CN104593891B - A kind of preparation method of the core sheath structure nanofiber of Fluorescence Increasing - Google Patents
A kind of preparation method of the core sheath structure nanofiber of Fluorescence Increasing Download PDFInfo
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Abstract
The present invention relates to the preparation method of the core sheath structure nanofiber of a kind of Fluorescence Increasing, including: first polyethylene of dispersing agent ketopyrrolidine is dissolved in solvent by (1), add nanometer silver, process by Ultrasound Instrument and obtain the homodisperse solution of nanometer silver, then the solution containing nanometer silver is mixed to get sheaths spinning liquid with the solution dissolved with macromolecule spinning base material；(2) macromolecule spinning base material and rare earth compounding being dissolved in organic solvent respectively, two kinds of solution are mixed to get sandwich layer spinning liquid；(3) coaxial electrostatic spinning technology is used to prepare the core sheath structure nanofiber of Fluorescence Increasing.This preparation method is simple and easy to do, low cost；Preparation process introduces dispersant and promotes nanometer silver dispersion；Nanometer silver and rare earth compounding are isolated and are dispersed in fiber sheaths and sandwich layer respectively by the core sheath structure nanofiber of the Fluorescence Increasing of preparation, the fluorescence of the local surface plasma resonance effect more efficient enhancing rare earth compounding of sheaths nanometer silver, has a extensive future at biomedical sector.
Description
Technical field
The invention belongs to the preparation field of core sheath structure nanofiber, particularly relate to the core sheath structure of a kind of Fluorescence Increasing
The preparation method of nanofiber.
Background technology
Rare earth compounding is because of wide excitation wavelength, and high fluorescent, the feature such as high-quantum efficiency and long-life is widely used in
The fields such as high-sensitivity detection, fluorescent probe, bio-imaging, but more and more urgent to the demand of more excellent fluorescence property.Closely
Studying discovery over Nian, nanometer silver can affect the fluorescence property of rare earth ion.Under the conditions of light irradiates, nanometer silver surface freely electricity
When the frequency of vibration of son is identical with the frequency of vibration of outer light, will resonate, here it is so-called local surface plasma
Covibration (LSPR) (Talanta, 2013,117:203-208).When rare earth compounding is close to nanometer silver surface, light excites down
The LSPR effect of nanometer silver can greatly strengthen the electromagnetic field of rare earth compounding around, improves launching efficiency or the spoke of rare earth compounding
Penetrate rate of decay, thus sensitization strengthens the fluorescence intensity of rare earth compounding.Conventional nano human lymph node rare earth compounding fluorescent material
Preparation include two kinds of methods: (a), at nanometer silver surface packing protective layer to avoid reuniting, the method such as recycling coating afterwards is attached
Upper rare earth compounding.The method preparation process is loaded down with trivial details, and first the Fluorescence Increasing material outer layer rare earth compounding obtained can be inhaled
Receive the energy of ambient light, thus reduce the LSPR effect of internal layer nanometer silver, and then weaken Fluorescence Increasing；B () directly joins with rare earth
Compound mixes.In the method, nanometer silver dispersion is uneven, and rare earth compounding can absorb part light energy, reduces the light of nanometer silver
Absorb, and then weaken the LSPR effect of nanometer silver, or energy transmission therebetween all can weaken Fluorescence Increasing.
First electrostatic spinning technique proposes in 1934 from Formhals in United States Patent (USP), develops day by day in recent decades
Maturation, has prepared uniaxial fiber, porous fibre, doughnut, multi-layer fiber by electrospinning.Electrospun fibers is straight
Greatly, porosity is high, additionally, electrostatic spinning can also obtain homodisperse nanometer for footpath little (as little as tens nanometers), specific surface area
Composite.Coaxial electrostatic spinning technology provides simple efficient side for preparing homodisperse core sheath structure nanofiber
Method, by adding different materials in sandwich layer and sheaths spinning liquid, controls electro-spinning process, it is possible to obtain pattern, structure-controllable
Core sheath structure fluorescent nano-fiber.Shipeng Wen etc. use this technology to be prepared for Eu (TTA)3Phen-SR/PVP core sheath is tied
Structure fluorescent fiber (J.Mater.Chem.C, 2013,1:1613-1617).Eu(TTA)3Phen is dispersed in silicone rubber fiber
In Ceng so that fiber has high fluorescent and high-quantum efficiency.
Present invention introduces polyethylene of dispersing agent ketopyrrolidine PVP and promote the dispersion of nanometer silver, and utilize coaxial electrostatic spinning
Technology, is separately added into nanometer silver and rare earth compounding in sheaths and sandwich layer spinning liquid, obtains homodisperse core sheath structure and receives
Rice fiber, sheaths nanometer silver is preferentially radiated by ambient light, causes LSPR effect, more efficiently strengthens the glimmering of rare earth compounding
Light, is better than traditional preparation method.
