CN105588824B - Application of the double-deck electrostatic spinning film sensor in the detection of nitro-aromatic substance - Google Patents
Application of the double-deck electrostatic spinning film sensor in the detection of nitro-aromatic substance Download PDFInfo
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Abstract
The invention discloses a kind of application of double-deck electrostatic spinning film sensor in the detection of nitro-aromatic substance, which includes double membrane structure, and bottom is gelatin electrostatic spinning film (GEL), this layer is placed on glass sheet surface as skeleton；Top layer using polystyrene as carrier, with fluorescence sense polymer P described in claim 1 carry out it is blended be prepared into electrostatic spinning film (PS P), which is sensing layer.Advantage is：I) gelatin has a large amount of amino and hydroxyl group, and make Nitro-aromatic Compounds in Different be gathered in P PS sensing layers to have the function that improve quenching rate to be enriched with nitro-aromatic by hydrogen bonding interaction between nitro-aromatic and gelatin.II) as in the stephanoporate framework below PS layers of P, gelatin layer can allow nitro-aromatic molecule up and down while to be spread in PS layers of P, substantially improve the permeability of PS layers of P for it.
Description
Technical field
The present invention relates to a kind of application of double-deck electrostatic spinning film sensor in the detection of nitro-aromatic substance.
Background technology
Nitro-aromatic such as 2,4,6-trinitrotoluene (TNT), 2,4- dinitrotoluene (DNT)s (DNT), picric acid (PA) etc. are all
Important explosive ingredient, for explosive use and transport must strict control, otherwise not only seriously affect social stability,
National security, while also causing damages to human health because it is with bio-toxicity and potential carcinogenesis.Therefore it explodes
The test problems of object have caused the highest attention of various countries, many countries to put into a large amount of fund and carried out scientific research.Fluorescence
Sensing method have high sensitivity, can acquisition parameter (such as fluorescence intensity, fluorescence spectrum pattern, fluorescence anisotropy, fluorescence lifetime
Deng) more, response time is fast and Instrument Design relative maturity the features such as most development prospect detection method.
Current fluorescent optical sensor is usually that fluorescent chemicals are prepared into film by the method for spin coating, and it is thin to form fluorescence
Film sensors.In order to ensure that there is film certain fluorescence intensity, polymer film must have certain thickness, and general thin
Compact texture often make diffusion of the determinand in film slower, thus response speed is slower.People are improved using a variety of methods
Polymer architecture increases the permeability of film, to increase diffusion velocity of the nitro-aromatic in film, improves quenching efficiency.
Electrostatic spinning technique is a kind of simple method for preparing nano material, can obtain the film material of high-permeability
Material.Electrostatic spinning film has many merits：Big specific surface area, high porosity, good penetrability and controllable form.
These advantages are all conducive to contacting with each other between analyte and probe.Film-sensing material is prepared with electrostatic spinning technique in recent years
Material is gradually used in the detection of many kinds of substance, such as detection of each metal ion species, the detection, etc. of nitro-aromatic.Commonly
Electrostatic spinning film sensor be by fluorescent sensing material solid substrate formed electrostatic spinning film.In detection gas
When determinand, gas molecule penetrates into film above film, causes the change in fluorescence of sensing material.
Currently, not being found the double-deck electrostatic spinning film sensor material answering in the detection of nitro-aromatic substance
With.
Invention content
The art of this patent is prepared for one layer of electrostatic spinning film with gelatin first in glass surface, the surface of this film again with
Sensing material is prepared for one layer of electrostatic spinning film.This duplicature fluorescent optical sensor has superior biography compared with monofilm
Perceptual energy.The gelatin static spinning membrane of wherein bottom can allow gas determinand can be simultaneously above and below sensing layer
It penetrates into simultaneously, improves sensing rate.On the other hand, gelatin molecule contains the electron riches group such as a large amount of hydroxyl, amino,
Hydrogen bond action can be generated with nitro-aromatic, thus have enrichment to nitro-aromatic, the sensitivity of sensor can be improved.Tool
For body：
The object of the present invention is to provide a kind of double-deck electrostatic spinning film sensors in the detection of nitro-aromatic substance
Using.
The present invention uses following technical scheme to achieve the above object：
It is a kind of bilayer electrostatic spinning film sensor nitro-aromatic substance detection in application.
