Nano sol is added in polymer template solution, is sufficiently mixed.Finally add certain density testing molecule crystal violet, magnetic
Power stirs 5min.Conventionally, mixed liquor is added drop-wise on silicon chip, detects testing molecule SERS signal.
Above content is only the design example and explanation to the present invention, affiliated those skilled in the art
Various modifications or supplement are made to described specific embodiment or is substituted using similar mode, without departing from invention
Design or surmount scope defined in the claims, protection scope of the present invention all should be belonged to.
Claims (6)
1. a kind of surface enhanced Raman scattering substrate of pH response types template assemblies, it is characterised in that：On its Raman scattering substrate
Template be that noble metal gold or silver particles are modified with the poly- divinyl pyridine sensitive to pH, template, template is adjusted with pH value
Produce and shrink with expanding, while gold or Nano silver grain gap in dynamic regulation substrate, so as to form adjustable focus.
2. a kind of method for the surface enhanced Raman scattering substrate for preparing pH response types template assemblies as claimed in claim 1, its
It is characterised by, first with initiator and crosslinking agent synthetic polymer template, recycles reduction of sodium citrate agent synthesis gold or silver
Nano-particle, the pH value of regulation polymer template solution is acidity, and gold, silver nano-particle is mixed, produces focus adjustable
Surface enhanced Raman scattering substrate.
3. preparation method as claimed in claim 2, it is characterised in that the preparation method of polymer template is：
50mL pure water is added in 250mL three-necked flask, heating water bath is passed through after nitrogen purification, 30min and added to 80 DEG C
Enter 0.55g polymer monomer -- divinyl pyridine and 0.04g crosslinking agent -- methylene diacrylamine, mix 10min
Afterwards, 0.050g potassium peroxydisulfate is rapidly joined as initiator, polymerisation starts；
Solution turned cloudy after 5~15min is reacted, 80 DEG C of reaction constant temperature continues 1h；Then stirring is cooled to room temperature, in order to remove it
In some oligomer and unconverted monomer, the polymer solution of gained is centrifuged with 5000r/min rotating speed, the time
For 10min, rear to use second distillation water washing 3 times, each ultrasound 10min, the poly- divinyl pyridine of gained is dispersed in 50mL
It is stand-by in ultra-pure water.
4. preparation method as claimed in claim 3, it is characterised in that the preparation method of gold or Nano silver grain is：
By 99mL redistilled water, the gold chloride or silver nitrate that 1mL concentration is 1%, 250mL three-necked flask is added sequentially to
In, magnetic agitation, heating water bath to seethe with excitement after, be rapidly added mass fraction be 1% sodium citrate solution 1mL as reduction
Agent, obtained gold or Nano silver grain；With secondary water supersound washing 3 times, it is dispersed in stand-by in 10mL distilled water.
5. preparation method as claimed in claim 4, it is characterised in that the preparation method of surface enhanced Raman scattering substrate is：
0.5mL polymer template is taken, with 0.1mol/L salt acid for adjusting pH value to acidity, 0.5mL gold or silver nanoparticle colloidal sol is taken
It is added in polymer template solution, is sufficiently mixed.
6. a kind of surface enhanced Raman scattering substrate detection molecules using pH response types template assemblies as claimed in claim 1
Method, it is characterised in that polymer template, gold or silver nanoparticle colloidal sol are mixed with testing molecule under sour environment, then adjusted
It is alkalescence to save the pH value of mixed solution, with the contraction of template, and gold or Nano silver grain gap reduce, and testing molecule is effective
It is locked between gold or Nano silver grain, it has been in SERS hotspot ranges, detection signal measuring obtains the testing molecule
SERS spectrograms.
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