Summary of the invention
The technical problem to be solved is to provide the preparation side of the core sheath structure nanofiber of a kind of Fluorescence Increasing
Method, in preparation process, introduces dispersant PVP, promotes the dispersion of nanometer silver, form uniform spinning liquid；In structure, utilize same
Nanometer silver and rare earth compounding are isolated and are dispersed in fiber sheaths and sandwich layer, sheaths nanometer respectively by axle electrostatic spinning technique
Silver can preferentially be excited by ambient light, causes LSPR effect, and the electromagnetic field of enhancing improves the launching efficiency of rare earth compounding,
Enhanced rad attenuation rate, thus strengthen fluorescence efficiently, overcome and directly mixed or including nanometer silver with rare earth compounding in the past
Layer strengthens the deficiency of fluorescence, and the core sheath structure nanofiber of the Fluorescence Increasing of preparation is better than conventional fluorescent reinforcing material.
The preparation method of the core sheath structure nanofiber of a kind of Fluorescence Increasing of the present invention, comprises the steps:
(1) preparation sheaths spinning liquid: first dispersant PVP is dissolved in solvent, adds nanometer silver, nanometer silver and dispersant
Mass ratio be 0.01:1～0.5:1, process by Ultrasound Instrument and 1～5h make nanometer silver be dispersed in solvent, then by high score
Sub-spinning base material is dissolved in solvent, and the mass ratio of dispersant PVP and macromolecule spinning base material is 1:1～1:15, two kinds of solution mixing
After magnetic agitation 1～3h at room temperature, obtain the sheaths spinning liquid that macromolecule spinning substrate mass mark is 4～18%；
(2) preparation sandwich layer spinning liquid: be that 100:5～100:30 divides by macromolecule spinning base material and rare earth compounding mass ratio
It is not dissolved in organic solvent, magnetic agitation 1～3h at room temperature after the mixing of two kinds of solution, obtain macromolecule spinning substrate mass mark
It it is the sandwich layer spinning liquid of 5～20%；
(3) core sheath structure nanofiber is prepared: use coaxial electrostatic spinning technology, by the sheaths spinning liquid prepared and core
Layer spinning liquid is respectively placed in outer tube and the inner tube of coaxial electrostatic spinning silk device, regulates spinning voltage 10～25KV, receiving range 5
～30cm, outer layer fltting speed is 0.5～2.0ml/h, and internal layer fltting speed is 0.1～1.0ml/h, prepares the core of Fluorescence Increasing
Sheath structure nano fiber, in fiber, the mol ratio of nanometer silver and rare earth compounding is 1:0.1～1:10, fibre diameter be 20～
1000nm。
In step of the present invention (1) and (2), macromolecule spinning base material is respectively Poly-L-lactic acid, polyvinylpyrrolidine
The mixture of one or more in ketone, polyvinyl alcohol, Polyethylene Glycol, Merlon, polyacrylic acid.
In step of the present invention (1), solvent selects N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dichloromethane
Alkane, chloroform, dimethyl sulfoxide, methanol, ethanol, trifluoroethanol, hexafluoroisopropanol, formic acid, acetic acid, acetone, deionized water
In the mixture of one or more, in described step (2) organic solvent select DMF, N, N-dimethyl second
The mixture of one or more in amide, dichloromethane, chloroform, dimethyl sulfoxide, formic acid, acetic acid.
Step of the present invention (2) middle rare earth coordination compound is terbium, europium, samarium, yttrium, dysprosium, cerium, ytterbium, erbium, neodymium, protactinium, thulium, holmium, lanthanum
The mixture of one or more in coordination compound.
In step of the present invention (1), the particle diameter of nanometer silver is 10～100nm.
The preparation method advantage of the core sheath structure nanofiber of a kind of Fluorescence Increasing of the present invention is:
(1) preparation method of the present invention is simple and easy to do, low cost；
(2) present invention introduces dispersant PVP and promote the dispersion of nanometer silver, save the tedious steps preparing protective layer, preparation
The core sheath structure nanofiber of Fluorescence Increasing nanometer silver and rare earth compounding are isolated and are dispersed in fiber sheaths respectively
And sandwich layer, the LSPR effect of sheaths nanometer silver more efficiently strengthens the fluorescence of rare earth compounding；
(3) the core sheath structure nanofiber of Fluorescence Increasing prepared by the present invention is before biomedical sector has wide application
Scape.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) figure of the core sheath structure nanofiber of the Fluorescence Increasing that the present invention (embodiment 2) provides
Fig. 2 is transmission electron microscope (TEM) figure of the core sheath structure nanofiber of the Fluorescence Increasing that the present invention (embodiment 4) provides
Fig. 3 is the glimmering of the core sheath structure nanofiber of the Fluorescence Increasing that the present invention (comparative example 4-A, embodiment 7-B) provides
Light excites spectrogram
Fig. 4 is the glimmering of the core sheath structure nanofiber of the Fluorescence Increasing that the present invention (comparative example 4-A, embodiment 7-B) provides
Light emission spectrogram
Detailed description of the invention
For making the purpose of the present invention, technical scheme clearer, below in conjunction with specific embodiment, the present invention is carried out in detail
Illustrate, but limit the present invention the most in any form.Those of ordinary skill in the art can according to the present invention make various accordingly
Deformation, but these all should belong to protection scope of the present invention.
