CN106592208A - Production method of precious metal nanoparticle/temperature-sensitive nanofiber composite film, and application of composite film in dynamic SERS detection - Google Patents
Production method of precious metal nanoparticle/temperature-sensitive nanofiber composite film, and application of composite film in dynamic SERS detection Download PDFInfo
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- CN106592208A CN106592208A CN201510660163.7A CN201510660163A CN106592208A CN 106592208 A CN106592208 A CN 106592208A CN 201510660163 A CN201510660163 A CN 201510660163A CN 106592208 A CN106592208 A CN 106592208A
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Abstract
The invention discloses a production method of a precious metal nanoparticle/temperature-sensitive nanofiber composite film, and an application of the composite film. The method comprises the following steps: synthesizing an amino group-containing temperature-sensitive polymer, dissolving the amino group-containing temperature-sensitive polymer in an organic solvent to form a solution with different concentrations, and electrospinning the solution to obtain nanofibers with different morphologies; and uniformly mixing and electrospinning a selected polymer with a good morphology concentration and different amounts of precious metal nanoparticles which are massively prepared once in order to obtain a precious metal nanoparticle well-ordered nanofiber composite film. The method overcomes random distribution caused by in situ reduction of the precious nanoparticles, and introduction of the temperature-sensitive polymer makes the nanofiber composite film have dynamic responsiveness. The nanofiber composite film has potential application prospect in the field of SERS detection of a hydrophobic/hydrophilic mixture.
Description
Technical field
The invention belongs to technical field of function materials, accurately says be a kind of noble metal nano particles/temperature sensitive copolymer nanofiber composite membrane preparation method, and its application in dynamic SERS is detected.
Background technology
Mainly it is made up of noble metal nano particles by the SERS substrates of extensive concern at present, wherein what SERS signal was played a decisive role is the surface plasma body resonant vibration that metal nanoparticle is affected internal electron to produce vibration and formed by external electromagnetic field（SPR）Effect.[1] It has been reported that, can produce " hot-spot " between adjacent nano-particle when the distance between nano-particle is less than 10nm, SPR effects produce therewith the enhancing of several orders of magnitude.[2]Therefore, the distance between noble metal nano particles are the main criterias for preparing efficient SERS substrates in SERS substrates.
Once being formed, nano-particle spacing therein can not change again the SERS substrates being previously reported by, and be extremely difficult to dynamic SERS detections.[3] In order to obtain more effective dynamic SERS substrates, the temperature sensitive copolymer with many stimuli responsives is introduced into be combined with noble metal nano particles becomes the dynamic SERS substrates that thorniness swashs response.Temperature sensitive copolymer can to external world stimulate and respond, and environmental stimuli is irritated including the external world and generally includes temperature, pH value, ionic strength change, light, magnetic field, and specific chemical substance or biological substance etc..[4]Using temperature sensitive copolymer, to external world stimuli responsive causes the characteristic of the change of polymer volume to prepare dynamic SERS substrates, the dynamic change of nano-particle spacing in SERS substrates can be caused by environmental stimuli, cause more " hot-spot " to be formed, produce higher SERS signal.
In recent years, electrostatic spinning technique is combined the advantage in the SERS substrates field for preparing with noble metal nano particles and is received a large amount of concerns of people.[5-7] For other nanofiber preparation methods, device is simple, and it is convenient to prepare, and with good Modulatory character, can prepare the nanofiber of different morphologies for electrostatic spinning.Additionally, electrostatic spinning still prepares the effective ways of composite nano fiber, functional nanoparticles can be added in nanofiber and prepare composite fibre by it.[8] These nano-particles can be searched along nanofiber to be wanted to be arranged, so as to reach better performance.[9] This confinement effect can make SERS substrates that more " hot-spot " is produced under stimuli responsive, therefore electrostatic spinning has a wide range of applications in SERS substrate preparation fields.
Mostly noble metal nano particles are all obtained by reducing after the completion of presoma and polymer electrospinning in electrospinning fibre.[10,11]The noble metal nano particles of the noble metal nano particles that in-situ reducing is obtained/polymer electrospinning fibre SERS substrates have uncontrollability, and this uncontrollability can cause certain obstruction to the formation of " hot-spot " in SERS substrates.Therefore, controllable noble metal nano particles mix electrospinning with the direct of polymer, have obvious advantage to possessing the preparation of nanofiber SERS substrates of more " hot-spot ".In addition the introducing of temperature sensitive copolymer has also obtained significant raising to strong and weak change of SERS signal.This dynamic SERS substrates have potential application prospect in the detection of micro parent/hydrophobic mixture.
The content of the invention
The purpose of the present invention be set up it is a kind of conveniently prepare the method for noble metal nano particles/temperature sensitive copolymer nanofiber composite membrane, and study application of the nano-fiber composite film in dynamic SERS detection fields.
