CN105088361B - A kind of method that utilization reverse micelle system and electrostatic spinning technique prepare SERS substrates - Google Patents
A kind of method that utilization reverse micelle system and electrostatic spinning technique prepare SERS substrates Download PDFInfo
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- CN105088361B CN105088361B CN201510385769.4A CN201510385769A CN105088361B CN 105088361 B CN105088361 B CN 105088361B CN 201510385769 A CN201510385769 A CN 201510385769A CN 105088361 B CN105088361 B CN 105088361B
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Abstract
The invention discloses a kind of method that utilization reverse micelle system and electrostatic spinning technique prepare SERS substrates, belong to the preparation field of composite nano materials.Be added in solvent for the nano-noble metal aqueous solution and surfactant first by methods described, and the precious metal solution of reverse micelle parcel is obtained；Then ε polycaprolactones or PLA are added in solvent and form polymer solution；The precious metal solution that reverse micelle is wrapped up is added in polymer solution again, obtains electrostatic spinning solution；Fibrofelt is prepared by electrostatic spinning technique；Surface etch is carried out to fibrofelt, SERS substrates are formed.Electrostatic spinning technique repeats the exposed degree of nano-noble metal particle aligned transfer under electrostatic field, the nano-noble metal particle that etching is obtained.The method of the invention is reproducible, can prepare large area, the repeatable SERS substrates for utilizing.
Description
Technical field
The invention belongs to the preparing technical field of composite nano materials, and in particular to one kind utilizes reverse micelle system and electrostatic
The method that spining technology prepares SERS substrates.
Background technology
Electrostatic spinning technique is the currently the only novel spinning technology that can directly, continuously prepare polymer nanofiber.
Have that porosity is high, specific surface area big with fiber obtained in electrostatic spinning technique, the fiber fineness and uniformity is high, draw ratio is big
The features such as.Using this series of advantages of electrostatic spinning, the nanofiber based on electrostatic spinning technique preparation was with carrier in recent years
Prepare the concern that metal nanoparticle gradually causes people.
SERS technology SERS is a kind of contactless can to provide single molecules level information to be measured
Dynamic Non-Destruction Measurement, and as the discovery and research of local surface plasma resonance phenomenon have obtained rapid deployment and hair
Exhibition.But recent decades are arrived, application of the SERS technologies in real life does not obtain due popularization.To find out its cause, wherein
One very big limiting factor is exactly the Cost Problems of cumbersome process prepared by SERS active-substrate and costliness, and prepared by substrate
When the application and popularization of this feature technology are also further hindered to the high request of equipment.Therefore, prepare it is quick, pollution-free,
Large area repeats the SERS sequence of substrates for being applied to system research for utilizing will make the application of SERS more extensive quick, right
The research of SERS mechanism also provides experiment basis.
Reverse micelle (Reverse micelle) is that surfactant (amphiphile, amphiphilic molecule) is dissolved in nonpolar organic solvent,
When its concentration exceedes critical micelle concentration (CMC), micella is formed in organic solvent.In reverse micelle, surfactant
Non-polar group outside with nonpolar organic solvent exposure, and polar group is then arranged in one polarity core (polar of interior formation
core).This polarity core has the ability of dissolving polar substances, after polarity karyolysis water or the aqueous solution, is formed in " pond "
(water pool).Reverse micelle is a kind of aggregation of the nanoscale for spontaneously forming, and is a kind of transparent, thermodynamically stable
W/O systems.So it is feasible to be wrapped up in the organic solvent solution of polymer aqueous noble metal solution using reverse micelle.
Using reverse micelle system and electrostatic spinning technique prepare SERS substrates at home and abroad study in report there is not yet.
The content of the invention
Crucial technical problem solved by the invention is to prepare large area, reproducible by the method for simple and fast
SERS substrates, for SERS measurement and SERS mechanism research.The present invention forms the side of reverse micelle using surfactant
Method, forms the nano-noble metal particle of dimensionally stable, is dispersed in macromolecule polymer solution, under the conditions of electrostatic field,
Electrostatic spinning forms the nanofiber mats of even thickness, by surface etching treatment, obtains SERS substrates.