Nitro-aromatic substance be 2,4,6- trinitrotoluenes (TNT), 2,4-DNT (DNT), picric acid (PA),
2,4- dinitrophenol (DNP) or derivatives thereof.
The bilayer electrostatic spinning film sensor is made of double membrane structure, and bottom is gelatin electrostatic spinning film
(GEL), this layer is placed on glass sheet surface as skeleton；Top layer using polystyrene as carrier, with fluorescence sense polymer P into
Row is blended to be prepared into electrostatic spinning film (PS-P), which is sensing layer.
Wherein, the fibre diameter in the gelatin electrostatic spinning film (GEL) is 20~35 microns, and the electrostatic spinning is thin
Film (PS-P) is the electrostatic spinning film of polystyrene doping fluorescent sensing polymer P, fiber bunchiness pearlitic texture, the beading
A diameter of 5~15 microns of shape structure, a diameter of 180nm~220nm of fiber, preferably 200nm.
Compared with individual PS-P electrostatic spinning films sensor, introduces gelatin electrostatic spinning layer GEL and have as casing play
It has many advantages：I) the electron rich group that contains a large amount of amino and hydroxyl in gelatin molecule, they and nitro virtue can be passed through
Interaction of hydrogen bond between hydrocarbon and effectively attract nitro-aromatic molecule, to make nitro-aromatic molecule around sensing material
Enrichment, improves the sensitivity of sensor.II) gelatin static spinning membrane is porous, it allows nitro-aromatic molecule simultaneously from P-
Enter simultaneously above and below PS film layers, improves the permeability of P-PS sensing membranes；And common P-PS monofilms sensing
Device only allows nitro-aromatic molecule to be penetrated into from top.
Bilayer electrostatic spinning film sensor of the invention is indicated with PS-P/GEL.Fluorescence sense polymer P therein is glimmering
Light conjugated polymer, the fluorescent conjugated polymer is preferably based on the copolymer of polyfluorene ethynylene Type of Collective object, but it is protected
It is not only the copolymer based on polyfluorene ethynylene Type of Collective object to protect range.Further preferably above-mentioned fluorescence sense polymer P,
Structural formula is as shown in Equation 1, by experimental verification and analysis, the double-deck electrostatic being prepared using above-mentioned fluorescence sense polymer P
The performance of spinning thin film sensor is more excellent.
The fluorescence sense polymer P, structural formula such as formula 1：
Wherein x：(0.1~2), y：(0.1~2), z：(0.1~2).
The preparation method of the fluorescence sense polymer P, includes the following steps：It is supportted with 2,5- dibromo thiophenes, polyphenylacetylene
Type of Collective object and 2, bis- bromo- 9,9- diphenylfluorenes of 7- are raw material, carry out the polymer for polymerizeing obtained structural formula such as formula 1.
Specific preparation method is as follows：
2,5- dibromo thiophenes, polyphenylacetylene support Type of Collective object and bis- bromo- 9,9- diphenylfluorenes of 2,7- are dissolved in anhydrous diisopropyl
PdCl is added under argon gas protection in amine (DIPA) and dry toluene2(PPh3)2,PPh3And CuI, 90~110 DEG C of 18~36h of reaction,
Then it purifies and fluorescence sense polymer P is made.
Polyphenylacetylene supports the structural formula such as formula 2 of Type of Collective object：
Wherein, the polyphenylacetylene support Type of Collective object, 2,5- dibromo thiophenes and 2, mole of bis- bromo- 9,9- diphenylfluorenes of 7-
Than being 1：(1~4)：(1~4), preferred molar ratio 1:1:1.By experimental verification and analysis, the fluorescence obtained under the conditions of this passes
The yield of sensitive polymeric P is higher.
The anhydrous diisopropylamine (DIPA) and dry toluene dissolve raw material in favor of reactant as solvent
Smoothly reaction, dosage is depending on the dosage of raw material.Preferably, 2,5- dibromo thiophenes, anhydrous diisopropylamine (DIPA) and nothing
The adding proportion of water-toluene is 1g：(5~15) ml：(100~200) ml, further preferred ratio are 1g：10ml：150ml.
It is more conducive to and is reacted by experimental verification and analysis, under the conditions of this.
