CN103063649A - Method for surface-enhanced Raman scattering spectrum detection by using silver-surface molecularly imprinted polymer - Google Patents
Method for surface-enhanced Raman scattering spectrum detection by using silver-surface molecularly imprinted polymer Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 27
- 238000001228 spectrum Methods 0.000 title claims abstract description 25
- 238000001514 detection method Methods 0.000 title claims abstract description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052709 silver Inorganic materials 0.000 claims abstract description 80
- 239000004332 silver Substances 0.000 claims abstract description 80
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- 239000000178 monomer Substances 0.000 claims abstract description 25
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 16
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 16
- 238000004132 cross linking Methods 0.000 claims description 15
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- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
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- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 230000000977 initiatory effect Effects 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
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- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
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- XZRMXDPWEPRYMF-UHFFFAOYSA-N (4-ethenylphenoxy)boronic acid Chemical compound OB(O)OC1=CC=C(C=C)C=C1 XZRMXDPWEPRYMF-UHFFFAOYSA-N 0.000 claims description 2
- FHTDDANQIMVWKZ-UHFFFAOYSA-N 1h-pyridine-4-thione Chemical compound SC1=CC=NC=C1 FHTDDANQIMVWKZ-UHFFFAOYSA-N 0.000 claims description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 2
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- -1 dimethyl benzene olefin Chemical class 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention provides a method for surface-enhanced Raman scattering spectrum detection by using a silver-surface molecularly imprinted polymer, and relates to the method for the surface-enhanced Raman scattering spectrum detection by using a molecularly imprinted polymer. The invention aims at solving intricate process and poor detection effect problems caused by poor combination between the molecularly imprinted polymer and a metal film in an existing method which needs to mix the molecularly imprinted polymer and other substances such as silver colloid or coat the molecularly imprinted polymer on other metal films such as a silver film. The method provided by the invention comprises the following steps of: I preparing silver particles of 500 nanometers to 5 microns; II, modifying the surface of the silver particles; III, preparing pre-assembled solution of target molecules and functional monomers; IV, preparing pre-polymerized solution of the molecularly imprinted polymer of the silver; V, preparing the particles of silver-core molecularly imprinted membrane shells; VI, preparing the silver-surface molecularly imprinted polymer; and VII, performing the Raman detection. The method provided by the invention is applied to the field such as clinical medicine analysis, quantitative analysis, trace analysis and single-molecule level.
Description
Technical field
The present invention relates to utilize molecularly imprinted polymer to carry out the method that Surface Enhanced Raman Scattering Spectrum detects.
Background technology
Molecularly imprinted polymer has affinity and selectivity is high, the ability of anti-adverse environment is strong, the advantages such as stability height and long service life, therefore, it has all represented good application prospect such as the fields such as stage enantiomer separation, clinical medicine analysis, chemobionics sensor, mimetic enzyme catalysis, film separation and Solid-Phase Extraction in the stratographic analysis in a lot of fields.Surface enhanced raman spectroscopy (SERS) technology has strengthened substrate and intermolecular energy transfer, has avoided the interference of fluorescence background, has increased the scattering area of sample, thereby has strengthened the signal of sample, and the precision that raman scattering spectrum is detected has produced leap.This shows that SERS has huge application prospect aspect Single Molecule Detection.
Molecular imprinting and Surface enhanced raman spectroscopy technology are combined, a kind of detection technique with high sensitivity, high selectivity, good stability can be provided, but existing method all needs other materials such as molecularly imprinted polymer and elargol are mixed on other metal films such as molecularly imprinted polymer being coated in silver, just can have surface-enhanced Raman effects, method complicated and exist molecular engram thing and metal film in conjunction with bad and impact detects the phenomenon of effect, and raising is to the detectability of trace materials.
Summary of the invention
The present invention will solve that existing method all needs other materials such as molecularly imprinted polymer and elargol are mixed or molecularly imprinted polymer is coated on other metal films such as silver, method complicated and exist molecular engram thing and metal film in conjunction with bad and impact detects the problem of effect, the method for utilizing the silver surface molecularly imprinted polymer to carry out the Surface Enhanced Raman Scattering Spectrum detection is provided.