Comparative example 1
(1) preparation sheaths spinning liquid: 0.19g PVP and 0.96g polyacrylic acid are dissolved in 4ml N, N-dimethyl methyl jointly
Amide and the mixed solvent of 6ml dichloromethane, obtain sheaths spinning liquid；
(2) preparation sandwich layer spinning liquid: 1.30g Poly-L-lactic acid is dissolved in 6ml chloroform, 0.40g RE (TTA)2
(phen) (AA) (RE=Sm3+、Nd3+And Pr3+Mol ratio is 1:1:1) be dissolved in 4ml dimethyl sulfoxide, after two kinds of solution mixing in
Magnetic agitation 2h under room temperature, obtains sandwich layer spinning liquid；
(3) core sheath structure nanofiber is prepared: use coaxial electrostatic spinning technology, by the sheaths spinning liquid prepared and core
Layer spinning liquid is respectively placed in outer tube and the inner tube of coaxial electrostatic spinning silk device, regulation spinning voltage 18KV, receiving range 15cm,
Relative humidity is 30～40%, and outer layer fltting speed is 1.8ml/h, and internal layer fltting speed is 1.0ml/h, prepares RE (TTA)2
(phen) (AA) core sheath structure nanofiber, fibre diameter is about 850nm, a diameter of about the 500nm of sandwich layer.Employing fluorescence divides
Light photometer records fibre fluorescence intensity and is shown in Table 1.
Embodiment 1
(1) preparation sheaths spinning liquid: first 0.19g dispersant PVP is dissolved in 4mlN, dinethylformamide, adds
0.04g nanometer silver (particle diameter about 20nm), processes 5h by Ultrasound Instrument and makes nanometer silver be dispersed in N, N-dimethyl formyl
In amine, then 0.96g polyacrylic acid is dissolved in 6ml dichloromethane, magnetic agitation 2h at room temperature after two kinds of solution mixing, obtain
Sheaths spinning liquid；
(2) identical with step (2) described in comparative example 1.
(3) identical with step (3) spinning condition described in comparative example 1, prepare the core sheath structure nanofiber of Fluorescence Increasing, fine
Tie up a diameter of about 750nm, a diameter of about the 400nm of sandwich layer.Use spectrofluorophotometer to record fibre fluorescence intensity to be shown in Table
1。
Comparative example 2
(1) preparation sheaths spinning liquid: 0.10g PVP, 0.30g Merlon and 0.30g polyacrylic acid are dissolved in 3ml jointly
N,N-dimethylacetamide and the mixed solvent of 7ml dichloromethane, obtain sheaths spinning liquid；
(2) preparation sandwich layer spinning liquid: 0.55g polyvinyl alcohol is dissolved in 7ml dimethyl sulfoxide, 0.03g Eu (TTA)3phen
It is dissolved in 3ml DMF, magnetic agitation 1h at room temperature after two kinds of solution mixing, obtain sandwich layer spinning liquid；
(3) core sheath structure nanofiber is prepared: use coaxial electrostatic spinning technology, by the sheaths spinning liquid prepared and core
Layer spinning liquid is respectively placed in outer tube and the inner tube of coaxial electrostatic spinning silk device, regulation spinning voltage 25KV, receiving range 5cm,
Relative humidity is 30～40%, and outer layer fltting speed is 1.5ml/h, and internal layer fltting speed is 0.5ml/h, prepares Eu (TTA)3Phen core sheath structure nanofiber, fibre diameter is about 700nm, a diameter of about the 300nm of sandwich layer.Use fluorescence spectrophotometer light
Degree measure fibre fluorescence intensity is shown in Table 1.
Embodiment 2
(1) preparation sheaths spinning liquid: first 0.10g dispersant PVP is dissolved in 3mlN, N-dimethyl acetylamide, adds
0.005g nanometer silver (particle diameter about 100nm), processes 3h by Ultrasound Instrument and makes nanometer silver be dispersed in N, N-dimethyl second
In amide, then 0.30g Merlon and 0.30g polyacrylic acid are dissolved in jointly 7ml dichloromethane, after two kinds of solution mixing in
Magnetic agitation 1h under room temperature, obtains sheaths spinning liquid；
(2) identical with step (2) described in comparative example 2.
