CN112748098A - Reusable specific surface enhanced Raman sensor and preparation method thereof - Google Patents
Reusable specific surface enhanced Raman sensor and preparation method thereof Download PDFInfo
- Publication number
- CN112748098A CN112748098A CN201911046868.4A CN201911046868A CN112748098A CN 112748098 A CN112748098 A CN 112748098A CN 201911046868 A CN201911046868 A CN 201911046868A CN 112748098 A CN112748098 A CN 112748098A
- Authority
- CN
- China
- Prior art keywords
- enhanced raman
- sio
- nano
- specific surface
- aua
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
Landscapes
- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention provides a reusable specific surface enhanced Raman sensor and a preparation method thereof, and SiO modified at amino2Adsorbing a layer of orderly arranged nano gold array on the surface of the microsphere opal structure, filling a pre-polymerization solution containing template molecules of a detection object in gaps of the opal structure, carrying out polymerization reaction, and eluting with a solvent to remove SiO2Microspheres and detection object template molecules to obtain the surface enhanced Raman sensor. The surface-enhanced Raman sensor has a structure similar to a sandwich structure, and the ordered nanogold array generates uniform hot spots, so that the consistency and the reproducibility of spectral signals of different positions of the surface-enhanced Raman sensor are ensured; the nano-gold array is positioned between the porous molecularly imprinted polymer layer and the supporting substrate, so that the nano-gold is prevented from being agglomerated, the stability of the surface enhanced Raman sensor is improved, and repeated utilization can be realized.
Description
Technical Field
The invention relates to the technical field of chemical and biological sensing, in particular to a reusable specific surface enhanced Raman sensor and a preparation method thereof.
Background
At present, the specific detection of target molecules in actual samples by using raman spectroscopy is quite difficult because actual sample systems are often complex in composition, and raman spectroscopy itself is not selective for specific molecules. In particular, when the content of the target molecule is low, or the sample contains structural analogues of the target molecule, the sensitivity and the anti-interference performance of the conventional Surface Enhanced Raman (SERS) sensor are not required.
The molecular imprinting technology takes a target analyte or a substitute molecule as a template, and generates covalent or non-covalent interaction through copolymerization reaction of a functional monomer, a cross-linking agent and a template molecule to obtain a three-dimensional supramolecular structure containing a specific recognition site, and the three-dimensional supramolecular structure has a functional group shape and a geometric shape which are complementary with the template molecule after the template is removed. The obtained Molecularly Imprinted Polymer (MIP) can specifically identify and recombine target molecules in a complex detection object to achieve the effects of selective separation and enrichment, and is already applied to analysis and detection in the fields of environment, food, medicine and the like. The Molecularly Imprinted Polymer (MIP) is applied to the preparation of a Surface Enhanced Raman Scattering (SERS) sensor, and the problem that specific detection cannot be realized by Raman spectroscopy can be solved. The literature reports that a structure of coating an imprinted polymer layer outside a metal nanoparticle, through dip dyeing with a target detection solution, a target molecule is immersed in a pore of a molecularly imprinted layer, and Surface Enhanced Raman (SERS) detection is realized under excitation of a "hot spot" formed by the metal nanoparticle, for example, Wang et al prepared a Surface Enhanced Raman (SERS) sensor (MIPs @ AgNPs) specific to bisphenol a by generating silver nanoparticles (AgNPs) in situ in a Molecularly Imprinted Polymer (MIPs) matrix in 2018 (Applied Surface Science, 2018, 457: 323-. Sunzhiqin et al disclose a dispersion type core-shell particle with gold nanoparticles as core and molecularly imprinted polymer as shell, which is used for specific Surface Enhanced Raman Spectroscopy (SERS) detection of aflatoxin B1 (Chinese patent invention, application number: 201710153653.7). Rongafrica et al disclose that specific Surface Enhanced Raman (SERS) detection of plasticizers is achieved by preparing molecularly imprinted nanofibers with adsorbed metal nanoparticles by electrospinning and then forming a fiber film (Chinese patent application No. 201811454890.8).
Although the development of specific Surface Enhanced Raman (SERS) sensors in conjunction with molecular imprinting techniques has been reported, several problems remain: first, there are severe mass transfer limitations on the Molecularly Imprinted Polymer (MIP) layer that prevent the target analyte from contacting the "hot spots" around the metal nanoparticles, although a thin Molecularly Imprinted Polymer (MIP) layer can reduce the mass transfer limitations, but correspondingly also reduces the amount of binding of the analyte, resulting in a weaker raman signal; secondly, the distribution of the metal nanoparticles is not controllable, so that 'hot spots' are not uniformly distributed in the Molecularly Imprinted Polymer (MIP), and the reproducibility of Raman signals can be reduced; in addition, because the metal nanoparticles have poor stability and are easy to agglomerate, the reusability is low, and few Surface Enhanced Raman (SERS) sensors can be reused after being recycled once, so the cost is high.
Disclosure of Invention
The invention overcomes the defects in the prior art, and provides a reusable specific surface enhanced Raman sensor and a preparation method thereof, the method combines the structures of a porous molecularly imprinted polymer (pMIP) and an ordered nanogold array (AuA), wherein the nanogold array (AuA) is positioned between a porous molecularly imprinted polymer (pMIP) layer and a supporting layer, so that the stability of 'hot spots' and the reproducibility of detection signals are ensured, and the porous molecularly imprinted polymer (pMIP) layer provides specific binding sites for target molecules, so that the specificity of target molecule detection is ensured.