The present invention utilizes the silver surface molecularly imprinted polymer to carry out the method that Surface Enhanced Raman Scattering Spectrum detects, and carries out according to the following steps: one, preparation 500nm-5 μ m silver particles: a, preparation 5～10mL concentration are the AgNO of 1mol/L
3Solution, 20～35mL concentration are the ascorbic acid solution of 1mol/L, 1～5mL concentration be 0.35mol/L citric acid solution b, the polyvinylpyrrolidone of 1～2g is dissolved in the distilled water of 3～8mL, obtain polyvinylpyrrolidonesolution solution; C, container is put into ice-water bath, add the AgNO of 60～100mL distilled water, step a preparation in the container
3The citric acid solution of solution, step a preparation and the polyvinylpyrrolidonesolution solution of step b are mixed, then under agitation, the ascorbic acid solution that adds step a preparation, reaction 15～30min carries out centrifugally, gets solid formation, with distilled water centrifuge washing 2～4 times, use again the absolute ethyl alcohol centrifuge washing 2～4 times, then carry out drying, namely get 500nm-5 μ m silver particles;
Two, to the silver particles modifying surface: the mixed solution A of 100～150mL, the silver particles of 1～2g step 1 preparation and two key silane reagents of 8～12mL are mixed, it is 40～90 ℃ in temperature, the nitrogen atmosphere protection is lower, stir 20～28h, then absolute ethanol washing is 2～4 times, the drier silver particles that can obtain the surface silicon alkanisation; Wherein mixed solution A is to be by volume (3～5) by the second alcohol and water: 1 mixes;
Three, the pre-assembled solution of preparation target molecule and function monomer: target molecule is dissolved in the chloroform soln, obtaining concentration is the target molecule chloroform soln of 0.005～0.007mol/L, then add function monomer, stirred 30 minutes, obtain the pre-assembled solution of target molecule and function monomer, wherein the mol ratio of target molecule and function monomer is 1: (1.3～6);
Four, the pre-polymer solution of the silver-colored molecularly imprinted polymer of preparation: add crosslinking chemical in the silver particles of the surface silicon alkanisation that makes to step 2, and then the target molecule of adding step 3 preparation and the pre-assembled solution of function monomer, ultrasonic 20～40min obtains the pre-polymer solution of silver-colored molecularly imprinted polymer; Wherein the mass volume ratio of the silver particles of surface silicon alkanisation and crosslinking chemical is 1g: (15～30) mL, and the mol ratio of crosslinking chemical and function monomer is (1.5～6): 1;
Five, the particle of preparation galactic nucleus molecular engram putamina: in the pre-polymer solution of the silver-colored molecularly imprinted polymer of step 4 preparation, add the chloroform soln that contains initiating agent, pass into N
2, stir, when being 40～90 ℃, temperature reacts 24h, obtain the particle of galactic nucleus molecular engram putamina; Wherein the mass ratio of crosslinking chemical and initiating agent is 1: (0.01～0.05), the volume ratio of methenyl choloride and crosslinking chemical are (20～40): 1;
Six, preparation silver surface molecularly imprinted polymer: d, the particle of galactic nucleus molecular engram putamina is added in the methanol solution washing 1 time, then the distilled water washing is 4～6 times; E, steps d repeat 2～4 times; F, put into the mixed solution B of 70～160mL, change mixed solution B behind vibration 2～4h; Then g, repeating step f operation carries out drying until detect among the mixed solution B till the driftlessness molecule, obtains the silver surface molecularly imprinted polymer; Wherein mixed solution B is that acetic acid and methyl alcohol are 1 by volume: (4～9) mix;
Seven, compound concentration is 10
-2～10
-15The target molecule organic solution of mol/L, then in the target molecule organic solution of 1～8ml, add 0.01～0.15g silver surface molecularly imprinted polymer, vibration absorption 6～24h, carry out Raman detection, Raman spectrogram after being enhanced is namely finished and is utilized the silver surface molecularly imprinted polymer to carry out the method that Surface Enhanced Raman Scattering Spectrum detects.