The PdCl2(PPh3)2, PPh3Catalysis reaction is carried out as catalyst, dosage is according to the dosage of raw material with CuI
Depending on.Preferably, 2,5- dibromo thiophenes, PdCl2(PPh3)2、PPh3Mass ratio with CuI is 1：0.1~0.2:1~1.5：0.1
~0.3.It is more conducive to catalyst by experimental verification and analysis, under the conditions of this and carries out catalysis reaction.
Preferably, be passed through argon gas time be 30 minutes, 100 DEG C of back flow reactions for 24 hours, by experimental verification with analysis,
This condition is the experiment parameter after optimization, and the yield of the fluorescence sense polymer P obtained with this condition is higher.
9,9- diphenylfluorene units are introduced in polyphenylacetylene supports Type of Collective object, it, can be with due to the steric hindrance of its rigidity
π-the π weakened between skeleton are stacked, and improve the permeability of polymer.Introducing thiophene unit simultaneously makes polymer have electron rich
Property, the electronics transfer between polymer and nitro-aromatic can be promoted, promote the generation of fluorescent quenching.It is as follows to synthesize equation：
The preparation method of electrostatic spinning film P-PS using the fluorescence sense polymer P a kind of, the fluorescence is passed
Sensitive polymeric P is dissolved in polystyrene (PS) in the mixed solution of DMF and THF, is stirred, and obtained solution is carried out Static Spinning
Silk, it is dry, obtain Electrospun nano-fibers film (electrostatic spinning film P-PS).
Wherein, the mass ratio of fluorescence sense polymer P and polystyrene (PS) is 1:1000~1500, preferably 1:
1000.It is preferred that stirring 12~36h, further preferably 15h.The effect for the Electrospun nano-fibers film that the condition obtains compared with
It is good.
The condition of the electrostatic spinning is：The a diameter of 0.5-2mm of syringe needle is sprayed, it is 20~30cm, voltage 15 to receive distance
~25kV, the flow velocity of solution is by syringe pump with 1mL H-1Constant rate of speed control.It is preferred that it is 25cm, voltage to receive distance
20kV.Above-mentioned condition makes electrostatic spinning effect more preferable, obtains the Electrospun nano-fibers film of ideal effect, obtained electrostatic
The thickness of spinning P-PS films is 18~22 microns (preferably 20 microns).
The mixed solution of the DMF and THF is 1ml with the adding proportion of polystyrene (PS)：(0.05~0.2) g, preferably
Ratio is 1ml：0.1g, wherein DMF：The volume ratio of THF is 3:1.
The drying condition is：25~30 DEG C of dry 8~12h, preferably 10h, to remove remaining organic solvent.
A kind of preparation method of gelatin electrostatic spinning film (GEL), includes the following steps：
By Gelatin in the mixed solution of 2,2,2- trifluoroethanols and THF, obtained solution is carried out electrostatic by stirring
Spinning, it is dry, obtain gelatin electrostatic spinning film (GEL).
Wherein, 18~36h is preferably stirred, further preferably for 24 hours.The effect for the gelatin film that the condition obtains is preferable.
The condition of the electrostatic spinning is：The a diameter of 0.5-2mm of syringe needle is sprayed, it is 20~30cm, voltage 15 to receive distance
~25kV, the flow velocity of solution is by syringe pump with 1mL H-1It is controlled with constant rate of speed.It is preferred that it is 25cm, voltage to receive distance
20kV.Above-mentioned condition makes electrostatic spinning effect more preferable, obtains the gelatin film of ideal effect, and the thickness of obtained gelatin film is 18
~22 microns (preferably 20 microns).
The volume ratio of the mixed solution of the 2,2,2 tfifluoroethyl alcohol and THF is 3:1.
The drying condition is：25~30 DEG C of dry 10h, to remove remaining organic solvent.
Electrostatic spinning in the present invention uses electrostatic spinning instrument.Electrostatic spinning instrument mainly comprises the following steps：
Reception device, liquid storaging device, high-voltage DC power supply and injection apparatus.The general maximum output voltage of power supply is in 30-100kV
DC high-voltage power supply electric field is provided, solution storage device is generally used to the electrostatic spinning solution of storage melting, spray syringe needle
Diameter is generally in 0.5-2mm, and syringe needle is connected with high voltage power supply, and the discharging modes of syringe needle can be generally divided into following two：
Vertical-type and horizontal type.Reception device is usually metal roller either metal plate.