The purpose of the invention is realized by the following technical scheme.
The reusable specific surface enhanced Raman sensor and the preparation method thereof are carried out according to the following steps:
In step 1, SiO is monodisperse2The diameter of the microsphere is 250-400nm, the volume ratio of 3-aminopropyltriethoxysilane to ethanol in the amino modification liquid is 1 (50-500), the reaction temperature of amino modification is 70-90 ℃, the reaction time is 1-5h, and the amino modification SiO is2SiO in microsphere-ethanol suspension2The mass concentration of the microspheres is 1-5 wt%.
In the step 2, the diameter of the nano gold particles is 10-50nm, the concentration of the nano gold solution is 1.0-1.5mmol/L, the organic solvent adopts n-hexane, cyclohexane, ethyl acetate or dichloromethane, the volume ratio of the organic solvent to the nano gold aqueous solution is 1 (1-4), the volume ratio of ethanol to the nano gold aqueous solution is 1 (1-4), and the time for volatilizing the organic solvent until the nano gold array (AuA) is exposed is 40-70 min.
In step 3, Acrylamide (AM), methacrylic acid (MAA) or Methyl Methacrylate (MMA) is used as the functional monomer, the concentration of the functional monomer is 8-16mg/mL, preferably 10-15mg/mL, Ethylene Glycol Dimethacrylate (EGDMA), Divinylbenzene (DVB) or N, N' -Methylenebisacrylamide (MBA) is used as the crosslinking agent, the concentration of the crosslinking agent is 0.1-0.6mL/mL, preferably 0.1-0.5mL/mL, Azobisisobutyronitrile (AIBN) or Ammonium Persulfate (APS) is used as the initiator, the concentration of the initiator is 6-15mg/mL, preferably 8-12mg/mL, the coloring agent (rhodamine 6G, Sudan red, basic orange II) is used as the template molecule, the plasticizer (dimethyl phthalate, di (2-ethyl) hexyl phthalate, the plasticizer (2-ethyl) is used as the template molecule, Diisobutylphthalate), antibiotics (tetracycline, norfloxacin, sulfapyridine) or mycotoxins (aflatoxins, ochratoxins, zearalenone, etc.), the concentration of template molecules is 1.6-2.8mg/mL, preferably 2-2.5 mg/mL.
In the step 3, acetonitrile, methanol, ethanol or cyclohexanol is adopted as a solvent for dissolving the pre-polymerization liquid mixture, the polymerization reaction temperature is 40-70 ℃, the reaction time is 10-15h, the hydrofluoric acid soaking time is 8-12h, and the methanol-glacial acetic acid soaking time for removing the imprinting template is 2-5 h.
The invention has the beneficial effects that: the ordered nanogold array (AuA) can generate uniform 'hot spots' within a certain distance of the plane of the nanogold array, so that the consistency and the reproducibility of Raman spectrum signals at different positions of the prepared Surface Enhanced Raman Scattering (SERS) sensor are ensured; the molecular imprinting method utilizes target molecules as imprinting templates, and the obtained molecular imprinting polymer has cavities which are complementary with the template molecule space, can specifically identify and combine the target molecules in a complex detection object, and can combine the target molecules with a nano-gold array to realize specific sensing detection of specific target molecules; the method has universality, and specific Surface Enhanced Raman (SERS) sensors aiming at different target molecules can be prepared by changing the imprinting template; the molecular imprinting polymer (pMIP) with a porous structure has high specific surface area and provides more specific binding sites for target molecules; the mutually communicated pore passages are convenient for the rapid diffusion of a detected object in a Surface Enhanced Raman Scattering (SERS) sensor, the response time is greatly shortened, and the detection time is 4-5 s; the Surface Enhanced Raman Scattering (SERS) sensor prepared by the method has a sandwich-like structure, the nanogold array (AuA) is positioned between the porous molecularly imprinted polymer (pMIP) layer and the polymethyl methacrylate (PMMA) supporting substrate, and the structure can prevent the agglomeration of nanogold after multiple detections, so that the Surface Enhanced Raman Scattering (SERS) sensor has high stability, and can be repeatedly utilized.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a Surface Enhanced Raman Scattering (SERS) sensor according to the present invention;
FIG. 2(a) shows the results of Raman spectroscopy on rhodamine 6G using the AuA-pMIP sensor prepared in example 1;
FIG. 2(b) is 778cm-1A correlation curve between the intensity of the characteristic peak and the concentration of rhodamine 6G;
FIGS. 3(a) and 3(c) are Raman spectra of rhodamine 6G and its structural analogs rhodamine B and crystal violet detected using the AuA-pMIP and AuA-pNIP sensors prepared in example 1;
FIG. 3(B) is a graph showing the comparison of the characteristic peak intensities of rhodamine 6G and its structural analogues, rhodamine B and crystal violet, detected using the AuA-pMIP and AuA-pNIP sensors prepared in example 1;
FIG. 3(d) is a histogram comparing the peak intensities of rhodamine 6G, rhodamine B and crystal violet at their respective Raman feature peaks;
FIG. 4(a) is a Raman spectrum result chart of rhodamine 6G repeatedly measured using the AuA-pMIP sensor prepared in example 1;
FIG. 4(b) is 778cm in multiple measurements and washes of rhodamine 6G using the AuA-pMIP sensor prepared in example 1-1A graph of the variation of the intensity of the characteristic peak;
FIG. 5 is a graph showing the results of Raman measurements on rhodamine 6G in actual juice samples using the AuA-pMIP sensor prepared in example 1.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
1) Using amino modifying liquid containing 3-aminopropyl triethoxy silane to make monodisperse SiO with 380nm diameter2Amino modification is carried out on the microspheres, the volume ratio of 3-aminopropyltriethoxysilane to ethanol in modification liquid is 1:200, reflux is carried out for 3h at 80 ℃, suspension is centrifugally separated, and ethanol and purified water are respectively used for washing to obtain amino-modified SiO2And (5) drying the microspheres for later use. Preparing amino modified SiO with the concentration of 2 percent (w/w)2Vertically inserting the glass slide into the suspension, standing at room temperature to evaporate the solvent, and obtaining regularly arranged SiO on the glass slide after the ethanol is completely evaporated2And (3) carrying out opal structure OPC.