The present invention is a kind of detection technique with high sensitivity, high selectivity, good stability, and lowest detectable limit can reach 10
-15Mol/L.The present invention utilizes molecular imprinting that different testing molecules is carried out trace, since the special groups of the function monomer that has in the molecularly imprinted polymer can and testing molecule between certain interaction occurs, add the size coupling of the hole that has in the molecularly imprinted polymer and the testing molecule for the treatment of trace, caused this molecularly imprinted polymer to very high extraction efficiency was arranged in to be measured minute.With silver as nuclear, molecularly imprinted polymer is as shell, changed traditional other materials such as molecularly imprinted polymer and elargol are mixed, the method that just can have surface-enhanced Raman effects, thereby greatly improved the convenience of using, also changed and molecularly imprinted polymer is coated in silver waits on other metal films, just had the method for surface-enhanced Raman effects, thus avoided molecular engram thing and metal film in conjunction with bad phenomenon.
Description of drawings
Fig. 1 is the scanning electron microscope diagram of the silver particles of test procedure one preparation;
Fig. 2 is the transmission electron microscope figure of the silver particles of test procedure one preparation;
Fig. 3 is the scanning electron microscope diagram of the silver surface molecularly imprinted polymer of test procedure six preparations;
Fig. 4 is the transmission electron microscope figure of the silver surface molecularly imprinted polymer of test procedure six preparations;
Fig. 5 is the Raman spectrogram of the silver surface molecularly imprinted polymer of test procedure six preparations.
Embodiment
Embodiment one: present embodiment utilizes the silver surface molecularly imprinted polymer to carry out the method that Surface Enhanced Raman Scattering Spectrum detects, and carries out according to the following steps: one, preparation 500nm-5 μ m silver particles: a, preparation 5～10mL concentration are the AgNO of 1mol/L
3Solution, 20～35mL concentration are the ascorbic acid solution of 1mol/L, 1～5mL concentration be 0.35mol/L citric acid b, the polyvinylpyrrolidone of 1～2g is dissolved in the distilled water of 3～8mL, obtain polyvinylpyrrolidonesolution solution; C, container is put into ice-water bath, add the AgNO of 60～100mL distilled water, step a preparation in the container
3The citric acid of solution, step a preparation and the polyvinylpyrrolidonesolution solution of step b are mixed, then under agitation, the ascorbic acid solution that adds step a preparation, reaction 15～30min carries out centrifugally, gets solid formation, with distilled water centrifuge washing 2～4 times, use again the absolute ethyl alcohol centrifuge washing 2～4 times, then carry out drying, namely get 500nm-5 μ m silver particles;
Two, to the silver particles modifying surface: the mixed solution A of 100～150mL, the silver particles of 1～2g step 1 preparation and two key silane reagents of 8～12mL are mixed, under the nitrogen atmosphere protection, temperature is 40～90 ℃, stir 20～28h, then absolute ethanol washing is 2～4 times, the drier silver particles that can obtain the surface silicon alkanisation; Wherein mixed solution A is to be by volume (3～5) by the second alcohol and water: 1 mixes;
Three, the pre-assembled solution of preparation target molecule and function monomer: target molecule is dissolved in the chloroform soln, obtaining concentration is the target molecule chloroform soln of 0.005～0.007mol/L, then add function monomer, stirred 30 minutes, obtain the pre-assembled solution of target molecule and function monomer, wherein the mol ratio of target molecule and function monomer is 1: (1.3～6);
Four, the pre-polymer solution of the silver-colored molecularly imprinted polymer of preparation: add crosslinking chemical in the silver particles of the surface silicon alkanisation that makes to step 2, and then the target molecule of adding step 3 preparation and the pre-assembled solution of function monomer, ultrasonic 20～40min obtains the pre-polymer solution of silver-colored molecularly imprinted polymer; Wherein the mass volume ratio of the silver particles of surface silicon alkanisation and crosslinking chemical is 1g: (15～30) mL, and the mol ratio of crosslinking chemical and function monomer is (1.5～6): 1;
