CN103411946A - Method for preparing surface-enhanced Raman spectrum base by using electrospinning technique - Google Patents
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Abstract
The invention discloses a method for preparing a surface-enhanced Raman spectrum base by using electrospinning technique, and belongs to the technical field of ultra-sensitive detection. The method comprises the following steps: preparing N,N- dimethyl formamide solution of a polymer; preparing an electrospinning mixed solution of inorganic metal nanometer seed and the polymer; preparing a polymer/inorganic metal nanometer seed complex fiber membrane, reducing the polymer/inorganic metal nanometer seed complex fiber membrane again by using the reducing agent; processing the prepared nanometer seed complex fiber membrane to obtain the surface-enhanced Raman spectrum base; mixing the surface-enhanced Raman spectrum base with a to-be-tested molecular solution to perform the surface-enhanced Raman detection so as to obtain the Raman spectrogram of the enhanced to-be-tested molecule. The SERS (surface enhanced Raman scattering) signal of the base is enhanced by more than 1 million in comparison with conventional Raman, and the preparation of the base can be produced in large scale, and the higher commercial value is realized.
Description
Technical field
The invention belongs to the super sensitivity detection technical field, be specifically related to a kind of method of utilizing electrostatic spinning technique to prepare overdelicate Surface enhanced raman spectroscopy (Surface Enhance Raman Spectrum, SERS) substrate.
Background technology
Carrying out the molecular level detection is an important goal of super sensitivity detection, is also that people are familiar with an intramundane important milestone.Raman spectrum can provide molecular vibration information, is a kind of Holographic Fingerprint recognition technology of molecular structure, has been widely used in the qualitative and quantitative analysis of various biologies, chemistry and material system.
Since from SERS, being found, people are devoted to prepare the substrate of high SERS activity always, find and have the reproducible substrate of SERS and be applied in quantitative test simultaneously.The researchist is applied to various substrates to detect and analysis field, and it is studied as theoretical model.Because the metal material of high SERS activity is mainly silver and gold (silver-colored activity is best, and usable range is wide), but the stability of these two kinds of nano materials is all bad.Can only stable existence several hours as Nano silver grain, golden nanometer particle can only stable existence 3～5 days, makes it the SERS activity and sharply descends owing between surface oxidation or nano particle, assembling.The SERS substrate of unique a kind of commercial offers is the stable golden nanometer particle of surfactant at present, and is kept in the sealing bag of nitrogen filling, and price is about 100 dollars/bag, has 5 in a packaging bag.
Electrostatic spinning is the special shape of polymeric fluid electrostatic atomization, and it is not fine droplet that the material is divided in now atomization, but the small jet of polymkeric substance can move quite long distance, finally is solidified into fiber.Electrostatic spinning, as a kind of New Processing of the simple and effective nanofiber produced, is played a great role in fields such as bio-medical material, filtration and protection, catalysis, the energy, photoelectricity, food engineering, cosmetics.Brought into play very important effect constructing one-dimensional nano structure material field electrostatic spinning technique, success prepared the various nano-fiber material of structure.This nanofiber has higher specific surface area and porosity, can increase the zone of action of sensing material and detected material, is expected to increase substantially sensor performance.