2) Taking a nano gold colloid solution with the diameter of 30nm, centrifuging, collecting precipitates, diluting the precipitates with double distilled water to the concentration of 1.177 mmol/L, and then adding n-hexane into the precipitates, wherein the volume ratio of the n-hexane to the nano gold colloid solution is 1:2, so as to form an organic-water two-phase interface; ethanol is quickly added into the two-phase solution, and the volume ratio of the ethanol to the nano-gold aqueous solution is 1:2, so that the nano-gold particles form an array which is arranged in order at the interface of the two phases; after the n-hexane volatilizes, a nanogold array AuA is formed on the water-air two-phase interface. SiO obtained in step 1)2Horizontally placing opal on the nano obtained in step 2)And (3) quickly lifting the surface of the mijin array after adsorption, transferring the nano-gold array to the surface of an opal structure, and drying by using nitrogen to obtain AuA-OPC.
3) Taking AuA-OPC obtained in the step 2), covering a layer of polymethyl methacrylate (PMMA) resin glass on the surface of AuA side to form a structure that the lower layer is a glass slide, the middle layer is OPC, the upper layer is AuA, the surface is covered with PMMA resin glass, and two ends are carefully fixed by two clamps. Preparing 1mL of mixed solution containing 12mg of functional monomer AM, 0.1mL of cross-linking agent EGDMA, 10mg of initiator AIBN and 2.12mg of template molecule rhodamine 6G, dissolving the mixed solution by using acetonitrile, and injecting the prepolymerization solution into the interlayer of the glass slide and the resin sheet. Polymerizing at 60 deg.C for 12h, and soaking in hydrofluoric acid for 10h to remove SiO2Microspheres, with methanol: glacial acetic acid (9:1, V/V) is soaked for 3h to remove the imprinting template rhodamine 6G, and finally the Surface Enhanced Raman Scattering (SERS) sensor with specific detection capability on the rhodamine 6G is obtained after the imprinting template rhodamine 6G is washed by double distilled water.
Example 2
1) Use of amino modifying liquid containing 3-aminopropyl triethoxy silane to make monodisperse SiO with diameter of 250nm2Amino modification is carried out on the microspheres, the volume ratio of 3-aminopropyltriethoxysilane to ethanol in modification liquid is 1:500, reflux is carried out for 5 hours at 70 ℃, suspension is centrifugally separated, and ethanol and purified water are respectively used for washing to obtain amino-modified SiO2And (5) drying the microspheres for later use. Preparing amino modified SiO with the concentration of 3 percent (w/w)2Vertically inserting the glass slide into the suspension, standing at room temperature to evaporate the solvent, and obtaining regularly arranged SiO on the glass slide after the ethanol is completely evaporated2And (3) carrying out opal structure OPC.
2) Taking a nano gold colloid solution with the diameter of 50nm, centrifuging, collecting precipitate, diluting the precipitate with double distilled water to the concentration of 1.2 mmol/L, and then adding ethyl acetate into the precipitate, wherein the volume ratio of the ethyl acetate to the nano gold colloid solution is 1:4, so as to form an organic-water two-phase interface; ethanol is quickly added into the two-phase solution, and the volume ratio of the ethanol to the nano-gold aqueous solution is 1:4, so that the nano-gold particles form an array which is arranged in order at the interface of the two phases; after the ethyl acetate is volatilized, a nanogold array AuA is formed at the interface of the water and the air. Will be described in detail1) Obtained SiO2Horizontally placing the opal on the surface of the nano-gold array obtained in the step 2), quickly lifting after adsorption, transferring the nano-gold array to the surface of an opal structure, and drying by using nitrogen to obtain AuA-OPC.