Five, the particle of preparation galactic nucleus molecular engram putamina: in the pre-polymer solution of the silver-colored molecularly imprinted polymer of step 4 preparation, add the chloroform soln that contains initiating agent, pass into N
2, stir, when being 40～90 ℃, temperature reacts 24h, obtain the particle of galactic nucleus molecular engram putamina; Wherein the mass ratio of crosslinking chemical and initiating agent is 1: (0.01～0.05), the volume ratio of methenyl choloride and crosslinking chemical are (20～40): 1;
Six, preparation silver surface molecularly imprinted polymer: d, the particle of galactic nucleus molecular engram putamina is added in the methanol solution washing 1 time, then the distilled water washing is 4～6 times; E, steps d repeat 2～4 times; F, put into the mixed solution B of 70～160mL, change mixed solution B behind vibration 2～4h; Then g, repeating step f operation carries out drying until detect among the mixed solution B till the driftlessness molecule, obtains the silver surface molecularly imprinted polymer; Wherein mixed solution B is that acetic acid and methyl alcohol are 1 by volume: (4～9) mix;
Seven, compound concentration is 10
-2～10
-15The target molecule organic solution of mol/L, then in the target molecule organic solution of 1～8ml, add 0.01～0.15g silver surface molecularly imprinted polymer, vibration absorption 6～24h, carry out Raman detection, Raman spectrogram after being enhanced is namely finished and is utilized the silver surface molecularly imprinted polymer to carry out the method that Surface Enhanced Raman Scattering Spectrum detects.
Present embodiment is a kind of detection technique with high sensitivity, high selectivity, good stability, and detectability can reach 10
-15Mol/L.Present embodiment utilizes molecular imprinting that different testing molecules is carried out trace, since the special groups of the function monomer that has in the molecularly imprinted polymer can and testing molecule between certain interaction occurs, add the size coupling of the hole that has in the molecularly imprinted polymer and the testing molecule for the treatment of trace, caused changing molecularly imprinted polymer to very high extraction efficiency was arranged in to be measured minute.With silver as nuclear, molecularly imprinted polymer is as shell, changed traditional other materials such as molecularly imprinted polymer and elargol are mixed, the method that just can have surface-enhanced Raman effects, thereby greatly improved the convenience of using, also changed and molecularly imprinted polymer is coated in silver waits on other metal films, just had the method for surface-enhanced Raman effects, thus avoided molecular engram thing and metal film in conjunction with bad phenomenon.
Embodiment two: what present embodiment and embodiment one were different is: the drying among the step c is dry 12h in 40 ℃ of vacuum drying chambers.Other is identical with embodiment one.
Embodiment three: what present embodiment and embodiment one were different is: two key silane reagents are methacryloxypropyl trimethoxy silane in the step 2.Other is identical with embodiment one.
Embodiment four: what present embodiment and embodiment one were different is: the target molecule in the step 3 is rhodamine 6G, benzoic acid, benzenethiol, 4-mercaptopyridine, mercaptoethylmaine or pyridine.Other is identical with embodiment one.
Embodiment five: what present embodiment and embodiment one were different is: the function monomer in the step 3 is a-methacrylic acid, 4-vinylpyridine or 4-vinyl phenyl boric acid.Other is identical with embodiment one.
Embodiment six: what present embodiment was different from one of embodiment one to five is: the crosslinking chemical in the step 4 is divinylbenzene or dimethyl benzene olefin(e) acid second diester.Other is identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different from one of embodiment one to five is: the initiating agent in the step 5 is azoisobutyronitrile.Other is identical with one of embodiment one to five.
Embodiment eight: what present embodiment was different from one of embodiment one to five is: the speed 350r/min that stirs in the step 5.Other is identical with one of embodiment one to five.