(3) identical with step (3) spinning condition described in comparative example 2, prepare the core sheath structure nanofiber of Fluorescence Increasing, fine
Tie up a diameter of about 600nm, a diameter of about the 300nm of sandwich layer.Use spectrofluorophotometer to record fibre fluorescence intensity to be shown in Table
1。
Comparative example 3
(1) preparation sheaths spinning liquid: 1.17g PVP is dissolved in 3ml deionized water and the mixed solvent of 7ml ethanol, obtains
Sheaths spinning liquid；
(2) preparation sandwich layer spinning liquid: 1.69g polyvinyl alcohol is dissolved in 7ml dichloromethane, 0.17g Ln (teta) (NO3)3
(Ln=La3+And Ce3+Mol ratio is 1:1) it is dissolved in 3ml dimethyl sulfoxide, magnetic agitation 2h at room temperature after two kinds of solution mixing,
Obtain sandwich layer spinning liquid；
(3) core sheath structure nanofiber is prepared: use coaxial electrostatic spinning technology, by the sheaths spinning liquid prepared and core
Layer spinning liquid is respectively placed in outer tube and the inner tube of coaxial electrostatic spinning silk device, regulation spinning voltage 20KV, receiving range 20cm,
Relative humidity is 30～40%, and outer layer fltting speed is 1.5ml/h, and internal layer fltting speed is 0.5ml/h, prepares Ln (teta)
(NO3)3Core sheath structure nanofiber, fibre diameter is about 500nm, a diameter of about the 200nm of sandwich layer.Use fluorescence spectrophotometer light
Degree measure fibre fluorescence intensity is shown in Table 1.
Embodiment 3
(1) preparation sheaths spinning liquid: first 0.15g dispersant PVP is dissolved in 3ml deionized water, adds 0.035g and receive
Meter Yin (particle diameter about 40nm), processes 1h by Ultrasound Instrument and makes nanometer silver be dispersed in deionized water, then will
1.02gPVP is dissolved in 7ml ethanol, magnetic agitation 2h at room temperature after two kinds of solution mixing, obtains sheaths spinning liquid；
(2) identical with step (2) described in comparative example 3.
(3) identical with step (3) spinning condition described in comparative example 3, prepare the core sheath structure nanofiber of Fluorescence Increasing, fine
Tie up a diameter of about 300nm, a diameter of about the 100nm of sandwich layer.Use spectrofluorophotometer to record fibre fluorescence intensity to be shown in Table
1。
Comparative example 4
(1) preparation sheaths spinning liquid: 0.14g PVP and 1.10g Poly-L-lactic acid are dissolved in 5ml N, N-dimethyl jointly
Methanamide and the mixed solvent of 5ml dichloromethane, obtain sheaths spinning liquid；
(2) preparation sandwich layer spinning liquid: 1.00g Poly-L-lactic acid is dissolved in 7ml dichloromethane, 0.10gTb (acac)3phen
It is dissolved in 3ml DMF, magnetic agitation 1h at room temperature after two kinds of solution mixing, obtain sandwich layer spinning liquid；
(3) core sheath structure nanofiber is prepared: use coaxial electrostatic spinning technology, by the sheaths spinning liquid prepared and core
Layer spinning liquid is respectively placed in outer tube and the inner tube of coaxial electrostatic spinning silk device, regulation spinning voltage 15KV, receiving range 18cm,
Relative humidity is 30～40%, and outer layer fltting speed is 1.5ml/h, and internal layer fltting speed is 0.6ml/h, prepares Tb (acac)3Phen core sheath structure nanofiber, fibre diameter is about 800nm, a diameter of about the 500nm of sandwich layer.Use fluorescence spectrophotometer light
Degree measure fibre fluorescence intensity is shown in Table 1.
Embodiment 4
(1) preparation sheaths spinning liquid: first 0.14g dispersant PVP is dissolved in 5mlN, dinethylformamide, adds
0.016g nanometer silver (particle diameter about 25nm), processes 1h by Ultrasound Instrument and makes nanometer silver be dispersed in N, N-dimethyl formyl
In amine, then 1.10g Poly-L-lactic acid is dissolved in 5ml dichloromethane, magnetic agitation 1h at room temperature after two kinds of solution mixing,
To sheaths spinning liquid；
(2) identical with step (2) described in comparative example 4.
(3) identical with step (3) spinning condition described in comparative example 4, prepare the core sheath structure nanofiber of Fluorescence Increasing, fine
Tie up a diameter of about 400nm, a diameter of about the 250nm of sandwich layer.Use spectrofluorophotometer to record fibre fluorescence intensity to be shown in Table
1。
The fluorescence intensity of the core sheath structure nanofiber of table 1. Fluorescence Increasing
| Embodiment | Fluorescence intensity (a.u.) |
| Comparative example 1 | 290 |
| Embodiment 1 | 403 |
| Comparative example 2 | 160 |
| Embodiment 2 | 232 |
| Comparative example 3 | 268 |
| Embodiment 3 | 319 |
| Comparative example 4 | 274 |
| Embodiment 4 | 490 |
Fluorescence intensity in contrast table 1, it can be seen that for different rare earth compoundings, nanometer silver increasing the most in various degree
The strong fluorescence intensity of core sheath structure nanofiber.