3) Taking AuA-OPC obtained in step 2), covering a layer of polymethyl methacrylate (PMMA) resin glass on the surface of AuA side, forming a structure that the lower layer is a glass slide, the middle layer is OPC, the upper layer is AuA, the surface is covered with PMMA resin glass, carefully fixing two ends by two clamps, preparing 1mL of mixed solution containing 15mg of functional monomer MAA, 0.2mL of cross-linking agent MBA, 12mg of initiator APS and 2.5mg of template molecule aflatoxin, dissolving by methanol, and injecting the prepolymerization solution into the interlayer of the glass slide and the resin sheet. Polymerizing for 15h at 70 ℃, and soaking for 10h by using hydrofluoric acid to remove SiO2Microspheres, with methanol: and soaking in glacial acetic acid (9:1, V/V) for 5h to remove the aflatoxin of the imprinting template, and finally cleaning with double distilled water to obtain the Surface Enhanced Raman Scattering (SERS) sensor with the aflatoxin having the specific detection capability.
Example 3
1) Use of amino modifying liquid containing 3-aminopropyl triethoxy silane to make monodisperse SiO with diameter of 300nm2Amino modification is carried out on the microspheres, the volume ratio of 3-aminopropyltriethoxysilane to ethanol in modification liquid is 1:50, reflux is carried out for 2 hours at 90 ℃, suspension is centrifugally separated, and ethanol and purified water are respectively used for washing to obtain amino-modified SiO2And (5) drying the microspheres for later use. Preparing amino modified SiO with the concentration of 1.5 percent (w/w)2Vertically inserting the glass slide into the suspension, standing at room temperature to evaporate the solvent, and obtaining regularly arranged SiO on the glass slide after the ethanol is completely evaporated2And (3) carrying out opal structure OPC.
2) Taking a nanogold solution with the diameter of 10nm, centrifuging, collecting precipitates, diluting the precipitates to the concentration of 1.1 mmol/L by using double distilled water, and then adding cyclohexane into the precipitates, wherein the volume ratio of the cyclohexane to the nanogold solution is 1:1, so as to form an organic-water two-phase interface; ethanol is quickly added into the two-phase solution, and the volume ratio of the ethanol to the nano-gold aqueous solution is 1:1, so that the nano-gold particles form an array which is arranged in order at the interface of the two phases; until cyclohexane volatilizesThen, a nano gold array AuA is formed at the water-air two-phase interface. SiO obtained in step 1)2Horizontally placing the opal on the surface of the nano-gold array obtained in the step 2), quickly lifting after adsorption, transferring the nano-gold array to the surface of an opal structure, and drying by using nitrogen to obtain AuA-OPC.
3) Taking AuA-OPC obtained in step 2), covering a layer of polymethyl methacrylate (PMMA) resin glass on the surface of AuA side, forming a structure that the lower layer is a glass slide, the middle layer is OPC, the upper layer is AuA, the surface is covered with PMMA resin glass, carefully fixing two ends by two clamps, preparing 1mL of mixed solution containing 10mg of functional monomer MMA, 0.05mL of cross-linking agent DVB, 8mg of initiator APS and 1.5mg of template molecule tetracycline, dissolving by ethanol, and injecting the prepolymerization solution into the interlayer of the glass slide and the resin sheet. Polymerizing at 40 deg.C for 10h, and soaking in hydrofluoric acid for 8h to remove SiO2Microspheres, with methanol: and (3) soaking in glacial acetic acid (9:1, V/V) for 2h to remove the imprinting template tetracycline, and finally washing with double distilled water to obtain the Surface Enhanced Raman Scattering (SERS) sensor with specific detection capability on the tetracycline.
Example 4
1) Use of amino modifying liquid containing 3-aminopropyl triethoxy silane to make monodisperse SiO with diameter of 400nm2Performing amino modification on the microspheres, wherein the volume ratio of 3-aminopropyltriethoxysilane to ethanol in modification liquid is 1:40, refluxing at 80 deg.C for 1h, centrifuging the suspension, and washing with ethanol and purified water respectively to obtain amino-modified SiO2And (5) drying the microspheres for later use. Preparing amino modified SiO with the concentration of 1.5 percent (w/w)2Vertically inserting the glass slide into the suspension, standing at room temperature to evaporate the solvent, and obtaining regularly arranged SiO on the glass slide after the ethanol is completely evaporated2And (3) carrying out opal structure OPC.
2) Taking a nano gold colloid solution with the diameter of 40nm, centrifuging, collecting precipitates, diluting the precipitates to the concentration of 1.15 mmol/L by using double distilled water, and then adding dichloromethane into the precipitates, wherein the volume ratio of the dichloromethane to the nano gold colloid solution is 1:3, so as to form an organic-water two-phase interface; ethanol is rapidly added into the two-phase solution, and the volume ratio of the ethanol to the nano-gold aqueous solution is 1:3, so that the nano-gold particles are in two phasesForming an orderly array at the interface; after the dichloromethane is volatilized, a nano gold array AuA is formed at the interface of the water and the air. SiO obtained in step 1)2Horizontally placing the opal on the surface of the nano-gold array obtained in the step 2), quickly lifting after adsorption, transferring the nano-gold array to the surface of an opal structure, and drying by using nitrogen to obtain AuA-OPC.