Embodiment nine: what present embodiment was different from one of embodiment one to eight is: in the step 6 with having or not target molecule in the UV spectrophotometer measuring mixed solution.Other is identical with one of embodiment one to eight.
Embodiment ten: what present embodiment was different from one of embodiment one to nine is: compound concentration is 10 in the step 7
-2～10
-15The target molecule organic solution of mol/L.Other is identical with one of embodiment one to nine.
By following verification experimental verification beneficial effect of the present invention:
Test: utilize the silver surface molecularly imprinted polymer to carry out the method that Surface Enhanced Raman Scattering Spectrum detects, carry out according to the following steps: one, preparation silver particles: a, preparation 8mL concentration are the AgNO of 1mol/L
3Solution, 30mL concentration are the ascorbic acid solution of 1mol/L, 2mL concentration be 0.35mol/L citric acid b, the polyvinylpyrrolidone of 1.35g is dissolved in the distilled water of 5mL, obtain polyvinylpyrrolidonesolution solution; C, container is put into ice-water bath, add the AgNO of 80mL distilled water, step a preparation in the container
3The citric acid solution of solution, step a preparation and the polyvinylpyrrolidonesolution solution of step b are mixed, then under agitation, the ascorbic acid solution that adds step a preparation, reaction 20min carries out centrifugally, gets solid formation, with distilled water centrifuge washing 3 times, use the absolute ethyl alcohol centrifuge washing 3 times, then dry 12h in 40 ℃ of vacuum drying chambers namely gets silver particles again;
Two, to the silver particles modifying surface: the mixed solution A of 140mL, the silver particles of 1.75g step 1 preparation and the methacryloxypropyl trimethoxy silane of 10mL are mixed, it is 60 ℃ in temperature, the nitrogen atmosphere protection is lower, stir 24h, then absolute ethanol washing is 3 times, the drier silver particles that can obtain the surface silicon alkanisation; Wherein mixed solution A is to be to mix at 4: 1 by volume by the second alcohol and water;
Three, the pre-assembled solution of preparation target molecule and function monomer: be that molecular engram with 1mmol is dissolved in the chloroform soln of 150mL, then the a-methacrylic acid that adds 4mmol mixes, stir 30min, carry out pre-assembled to mercaptobenzoic acid and function monomer, obtain pre-assembled solution.
Four, the pre-polymer solution of the silver-colored molecularly imprinted polymer of preparation: add the divinylbenzene of 20mmol in the silver particles of the surface silicon alkanisation that makes to step 2, and then add the pre-assembled solution that step 3 makes, ultrasonic 30min obtains pre-polymer solution.
Five, the particle of preparation galactic nucleus molecular engram putamina: in the pre-polymer solution of the silver-colored molecularly imprinted polymer of step 4 preparation, add the chloroform soln that contains the 0.090g azoisobutyronitrile, pass into N
2, stir, when being 90 ℃, temperature reacts 24h, obtain the particle of galactic nucleus molecular engram putamina;
Six, preparation silver surface molecularly imprinted polymer: d, the particle of galactic nucleus molecular engram putamina is added in the methanol solution washing 1 time, then the distilled water washing is 5 times; E, steps d repeat 3 times; F, put into the mixed solution B of 100mL, change mixed solution B behind the vibration 3h; Then g, repeating step f operation carries out drying until detect among the mixed solution B till the driftlessness molecule, obtains the silver surface molecularly imprinted polymer; Wherein mixed solution B is that acetic acid and methyl alcohol are to mix at 1: 4 by volume;
Seven, compound concentration is 10
-3, 10
-9, 10
-12, 10
-15Mol/L to the mercaptobenzoic acid ethanolic solution, then to 5ml to adding 0.01g silver surface molecularly imprinted polymer in the mercaptobenzoic acid ethanolic solution, vibration absorption 8h, carry out Raman detection, Raman spectrogram (Fig. 5) after being enhanced is namely finished and is utilized the silver surface molecularly imprinted polymer to carry out the method that Surface Enhanced Raman Scattering Spectrum detects.