The technology close with the present invention is disclosed Chinese patent on September 19th, 2012 " a kind of surface-enhanced Raman scattering activity substrate and preparation method thereof ", publication number CN102677212.It discloses a kind of surface-enhanced Raman scattering activity substrate and preparation method thereof.The method adds HAuCl in the polyvinyl alcohol water solution of certain mass concentration
4and AgNO
3solution, add again sodium citrate, fully after reaction, make polyvinyl alcohol (PVA)/Au-Ag alloy nano particle spinning liquid, adopt again the electrostatic spinning technique of run-in index, obtaining a kind of structure is the surface-enhanced Raman scattering activity substrate of polyvinyl alcohol (PVA)/Au-Ag alloy nano particle composite nano fiber, because the gold-silver alloy nano particle all can occur absorbing in green range at blue light, its plasma resonance wavelength can carry out controllable adjustment between silver and gold, therefore the surface-enhanced Raman scattering activity base material is provided, applicable wavelength coverage is than gold, the substrate of silver single component is more extensive.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing electrostatic spinning technique to prepare polymer/inorganic metal nano tunica fibrosa (as overdelicate Surface enhanced raman spectroscopy substrate), and this nano fibrous membrane combines with Raman technology, as overdelicate surface-enhanced Raman scattering activity substrate, application prospect is very widely arranged.Electrostatic spinning technique and these two kinds of technology of Surface enhanced raman spectroscopy technology are combined, can improve activity and the sensitivity of Raman substrate, overcome tradition and prepared the limitation such as the operation steps existed in Raman substrate method is complicated, nano particle is easily assembled, the pot-life is shorter, detection efficiency is low.
The present invention utilizes secondary reduction to combine with electrostatic spinning technique, in ratio by telomerized polymer and solvent, spinning process, pitch angle, spinneret and the receiving screen spacing of spinneret can obtain the fiber membrane of different-diameter, different-thickness, after adding inorganic salts reduction, can prepare the inorganic metal nano particle that is applicable to Raman detection, the density of polymeric fiber surface and inner inorganic metal nano particle can be regulated.By method of the present invention, regulate the dense degree of different nano particles, can construct out special " heat " structure (the sub-wavelength zone of high local strong-electromagnetic field) with higher Electromagnetic enhancement effect, and the Nano silver grain of polymer fiber inside can adsorb more probe molecule by swelling action, improve the sensitivity of Raman detection to reach the detection of single molecules level.
The method of utilizing electrostatic spinning technique to prepare overdelicate Surface enhanced raman spectroscopy substrate of the present invention, its step is as follows: the DMF solution that (a) prepares polymkeric substance; (b) prepare the electrostatic spinning mixed solution of inorganic metal nanometer seed and polymkeric substance; (c) prepare polymer/inorganic metal nano seed composite cellulosic membrane; (d) with reductive agent reductive polymerization thing/inorganic metal nanometer seed composite cellulosic membrane again; (e) process the nanometer seed composite cellulosic membrane prepared, obtain the Surface enhanced raman spectroscopy substrate; (f) the Surface enhanced raman spectroscopy substrate is mixed with testing molecule solution, carry out the surface-enhanced Raman detection, obtain the Raman spectrogram of testing molecule.
Preparing the DMF solution of polymkeric substance, is that polymkeric substance is dissolved in to N, in dinethylformamide, rapid stirring under the water bath condition of 80～100 degrees centigrade, thus prepare the N of polymkeric substance, dinethylformamide solution, solution concentration are 5～15wt%.
In said method, said polymkeric substance mainly comprises and dissolves in N, the polymkeric substance of dinethylformamide solvent, as polyacrylonitrile, polyamide, polyurethane, polystyrene, polyactide, polyethylene oxide etc., N, dinethylformamide can be reduced to inorganic salts less inorganic metal nanometer seed as reductive agent as solvent the time, inorganic metal nanometer seed is at the N of polymkeric substance, dispersed in dinethylformamide solution, in spinning process, also can be dispersed in spinning fibre, make fibrous inside comprise a large amount of little metal nano seeds, and fiber is outside by a large amount of inorganic metal nanometer seeds with not by N, dinethylformamide reduces inorganic salts completely and occupies, after again reducing, promote the growth of certain crystal face of outside inorganic metal seed, control growth time and can obtain being suitable as the inorganic nano-particle of Surface enhanced raman spectroscopy substrate.The polymer/inorganic nanometer tunica fibrosa obtained can cut randomly, and the tunica fibrosa that has like this SERS activity directly is immersed in testing molecule solution, then carries out the Raman spectrum that Raman detection can obtain testing molecule.
The preparation of the electrostatic spinning mixed solution of inorganic metal nanometer seed and polymkeric substance, inorganic salts (silver nitrate or gold chloride etc.) to be joined to the N of polymkeric substance with the concentration of 5～30wt%, in dinethylformamide solution, stirred 24～48 hours, thereby obtain the electrostatic spinning mixed solution, wherein inorganic salts are reduced to inorganic metal nanometer seed.
Prepare polymer/inorganic metal nano seed composite cellulosic membrane, that above-mentioned electrostatic spinning mixed solution is packed in the anodal spinning head of electrospinning device, under various different electrostatic spinning conditions, can obtain the composite cellulosic membrane of different-diameter size, for example, can change spinneret and dash receiver spacing (15～20cm), with respect to the horizontal plane angle (of spinneret<=5 °) and spinning voltage (10～15kv) etc., composite cellulosic membrane is collected on negative pole aluminium foil receiving screen, and the diameter of composite cellulosic membrane is 200～1000nm.
With reductive agent reductive polymerization thing/inorganic metal nanometer seed composite cellulosic membrane again, that composite cellulosic membrane is carried out to secondary reduction with the solution of the reductive agent of volumetric concentration 5%, the particle diameter that obtains the surface inorganic metal nanoparticle is 20～100nm, and the particle diameter of inner inorganic metal nano particle is the composite cellulosic membrane of 5～20nm.The secondary reduction agent is hydrazine hydrate, sodium citrate, ascorbic acid, sodium borohydride etc.
The composite cellulosic membrane that processing prepares, be by the distilled water cleaning down of the composite cellulosic membrane after secondary reduction, is laid on glass sheet, is placed in 60～80 ℃ of drying 6～10h in vacuum drying chamber.
The Surface enhanced raman spectroscopy substrate is mixed with testing molecule solution, is testing molecule to be dissolved in to ethanol or water to be mixed with concentration be 10
-3～10
-8The solution of mol/L, then be placed in this solution by the Surface enhanced raman spectroscopy substrate and soak 30～60min, with dry after alcohol flushing, after vaporing away ethanol, carries out the surface-enhanced Raman detection after taking-up, obtains the Raman spectrogram of testing molecule.Raman spectrometer is the burnt Raman spectrometer of copolymerization, and the wavelength coverage that detects the excitation source adopted is 400～1000nm.Testing molecule is rhodamine 6G, to mercaptobenzoic acid, p-Mercaptoaniline, p-aminobenzoic acid etc.
The present invention utilizes electrostatic spinning technique to prepare polymer/inorganic metal nano composite cellulosic membrane, due to N, dinethylformamide as solvent simultaneously as reductive agent, can by long-time gentle agitation, make the reduction of part inorganic salts become inorganic metal nanometer seed simultaneously in dissolve inorganic salts, make during seed metallization is dispersed in polymer fiber carrying out the electrostatic spinning process, and the seed metallization of fiber outside is grown up to 70～100nm, the most applicable Raman detection of this size, and the inorganic metal nanometer seed of fibrous inside is grown up to the nano particle of 5～20nm left and right.As the surface-enhanced Raman scattering activity substrate time, the outside and inner common absorption molecules detected of fiber, make detectability lower than conventional Raman substrate.Simultaneously, this substrate can be regulated the thickness of substrate by controlling the electrostatic spinning time, can change arbitrarily shapes of substrates by cutting, but and under nitrogen protection long preservation.The present invention is for Molecular Detection provides more flexibly, the higher surface enhanced Raman substrate of sensitivity.
Raman finger-print according to testing molecule, can detect specific testing molecule.The present invention is in the huge application that has of the research of Raman substrate.Raman substrate of the present invention and testing molecule mechanism of action aspect also have potential researching value, and for the detection in trace or Single Molecule Detection research system provide sizable may.
The accompanying drawing explanation
The described awkward silence at a meeting emission scan Electronic Speculum figure (upper right corner is that engineer's scale is the enlarged drawing of 100nm) with tunica fibrosa of nanoscale composite structure of Fig. 1: embodiment 1;
The ultraviolet-visible absorption spectroscopy of the described nano-composite fiber film of Fig. 2: embodiment 1;
The described preparation of Fig. 3: embodiment 1 Ju Bing Xi Jing ∕ silver nanoparticle composition fiber detects the Raman spectrogram of PATP solution as the Surface enhanced raman spectroscopy substrate;
The awkward silence at a meeting emission scan Electronic Speculum figure of the described Ju Bing of Fig. 4: embodiment 2 Xi Jing ∕ silver nanoparticle composition fiber;
The transmission electron microscope picture of the described Ju Bing of Fig. 5: embodiment 3 Xi Jing ∕ silver nanoparticle composition fiber.
Embodiment
Embodiment 1:
Utilize electrostatic spinning technique to prepare polyacrylonitrile/silver nanoparticle composition fiber as the substrate of hypersensitive Surface enhanced raman spectroscopy.
A) preparing polyacrylonitrile and DMF (DMF) solution is that the heating of the polyacrylonitrile of 0.3123g is dissolved in 3mL DMF, and mass concentration is 9wt%, and magnetic agitation 1h dissolves cooling rear stand-by fully.
B) the electrostatic spinning mixed solution for preparing inorganic metal nanometer seed and polymkeric substance is that silver nitrate joins in above-mentioned mixed solution, the mass concentration of silver nitrate is 30wt%, the dark condition lower magnetic force stirs 24h, and solution becomes yellow by micro-yellow, has illustrated that silver-colored seed generates.
C) polymer/silver nano particle mixed solution is drawn in the spinning syringe, the 15KV high-pressure spinning, the distance of spinneret and aluminium foil receiving screen is 17cm, the spinneret pitch angle is 5 degree, the spinning flow control is at 0.1mL/h, the spinning time is 12h, and the nano-composite fiber membrane area obtained is approximately 100cm
2, thickness can be regulated with the length of spinning time, and the thickness of spinning 12h is about 0.5～0.8mm.
The nano-composite fiber film that d) will obtain is cut to 1*1cm
2Be immersed in the hydrazine hydrate solution of 20mL, 5% (v/v), reductase 12 h under the ice-water bath condition, the tunica fibrosa color is celadon.
E) with distilled water flushing 3 times to remove unnecessary hydrazine hydrate molecule, the tunica fibrosa after rinsing is placed on slide, 60 ℃, 6h are dried.The tunica fibrosa obtained is that surface enhanced Raman substrate carries out awkward silence at a meeting emission surface sweeping electron microscope and ultraviolet-visible pectrophotometer characterizes, as shown in Figure 1 and Figure 2, the diameter that Fig. 1 can obtain composition fiber is 680nm, the particle diameter of the nano particle of fiber surface is distributed in 70～100nm, this Size Distribution is corresponding with the ultra-violet absorption spectrum of Fig. 2, the absorption maximum peak position is at 420nm, and the coupling that is absorbed as nano particle at 685nm place produces.
The surface enhanced Raman substrate that f) will prepare is placed in the ethanolic solution of the p-Mercaptoaniline of variable concentrations, under the ice-water bath condition, react 30min, after reacting completely, tunica fibrosa is pulled out, with alcohol flushing 3 times, remove unnecessary probe molecule, after natural air drying, for Raman detection, obtain spectrogram as shown in Figure 3.As can be seen here, our substrate for preparing tentatively can detect the 1*10 of p-Mercaptoaniline/ethanolic solution at present
-6Mol/L, and under this concentration, have very high relative intensity.
Embodiment 2
Prepare polyacrylonitrile and N, dinethylformamide solution is that a certain amount of polymkeric substance heating is dissolved in 3mLDMF, make the mixed solution that mass ratio is 9wt%, the silver nitrate that adds 5wt%, the dark condition lower magnetic force stirs 24h, polymer/silver nano particle mixed solution is drawn in the spinning syringe, the 15KV high-pressure spinning, the distance of spinneret and aluminium foil receiving screen is 17cm, the spinneret pitch angle is 5 degree, the spinning flow control is at 0.1mL/h, and the spinning time is 12h, and the nano-composite fiber membrane area obtained is approximately 100cm
2, the thickness of spinning 12h is about 0.5～0.8mm.The nano-composite fiber film obtained is cut to 1*1cm
2Be immersed in the hydrazine hydrate solution of 20mL, 5% (v/v), reductase 12 h under the ice-water bath condition, the tunica fibrosa color is celadon.With distilled water flushing 3 times, the tunica fibrosa after rinsing is placed on slide to 60 ℃ of oven dry.The tunica fibrosa obtained carries out awkward silence at a meeting emission surface sweeping electron microscope such as Fig. 4, and the mean diameter that can obtain composition fiber is 680nm, and the particle diameter of the nano particle of fiber surface is distributed in 70～100nm, but Nano silver grain is less, and relative density is lower.
Embodiment 3
Prepare polyacrylonitrile and N, dinethylformamide solution is that a certain amount of polymkeric substance heating is dissolved in 3mLDMF, make the mixed solution that mass ratio is 9wt%, the silver nitrate that adds 30wt%, the dark condition lower magnetic force stirs 24h, polymer/silver nano particle mixed solution is drawn in the spinning syringe, the 15KV high-pressure spinning, the distance of spinneret and aluminium foil receiving screen is 17cm, the spinneret pitch angle is 5 degree, the spinning flow control is at 0.1mL/h, and the spinning time is 12h, and the nano-composite fiber membrane area obtained is approximately 100cm
2, the thickness of spinning 12h is about 0.5～0.8mm.The nano-composite fiber film obtained is cut to 1*1cm
2Be immersed in the hydrazine hydrate solution of 20mL, 5% (v/v), under the ice-water bath condition, reduce 5min, the tunica fibrosa color is celandine green.With distilled water flushing 3 times, the tunica fibrosa after rinsing is placed on slide to 60 ℃ of oven dry.The diameter that can be obtained composition fiber by the awkward silence at a meeting transmission electromicroscopic photograph of Fig. 5 is 607nm, and the particle diameter of the nano particle of fiber surface is distributed in 30～40nm.
Claims (10)
1. method of utilizing electrostatic spinning technique to prepare the Surface enhanced raman spectroscopy substrate, its step is as follows:
(a) prepare the DMF solution of polymkeric substance;
(b) prepare the electrostatic spinning mixed solution of inorganic metal nanometer seed and polymkeric substance;
(c) prepare polymer/inorganic metal nano seed composite cellulosic membrane;
(d) with reductive agent reductive polymerization thing/inorganic metal nanometer seed composite cellulosic membrane again;
(e) process the nanometer seed composite cellulosic membrane prepared, obtain the Surface enhanced raman spectroscopy substrate;
(f) the Surface enhanced raman spectroscopy substrate is mixed with testing molecule solution, carry out the surface-enhanced Raman detection, the Raman spectrogram of the testing molecule be enhanced.
2. a kind of method of utilizing electrostatic spinning technique to prepare the Surface enhanced raman spectroscopy substrate as claimed in claim 1, it is characterized in that: the N for preparing polymkeric substance, dinethylformamide solution, that polymkeric substance is dissolved in to N, in dinethylformamide, rapid stirring under the water bath condition of 80～100 degrees centigrade, thus prepare the N of polymkeric substance, dinethylformamide solution, solution concentration are 5～15wt%.
3. a kind of method of utilizing electrostatic spinning technique to prepare the Surface enhanced raman spectroscopy substrate as claimed in claim 1 or 2, it is characterized in that: polymkeric substance is polyacrylonitrile, polyamide, polyurethane, polystyrene, polyactide or polyethylene oxide.
4. a kind of method of utilizing electrostatic spinning technique to prepare the Surface enhanced raman spectroscopy substrate as claimed in claim 1, it is characterized in that: the electrostatic spinning mixed solution for preparing inorganic metal nanometer seed and polymkeric substance, that inorganic salts silver nitrate or gold chloride are joined to the N of polymkeric substance with the concentration of 5～30wt%, in dinethylformamide solution, stirred 24～48 hours, thereby obtain the electrostatic spinning mixed solution, wherein inorganic salts are reduced to inorganic metal nanometer seed.
5. a kind of method of utilizing electrostatic spinning technique to prepare the Surface enhanced raman spectroscopy substrate as claimed in claim 1, it is characterized in that: prepare polymer/inorganic metal nano seed composite cellulosic membrane, that above-mentioned electrostatic spinning mixed solution is packed in electrospinning device and carried out spinning, composite cellulosic membrane is collected on negative pole aluminium foil receiving screen, and the diameter of composite cellulosic membrane is 200～1000nm.
6. a kind of method of utilizing electrostatic spinning technique to prepare the Surface enhanced raman spectroscopy substrate as claimed in claim 1, it is characterized in that: with reductive agent reductive polymerization thing/inorganic metal nanometer seed composite cellulosic membrane again, that composite cellulosic membrane is carried out to secondary reduction with the solution of the reductive agent of volumetric concentration 5%, the particle diameter that obtains the surface inorganic metal nanoparticle is 20～100nm, and the particle diameter of inner inorganic metal nano particle is the composite cellulosic membrane of 5～20nm.
7. a kind of method of utilizing electrostatic spinning technique to prepare the Surface enhanced raman spectroscopy substrate as claimed in claim 6, it is characterized in that: the secondary reduction agent is hydrazine hydrate, sodium citrate, ascorbic acid or sodium borohydride.
8. a kind of method of utilizing electrostatic spinning technique to prepare the Surface enhanced raman spectroscopy substrate as claimed in claim 1, it is characterized in that: process the composite cellulosic membrane prepared, by the distilled water cleaning down of the composite cellulosic membrane after secondary reduction, be laid on glass sheet, be placed in 60～80 ℃ of drying 6～10h in vacuum drying chamber, thereby obtain the Surface enhanced raman spectroscopy substrate.
9. a kind of method of utilizing electrostatic spinning technique to prepare the Surface enhanced raman spectroscopy substrate as claimed in claim 1, it is characterized in that: the Surface enhanced raman spectroscopy substrate is mixed with testing molecule solution, is testing molecule to be dissolved in to ethanol or water to be mixed with concentration be 10
-3～10
-8The solution of mol/L, then be placed in this solution by the Surface enhanced raman spectroscopy substrate and soak 30～60min, with dry after alcohol flushing, after vaporing away ethanol, carries out the surface-enhanced Raman detection, the Raman spectrogram of the testing molecule be enhanced after taking-up.
10. a kind of method of utilizing electrostatic spinning technique to prepare the Surface enhanced raman spectroscopy substrate as described as claim 1 or 9 is characterized in that: testing molecule is rhodamine 6G, to mercaptobenzoic acid, p-Mercaptoaniline or p-aminobenzoic acid.
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| CN114184592A (en) * | 2021-11-24 | 2022-03-15 | 厦门大学 | Electronegative molecule SERS detection method based on electronegative SERS substrate |
| CN114184592B (en) * | 2021-11-24 | 2023-12-05 | 厦门大学 | Electronegative molecule SERS detection method based on electronegative SERS substrate |
| CN115252518A (en) * | 2022-07-28 | 2022-11-01 | 上海应用技术大学 | Instant plant extract/polymer composite fiber membrane and preparation thereof |
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