The purpose of the present invention can be accomplished by the following technical programs：
The preparation method of the noble metal nano particles/temperature sensitive copolymer nanofiber composite membrane of the present invention（Fig. 1）, concrete steps include：
1）With acrylamide monomer, the functional monomer containing amino, distilled water is solvent, and deoxygenation was boiled before initiator is not added, and then carries out polymerisation, obtains temperature sensitive copolymer；
2）Disposably noble metal nano particles are prepared in a large number；
3）By step 1）In copolymer select different concentration to carry out electrospinning（Fig. 2）, select suitable concentration and contain step 2）In different amounts of noble metal nano particles be dissolved in organic solvent after ultrasonic mixing it is uniform after electrospinning（Fig. 3）, after the completion of electrospinning nano-fiber composite film is crosslinked using glutaraldehyde steam, can finally prepare dynamic SERS substrates；
One or more of monomer described in described acrylamide monomer in N-isopropylacrylamide, isopropyl methyl acrylamide and carboxyl N-isopropylacrylamide；
Described initiator is one or more in azo, peroxide；
Described organic solvent is selected from N, one or more in N '-dimethyl formamide, acetone, tetrahydrofuran and methyl alcohol；
Described noble metal nano particles are one or more in gold, silver nano-particle；
The concentration of described temperature sensitive copolymer is 10%-40%（Fig. 2）；
Described noble metal nano particles concentration in a polymer solution is 300mM-700mM（Fig. 3）;
A diameter of 0.7mm-1.2mm of jet blower in described electric spinning equipment；
The time of described EFI is 30min-100min（Fig. 4）；
Using the temperature-sensing property of copolymer, LASER HEATING is carried out to it, it can be found that as the increase of light application time, SERS signal constantly strengthen, finally tending towards stability（Fig. 5）, illustrate that the SERS substrates have good temperature-responsive, there is potential application prospect to microscratch amount thing to be checked.In addition; the process of the glutaraldehyde vapor crosslinking after the completion of electrospinning causes noble metal nano particles to be coated on completely in nanofiber; can either so protect noble metal nano particles free from the influence of the external environment, the Thermo-sensitive that can also utilize copolymer enables determinand preferably to penetrate into the higher SERS signal of precious metal surface generation.Therefore, the noble metal nano particles/temperature sensitive copolymer nanofiber composite membrane has good reappearance and higher stability as SERS substrates（Fig. 6）
The temperature-responsive of the nano-fiber composite film of noble metal nano particles/temperature sensitive copolymer makes it exist in the SERS detection fields of parent/hydrophobic mixture and is widely applied value（Fig. 7）.
The present invention for it is a kind of novel, simple to operate and can large area prepare the production technology of noble metal nano particles/temperature sensitive copolymer nanofiber composite membrane.It is that monomer using acrylamide obtains the temperature sensitive copolymer containing amino with the functional monomer copolymerization containing amino, then mix with disposable substantial amounts of noble metal nano particles and disperse in organic solvent, to be well mixed rear electrospinning and obtain nano-fiber composite film.The intelligent nano composite fiber membrane has very high using value.This preparation method overcomes the uncontrollability of the noble metal nano particles that in-situ reducing is obtained, while the addition of temperature sensitive copolymer causes nanofiber to have stimulates to external world corresponding characteristic, has wide practical use in dynamic SERS detection fields.
Description of the drawings
Fig. 1 is the schematic diagram for preparing noble metal nano particles/temperature sensitive copolymer nanofiber composite membrane.
Fig. 2 schemes for the nanofiber SEM of the temperature sensitive copolymer of variable concentrations.（A）-（D）The concentration of polymer is respectively 10%, 20%, 30% and 40%.
Fig. 3 schemes for the TEM of the Nano silver grain/temperature sensitive copolymer nanofiber composite membrane of variable concentrations.（A）-（E）The concentration of middle Nano silver grain is respectively 300mM, 400mM, 500mM, 600mM and 700mM.
Fig. 4 is time-optimized for the electrospinning of nano-fiber composite film.SERS signal changes with the different of electrospinning time.
Fig. 5 is that the continuous enhanced SERS spectra figure of SERS signal is obtained to electrospinning fibre composite membrane laser heating using raman laser.
Fig. 6 is nano-fiber composite film as SERS substrate reappearances.
Fig. 7 is nano-fiber composite film as SERS substrate stability.
Fig. 8 is that mixture is made a distinction using the Thermo-sensitive of nano-fiber composite film.
Specific embodiment
Following examples are intended to illustrate rather than limitation of the invention further.
Embodiment
1. temperature sensitive poly-（NIPA）The preparation of copolymer and sign
Copolymer is prepared using Raolical polymerizable.It is specific as follows：By monomer（NIPA）With functional monomer（Methacrylic acid（2- amino ethyl esters）Hydrochloride）With 10:1 weight ratio is dissolved in distilled water, and heating is boiled after 30min, by initiator（2,2- azos-（2- methyl-propyl miaows）- hydrochloride）（It is 50 with monomer weight ratio：1）In being added to mixed solution, 70o6h is reacted under C.After the completion of reaction, precipitated with ether, kept dry after filtration.