The test method of the fluorescent quenching rate of sensor：
The fluorescence intensity F0 of sensing material, then measures nitro-aromatic class first in the absence of measurement nitro-aromatic substance
The fluorescence intensity F of sensing material in the presence of substance, makes the working curve of fluorescence intensity and time, and draws out the double-deck Static Spinning
Comparison diagram of the silk thin film sensor to different nitro-aromatic substances.
The method of concrete operations is：By taking DNT as an example, the quenching efficiency of sensor in being saturated nitro-aromatic substance steam
It is measured according to following method：100 milligrams of DNT are added in cuvette and with a filter paper cover it, to prevent DNT
Being in direct contact between sensor.Then cuvette is shelved at room temperature 3 hours, to reach gas balance.Then,
The cuvette is placed in Fluorescence Spectrometer, and inventive sensor is immediately inserted into cuvette, sensor is towards laser
Source.Every 30 seconds test first order fluorescence spectrum.
The beneficial effects of the invention are as follows：
(1) the novel double-deck electrostatic spinning film sensor has been synthesized by electrostatic spinning technique in the present invention, be used for nitre
The detection of base aromatic compound.The P-PS layers on upper layer have fluorescence quenching to nitro-aromatic compound, are sensing materials
Layer；The GEL layers of bottom are gelatin casing play, and the sensing capabilities of the two layer transducer are improved by following multiple functions：I) it is bright
Glue has a large amount of amino and hydroxyl group, interaction of hydrogen bond can be generated between gelatin, to make nitro-aromatic sense
Device is nearby enriched with, and can be reduced detection limit, be improved response sensitivity.II) GEL layers as the stephanoporate framework below P-PS layers,
It can allow nitro-aromatic molecule above and below P-PS layers while diffuse into, to substantially improve P-PS layers of infiltration
Property.Therefore, the P-PS/GLE compared to single layer P-PS film two layer transducers is shown to nitro-aromatic preferably sensing capabilities.
(2) heretofore described fluorescent conjugated polymer is preferably based on the copolymer of polyfluorene ethynylene Type of Collective object still
Its protection domain is not only the copolymer based on polyfluorene ethynylene Type of Collective object.In the polymer P of the present invention, thiophene monomer is
Electron rich unit, introducing can be effectively facilitated polymer and the intermolecular electronics transfer of nitro-aromatic, poly- to improve
Close fluorescent quenching efficiency of the object to nitro-aromatic；9,9- diphenylfluorenes are the three-D space structure of rigidity, can effectively prevent gathering
The accumulation for closing object chain, prevents polymer fluorescent self-quenching, in addition it can increase the gas permeability of film, improves nitro-aromatic molecule and exists
Diffusion rate in film improves response sensitivity.
Description of the drawings
Fig. 1 is the double-deck electrostatic spinning film sensor material schematic diagram.
Fig. 2 is electrostatic spinning process schematic.
Fig. 3 is the fluorescence of the THF solution of polymer P, electrostatic spinning film P-PS, the double-deck electrostatic spinning film P-GLE/PS
Spectrogram (excitation wavelength 390nm).
Fig. 4 a are the scanning electron microscope spectrograms of gelatin.
Fig. 4 b are the scanning electron microscope spectrograms of electrostatic spinning film P-PS.
Fig. 4 c are the scanning electron microscope spectrograms of the double-deck static spinning membrane P-PS/GLE.
Fig. 4 d are the diameter distribution profiles of electrostatic spinning film P-PS.
Fig. 5 a are that electrostatic spinning film P-PS fluorescence spectrums in DNT saturated vapors change with time situation.
Fig. 5 b are that fluorescence spectrums of the double-deck static spinning membrane P-PS/GLE in DNT saturated vapors changes with time feelings
Condition.
Fig. 5 c are that the quenching rate of the electrostatic spinning film P-PS and double-deck static spinning membrane P-PS/GLE changes with time.
Fig. 5 d are the I of electrostatic spinning film P-PS and the double-deck static spinning membrane P-PS/GEL0/ I-1 is in 40 minutes
Change curve, wherein I0For fluorescence intensities of P-PS/GEL in the presence of no DNT, I be P-PS/GEL in being saturated DNT steam certain
The fluorescence intensity at one moment.
Fig. 6：The double-deck electrostatic spinning film P-PS/GLE changes over time song to the quenching rate of DNP, DNT, PA and TNT
Line.
Fig. 7：The invertibity of the double-deck electrostatic spinning film P-PS/GLE fluorescent quenching processes.
Specific implementation mode
Present invention will be further explained below with reference to the attached drawings and examples.
Reagent and instrument：
Embodiment 1
A kind of synthetic method of fluorescence sense polymer P, includes the following steps：
2,5- dibromo thiophenes (200mg, 0.9mmol), polyphenylacetylene support Type of Collective object (376mg, 0.9mmol) and 2,7- bis-
Bromo- 9,9- diphenylfluorenes (426.6mg, 0.9mol) are dissolved in anhydrous diisopropylamine (DIPA, 2mL) and dry toluene (30mL), set
Is passed through argon gas and protects 30 minutes in 50ml three-necked flasks, and PdCl is added2(PPh3)2(36mg,2.6×10-2mmol),PPh3
(270mg, 0.90mmol) and CuI (40.5mg, 0.3mmol).100 DEG C of back flow reactions are for 24 hours.Then fluorescence is obtained according to purification to pass
Sensor polymer P, structural formula is as shown in Chinese style 1 of the present invention.
Fluorescent optical sensor polymer P:Dark yellow solid (400mg, 69%)1H NMR:(CDCl3,400MHz),δ(ppm):
0.0-2.0 (m, 20H), 7.0-7.2 (m, 3H), 7.4 (d, 1H, J=7.2HZ), 6.0 (d, 3H, J=5.5HZ), 7.6-7.9 (m,
2H).FT-IR(KBr):3060,2967,2921,2850,2198,1710,1600,1452,1414,1259,1103,1026,
886,823,753,692,513cm-1Calcd for(C58H48S1Br2)n:C:82.72,S:2.55,H:6.419,N:
0.049.GPC(THF):Mn=4426, Mw=7852, PDI=1.7.
A kind of synthetic method of 2 fluorescence sense polymer P of embodiment, includes the following steps：
2,5- dibromo thiophenes (210mg), polyphenylacetylene support Type of Collective object (378mg) and bis- bromo- 9,9- diphenylfluorenes of 2,7-
(438mg) is dissolved in anhydrous diisopropylamine (DIPA, 2.5mL) and dry toluene (22mL), is placed in 50ml three-necked flasks and is passed through argon
PdCl is added in gas shielded 40 minutes2(PPh3)2(21mg),PPh3(252mg) and CuI (63mg).90 DEG C of back flow reaction 36h.So
Fluorescent optical sensor polymer P is obtained according to purification afterwards, structural formula is as shown in Chinese style 1 of the present invention.
Implement 3
The preparation of electrostatic spinning P-PS films：Fluorescence sense polymer P (0.4 milligram) and PS (0.4 gram) are dissolved in 4 milliliters
Mixed solution (DMF：THF=3:1) it, and stirs 24 hours.Obtained solution is transferred to the syringe of electrostatic spinning apparatus.With
20 kilovolts are spinning voltage, and it is 25 centimetres to receive distance, carries out electrostatic spinning.The flow velocity of solution is by syringe pump with 1mL H-1
It is controlled with constant rate of speed.Finally Electrospun nano-fibers film is formed in glass slide (1.0 1.7 centimetres of cm x).It is described quiet
Electrospun nano-fibers film (20 microns) is dried in vacuo 10 hours at 30 DEG C, to remove remaining organic solvent.
Embodiment 4
The preparation of electrostatic spinning P-PS films：Fluorescence sense polymer P (0.4 milligram) and PS (0.5 gram) are dissolved in 5 milliliters
Mixed solution (DMF：THF=3:1) it, and stirs 36 hours.Obtained solution is transferred to the syringe of electrostatic spinning apparatus.With
20 kilovolts are spinning voltage, and it is 25 centimetres to receive distance, carries out Electrospun.The flow velocity of solution is by syringe pump with 1mL H-1With
Constant rate of speed controls.Finally Electrospun nano-fibers film is formed in glass slide (1.0 1.7 centimetres of cm x).The electrostatic
Spinning nano fibrous membrane (20 microns) is dried in vacuo 12 hours at 30 DEG C, to remove remaining organic solvent.
Embodiment 5
The preparation of the double-deck electrostatic spinning film sensor：The nano fibrous membrane of the bilayer is by two continuous spinning process
Manufacture.
One layer of gelatin film is prepared by carrier of sheet glass first, gelatin (0.4 milligram) is dissolved in the mixed solution of 4mL
(2,2,2 tfifluoroethyl alcohol:THF=3:1) it, and stirs 24 hours.Obtained solution is transferred to the injection of electrostatic electric spinning device
Device.With 20 kilovolts for spinning voltage, it is 25 centimetres to receive distance, carries out electrostatic spinning.The flow velocity of solution by syringe pump with
1mLH-1It is controlled with constant rate of speed.Finally Electrospun nano-fibers film is formed in glass slide (1.0 1.7 centimetres of cm x).It connects
It is 30 seconds between time receiving, at the end, the thickness of the gelatin film is 20 microns.
Then, the glass slide that will be covered with one layer of gelatin film receives the film of P-PS as carrier, the film of P-PS
Preparation method is：Polymer P (0.4 milligram) and PS (0.4 gram) are dissolved in 4 milliliters of mixed solution (DMF：THF=3:1) it, and stirs
It mixes 24 hours.Obtained solution is transferred in the syringe of electrostatic spinning apparatus.With 20 kilovolts for spinning voltage, distance is received
It is 25 centimetres, carries out electrostatic spinning.The flow velocity of solution is by syringe pump with 1mL H-1It is controlled with constant rate of speed.Finally covering
There is the glass slide (1.0 1.7 centimetres of cm x) of gelatin film to form Electrospun nano-fibers film, receiving time is controlled at 1 point
Clock.
After the completion of spinning process, duplicature is dried in vacuo 10 hours at 25 DEG C, to remove remaining organic solvent.
Effect experiment is carried out using embodiment 1,3 and 5：
Fluorescence spectrum of 1 polymer P of experimental example in THF, film P-PS/GLE and P-PS film
In order to be best understood from influence of the electrostatic spinning film to polymer P.Give the THF solution (C of polymer PP=
1×10-3Grams per liter), the fluorescence spectrum of P-PS/GLE films and P-PS films.As shown in figure 3, the fluorescence of the P-PS/GLE and P-PS of film
The wavelength of emission peak is 444 nanometers and 447 nanometers, and the difference of the THF solution (442 nanometers) of both of which and the polymer P is not
Greatly.These statistics indicate that, polymer P has good dispersibility in PS matrix, and does not have strong π-π between polymer P
It stacks, it can be said that the big feature of bright electrospun fibers film porosity is conducive to prevent pi-pi accumulation.
The pattern of the double-deck static spinning membrane P-PS/GLE of experimental example 2
For the more vivid pattern for showing double-layer structure sensor, gelatin and P-PS films is set forth in the present invention
Form.As shown in figures 4 a and 4b.The diameter of gelatin fiber is concentrated mainly in the range of 20-35 microns (Fig. 4 a).Bright
It is one layer of P-PS Electrospun nano-fibers film on glued membrane.In this double-layer structure (Fig. 4 c), above one layer be polyphenyl second
The electrostatic spinning film of alkene doped polymer P, fiber bunchiness pearlitic texture (diameter of pearl is at 5 microns -15 microns) fiber
Diameter is distributed in 200 rans.It can find out from the diameter scatter diagram of Fig. 4 d, bottom is one layer of GLE, due to its gelatin
Fibre diameter is thicker and intensity is stronger so being used as sensor structure holder.In addition, GLE layers provide a large amount of poroid knot
Structure allows nitro-aromatic molecule to be spread above and below p-ps electrostatic spinning films.Obviously, these duplicatures of P-PS/GLE show to compare
The advantage of traditional electrostatic spinning film bigger, because conventional nanofibers film is to be in direct contact on the glass substrate and nitro
Aromatic hydrocarbons is only diffused into lower section only from above.For the sensing layer of same thickness, this double-layer structure can be accelerated to transmit DNT steams
Rate, therefore also solve the problems, such as that sensor thickness is far-reaching to rate is quenched to a certain extent.
The sensing capabilities of 3 duplicature P-PS/GLE of experimental example
In P-PS/GLE bilayers film sensors in the research of DNT sensing capabilities, sensor being placed on the saturated vapor of DNT
It is tested in pressure.As shown in Fig. 5 a~Fig. 5 b, the fluorescence intensity of sensor with the time for exposure in DNT steam extension
And reduce (Fig. 5 a and Fig. 5 b).As shown in Figure 5 c, the significant increase of quenching rate of two sensors in 5 minutes, then increases
Rate slowly increases reaches balance after 40 minutes.Traditional single layer P-PS sensors, duplicature are compared in 40 minutes
P-PS/GLE shows higher quenching efficiency.In figure 5d, the changes of the I0/I-1 of two layer transducer at any time in DNT gases
Change curve.As can be seen from the figure the value of sensor P-PS/GLE is greater than the value of traditional sensors P-PS.It can from result above
With find out sensor P-PS/GLE to the sensing capabilities of DNT want more stronger (I) that this is mainly made of following reason due to
Gelatin layer, which contains a large amount of amino and hydroxyl, can effectively be such that DNT molecules on the sensor surface, increase by hydrogen bond action enrichment
More touch opportunities between nitro-aromatic and sensor.(II) gelatin can be into one as the stephanoporate framework in the bottom of duplicature
Step improves the permeability of sensor.Therefore sensor P-PS/GLE shows higher quenching rate.
Selectivity of the experimental example 4P-PS/GLE films to nitro-aromatic
The quenching mechanism of conjugated polymer sensor is generally considered what electronics was determined for receptor mechanism, fluorophor
As electron donor, nitro-aromatic is transferred to nitro-aromatic as electron acceptor, electronics from fluorophor.In principle, this machine
System allows sensor in response to the electron-defect compound of several types.But fluorescent quenching is determined by many factors, such as
The binding constant (KB) of vapour pressure, reduction potential, and analyte can also influence sensing capabilities.
The different nitro explosive of four kinds of P-PS/GLE electrostatic spinning films pair has carried out sensing capabilities test, including DNP,
DNT, PA and TNT.Operating process is as follows：Two layer transducer is put into saturation nitro-aromatic steam at room temperature.After forty minutes
Measure its quenching rate.The results are shown in Figure 6, and four kinds of nitro-aromatic explosives of electrostatic spinning film pair have apparent different sudden
It goes out rate.The size order for quenching efficiency is DNT>DNP>TNT>PA.In 30 minutes, sensor reaches the quenching rate of DNT
70%, sensor is significantly larger than the quenching rate of DNT the quenching rate of other nitro-aromatics.Although DNT oxidation-reduction potential (-
1.0V) than TNT (- 0.7V) than it is small, but its saturated vapour pressure is 18 times of TNT, this may be have to DNT it is higher
One of the reason of quenching rate.DNT and DNP has similar vapour pressure, but compares DNP, and DNT still shows higher quenching
Rate.This may be since the hydroxyl of DNP exists so that DNP has lower reduction potential.PA has minimum quenching efficiency, and this can
It is attributed to the double action of hydroxyl：On the one hand being electric drive effect keeps the redox potential of PA smaller, is on the other hand point
Hydrogen bond action reduces the saturated vapour pressure of PA between son.
The invertibity that experimental example 5P-PS/GLE electrostatic films detect nitro-aromatic
Invertibity is an important parameter in the practical application of sensor.In being tested to reversibility test, DNT is selected
It selects as analyte, by checking DNT Molecular Detections the invertibity of Static Spinning film, as a result such as (Fig. 7).P-PS/GLE
Electrostatic spinning film is placed in DNT steams, when quenching thorough, is taken out sensor and is immersed in methanol solution 1 hour, to wash off
DNT steams are absorbed, it is then 2 hours dry in 30 DEG C of vacuum drying ovens.By above procedure, the fluorescence intensity of the film almost can be with
Restore.After repeating five cycles, the signal strength of electrostatic spinning film is not remarkably decreased, and it is good that this shows that the sensor has
Good invertibity.This conclusion is of great significance to the manufacture of sensor.
In above-mentioned research process, novel double-layer nanometer fiber film sensors have been synthesized simultaneously by electrostatic spinning technique
For testing Nitro-aromatic Compounds in Different, the P-PS layers on upper layer detect the gelatin of nitro-aromatic and bottom as master reference material
Skeleton has following multiple functions, to improve the sensing capabilities of the two layer transducer：I) gelatin have a large amount of amino and hydroxyl base
Group, nitro-aromatic is enriched with by hydrogen bonding interaction between nitro-aromatic and gelatin so that Nitro-aromatic Compounds in Different is poly-
Collection has the function that improve quenching rate in P-PS sensing layers.II), it is bright as in the stephanoporate framework below P-PS layers
Glue-line can allow nitro-aromatic molecule up and down while to be spread at P-PS layers, substantially improve P-PS layers of permeability.Therefore, it compares
It is shown to nitro-aromatic preferably sensing capabilities in the P-PS/GLE of single layer P-PS film two layer transducers.
Experimental example 6
Spin-coating film：In order to be compared, identical mixed liquor is spin-coated on glass slide, film is made.0.4 milligram of polymer P
It is dissolved in 4 milliliters of mixed solution (DMF with 0.4g polystyrene：THF=3:1) it, then stirs 24 hours.Use spinner KW-
The spin-coating film of (10 × 20 × 1 millimeter) is prepared on slide under 4A instruments and spin rate 2000rpm.The film is dried in vacuo.Use ring
The thickness of border scanning electron microscope (SEM) film is confirmed as 50 nanometers.
By experimental verification, spin-coating film effect is good not as good as the effect of static spinning membrane detection nitro-aromatic.
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not protects model to the present invention
The limitation enclosed, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not
Need to make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.
Claims (5)
1. a kind of application of bilayer electrostatic spinning film sensor in nitro-aromatic class analyte detection, it is characterized in that：The double-deck electrostatic
Spinning thin film sensor is made of double membrane structure, and bottom is gelatin electrostatic spinning film, this layer is placed on as skeleton
Glass sheet surface；For top layer using polystyrene as carrier, the progress of fluorescence sense polymer P is blended to be prepared into electrostatic spinning film,
The layer is sensing layer；
The preparation method of the gelatin electrostatic spinning film is：Mixing by Gelatin in 2,2,2 tfifluoroethyl alcohol and THF is molten
In liquid, obtained solution is carried out electrostatic spinning, is used for receiving the film of electrostatic spinning using sheet glass as carrier, obtains by stirring
The gelatin film of load on the glass sheet；
The fluorescence sense polymer P is fluorescent conjugated polymer, and structural formula is：
Wherein x:(0.1~2), y:(0.1~2), z:(0.1~2).
2. application as described in claim 1, it is characterized in that：Gelatin fiber in the gelatin electrostatic spinning film it is a diameter of
20~35 microns, the electrostatic spinning film be polystyrene doping fluorescent sensing polymer P electrostatic spinning film, fiber at
Beading structure, a diameter of 5~15 microns of the pearlitic texture, a diameter of 180nm~220nm of fiber.
3. application as described in claim 1, characterized in that the preparation method of the double-deck electrostatic spinning film sensor, including such as
Lower step：
(1) gelatin electrostatic spinning film is prepared：By Gelatin in the mixed solution of 2,2,2- trifluoroethanols and THF, stirring,
Obtained solution is subjected to electrostatic spinning, is used for receiving the film of electrostatic spinning using sheet glass as carrier, obtains and be supported on glass
The gelatin film of on piece；
(2) fluorescence sense polymer P and polystyrene are dissolved in DMF and THF mixed solutions, are stirred, the solution that will be obtained
Electrostatic spinning is carried out, is used for receiving the film of electrostatic spinning with the sheet glass of the covering gelatin film in step (1), after the completion of spinning,
It is dried to get the double-deck electrostatic spinning film sensor.
4. application as claimed in claim 3, characterized in that in step (1) and (2), the condition of the electrostatic spinning is：Receive
Distance is 20~30cm, and 15~25kV of voltage, the flow velocity of solution is by syringe pump with 1mL H-1Constant rate of speed controlled.
5. application as described in claim 1, characterized in that the preparation method of the fluorescence sense polymer P, including walk as follows
Suddenly：
Type of Collective object and 2 is supportted with 2,5- dibromo thiophenes, polyphenylacetylene, bis- bromo- 9,9- diphenylfluorenes of 7- are raw material, carry out polymerization system
Obtain the polymer of structural formula such as formula 1；Wherein, the structural formula such as formula 2 of the polyphenylacetylene support Type of Collective object：
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| CN108680543B (en) * | 2018-04-03 | 2020-12-08 | 齐鲁工业大学 | Method for detecting nitroaromatic explosives |
| CN108729025B (en) * | 2018-04-03 | 2020-02-11 | 齐鲁工业大学 | Fluorescence sensor based on amino modified polystyrene and preparation method thereof |
| CN110384990B (en) * | 2018-04-19 | 2021-01-12 | 北京化工大学 | Functionalized nanofiber three-dimensional mesh flexible sensing film and preparation method and application thereof |
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