3) Taking AuA-OPC obtained in step 2), covering a layer of polymethyl methacrylate (PMMA) resin glass on the surface of AuA side, forming a structure that the lower layer is a glass slide, the middle layer is OPC, the upper layer is AuA, the surface is covered with PMMA resin glass, carefully fixing two ends by two clamps, preparing 1mL of mixed solution containing 10mg of functional monomer AM, 0.15mL of cross-linking agent EGDMA, 10mg of initiator AIBN and 2mg of template molecule dimethyl phthalate, dissolving by cyclohexanol, and injecting the prepolymerization solution into the interlayer of the glass slide and the resin sheet. Polymerizing for 14h at 60 ℃, and soaking for 12h by using hydrofluoric acid to remove SiO2Microspheres, with methanol: glacial acetic acid (9:1, V/V) is soaked for 5h to remove imprinting template dimethyl phthalate, and finally the imprinting template dimethyl phthalate is cleaned by double distilled water to obtain a Surface Enhanced Raman Scattering (SERS) sensor with specificity detection capability on dimethyl phthalate.
The test process and the test result are as follows:
the technical effects of the present invention will be described in detail with reference to the Surface Enhanced Raman (SERS) sensor prepared in example 1 as a test example.
1) Raman spectrum detection effect of rhodamine 6G with different concentrations
FIG. 2(a) shows a Surface Enhanced Raman (SERS) sensor pair prepared using example 1 at a concentration of 10-10-10-4And (3) performing Raman spectrum test on the rhodamine 6G solution at mol/L. It can be seen that the concentration of rhodamine 6G is increased at 778cm-1The intensity of the characteristic peak is gradually increased. When the concentration of the rhodamine 6G solution is reduced to 1 multiplied by 10-10When the molecular weight is mol/L, the Raman characteristic peak of the molecule can be still detected, which shows that the detection limit of the Surface Enhanced Raman Scattering (SERS) sensor to rhodamine 6G can reach 10-10In the order of mol/L.
FIG. 2(b) rhodamine 6G at 778cm-1Characteristic peak intensity ofAs ordinate, the logarithmic concentration value of rhodamine 6G (log [ R6G (mol/L))]) Establishing a relation between the intensity and the concentration of the characteristic peak by the abscissa, and obtaining a linear equation of which I is 233.77 × log [ R6G ]]+2334.75, linear correlation coefficient R2>0.99, this is indicated at 1X 10-10-1×10-4In the mol/L concentration range, the Raman characteristic peak intensity and the logarithm of the concentration of rhodamine 6G have good linear relation, which indicates that the prepared Surface Enhanced Raman (SERS) substrate can realize the quantitative detection of the rhodamine 6G.
2) Specific detection Effect
In order to prove the specific detection capability of the Surface Enhanced Raman (SERS) sensor prepared in example 1 on rhodamine 6G, rhodamine B and crystal violet solution which are molecular structural analogues of rhodamine 6G are prepared, and the concentration of the rhodamine B and the crystal violet solution is 10 and is the same as that of the rhodamine 6G-6mol/L. The Raman characteristic peak of rhodamine B is 1290cm-1Raman characteristic peak of crystal violet 922cm-1778cm from the characteristic peak of rhodamine 6G-1Are not overlapped.
In order to prove the effect of the molecularly imprinted polymer on specific detection, a non-imprinted Surface Enhanced Raman (SERS) sensor is prepared at the same time, and the preparation method is the same as that of example 1 except that no imprinted template rhodamine 6G is added into the pre-polymerization solution.
FIG. 3(a) is a graph showing the detection 10 of imprinted Surface Enhanced Raman (SERS) sensors and non-imprinted SERS sensors obtained in example 1-6Raman spectrum of mol/L rhodamine 6G. Can be seen at 778cm-1The peak intensity detected by the imprinted Surface Enhanced Raman (SERS) sensor is far higher than that of the non-imprinted Surface Enhanced Raman (SERS) sensor, which shows that the imprinted Surface Enhanced Raman (SERS) sensor has higher sensitivity to rhodamine 6G.
FIGS. 3(b) and (c) are graphs showing the detection 10 by the imprinted Surface Enhanced Raman Scattering (SERS) sensor and the non-imprinted Surface Enhanced Raman Scattering (SERS) sensor obtained in example 1, respectively-6Raman spectra of mol/L rhodamine B and crystal violet. It can be seen that the thickness of the film is 1290cm-1The Raman characteristic peak of rhodamine B is 922cm-1The peak intensity detected by the imprinting Surface Enhanced Raman Scattering (SERS) sensor is equivalent to that of a non-imprinting Surface Enhanced Raman Scattering (SERS) sensor at the characteristic peak of the crystal violet Raman, which shows that the imprinting Surface Enhanced Raman Scattering (SERS) sensor has no obvious specificity to rhodamine B and crystal violet.
Fig. 3(d) is a comparison of peak intensities of rhodamine 6G, rhodamine B, and crystal violet at respective raman characteristic peaks, which demonstrates the specific detection effect of the Surface Enhanced Raman (SERS) sensor prepared in example 1 on rhodamine 6G.
3) Reusability of Surface Enhanced Raman (SERS) sensors
FIG. 4(a) is a graph showing the use of a Surface Enhanced Raman (SERS) sensor pair 10 prepared in example 1-4And (5) detecting the rhodamine 6G solution for multiple times at mol/L. And after each measurement, the surface of the sensor is cleaned by using ethanol, and the ethanol is used for measuring the Raman spectrum of the rhodamine 6G again after the ethanol is completely evaporated. As can be seen, the same Surface Enhanced Raman Scattering (SERS) sensor has no obvious change in characteristic peak position and intensity after repeated measurement and ethanol cleaning for many times, and the Raman spectrum peak type of rhodamine 6G.