Silver particles to one preparation of this test procedure is carried out the electron scanning Electronic Speculum, the result as shown in Figure 1, as shown in Figure 1: the Ag particle for the rule spherical structure and be evenly distributed, mean grain size is 2.5 μ m, the Ag microsphere surface is coarse and uneven, and each Ag microballoon is by a large amount of Ag nanoassembles.Silver particles is carried out transmission electron microscope scanning, the result as shown in Figure 2, as shown in Figure 2: the TEM by the microballoon edge characterizes the conclusion that has further proved SEM.
Silver surface molecularly imprinted polymer to six preparations of this test procedure carries out the electron scanning Electronic Speculum, the result as shown in Figure 3, as shown in Figure 4: obvious variation has occured in the Ag particle surface, by the surface molecule print method in the grafting of Ag particle surface the MIP layer, obtained size uniform, finely dispersed core-shell type Ag-MIP microballoon.Silver particles is carried out transmission electron microscope scanning, the result as shown in Figure 2, as shown in Figure 2: see that more clearly the Ag microsphere surface coats one deck MIP film, the black part that transmittance is low is divided into Ag, is about 40nm at its surface coated MIP film thickness.
The used Raman spectrometer of this test is the burnt Raman spectrometer of copolymerization, and detecting the excitation source wavelength coverage that adopts is the 400-1000 nanometer.As shown in Figure 5, along with the concentration of mercaptobenzoic acid solution is descended, adsorbed slightly also thereupon weakening of silver to mercaptobenzoic acid-molecularly imprinted polymer Surface enhanced raman spectroscopy.As can be seen from Figure 5 the lowest detectable limit of this detection method can reach 10
-15Mol/L.
Claims (10)
1. utilize the silver surface molecularly imprinted polymer to carry out the method that Surface Enhanced Raman Scattering Spectrum detects, it is characterized in that utilizing the silver surface molecularly imprinted polymer to carry out the method that Surface Enhanced Raman Scattering Spectrum detects and carry out according to the following steps: one, preparation 500nm-5 μ m silver particles: a, preparation 5～10mL concentration are the AgNO of 1mol/L
3Solution, 20～35mL concentration are the ascorbic acid solution of 1mol/L, 1～5mL concentration be 0.35mol/L citric acid solution b, the polyvinylpyrrolidone of 1～2g is dissolved in the distilled water of 3～8mL, obtain polyvinylpyrrolidonesolution solution; C, container is put into ice-water bath, add the AgNO of 60～100mL distilled water, step a preparation in the container
3The citric acid solution of solution, step a preparation and the polyvinylpyrrolidonesolution solution of step b are mixed, then under agitation, the ascorbic acid solution that adds step a preparation, reaction 15～30min carries out centrifugally, gets solid formation, with distilled water centrifuge washing 2～4 times, use again the absolute ethyl alcohol centrifuge washing 2～4 times, then carry out drying, namely get 500nm-5 μ m silver particles;
Two, to the silver particles modifying surface: the mixed solution A of 100～150mL, the silver particles of 1～2g step 1 preparation and two key silane reagents of 8～12mL are mixed, under the nitrogen atmosphere protection, 40～90 ℃ of temperature, stir 20～28h, then absolute ethanol washing is 2～4 times, the drier silver particles that can obtain the surface silicon alkanisation; Wherein mixed solution A is to be by volume (3～5) by the second alcohol and water: 1 mixes;
Three, the pre-assembled solution of preparation target molecule and function monomer: target molecule is dissolved in the chloroform soln, obtaining concentration is the target molecule chloroform soln of 0.005～0.007mol/L, then add function monomer, stirred 30 minutes, obtain the pre-assembled solution of target molecule and function monomer, wherein the mol ratio of target molecule and function monomer is 1: (1.3～6);
Four, the pre-polymer solution of the silver-colored molecularly imprinted polymer of preparation: add crosslinking chemical in the silver particles of the surface silicon alkanisation that makes to step 2, and then the target molecule of adding step 3 preparation and the pre-assembled solution of function monomer, ultrasonic 20～40min obtains the pre-polymer solution of silver-colored molecularly imprinted polymer; Wherein the mass volume ratio of the silver particles of surface silicon alkanisation and crosslinking chemical is 1g: (15～30) mL, and the mol ratio of crosslinking chemical and function monomer is (1.5～6): 1;