2. the preparation of electrospinning liquid and its electrospinning condition
Dried copolymer is dissolved in into N, in N '-dimethyl formamide solvent, the copolymer electrospinning liquid of variable concentrations is prepared, it is standby.The copolymer solution of suitable concn and the disposable a large amount of Nano silver grains for preparing are selected using being well mixed after ultrasonic device 15min（Same amount Nano silver grain is not added）, it is standby.All of electro-spinning process is all carried out according to following parameter：Flow velocity is 1mL/h, and needle point is 20 ㎝ with collector spacing, and voltage is 19kV, and humidity is less than 50%, and indoor temperature is 25oC。
3. the crosslinking and its post processing of nano-fiber composite film
The nano fibrous membrane that electrospinning is completed is placed in glutaraldehyde steam and is crosslinked, crosslinking causes Nano silver grain to be completely covered by nanofiber, crosslinking is placed on nano-fiber composite film in distilled water to remove unreacted glutaraldehyde after terminating.
The preferred embodiments of the present invention are the foregoing is only, the present invention is not limited to, for a person skilled in the art, the present invention there can be change and change.All any modification, improvement within the spirit and principles in the present invention, made etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of noble metal nano particles/temperature sensitive copolymer nanofiber composite membrane, it is characterised in that：Comprise the following steps that,
1）With acrylamide monomer, the functional monomer containing amino, distilled water is solvent, and deoxygenation was boiled before initiator is not added, and then carries out polymerisation, obtains temperature sensitive copolymer；
2）Disposably noble metal nano particles are prepared in a large number；
3）By step 1）In polymer with contain step 2）In noble metal nano particles be dissolved in organic solvent after be well mixed electrospinning, just can prepare dynamic SERS substrates.
2. in claim 1 noble metal nano particles/temperature sensitive copolymer nanofiber composite membrane preparation method, it is characterised in that：One or more of monomer described in described acrylamide monomer in N-isopropylacrylamide, isopropyl methyl acrylamide and carboxyl N-isopropylacrylamide.
3. in claim 1 noble metal nano particles/temperature sensitive copolymer nanofiber composite membrane preparation method, it is characterised in that：Described initiator is azo, peroxide.
4. in claim 1 noble metal nano particles/temperature sensitive copolymer nanofiber composite membrane preparation method, it is characterised in that：Described organic solvent is selected from N, one or more in N '-dimethyl formamide, acetone, tetrahydrofuran and methyl alcohol.
5. in claim 1 noble metal nano particles/temperature sensitive copolymer nanofiber composite membrane preparation method, it is characterised in that：One or more of described noble metal nano particles in gold, silver nano-particle.
6. in claim 1 noble metal nano particles/temperature sensitive copolymer nanofiber composite membrane preparation method, it is characterised in that：The concentration of described temperature sensitive copolymer is the one kind in 10%-40%.
7. in claim 1 noble metal nano particles/temperature sensitive copolymer nanofiber composite membrane preparation method, it is characterised in that：Described noble metal nano particles concentration in a polymer solution is 300mM-700mM.
8. in claim 1 noble metal nano particles/temperature sensitive copolymer nanofiber composite membrane preparation method, it is characterised in that：A diameter of 0.7mm-1.2mm of jet blower in described electric spinning equipment.
9. in claim 1 noble metal nano particles/temperature sensitive copolymer nanofiber composite membrane preparation method, it is characterised in that：The time of described EFI is 30min-100min.
10. the nano-fiber composite film of noble metal nano particles/temperature sensitive copolymer is applied to the SERS detection fields of parent/hydrophobic mixture in claim 1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103411946A (en) * | 2013-06-24 | 2013-11-27 | 吉林大学 | Method for preparing surface-enhanced Raman spectrum base by using electrospinning technique |
| CN104911819A (en) * | 2015-06-16 | 2015-09-16 | 东华大学 | Preparation method for temperature stimuli-responsive nanofiber membrane carrying with precious-metal nanorod |
| CN104928851A (en) * | 2015-06-24 | 2015-09-23 | 东华大学 | Preparation method for silver-loaded nano particle temperature stimuli responsiveness hybrid nanofiber membrane |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103411946A (en) * | 2013-06-24 | 2013-11-27 | 吉林大学 | Method for preparing surface-enhanced Raman spectrum base by using electrospinning technique |
| CN104911819A (en) * | 2015-06-16 | 2015-09-16 | 东华大学 | Preparation method for temperature stimuli-responsive nanofiber membrane carrying with precious-metal nanorod |
| CN104928851A (en) * | 2015-06-24 | 2015-09-23 | 东华大学 | Preparation method for silver-loaded nano particle temperature stimuli responsiveness hybrid nanofiber membrane |
Non-Patent Citations (1)
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| 王家勤主编: "《生物化学品 第1版》", 30 June 2001, 中国物资出版社 * |
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