FIG. 4(b) shows 778cm after 8 repeated measurements and ethanol washes-1The change of the Raman characteristic peak intensity shows that the relative standard deviation of multiple measurements is 8.92 percent, which indicates that the Surface Enhanced Raman Scattering (SERS) sensor has good result reproducibility and reusability.
4) Detection effect on target molecules in actual samples
FIG. 5 shows the detection of rhodamine 6G in an actual fresh orange succus sample by using the Surface Enhanced Raman Scattering (SERS) sensor obtained in example 1. Adding 0.1-10nmol/L rhodamine 6G into the actual sample, and showing that the concentration of the rhodamine 6G is 778cm along with the increase of the concentration of the rhodamine 6G-1The raman characteristic peak intensity of (a) is also gradually increased. Using I-233.77 × log [ R6G ]]The +2334.75 equation quantifies rhodamine 6G in real juice samples, and the results agree with the add-on values with relative standard deviations between 1.74% and 4.56%. For actual juice samples, the detection limit of the Surface Enhanced Raman Scattering (SERS) sensor on rhodamine 6G can also reach 10-10In the order of mol/L.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. The preparation method of the reusable specific surface enhanced Raman sensor is characterized by comprising the following steps: the method comprises the following steps:
step 1, SiO2Preparation of opal structure: use of amino-modified liquid to monodisperse SiO2Carrying out amino modification on the microspheres to obtain amino-modified SiO2Microspheres, amino-modified SiO2Dispersing the microspheres in absolute ethyl alcohol to obtain amino modified SiO2Suspending microsphere-ethanol solution, vertically inserting glass slide into the suspension, standing at room temperature of 20-25 deg.C for evaporating solvent, and completely evaporating solvent to obtain SiO2Opal structure (OPC);
step 2, the nano gold array (AuA) is arranged on SiO2Load on opal structure (OPC): dispersing nano-gold into water, adding an organic solvent into the nano-gold solution to form an organic-water two-phase interface, adding ethanol into the two-phase solution to form an orderly array of nano-gold particles at the two-phase interface, volatilizing the upper organic solvent to form an ordered nano-gold array (AuA) on the water-air two-phase interface, and preparing the SiO prepared in the step 12The opal structure (OPC) is placed on the surface of the nano-gold array (AuA), and is quickly lifted after being adsorbed, so that the ordered nano-gold array (AuA) is transferred to SiO2Drying the surface of opal structure (OPC) to obtain SiO loaded with nano-gold array2Opal structure (AuA-OPC);
step 3, formation of a porous imprinted polymer (pMIP) layer: SiO loaded with nano-gold array prepared in step 22An opal structure (AuA-OPC) is prepared by covering a layer of polymethyl methacrylate (PMMA) resin sheet on one side of nanogold array (AuA) to form a lower layer which is a glass slide, and a middle layer which is a glass slideIs SiO2An opal structure (OPC) is arranged, the upper layer is a nanogold array (AuA), the surface of the nanogold array (AuA) is covered with a structure of a polymethyl methacrylate (PMMA) resin sheet, a prepolymerization solution mixture containing a functional monomer, a cross-linking agent, an initiator and a template molecule is prepared, after dissolution, the prepolymerization solution mixture solution is injected into the interlayer between a glass slide and the polymethyl methacrylate (PMMA) resin sheet, polymerization reaction is carried out, then hydrofluoric acid is used for soaking, a methanol-glacial acetic acid mixed solution is used for cleaning, a porous imprinted polymer (pMIP) layer is formed on the surface of the nanogold array (AuA), and after cleaning, a Surface Enhanced Raman Scattering (SERS) sensor (AuA-pMIP) is obtained.
2. The method of claim 1, wherein the specific surface-enhanced Raman sensor is a reusable specific surface-enhanced Raman sensor comprising: in step 1, SiO is monodisperse2The diameter of the microsphere is 250-400nm, the volume ratio of 3-aminopropyltriethoxysilane to ethanol in the amino modification liquid is 1 (40-600), preferably 1 (50-500), the reaction temperature of amino modification is 60-100 ℃, preferably 70-90 ℃, the reaction time is 1-6h, preferably 1-5h, and the reaction time of amino modification SiO is 1-6h2SiO in microsphere-ethanol suspension2The mass concentration of the microspheres is 1-6 wt%, preferably 1-5 wt%.
3. The method of claim 1, wherein the specific surface-enhanced Raman sensor is a reusable specific surface-enhanced Raman sensor comprising: in the step 2, the diameter of the nano gold particles is 10-50nm, the concentration of the nano gold solution is 0.8-2.0mmol/L, preferably 1.0-1.5mmol/L, the organic solvent is n-hexane, cyclohexane, ethyl acetate or dichloromethane, the volume ratio of the organic solvent to the nano gold aqueous solution is 1 (1-5), preferably 1 (1-4), the volume ratio of ethanol to the nano gold aqueous solution is 1 (1-5), preferably 1 (1-4), and the time for volatilizing the organic solvent until the nano gold array (AuA) is exposed is 30-80min, preferably 40-70 min.