Five, the particle of preparation galactic nucleus molecular engram putamina: in the pre-polymer solution of the silver-colored molecularly imprinted polymer of step 4 preparation, add the chloroform soln that contains initiating agent, pass into N
2, stir, when being 40～90 ℃, temperature reacts 24h, obtain the particle of galactic nucleus molecular engram putamina;
Six, preparation silver surface molecularly imprinted polymer: d, the particle of galactic nucleus molecular engram putamina is added in the methanol solution washing 1 time, then the distilled water washing is 4～6 times; E, steps d repeat 2～4 times; F, put into the mixed solution B of 70～160mL, change mixed solution B behind vibration 2～4h; Then g, repeating step f operation carries out drying until detect among the mixed solution B till the driftlessness molecule, obtains the silver surface molecularly imprinted polymer; Wherein mixed solution B is that acetic acid and methyl alcohol are 1 by volume: (4～9) mix;
Seven, compound concentration is 10
-2～10
-15The target molecule organic solution of mol/L, then in the target molecule organic solution of 1～8ml, add 0.01～0.15g silver surface molecularly imprinted polymer, vibration absorption 6～24h, carry out Raman detection, Raman spectrogram after being enhanced is namely finished and is utilized the silver surface molecularly imprinted polymer to carry out the method that Surface Enhanced Raman Scattering Spectrum detects.
2. the silver surface molecularly imprinted polymer that utilizes according to claim 1 carries out the method that Surface Enhanced Raman Scattering Spectrum detects, and it is characterized in that the drying among the step c is dry 12h in 40 ℃ of vacuum drying chambers.
3. the silver surface molecularly imprinted polymer that utilizes according to claim 1 carries out the method that Surface Enhanced Raman Scattering Spectrum detects, and it is characterized in that two key silane reagents are methacryloxypropyl trimethoxy silane in the step 2.
4. the silver surface molecularly imprinted polymer that utilizes according to claim 1 carries out the method that Surface Enhanced Raman Scattering Spectrum detects, it is characterized in that the target molecule in the step 3 is rhodamine 6G, benzoic acid, benzenethiol, 4-mercaptopyridine, mercaptoethylmaine or pyridine.
5. the silver surface molecularly imprinted polymer that utilizes according to claim 4 carries out the method that Surface Enhanced Raman Scattering Spectrum detects, and it is characterized in that the function monomer in the step 3 is a-methacrylic acid, 4-vinylpyridine or 4-vinyl phenyl boric acid.
6. the silver surface molecularly imprinted polymer that utilizes according to claim 5 carries out the method that Surface Enhanced Raman Scattering Spectrum detects, and it is characterized in that the crosslinking chemical in the step 4 is divinylbenzene or dimethyl benzene olefin(e) acid second diester.
7. the silver surface molecularly imprinted polymer that utilizes according to claim 5 carries out the method that Surface Enhanced Raman Scattering Spectrum detects, and it is characterized in that the initiating agent in the step 5 is azoisobutyronitrile.
8. the silver surface molecularly imprinted polymer that utilizes according to claim 6 carries out the method that Surface Enhanced Raman Scattering Spectrum detects, and it is characterized in that the speed 350r/min that stirs in the step 5.
9. the silver surface molecularly imprinted polymer that utilizes according to claim 8 carries out the method that Surface Enhanced Raman Scattering Spectrum detects, and it is characterized in that in the step 6 with having or not target molecule in the UV spectrophotometer measuring mixed solution.
10. the silver surface molecularly imprinted polymer that utilizes according to claim 9 carries out the method that Surface Enhanced Raman Scattering Spectrum detects, and it is characterized in that compound concentration is 10 in the step 7
-2～10
-15The target molecule organic solution of mol/L.
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