Embodiment 5
(1) preparation sheaths spinning liquid: first 0.15g dispersant PVP is dissolved in 3mlN, dinethylformamide, adds
0.051g nanometer silver (particle diameter about 60nm), processes 1h by Ultrasound Instrument and makes nanometer silver be dispersed in N, N-dimethyl formyl
In amine, then poly-for 0.37g propanoic acid acid is dissolved in 7ml dichloromethane, magnetic agitation 3h at room temperature after two kinds of solution mixing, obtain
Sheaths spinning liquid；
(2) preparation sandwich layer spinning liquid: 1.00g polyvinyl alcohol is dissolved in 5ml chloroform, 0.10gTb (acac)3Phen is molten
In 5ml dimethyl sulfoxide, magnetic agitation 2h at room temperature after two kinds of solution mixing, obtain sandwich layer spinning liquid；
(3) core sheath structure nanofiber is prepared: use coaxial electrostatic spinning technology, by the sheaths spinning liquid prepared and core
Layer spinning liquid is respectively placed in outer tube and the inner tube of coaxial electrostatic spinning silk device, regulation spinning voltage 12KV, receiving range 15cm,
Relative humidity is 30～40%, and outer layer fltting speed is 0.5ml/h, and internal layer fltting speed is 0.1ml/h, prepares Fluorescence Increasing
Core sheath structure nanofiber, fibre diameter is about 300nm, a diameter of about the 150nm of sandwich layer.Employing spectrofluorophotometer is surveyed
Obtain fibre fluorescence intensity and be shown in Table 2.
Embodiment 6
(1) preparation sheaths spinning liquid: first 0.06g dispersant PVP is dissolved in 4mlN, N-dimethyl acetylamide, adds
0.028g nanometer silver (particle diameter about 30nm), processes 2h by Ultrasound Instrument and makes nanometer silver be dispersed in N, N-dimethylacetamide
In amine, then 0.68g polyvinyl alcohol is dissolved in 6ml ethanol, magnetic agitation 2h at room temperature after two kinds of solution mixing, obtain sheaths
Spinning liquid；
(2) preparation sandwich layer spinning liquid: 1.00gPVP is dissolved in 5ml dimethyl sulfoxide, 0.10gTb (acac)3Phen is dissolved in
5ml N,N-dimethylacetamide, magnetic agitation 2h at room temperature after the mixing of two kinds of solution, obtain sandwich layer spinning liquid；
(3) core sheath structure nanofiber is prepared: use coaxial electrostatic spinning technology, by the sheaths spinning liquid prepared and core
Layer spinning liquid is respectively placed in outer tube and the inner tube of coaxial electrostatic spinning silk device, regulation spinning voltage 15KV, receiving range 30cm,
Relative humidity is 30～40%, and outer layer fltting speed is 2.0ml/h, and internal layer fltting speed is 1.0ml/h, prepares Fluorescence Increasing
Core sheath structure nanofiber, fibre diameter is about 900nm, a diameter of about the 550nm of sandwich layer.Employing spectrofluorophotometer is surveyed
Obtain fibre fluorescence intensity and be shown in Table 2.
Embodiment 7
(1) preparation sheaths spinning liquid: first 0.08g dispersant PVP is dissolved in 3ml deionized water, adds 0.012g and receive
Meter Yin (particle diameter about 50nm), processes 1h by Ultrasound Instrument and makes nanometer silver be dispersed in DMF, so
After 0.80g polyacrylic acid is dissolved in 3ml ethanol, 2ml acetic acid and the mixed solvent of 2ml acetone, in room temperature after two kinds of solution mixing
Lower magnetic agitation 1h, obtains sheaths spinning liquid；
(2) preparation sandwich layer spinning liquid: 1.00g Poly-L-lactic acid is dissolved in 7ml dichloromethane, 0.10gTb (acac)3phen
It is dissolved in 3ml DMF, magnetic agitation 2h at room temperature after two kinds of solution mixing, obtain sandwich layer spinning liquid；
(3) core sheath structure nanofiber is prepared: use coaxial electrostatic spinning technology, by the sheaths spinning liquid prepared and core
Layer spinning liquid is respectively placed in outer tube and the inner tube of coaxial electrostatic spinning silk device, regulation spinning voltage 18KV, receiving range 12cm,
Relative humidity is 30～40%, and outer layer fltting speed is 1.2ml/h, and internal layer fltting speed is 0.6ml/h, prepares Fluorescence Increasing
Core sheath structure nanofiber, fibre diameter is about 750nm, a diameter of about the 400nm of sandwich layer.Employing spectrofluorophotometer is surveyed
Obtain fibre fluorescence intensity and be shown in Table 2.
Embodiment 8
(1) preparation sheaths spinning liquid: first 0.14g dispersant PVP is dissolved in 3ml ethanol, adds 0.025g nanometer silver
(particle diameter about 70nm), processes 2h by Ultrasound Instrument and makes nanometer silver be dispersed in DMF, then will
0.37g Poly-L-lactic acid, 0.30g PVP and 0.30g polyacrylic acid are dissolved in 4ml dichloromethane and 3mlN, N-dimethyl methyl jointly
The mixed solvent of amide, magnetic agitation 1h at room temperature after the mixing of two kinds of solution, obtain sheaths spinning liquid；
(2) preparation sandwich layer spinning liquid: 1.00gPVP is dissolved in 6ml dimethyl sulfoxide, 0.10gTb (acac)3Phen is dissolved in
4ml DMF, magnetic agitation 3h at room temperature after the mixing of two kinds of solution, obtain sandwich layer spinning liquid；
(3) core sheath structure nanofiber is prepared: use coaxial electrostatic spinning technology, by the sheaths spinning liquid prepared and core
Layer spinning liquid is respectively placed in outer tube and the inner tube of coaxial electrostatic spinning silk device, regulation spinning voltage 21KV, receiving range 10cm,
Relative humidity is 30～40%, and outer layer fltting speed is 1.5ml/h, and internal layer fltting speed is 0.6ml/h, prepares Fluorescence Increasing
Core sheath structure nanofiber, fibre diameter is about 600nm, a diameter of about the 300nm of sandwich layer.Employing spectrofluorophotometer is surveyed
Obtain fibre fluorescence intensity and be shown in Table 2.
Embodiment 9
(1) preparation sheaths spinning liquid: first 0.16g dispersant PVP is dissolved in 5ml deionized water, adds 0.013g and receive
Meter Yin (particle diameter about 10nm), processes 1h by Ultrasound Instrument and makes nanometer silver be dispersed in deionized water, then will
0.95gPVP is dissolved in 5ml acetone, magnetic agitation 2h at room temperature after two kinds of solution mixing, obtains sheaths spinning liquid；
(2) preparation sandwich layer spinning liquid: 1.00g Poly-L-lactic acid is dissolved in 5ml chloroform, 0.10gTb (acac)3phen
It is dissolved in 5ml N,N-dimethylacetamide, magnetic agitation 2h at room temperature after two kinds of solution mixing, obtain sandwich layer spinning liquid；
(3) core sheath structure nanofiber is prepared: use coaxial electrostatic spinning technology, by the sheaths spinning liquid prepared and core
Layer spinning liquid is respectively placed in outer tube and the inner tube of coaxial electrostatic spinning silk device, regulation spinning voltage 15KV, receiving range 15cm,
Relative humidity is 30～40%, and outer layer fltting speed is 1.2ml/h, and internal layer fltting speed is 0.6ml/h, prepares Fluorescence Increasing
Core sheath structure nanofiber, fibre diameter is about 700nm, a diameter of about the 350nm of sandwich layer.Employing spectrofluorophotometer is surveyed
Obtain fibre fluorescence intensity and be shown in Table 2.
Embodiment 10
(1) preparation sheaths spinning liquid: first 0.34g dispersant PVP is dissolved in 4mlN, dinethylformamide, adds
0.058g nanometer silver (particle diameter about 80nm), processes 3h by Ultrasound Instrument and makes nanometer silver be dispersed in N, N-dimethyl formyl
In amine, then 1.70g Poly-L-lactic acid is dissolved in 6ml chloroform, magnetic agitation 1h at room temperature after two kinds of solution mixing,
To sheaths spinning liquid；
(2) preparation sandwich layer spinning liquid: 1.00g polyacrylic acid is dissolved in 5ml dichloromethane, 0.10gTb (acac)3Phen is molten
In 5ml dimethyl sulfoxide, magnetic agitation 1h at room temperature after two kinds of solution mixing, obtain sandwich layer spinning liquid；
(3) core sheath structure nanofiber is prepared: use coaxial electrostatic spinning technology, by the sheaths spinning liquid prepared and core
Layer spinning liquid is respectively placed in outer tube and the inner tube of coaxial electrostatic spinning silk device, regulation spinning voltage 24KV, receiving range 15cm,
Relative humidity is 30～40%, and outer layer fltting speed is 1.2ml/h, and internal layer fltting speed is 0.6ml/h, prepares Fluorescence Increasing
Core sheath structure nanofiber, fibre diameter is about 500nm, a diameter of about the 200nm of sandwich layer.Employing spectrofluorophotometer is surveyed
Obtain fibre fluorescence intensity and be shown in Table 2.
Embodiment 11
(1) preparation sheaths spinning liquid: first 0.39g dispersant PVP is dissolved in 3ml deionized water, adds 0.032g and receive
Meter Yin (particle diameter about 20nm), processes 4h by Ultrasound Instrument and makes nanometer silver be dispersed in deionized water, then will
3.13gPVP is dissolved in 3ml hexafluoroisopropanol and the mixed solvent of 4ml methanol, magnetic agitation at room temperature after two kinds of solution mixing
2h, obtains sheaths spinning liquid；
(2) preparation sandwich layer spinning liquid: 1.00g polyvinyl alcohol is dissolved in 6ml chloroform, 0.10gTb (acac)3Phen is molten
In 4ml DMF, magnetic agitation 1h at room temperature after two kinds of solution mixing, obtain sandwich layer spinning liquid；
(3) core sheath structure nanofiber is prepared: use coaxial electrostatic spinning technology, by the sheaths spinning liquid prepared and core
Layer spinning liquid is respectively placed in outer tube and the inner tube of coaxial electrostatic spinning silk device, regulation spinning voltage 10KV, receiving range 12cm,
Relative humidity is 30～40%, and outer layer fltting speed is 1.5ml/h, and internal layer fltting speed is 0.5ml/h, prepares Fluorescence Increasing
Core sheath structure nanofiber, fibre diameter is about 850nm, a diameter of about the 550nm of sandwich layer.Employing spectrofluorophotometer is surveyed
Obtain fibre fluorescence intensity and be shown in Table 2.
Embodiment 12
(1) preparation sheaths spinning liquid: first 0.30g dispersant PVP is dissolved in 3mlN, dinethylformamide, adds
0.019g nanometer silver (particle diameter about 30nm), processes 2h by Ultrasound Instrument and makes nanometer silver be dispersed in N, N-dimethyl formyl
In amine, then 2.33g polyacrylic acid is dissolved in 7ml dichloromethane, magnetic agitation 3h at room temperature after two kinds of solution mixing, obtain
Sheaths spinning liquid；
(2) preparation sandwich layer spinning liquid: 1.00g Merlon is dissolved in 7ml dichloromethane, 0.10gTb (acac)3Phen is molten
In 3ml DMF, magnetic agitation 3h at room temperature after two kinds of solution mixing, obtain sandwich layer spinning liquid；
(3) core sheath structure nanofiber is prepared: use coaxial electrostatic spinning technology, by the sheaths spinning liquid prepared and core
Layer spinning liquid is respectively placed in outer tube and the inner tube of coaxial electrostatic spinning silk device, regulation spinning voltage 15KV, receiving range 12cm,
Relative humidity is 30～40%, and outer layer fltting speed is 1.2ml/h, and internal layer fltting speed is 0.6ml/h, prepares Fluorescence Increasing
Core sheath structure nanofiber, fibre diameter is about 650nm, a diameter of about the 350nm of sandwich layer.Employing spectrofluorophotometer is surveyed
Obtain fibre fluorescence intensity and be shown in Table 2.
The fluorescence intensity of the core sheath structure nanofiber of table 2. Fluorescence Increasing
| Embodiment | Fluorescence intensity (a.u.) |
| Embodiment 5 | 352 |
| Embodiment 6 | 385 |
| Embodiment 7 | 441 |
| Embodiment 8 | 398 |
| Embodiment 9 | 425 |
| Embodiment 10 | 365 |
| Embodiment 11 | 397 |
| Embodiment 12 | 410 |
| Comparative example 4 | 274 |
Fluorescence intensity in contrast table 2, it can be seen that fine relative to the core sheath structure fluorescence not containing nanometer silver in comparative example 4
Dimension, the fluorescence intensity of the core sheath structure nanofiber that embodiment 5-12 difference preparation condition obtains has had increasing in various degree
By force.
Comparative example 5
(1) preparation sheaths spinning liquid: 1.00g Poly-L-lactic acid is dissolved in 7ml dichloromethane, 0.10gTb (acac)3phen
It is dissolved in 3ml DMF, magnetic agitation 1h at room temperature after two kinds of solution mixing, obtain sandwich layer spinning liquid；
(2) preparation sandwich layer spinning liquid: first 0.14g dispersant PVP is dissolved in 5mlN, dinethylformamide, adds
0.016g nanometer silver (particle diameter about 25nm), processes 1h by Ultrasound Instrument and makes nanometer silver be dispersed in N, N-dimethyl formyl
In amine, then 1.10g Poly-L-lactic acid is dissolved in 5ml dichloromethane, magnetic agitation 1h at room temperature after two kinds of solution mixing,
To sheaths spinning liquid；
(3) core sheath structure nanofiber is prepared: use coaxial electrostatic spinning technology, by the sheaths spinning liquid prepared and core
Layer spinning liquid is respectively placed in outer tube and the inner tube of coaxial electrostatic spinning silk device, regulation spinning voltage 15KV, receiving range 18cm,
Relative humidity is 30～40%, and outer layer fltting speed is 1.5ml/h, and internal layer fltting speed is 0.6ml/h, prepares Fluorescence Increasing
Core sheath structure nanofiber, fibre diameter is about 900nm, a diameter of about the 650nm of sandwich layer.Employing spectrofluorophotometer is surveyed
Obtain fibre fluorescence intensity and be shown in Table 3.