4. The method of claim 1, wherein the specific surface-enhanced Raman sensor is a reusable specific surface-enhanced Raman sensor comprising: in step 3, Acrylamide (AM), methacrylic acid (MAA) or Methyl Methacrylate (MMA) is used as the functional monomer, and the concentration of the functional monomer is 8-16mg/mL, preferably 10-15 mg/mL.
5. The method of claim 1, wherein the specific surface-enhanced Raman sensor is a reusable specific surface-enhanced Raman sensor comprising: in step 3, Ethylene Glycol Dimethacrylate (EGDMA), Divinylbenzene (DVB), or N, N' -Methylenebisacrylamide (MBA) is used as the crosslinking agent, the concentration of the crosslinking agent is 0.1-0.6mL/mL, preferably 0.1-0.5mL/mL, Azobisisobutyronitrile (AIBN) or Ammonium Persulfate (APS) is used as the initiator, and the concentration of the initiator is 6-15mg/mL, preferably 8-12 mg/mL.
6. The method of claim 1, wherein the specific surface-enhanced Raman sensor is a reusable specific surface-enhanced Raman sensor comprising: in step 3, the template molecules adopt dyes (rhodamine 6G, Sudan red, basic orange II), plasticizers (dimethyl phthalate, di (2-ethyl) hexyl phthalate, diisobutyl phthalate), antibiotics (tetracycline, norfloxacin, sulfapyridine) or mycotoxins (aspergillus flavus, ochratoxin, zearalenone and the like), and the concentration of the template molecules is 1.6-2.8mg/mL, preferably 2-2.5 mg/mL.
7. The method of claim 1, wherein the specific surface-enhanced Raman sensor is a reusable specific surface-enhanced Raman sensor comprising: in the step 3, acetonitrile, methanol, ethanol or cyclohexanol is adopted as a solvent for dissolving the pre-polymerization liquid mixture, the polymerization reaction temperature is 30-80 ℃, the preferable temperature is 40-70 ℃, the reaction time is 8-16h, the preferable time is 10-15h, the hydrofluoric acid soaking time is 8-12h, and the methanol-glacial acetic acid soaking time is 2-5h for removing the imprinting template.
8. The specific surface-enhanced Raman sensor prepared by the method for preparing the reusable specific surface-enhanced Raman sensor according to any one of claims 1 to 7.
9. The use of a specific surface enhanced raman sensor according to claim 8 in the specific detection of rhodamine 6G.
10. Use according to claim 9, characterized in that: the method is characterized in that a specific surface enhanced Raman sensor is used for detecting rhodamine 6G, and the linear equation between the characteristic peak intensity and the rhodamine 6G concentration is obtained and is I (233.77 × log) (R6G)]+2334.75, linear correlation coefficient R2>0.99, I is the characteristic peak intensity, [ R6G]The concentration range of the detected rhodamine 6G is 1 multiplied by 10 for the concentration of the rhodamine 6G-10-1×10-4The detection limit of the specific surface enhanced Raman sensor to rhodamine 6G is 10-10In the order of mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911046868.4A CN112748098B (en) | 2019-10-30 | 2019-10-30 | Reusable specific surface enhanced Raman sensor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911046868.4A CN112748098B (en) | 2019-10-30 | 2019-10-30 | Reusable specific surface enhanced Raman sensor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112748098A true CN112748098A (en) | 2021-05-04 |
| CN112748098B CN112748098B (en) | 2022-09-16 |
Family
ID=75640778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911046868.4A Active CN112748098B (en) | 2019-10-30 | 2019-10-30 | Reusable specific surface enhanced Raman sensor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112748098B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114184600A (en) * | 2021-12-30 | 2022-03-15 | 江苏海洋大学 | Method for quantifying solute in water based on background subtraction of Raman spectrum |
| CN114216892A (en) * | 2021-11-30 | 2022-03-22 | 厦门大学 | Method for rapidly and accurately detecting zearalenone toxin in grain based on SERS (surface enhanced Raman scattering) |
| CN116642873A (en) * | 2023-06-05 | 2023-08-25 | 江南大学 | Reusable SERS (surface enhanced Raman Scattering) sensing chip and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004170334A (en) * | 2002-11-22 | 2004-06-17 | Japan Science & Technology Agency | Raman scattering measuring sensor, and its manufacturing method |
| WO2013063772A1 (en) * | 2011-11-02 | 2013-05-10 | Empire Technology Development Llc | Imprinted photonic polymers and methods for their preparation and use |
| CN106928397A (en) * | 2017-03-15 | 2017-07-07 | 集美大学 | Aflatoxin B1 molecule SERS detection methods based on molecularly imprinted polymer gold filled core-shell nano |
| CN107132212A (en) * | 2017-06-09 | 2017-09-05 | 天津大学 | The preparation method of the SERS senser element with side effect based on photonic crystal |
| CN107478636A (en) * | 2017-06-28 | 2017-12-15 | 江西师范大学 | Manufacturing method of economical high-precision surface-enhanced Raman active substrate |
-
2019
- 2019-10-30 CN CN201911046868.4A patent/CN112748098B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004170334A (en) * | 2002-11-22 | 2004-06-17 | Japan Science & Technology Agency | Raman scattering measuring sensor, and its manufacturing method |