The invention provides a kind of method that utilization reverse micelle system and electrostatic spinning technique prepare SERS substrates, specific step
It is rapid as follows：
The first step, surfactant is added in solvent, magnetic agitation, and inverse micellar solution is obtained.By nano-noble metal
The aqueous solution is added in the inverse micellar solution, magnetic agitation, and the precious metal solution of reverse micelle parcel is obtained.
Described surfactant is double (2- ethylhexyls) Disodium sulfosuccinate (AOT), dodecyl sodium sulfate
(SDS), cetyl trimethylammonium bromide (CTAB), hexadecyltrimethylammonium chloride (CTAC) or polyethenoxy ether class.Institute
The nano-noble metal aqueous solution stated is nano-silver water solution, nanometer gold solution or the nanometer gold silver alloy aqueous solution.Described
Solvent be chloroform, dichloromethane, hexafluoroisopropanol or N,N-dimethylformamide in one or more.
Second step, ε-polycaprolactone (PCL) or PLA (PLA) polymer is dissolved in solvent, magnetic agitation, is obtained poly-
Polymer solution, it is standby.
Described solvent be chloroform, dichloromethane, hexafluoroisopropanol or N,N-dimethylformamide in one or two
More than.
3rd step, under the conditions of magnetic agitation, the precious metal solution of the reverse micelle parcel that the first step is prepared is added
In the polymer solution prepared to second step, stir, 30~60min of ultrasound, obtains electrostatic spinning molten under the conditions of ice-water bath
Liquid.
4th step, electrostatic spinning is carried out by electrostatic spinning solution obtained in the 3rd step, prepares fibrofelt.The electrostatic spinning
Process conditions are：Flow velocity 1.5mL/h, voltage is 8~20kV, and it is 12~18cm to receive distance.
5th step, surface etch is carried out by fibrofelt obtained in the 4th step, the SERS substrates after being etched.
The advantage of the invention is that：
1st, the present invention selects reverse micelle technology, can control the particle diameter of nano-noble metal particle, keeps nano-noble metal
The scattered homogeneity of grain.
2nd, the present invention makes nano-noble metal particle under electrostatic field using electrostatic spinning technique, and aligned transfer is etched
The exposed degree of the noble metal nano particles for obtaining is repeated.
3rd, SERS areas of base prepared by the present invention are big, repeat utilization.
4th, preparation method of the present invention is reproducible, prepares quickly, pollution-free.
Brief description of the drawings
Fig. 1 is simulation reverse micelle nanometer metal structure figure；
Fig. 2A, 2B are the SEM figures of the composite fibrofelt that the Static Spinning Ag for preparing is wrapped in PCL；
Fig. 3 A, 3B are the TEM figures of the composite fibrofelt that the Static Spinning Ag for preparing is wrapped in PCL；
Fig. 4 is that the composite fibrofelt that the Ag for preparing is wrapped in PCL is schemed to the SERS of 4-MBA；
Fig. 5 is the front and rear SERS figures to 4-MBA of composite fibrofelt etching that the Ag for preparing is wrapped in PCL.
Specific embodiment
The present invention is further elaborated with reference to the accompanying drawings and examples.
The present invention provides a kind of method that utilization reverse micelle system and electrostatic spinning technique prepare SERS substrates, specific steps
It is as follows：
The first step, will double (2- ethylhexyls) Disodium sulfosuccinate (AOT), dodecyl sodium sulfate (SDS), hexadecanes
Base trimethylammonium bromide (CTAB), hexadecyltrimethylammonium chloride (CTAC) or polyethenoxy ether class surfactant are added to
In solvent, magnetic agitation is completely dissolved surfactant, obtains inverse micellar solution.The nano-noble metal aqueous solution is added to
In above-mentioned inverse micellar solution, magnetic agitation is obtained the precious metal solution of reverse micelle parcel.
The described nano-noble metal aqueous solution is that nano-silver water solution, nanometer gold solution or nanometer gold silver alloy are water-soluble
Liquid.Described solvent be chloroform, dichloromethane, hexafluoroisopropanol, N,N-dimethylformamide in one or more.
Second step, ε-polycaprolactone (PCL) or PLA (PLA) polymer is dissolved in solvent, more than magnetic agitation 1h,
Polymer solution is obtained.
Described solvent be chloroform, dichloromethane, hexafluoroisopropanol, N,N-dimethylformamide in one or two with
On.
3rd step, under the conditions of magnetic agitation, by first step system to the precious metal solution of reverse micelle parcel be added to the
In polymer solution obtained in two steps, more than magnetic agitation 1h stirs, 30~60min of ultrasound under the conditions of ice-water bath, preferably
30~45min, obtains electrostatic spinning solution.
4th step, electrostatic spinning is carried out by electrostatic spinning solution prepared by the 3rd step, prepares fibrofelt.The fiber of preparation is most
It is deposited on aluminium foil in fibrofelt form eventually, fibrofelt is placed in vacuum drying chamber and is dried, obtain SERS substrates, is stored in dry
It is standby in dry device (more than drying time 24h).
The electrostatic spinning process condition is：Flow velocity 1.5mL/h, voltage is 8~20kV, and it is 12~18cm to receive distance.
Preferred processing condition is flow velocity 1.5mL/h, and voltage is 8~15kV, and it is 12~15cm to receive distance.
5th step, surface etch is carried out by the fibrofelt obtained by the 4th step.Above-mentioned fibrofelt is put into and closed fills two
In NMF (DMF) or the culture dish of acetone, above-mentioned culture dish is put into constant-temperature table and is shaken.Fibrofelt is taken out, is used
Alternately washing 3 times of second alcohol and water, are vacuum dried (drying time 24h), the SERS substrates after being etched.Constant-temperature table temperature is
50~60 DEG C, the concussion time is 3~5h, preferably 3~4h.
The SERS substrates that above-mentioned preparation method is obtained, the average fibre diameter before fibrofelt etching is 789nm ± 107nm,
Fibrofelt its SERS effect after over etching has larger enhancing.
Embodiment 1：
The first step, by the SDS addition 2mL of 0.2g to chloroform, magnetic agitation is completely dissolved SDS, obtains reverse micelle molten
Liquid.By the nano-silver water solution of 0.5mL, drop by drop (each drop is 0.2mL) it is added under the conditions of magnetic agitation above-mentioned
In inverse micellar solution, continue to stir 30min, obtain the Nano silver solution of reverse micelle parcel.
Second step, the PCL particles of 0.6g are added in 4mL chloroforms, and magnetic agitation 1h is completely dissolved PCL, obtains
PCL solution.
3rd step, under magnetic stirring, the Nano silver solution of reverse micelle parcel prepared by the first step is added dropwise to the
In PCL solution prepared by two steps, magnetic agitation 1h, ultrasound 30min, obtains electrostatic spinning solution in ice-water bath.
4th step, electrostatic spinning is carried out by electrostatic spinning solution obtained in the 3rd step, prepares fibrofelt.Electrostatic spinning is set
Process conditions are：Flow velocity 1.5mL/h, voltage is 15kV, and it is 12cm to receive distance.The fiber of preparation is final heavy in fibrofelt form
Be placed on for fibrofelt after drying 24h in vacuum drying chamber by product on aluminium foil, obtains SERS substrates, is stored in standby in drier.
5th step, fibrofelt obtained in the 4th step is put into the closed culture dish for filling DMF, and above-mentioned culture dish is put
Shaken in constant-temperature table, constant-temperature table temperature is 60 DEG C, the concussion time is 4h.Fibrofelt is taken out, is alternately washed with second alcohol and water
Wash 3 times, be vacuum dried 24h, the SERS substrates after being etched.
Fig. 1 is the simulation drawing of the reverse micelle coating noble metal particle of guess.SERS substrates to preparing carry out SEM surveys
Examination, as shown in Figure 2 A and 2 B, the average fibre diameter of spinning gained fibrofelt is 789nm ± 107nm to effect, and single fiber is thick
It is thin uniform, in the absence of bead structure.TEM tests effect such as Fig. 3 A and 3B, metal nanoparticle and PCL in the case where reverse micelle is acted on very
Good is compatible.SERS tests effect as shown in figure 4, the fibrofelt for preparing has Raman enhancing effect, 10 to 4-MBA-4M concentration
4-MBA SERS spectrograms laser intensity decay 1/2 when surveyed, 1594cm-1The phenyl ring breathing vibration intensity at place is still
Strengthen 3 times, 1078cm with respect to 4-MBA powder-1Also relative nearly 2 times of the enhancing of the ring around suction/C-S stretching vibration peaks at place.Fibrofelt
Its SERS effect has larger enhancing after over etching, and its SERS effect is as shown in figure 5, all Ramans of the SERS spectrograms after etching
The intensity at peak is all substantially 2 times before etching.
Embodiment 2：
The first step, the AOT of 0.15g is added in 2mL dichloromethane, magnetic agitation, dissolves AOT, and reverse micelle is obtained
Solution；By the nano-silver water solution of 0.5mL, drop by drop (each drop is 0.2mL) is added to instead under the conditions of magnetic agitation
In micellar solution, magnetic agitation 30min obtains the Nano silver solution of reverse micelle parcel.
Second step, the PLA particles of 0.3g are added in 3mL dichloromethane, and magnetic agitation 1h is completely dissolved PLA, obtains
To PLA solution.
3rd step, under magnetic stirring, the Nano silver solution of reverse micelle parcel prepared by the first step is added dropwise to the
In PLA solution prepared by two steps, magnetic agitation 1h, ultrasound 45min, obtains electrostatic spinning solution in ice-water bath.
4th step, electrostatic spinning is carried out by electrostatic spinning solution obtained in the 3rd step.Setting spinning process condition is：Flow velocity
1.5mL/h, voltage is 8kV, and it is 15cm to receive distance.The fiber of preparation is finally deposited on aluminium foil in fibrofelt form, by fibre
Dimension felt is placed in vacuum drying chamber after drying 24h, obtains SERS substrates, is stored in standby in drier.
5th step, fibrofelt obtained in the 4th step is placed in the culture dish for filling acetone, and culture dish is placed on into constant temperature
Shaken in shaking table, constant-temperature table temperature is 50 DEG C, the concussion time is 3h.Fibrofelt is taken out, is alternately washed 3 times with second alcohol and water,
Vacuum drying 24h, the SERS substrates after being etched.
Average fibre diameter of the above-mentioned spinning gained fibrofelt before etching is 789nm ± 107nm, and single fiber thickness is equal
It is even, in the absence of bead structure.The fibrofelt for preparing has Raman enhancing effect to 4-MBA.
Embodiment 1 and 2 is only illustrative of the invention and is not intended to limit the scope of the invention.In addition, it is to be understood that reading
After the content of instruction of the present invention, those skilled in the art can make various changes or modifications to the present invention, these shapes of equal value
Formula equally falls within the application appended claims limited range.
Claims (5)
1. a kind of method that utilization reverse micelle system and electrostatic spinning technique prepare SERS substrates, it is characterised in that include down
Row step：
The first step, by surfactant addition solvent orange 2 A, magnetic agitation is obtained inverse micellar solution；By the nano-noble metal aqueous solution
It is added in the inverse micellar solution, magnetic agitation, the precious metal solution of reverse micelle parcel is obtained；Described surfactant is
Double (2- ethylhexyls) Disodium sulfosuccinates, dodecyl sodium sulfate, cetyl trimethylammonium bromide, cetyl front three
Ammonium chloride or polyethenoxy ether class；Described solvent orange 2 A is chloroform, dichloromethane, hexafluoroisopropanol or N, N- dimethyl formyl
One or more in amine；
Second step, ε-polycaprolactone or polylactic acid polymer is dissolved in solvent B, magnetic agitation, and polymer solution is obtained；It is described
Solvent B be one or more in chloroform, dichloromethane, hexafluoroisopropanol or N,N-dimethylformamide；
3rd step, under the conditions of magnetic agitation, second step is added to by the precious metal solution of reverse micelle parcel obtained in the first step
In the polymer solution of preparation, stir, 30~60min of ultrasound, obtains electrostatic spinning solution under the conditions of ice-water bath；
4th step, electrostatic spinning is carried out by the 3rd step gained electrostatic spinning solution, prepares fibrofelt；
5th step, surface etch is carried out by the fibrofelt obtained by the 4th step, the SERS substrates after being etched.
2. the method that a kind of utilization reverse micelle system according to claim 1 and electrostatic spinning technique prepare SERS substrates,
It is characterized in that：The described nano-noble metal aqueous solution is nano-silver water solution, nanometer gold solution or nanometer gold silver alloy
The aqueous solution.
3. the method that a kind of utilization reverse micelle system according to claim 1 and electrostatic spinning technique prepare SERS substrates,
It is characterized in that：The process conditions of the electrostatic spinning described in the 4th step are：Flow velocity 1.5mL/h, voltage is 8~20kV, is received
Distance is 12~18cm.
4. the method that a kind of utilization reverse micelle system according to claim 1 and electrostatic spinning technique prepare SERS substrates,
It is characterized in that：Described surface etch is that fibrofelt is put into the closed culture dish for filling dimethylformamide or acetone
In, above-mentioned culture dish is put into constant-temperature table and is shaken；Fibrofelt is taken out, with alternately washing 3 times of second alcohol and water, vacuum drying.
5. the method that a kind of utilization reverse micelle system according to claim 4 and electrostatic spinning technique prepare SERS substrates,
It is characterized in that：The temperature of described constant-temperature table is 50~60 DEG C, and the concussion time is 3~5h.
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| WO2018186805A1 (en) * | 2017-04-05 | 2018-10-11 | National University Of Singapore | Flexible surface plasmon resonance film |
| CN111141720B (en) * | 2019-12-31 | 2022-08-30 | 江苏佳信检测技术有限公司 | SERS-based flexible biosensor and detection method of rhodamine B in food |
| CN112903389A (en) * | 2021-01-25 | 2021-06-04 | 潍坊医学院 | Sampling machine with uniform SERS enhanced substrate and preparation method |
| CN113584723A (en) * | 2021-08-02 | 2021-11-02 | 岭南师范学院 | Liquid metal nanoparticle composite nanofiber membrane and preparation method and application thereof |
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| CN101935017A (en) * | 2010-07-29 | 2011-01-05 | 中国科学院生态环境研究中心 | Method for synthesizing noble metal superfine nanowire water phase and establishing noble metal nanopore membrane by self-precipitation thereof |
| KR20110003076A (en) * | 2009-07-03 | 2011-01-11 | 이화여자대학교 산학협력단 | The method for the preparation of gold nanostructure using galvanic displacement reaction and gold nanostructure with improved surface enhanced raman scattering |
| CN102951603A (en) * | 2011-08-19 | 2013-03-06 | 新加坡科技研究局 | Methods to form substrates for optical sensing by surface enhanced raman spectroscopy (sers) and substrates formed by methods |
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| KR20110003076A (en) * | 2009-07-03 | 2011-01-11 | 이화여자대학교 산학협력단 | The method for the preparation of gold nanostructure using galvanic displacement reaction and gold nanostructure with improved surface enhanced raman scattering |
| CN101935017A (en) * | 2010-07-29 | 2011-01-05 | 中国科学院生态环境研究中心 | Method for synthesizing noble metal superfine nanowire water phase and establishing noble metal nanopore membrane by self-precipitation thereof |
| CN102951603A (en) * | 2011-08-19 | 2013-03-06 | 新加坡科技研究局 | Methods to form substrates for optical sensing by surface enhanced raman spectroscopy (sers) and substrates formed by methods |
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