Comparative example 6
(1) preparation spinning liquid: 0.14gPVP and 2.10g Poly-L-lactic acid is dissolved in 12ml dichloromethane, 0.10g jointly
Tb(acac)3Phen is dissolved in 4mlN, dinethylformamide, and 0.016g nanometer silver (particle diameter about 25nm) is used at Ultrasound Instrument
Reason 1h is scattered in 4ml DMF, magnetic agitation 1h at room temperature after three kinds of solution mixing, obtains spinning liquid；
(2) preparing nanofiber: use electrostatic spinning technique, moved in syringe by the spinning liquid prepared, regulation is spun
Filament voltage 15KV, receiving range 18cm, relative humidity is 30～40%, and fltting speed is 1.5ml/h, prepares nanofiber, fine
Tie up a diameter of 200～700nm.Use spectrofluorophotometer to record fibre fluorescence intensity and be shown in Table 3.
The fluorescence intensity of the nanofiber of table 3. Fluorescence Increasing
| Embodiment | Fluorescence intensity (a.u.) |
| Embodiment 4 | 490 |
| Comparative example 5 | 248 |
| Comparative example 6 | 187 |
Fluorescence intensity in contrast table 3, it can be seen that identical spinning matrix, spinning condition, nanometer silver coordinate with rare earth
The content of thing, different preparation methoies and nanometer silver are in sandwich layer or the position of sheaths, and prepared fibre fluorescence intensity difference is the biggest.
The core sheath structure nanofiber (embodiment 4) of the Fluorescence Increasing that the present invention prepares is better than traditional nanometer silver in sandwich layer (contrast
Example 5) and nanofiber prepared by (comparative example 6) is directly mixed with rare earth compounding, also further demonstrate that grinding of the present invention
Study carefully meaning.
Claims (5)
1. the preparation method of the core sheath structure nanofiber of a Fluorescence Increasing, it is characterised in that step is:
(1) preparation sheaths spinning liquid: first dispersant PVP is dissolved in solvent, adds the matter of nanometer silver, nanometer silver and dispersant
Amount ratio is 0.01:1～0.5:1, processes 1～5h by Ultrasound Instrument and makes nanometer silver be dispersed in solvent, is then spun by macromolecule
Silk base material is dissolved in solvent, and the mass ratio of dispersant PVP and macromolecule spinning base material is 1:1～1:15, after the mixing of two kinds of solution in
Magnetic agitation 1～3h under room temperature, obtains the sheaths spinning liquid that macromolecule spinning substrate mass mark is 4～18%；
(2) preparation sandwich layer spinning liquid: by macromolecule spinning base material and rare earth compounding mass ratio be 100:5～100:30 is the most molten
In organic solvent, magnetic agitation 1～3h at room temperature after the mixing of two kinds of solution, obtaining macromolecule spinning substrate mass mark is 5
～the sandwich layer spinning liquid of 20%；
(3) core sheath structure nanofiber is prepared: use coaxial electrostatic spinning technology, the sheaths spinning liquid prepared and sandwich layer are spun
Silk liquid be respectively placed in outer tube and the inner tube of coaxial electrostatic spinning silk device, regulate spinning voltage 10～25KV, receiving range 5～
30cm, outer layer fltting speed is 0.5～2.0ml/h, and internal layer fltting speed is 0.1～1.0ml/h, prepares the core sheath of Fluorescence Increasing
Structure nano fiber, in fiber, the mol ratio of nanometer silver and rare earth compounding is 1:0.1～1:10, fibre diameter be 20～
1000nm。
The preparation method of the core sheath structure nanofiber of a kind of Fluorescence Increasing the most according to claim 1, it is characterised in that:
In described step (1) and (2), macromolecule spinning base material is Poly-L-lactic acid, polyvinylpyrrolidone, polyvinyl alcohol, poly-second two
The mixture of one or more in alcohol, Merlon, polyacrylic acid.
The preparation method of the core sheath structure nanofiber of a kind of Fluorescence Increasing the most according to claim 1, it is characterised in that:
In described step (1), solvent selects N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dichloromethane, chloroform, diformazan
One or more in base sulfoxide, methanol, ethanol, trifluoroethanol, hexafluoroisopropanol, formic acid, acetic acid, acetone, deionized water
Mixture, in described step (2) organic solvent select DMF, N,N-dimethylacetamide, dichloromethane, three
The mixture of one or more in chloromethanes, dimethyl sulfoxide, formic acid, acetic acid.
The preparation method of the core sheath structure nanofiber of a kind of Fluorescence Increasing the most according to claim 1, it is characterised in that:
Described step (2) middle rare earth coordination compound is the one in terbium, europium, samarium, yttrium, dysprosium, cerium, ytterbium, erbium, neodymium, protactinium, thulium, holmium, Lanthanide complex
Or several mixture.
The preparation method of the core sheath structure nanofiber of a kind of Fluorescence Increasing the most according to claim 1, it is characterised in that:
In described step (1), the particle diameter of nanometer silver is 10～100nm.
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