| WO2013063772A1 (en) * | 2011-11-02 | 2013-05-10 | Empire Technology Development Llc | Imprinted photonic polymers and methods for their preparation and use |
| CN106928397A (en) * | 2017-03-15 | 2017-07-07 | 集美大学 | Aflatoxin B1 molecule SERS detection methods based on molecularly imprinted polymer gold filled core-shell nano |
| CN107132212A (en) * | 2017-06-09 | 2017-09-05 | 天津大学 | The preparation method of the SERS senser element with side effect based on photonic crystal |
| CN107478636A (en) * | 2017-06-28 | 2017-12-15 | 江西师范大学 | Manufacturing method of economical high-precision surface-enhanced Raman active substrate |
Non-Patent Citations (4)
| Title |
|---|
| LONG WU ET AL.: "Surface-Imprinted Gold Nanoparticle-Based Surface-Enhanced Raman Scattering for Sensitive and Specific Detection of Patulin in Food Samples", 《FOOD ANALYTICAL METHODS》 * |
| 崔艳光: "用于对硫磷快速检测的金纳米颗粒掺杂的反蛋白石光子晶体传感技术研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 谭文渊等: "表面增强拉曼散射技术对白酒中克百威残留的定性检测", 《食品科学》 * |
| 赵文斌等: "基于光子晶体带边效应的表面增强拉曼基底", 《分析化学》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114216892A (en) * | 2021-11-30 | 2022-03-22 | 厦门大学 | Method for rapidly and accurately detecting zearalenone toxin in grain based on SERS (surface enhanced Raman scattering) |
| CN114216892B (en) * | 2021-11-30 | 2024-02-06 | 厦门大学 | Method for rapidly and accurately detecting zearalenone toxin in grains based on SERS |
| CN114184600A (en) * | 2021-12-30 | 2022-03-15 | 江苏海洋大学 | Method for quantifying solute in water based on background subtraction of Raman spectrum |
| CN114184600B (en) * | 2021-12-30 | 2023-07-25 | 江苏海洋大学 | Method for quantifying solute in water based on Raman spectrum background subtraction |
| CN116642873A (en) * | 2023-06-05 | 2023-08-25 | 江南大学 | Reusable SERS (surface enhanced Raman Scattering) sensing chip and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112748098B (en) | 2022-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112748098B (en) | Reusable specific surface enhanced Raman sensor and preparation method thereof | |
| Niu et al. | Core-shell nanoparticles coated with molecularly imprinted polymers: a review | |
| Wei et al. | Detection of glycoprotein through fluorescent boronic acid-based molecularly imprinted polymer | |
| Bompart et al. | Chemical nanosensors based on composite molecularly imprinted polymer particles and surface‐enhanced Raman scattering | |
| CN110243889B (en) | Based on CsPbBr3Molecular imprinting photoelectrochemical sensor with/GO (graphene oxide) homotype heterostructure as well as preparation method and application thereof | |
| Li et al. | Thermo-responsive molecularly imprinted sensor based on the surface-enhanced Raman scattering for selective detection of R6G in the water | |
| CN110736725B (en) | Preparation method and application of molecularly imprinted fluorescent sensor for simultaneously and visually detecting two viruses | |
| CN109540867B (en) | Plasticizer Raman spectrum detection method based on molecularly imprinted nanofiber membrane | |
| Stringer et al. | Comparison of molecular imprinted particles prepared using precipitation polymerization in water and chloroform for fluorescent detection of nitroaromatics | |
| Lee et al. | Multifunctional hybrid polymer‐based porous materials | |
| CN108801989B (en) | Aptamer-molecularly imprinted fluorescent sensor for detecting cytochrome c and preparation method thereof | |
| CN108132351B (en) | Nano probe device for Raman enhanced protein detection and preparation method thereof | |
| CN112592440A (en) | Preparation method of defective graphene SERS substrate | |
| Latif et al. | Nanostructured molecularly imprinted photonic polymers for sensing applications | |
| Dong et al. | A novel polymerization of ultrathin sensitive imprinted film on surface plasmon resonance sensor | |
| Liu et al. | Three-dimensional Ag NPs-cellulose fiber/polyacrylamide hydrogels as a novel SERS platform for the efficient determination of thiram in fruits and juice | |
| Zhu et al. | Synthesis of molecularly imprinted polymer via visible light activated RAFT polymerization in aqueous media at room temperature for highly selective electrochemical assay of glucose | |
| CN106519150B (en) | A kind of preparation method of fluorescence polarization fluorescence magnetic molecular engram sensor | |
| CN108760694B (en) | Detection method of cytochrome c based on aptamer-molecularly imprinted fluorescent sensor | |
| CN113444262A (en) | Temperature response hydrogel and preparation method and application thereof | |
| Lu et al. | Flow injection chemiluminescence sensor using core-shell molecularly imprinted polymers as recognition element for determination of dapsone | |
| Noee et al. | Imprinted microspheres and nanoparticles with diclofenac sodium: effect of solvent on the morphology and recognition properties | |
| CN106947018B (en) | A kind of high-performance and highly controllable hud typed trace sensor and preparation method and purposes | |
| Riedel et al. | Surface Imprinted Micro-and Nanoparticles | |
| Li et al. | On-chip determination of glycated hemoglobin with a novel boronic acid copolymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |