CN105588824A - Application of double-layer electrostatic spun film sensor in detection of nitro-aromatic substances - Google Patents
Application of double-layer electrostatic spun film sensor in detection of nitro-aromatic substances Download PDFInfo
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- CN105588824A CN105588824A CN201610051304.XA CN201610051304A CN105588824A CN 105588824 A CN105588824 A CN 105588824A CN 201610051304 A CN201610051304 A CN 201610051304A CN 105588824 A CN105588824 A CN 105588824A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N2021/6417—Spectrofluorimetric devices
- G01N2021/6419—Excitation at two or more wavelengths
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
The invention discloses an application of a double-layer electrostatic spun film sensor in detection of nitro-aromatic substances. The sensor comprises a double-layer film structure, wherein the bottom layer is a gelatin electrostatic spun film (GEL) and is taken as a framework layer to be arranged on the surface of a glass sheet; the top layer adopts PS (polystyrene) as a carrier which is blended with a fluorescent sensing polymer P described in the claim 1, an electrostatic spun film PS-P is prepared, and the layer is a sensing layer. The application of the double-layer electrostatic spun film sensor has the advantages as follows: i) the gelatin contains a large quantities of amino groups and hydroxyl groups, nitro-aromatic compounds are enriched through hydrogen bond interaction between the nitro-aromatic compounds and the gelatin, so that the nitro-aromatic compounds are gathered on the PS-P sensing layer, and the quenching rate is increased; ii) as a porous framework below the PS-P layer, the GEL layer allows upper and lower simultaneous diffusion of nitro-aromatic molecules on the PS-P layer, and the permeability of the PS-P layer is improved greatly.
Description
Technical field
The present invention relates to the application of a kind of double-deck electrostatic spinning film sensor in nitro-aromatic class material detects.
Background technology
Nitro-aromatic is as TNT (TNT), 2, and 4-dinitrotoluene (DNT) (DNT), picric acid (PA) etc. is allImportant explosive composition, for explosive use and transport must strict control, otherwise not only have a strong impact on social stability,National security, simultaneously also because it has bio-toxicity and potential carcinogenesis works the mischief to human health. Therefore blastThe test problems of thing has caused showing great attention to of various countries, and a lot of countries have dropped into a large amount of funds and carried out scientific research. FluorescenceThat sensing method has is highly sensitive, can acquisition parameter (as fluorescence intensity, fluorescence spectrum pattern, fluorescence anisotropy, fluorescence lifetimeDeng) fast and Instrument Design of many, response time is relatively ripe etc., and feature becomes the detection method most with DEVELOPMENT PROSPECT.
Current fluorescent optical sensor is generally that fluorescent chemicals is prepared into film by the method for spin coating, forms fluorescence thinFilm sensors. In order to ensure that film has certain fluorescence intensity, polymer film must have certain thickness, and general thinCompact texture often make the diffusion of determinand in film slower, thereby response speed is slower. People adopt several different methods to improvePolymer architecture, the permeability of increase film, to increase the diffusion velocity of nitro-aromatic in film, improves quencher efficiency.
Electrostatic spinning technique is a kind of simple method of preparing nano material, can obtain the film material of high-permeabilityMaterial. Electrostatic spinning film has many merits: large specific area, high porosity, good penetrability and controllable form.These advantages are all conducive to being in contact with one another between analyte and probe. Prepare film-sensing material with electrostatic spinning technique in recent yearsMaterial is used in the detection of many kinds of substance gradually, as the detection of the detection of each metal ion species, nitro-aromatic, etc. CommonElectrostatic spinning film sensor be fluorescent sensing material to be formed to electrostatic spinning film on solid matrix surface. Detecting gasWhen determinand, gas molecule penetrates into film from the top of film, causes the change in fluorescence of sensing material.
At present, do not find double-deck electrostatic spinning film sensor material answering in nitro-aromatic class material detectsWith.
Summary of the invention
First the art of this patent has prepared one deck electrostatic spinning film with gelatin at glass surface, on the surface of this film again withSensing material has been prepared one deck electrostatic spinning film. This duplicature fluorescent optical sensor, compared with monofilm, has superior biographyPerception energy. Wherein the gelatin static spinning membrane of bottom can allow gas determinand can be simultaneously from the above and below of sensing layerPenetrate into simultaneously, improved sensing speed. On the other hand, gelatin molecule contains a large amount of electron rich such as hydroxyl, amino groups,Can produce hydrogen bond action with nitro-aromatic, thereby nitro-aromatic is had to enrichment, can improve the sensitivity of sensor. ToolBody:
The object of this invention is to provide a kind of double-deck electrostatic spinning film sensor nitro-aromatic class material detect inApplication.
The present invention is for achieving the above object and by the following technical solutions:
The application of a kind of double-deck electrostatic spinning film sensor in nitro-aromatic class material detects.
Nitro-aromatic class material is TNT (TNT), 2,4-dinitrotoluene (DNT) (DNT), picric acid (PA),2,4-DNP (DNP) or derivatives thereof.
Described double-deck electrostatic spinning film sensor is made up of double membrane structure, and its bottom is gelatin electrostatic spinning film(GEL), this layer is placed in glass sheet surface as casing play; Top layer, using polystyrene as carrier, enters with fluorescence sense polymer PRow blending is prepared into electrostatic spinning film (PS-P), and this layer is sensing layer.
Wherein, the fibre diameter in described gelatin electrostatic spinning film (GEL) is 20～35 microns, and described electrostatic spinning is thinFilm (PS-P) is the electrostatic spinning film of polystyrene doping fluorescent sensing polymer P, fiber bunchiness pearlitic texture, described beadingThe diameter of shape structure is 5～15 microns, and the diameter of fiber is 180nm～220nm, preferably 200nm.
Compared with independent PS-P electrostatic spinning film sensor, introduce gelatin electrostatic spinning layer GEL as casing play toolHave many advantages: I) the electron rich group that contains a large amount of amino and hydroxyl in gelatin molecule, can be by them and nitro virtueInteraction of hydrogen bond between hydrocarbon and effectively attract nitro-aromatic molecule, thus make nitro-aromatic molecule around sensing materialEnrichment, the sensitivity that improves sensor. II) gelatin static spinning membrane is porous, its allows nitro-aromatic molecule simultaneously from P-The above and below of PS thin layer enters simultaneously, has improved the permeability of P-PS sensing membrane; And common P-PS monofilm sensingDevice only allows nitro-aromatic molecule to penetrate into from top.
The double-deck electrostatic spinning film sensor of the present invention represents with PS-P/GEL. Fluorescence sense polymer P is wherein glimmeringLight conjugated polymer, described fluorescent conjugated polymer is preferably the copolymer based on poly-fluorenes ethynylene base polymer, but its guarantorThe scope of protecting is not only the copolymer based on poly-fluorenes ethynylene base polymer. More preferably above-mentioned fluorescence sense polymer P,Structural formula as shown in Equation 1, passes through experimental verification and analysis, the double-deck static that adopts above-mentioned fluorescence sense polymer P to prepareThe performance of spinning thin film sensor is more excellent.
Described fluorescence sense polymer P, its structural formula is suc as formula 1:
Wherein x:(0.1～2), y:(0.1～2), z:(0.1～2).
The preparation method of described fluorescence sense polymer P, comprises the steps: with 2,5-dibromo thiophene, polyphenylacetylene supportBase polymer and 2,7-bis-are bromo-9, and 9-diphenylfluorene is raw material, carry out polymerization and make structural formula suc as formula 1 polymer.
Concrete preparation method is as follows:
2,5-dibromo thiophene, polyphenylacetylene support base polymer and 2,7-bis-are bromo-9, and 9-diphenylfluorene is dissolved in anhydrous diisopropylAmine (DIPA) and dry toluene, under argon shield, add PdCl2(PPh3)2,PPh3And CuI, 90～110 DEG C of reaction 18～36h,Then purify and make fluorescence sense polymer P.
The structural formula of polyphenylacetylene support base polymer is suc as formula 2:
Wherein, described polyphenylacetylene support base polymer, 2,5-dibromo thiophene and 2,7-bis-are bromo-9,9-diphenylfluorene moleThan being 1:(1～4): (1～4), preferred molar ratio is 1:1:1. Through experimental verification and analysis, the fluorescence obtaining under this condition passesThe productive rate of sensitive polymeric P is higher.
Described anhydrous diisopropylamine (DIPA) and dry toluene dissolve raw material to be beneficial to reactant as solventReaction smoothly, its consumption is determined according to the consumption of raw material. Preferably, 2,5-dibromo thiophene, anhydrous diisopropylamine (DIPA) and nothingThe adding proportion of water-toluene is 1g:(5～15) ml:(100～200) ml, further preferred ratio is 1g:10ml:150ml.Through experimental verification and analysis, under this condition, be more conducive to react.
Described PdCl2(PPh3)2，PPh3Carry out catalytic reaction with CuI as catalyst, its consumption is according to the consumption of raw materialAnd determine. Preferably, 2,5-dibromo thiophene, PdCl2(PPh3)2、PPh3With the mass ratio of CuI be 1:0.1～0.2:1～1.5:0.1～0.3. Through experimental verification and analysis, under this condition, be more conducive to catalyst and carry out catalytic reaction.
Preferably, the time that passes into argon gas is 30 minutes, at 100 DEG C of back flow reaction 24h, and through experimental verification and analysis,This condition is the experiment parameter after optimizing, and the productive rate of the fluorescence sense polymer P obtaining is with this understanding higher.
In polyphenylacetylene support base polymer, introduce 9,9-diphenylfluorene unit, sterically hindered due to its rigidity, canWeaken π-π between skeleton stacking, improve the permeability of polymer. Introduce thiophene unit makes polymer have electron rich simultaneouslyProperty, can promote that the electronics between polymer and nitro-aromatic shifts, promote the generation of fluorescent quenching. Synthetic equation is as follows:
Adopt a preparation method of the electrostatic spinning film P-PS of described fluorescence sense polymer P, described fluorescence is passedSensitive polymeric P and polystyrene (PS) are dissolved in the mixed solution of DMF and THF, stir, and the solution obtaining is carried out to Static SpinningSilk, dry, obtain electrostatic spinning nano tunica fibrosa (electrostatic spinning film P-PS).
Wherein, the mass ratio of fluorescence sense polymer P and polystyrene (PS) is 1:1000～1500, is preferably 1:1000. Preferably stir 12～36h, more preferably 15h. The effect of the electrostatic spinning nano tunica fibrosa that described condition obtainsGood.
The condition of described electrostatic spinning is: spraying syringe needle diameter is 0.5-2mm, and accepting distance is 20～30cm, voltage 15～25kV, the flow velocity of solution by syringe pump with 1mLH-1Constant rate of speed control. Preferably accepting distance is 25cm, voltage20kV. Above-mentioned condition makes electrostatic spinning better effects if, obtains the electrostatic spinning nano tunica fibrosa of ideal effect, the static obtainingThe thickness of spinning P-PS film is 18～22 microns (preferably 20 microns).
The adding proportion of the mixed solution of described DMF and THF and polystyrene (PS) is 1ml:(0.05～0.2) g, preferablyRatio is 1ml:0.1g, and wherein the volume ratio of DMF:THF is 3:1.
Described drying condition is: 25～30 DEG C of dry 8～12h, preferably 10h, to remove residual organic solvent.
The preparation method of a kind of gelatin electrostatic spinning film (GEL), comprises the following steps:
Gelatin is dissolved in the mixed solution of 2,2,2-trifluoroethanol and THF, stirs, the solution obtaining is carried out to staticSpinning, dry, obtain gelatin electrostatic spinning film (GEL).
Wherein, preferably stir 18～36h, more preferably 24h. The effect of the gelatin film that described condition obtains is better.
The condition of described electrostatic spinning is: spraying syringe needle diameter is 0.5-2mm, and accepting distance is 20～30cm, voltage 15～25kV, the flow velocity of solution by syringe pump with 1mLH-1With constant rate of speed control. Preferably accepting distance is 25cm, voltage20kV. Above-mentioned condition makes electrostatic spinning better effects if, obtains the gelatin film of ideal effect, and the thickness of the gelatin film obtaining is 18～22 microns (preferably 20 microns).
Described 2,2, the volume ratio of the mixed solution of 2-trifluoroethanol and THF is 3:1.
Described drying condition is: 25～30 DEG C of dry 10h, and to remove residual organic solvent.
Electrostatic spinning in the present invention adopts electrostatic spinning instrument. Electrostatic spinning instrument mainly consists of the following components:Receiving system, liquid storaging device, high-voltage DC power supply and injection apparatus. The general maximum output voltage of power supply is at 30-100kVDC high-voltage power supply electric field is provided, solution storage device is generally used for storing the electrostatic spinning solution of melting, spray syringe needleDiameter is generally at 0.5-2mm, and syringe needle is connected with high voltage source, and the discharging modes of syringe needle generally can be divided into following two kinds:Vertical-type and horizontal type. Receiving system is generally metal roller or metal plate.
The method of testing of the fluorescent quenching rate of sensor:
First when measuring nitro-aromatic class material and not existing, the fluorescence intensity F0 of sensing material, then measures nitro-aromatic classThe fluorescence intensity F of sensing material when material exists, makes fluorescence intensity and the working curve of time, and draws out double-deck Static SpinningThe comparison diagram of silk thin film sensor to different nitro-aromatic class materials.
The method of concrete operations is: taking DNT as example, and the quencher efficiency of sensor in saturated nitro-aromatic class material steamMeasure according to following method: in cuvette, add 100 milligrams of DNT also to cover thereon with a filter paper, to prevent DNTAnd direct contact between sensor. Then cuvette is at room temperature shelved to 3 hours, so that it reaches gas balance. Then,This cuvette is placed in XRF, and sensor of the present invention is inserted in cuvette immediately, sensor is towards laserSource. Every 30 seconds test first order fluorescence spectrum.
The invention has the beneficial effects as follows:
(1) synthesized novel double-deck electrostatic spinning film sensor in the present invention by electrostatic spinning technique, for nitreThe detection of base aromatic compound. The P-PS layer on upper strata has fluorescence quenching to nitro-aromatic compound, is sensing materialLayer; The GEL layer of bottom is gelatin casing play, improves the sensing capabilities of this bilayer sensor: I by following several functions) brightGlue has a large amount of amino and oh group, produces interaction of hydrogen bond, thereby make nitro-aromatic in sensing between energy and gelatinNear enrichment device, can reduce detectability, improves response sensitivity. II) GEL layer is as the stephanoporate framework below P-PS layer,Can allow nitro-aromatic molecule to diffuse into from the above and below of P-PS layer simultaneously, thereby greatly improve the infiltration of P-PS layerProperty. Therefore, show nitro-aromatic sensing capabilities better than the P-PS/GLE of the double-deck sensor of individual layer P-PS film.
(2) fluorescent conjugated polymer described in the present invention is preferably copolymer based on poly-fluorenes ethynylene base polymer stillIts protection domain is not only the copolymer based on poly-fluorenes ethynylene base polymer. In polymer P of the present invention, thiophene monomer isElectron rich unit, its introducing can promote polymer and the intermolecular electronics of nitro-aromatic to shift effectively, thereby has improved poly-The fluorescent quenching efficiency of compound to nitro-aromatic; 9,9-diphenylfluorene is the three-D space structure of rigidity, can effectively prevent from gatheringThe accumulation of compound chain, prevents polymer fluorescent self-quenching, can also increase in addition the gas permeability of film, improves nitro-aromatic molecule and existsDiffusion rate in film, improves response sensitivity.
Brief description of the drawings
Fig. 1 is double-deck electrostatic spinning film sensor material schematic diagram.
Fig. 2 is electrostatic spinning process schematic diagram.
Fig. 3 is the THF solution of polymer P, the fluorescence of electrostatic spinning film P-PS, double-deck electrostatic spinning film P-GLE/PSSpectrogram (excitation wavelength is 390nm).
Fig. 4 a is the ESEM spectrogram of gelatin.
Fig. 4 b is the ESEM spectrogram of electrostatic spinning film P-PS.
Fig. 4 c is the ESEM spectrogram of double-deck static spinning membrane P-PS/GLE.
Fig. 4 d is the diameter distribution map of electrostatic spinning film P-PS.
Fig. 5 a is electrostatic spinning film P-PS fluorescence spectrum situation over time in DNT saturated vapor.
Fig. 5 b is the fluorescence spectrum over time feelings of double-deck static spinning membrane P-PS/GLE in DNT saturated vaporCondition.
Fig. 5 c be electrostatic spinning film P-PS and double-deck static spinning membrane P-PS/GLE quencher rate over time.
Fig. 5 d is the I of electrostatic spinning film P-PS and double-deck static spinning membrane P-PS/GEL0/ I-1 is in 40 minutesChange curve, wherein I0For the fluorescence intensity of P-PS/GEL in the time existing without DNT, I be P-PS/GEL in saturated DNT steam certainThe fluorescence intensity in one moment.
Fig. 6: double-deck electrostatic spinning film P-PS/GLE is to DNP, DNT, the temporal evolution song of the quencher rate of PA and TNTLine.
Fig. 7: the invertibity of double-deck electrostatic spinning film P-PS/GLE fluorescent quenching process.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is further described.
Reagent and instrument:
Embodiment 1
A synthetic method for fluorescence sense polymer P, comprises the following steps:
2,5-dibromo thiophene (200mg, 0.9mmol), polyphenylacetylene support base polymer (376mg, 0.9mmol) and 2,7-bis-Bromo-9,9-diphenylfluorene (426.6mg, 0.9mol) is dissolved in anhydrous diisopropylamine (DIPA, 2mL) and dry toluene (30mL), putsIn 50ml there-necked flask. pass into argon shield 30 minutes, add PdCl2(PPh3)2(36mg,2.6×10-2mmol),PPh3(270mg, 0.90mmol) and CuI (40.5mg, 0.3mmol). 100 DEG C of back flow reaction 24h. Then obtaining fluorescence according to purification passesSensor polymer P, structural formula is as shown in Chinese style 1 of the present invention.
Fluorescent optical sensor polymer P: buff solid (400mg, 69%).1HNMR:(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-1Calcdfor(C58H48S1Br2)n:C:82.72,S:2.55,H:6.419,N:0.049.GPC(THF):Mn＝4426,Mw＝7852,PDI＝1.7。
The synthetic method of 2 one kinds of fluorescence sense polymer Ps of embodiment, comprises the following steps:
2,5-dibromo thiophene (210mg), polyphenylacetylene support base polymer (378mg) and 2,7-bis-are bromo-9,9-diphenylfluorene(438mg) be dissolved in anhydrous diisopropylamine (DIPA, 2.5mL) and dry toluene (22mL), be placed in 50ml there-necked flask. pass into argonGas protection 40 minutes, adds PdCl2(PPh3)2(21mg),PPh3(252mg) and CuI (63mg). 90 DEG C of back flow reaction 36h. SoObtain fluorescent optical sensor polymer P 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 film: fluorescence sense polymer P (0.4 milligram) and PS (0.4 gram) are dissolved in 4 millilitersMixed solution (DMF:THF=3:1), and stir 24 hours. The solution obtaining is transferred to the syringe of electrostatic spinning apparatus. With20 kilovolts is spinning voltage, and accepting distance is 25 centimetres, carries out electrostatic spinning. The flow velocity of solution by syringe pump with 1mLH-1With constant rate of speed control. Finally form electrostatic spinning nano tunica fibrosa at glass slide (1.0 1.7 centimetres of cm x). Described quietElectrospun nano fibrous membrane (20 microns) is 30 DEG C of vacuum drying 10 hours, to remove residual organic solvent.
Embodiment 4
The preparation of electrostatic spinning P-PS film: fluorescence sense polymer P (0.4 milligram) and PS (0.5 gram) are dissolved in 5 millilitersMixed solution (DMF:THF=3:1), and stir 36 hours. The solution obtaining is transferred to the syringe of electrostatic spinning apparatus. With20 kilovolts is spinning voltage, and accepting distance is 25 centimetres, carries out Electrospun. The flow velocity of solution by syringe pump with 1mLH-1WithConstant rate of speed control. Finally form electrostatic spinning nano tunica fibrosa at glass slide (1.0 1.7 centimetres of cm x). Described staticSpinning nano fibrous membrane (20 microns) is 30 DEG C of vacuum drying 12 hours, to remove residual organic solvent.
Embodiment 5
The preparation of double-deck electrostatic spinning film sensor: this double-deck nano fibrous membrane is the spinning process continuous by twoManufacture.
First prepare one deck gelatin film taking sheet glass as carrier, gelatin (0.4 milligram) is dissolved in the mixed solution of 4mL(2,2,2-trifluoroethanol: THF=3:1), and stir 24 hours. The solution obtaining is transferred to the injection of static electric spinning deviceDevice. Taking 20 kilovolts as spinning voltage, accepting distance is 25 centimetres, carries out electrostatic spinning. The flow velocity of solution by syringe pump with1mLH-1With constant rate of speed control. Finally form electrostatic spinning nano tunica fibrosa at glass slide (1.0 1.7 centimetres of cm x). ConnectBetween the time receiving, be 30 seconds, in the time finishing, the thickness of this gelatin film is 20 microns.
Then, the glass slide that is coated with one deck gelatin film is received to the film of P-PS as carrier, the film of P-PSPreparation method is: polymer P (0.4 milligram) and PS (0.4 gram) are dissolved in 4 milliliters of mixed solutions (DMF:THF=3:1), and stirMix 24 hours. The solution obtaining is transferred in the syringe of electrostatic spinning apparatus. Taking 20 kilovolts as spinning voltage, receiving rangeBe 25 centimetres, carry out electrostatic spinning. The flow velocity of solution by syringe pump with 1mLH-1With constant rate of speed control. Finally coveringHave the glass slide (1.0 1.7 centimetres of cm x) of gelatin film to form electrostatic spinning nano tunica fibrosa, time of reception is controlled at 1 pointClock.
After spinning process completes, duplicature vacuum drying 10 hours at 25 DEG C, to remove residual organic solvent.
Adopt embodiment 1,3 and 5 to carry out effect experiment:
Experimental example 1 polymer P is at THF, the fluorescence spectrum in film P-PS/GLE and P-PS film
In order to understand better the impact of electrostatic spinning film on polymer P. Provide the THF solution (C of polymer PP＝1×10-3Grams per liter), the fluorescence spectrum of P-PS/GLE film and P-PS film. As shown in Figure 3, the P-PS/GLE of film and the fluorescence of P-PSThe wavelength of emission peak is 444 nanometers and 447 nanometers, the two all with the difference of the THF solution (442 nanometer) of this polymer P notGreatly. These data show, polymer P has good dispersiveness in PS matrix, and between polymer P, there is no strong π-πStacking, therefore can illustrate that the large feature of 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 more vivid represent double-decker sensor pattern, the present invention has provided respectively gelatin and P-PS filmForm. As shown in Fig. 4 a and Fig. 4 b. The diameter of gelatin fiber mainly concentrates on 20-35 micron (in Fig. 4 scope a). BrightIt on glued membrane, is one deck P-PS electrostatic spinning nano tunica fibrosa. This double-decker (Fig. 4 c) in, above one deck be polyphenyl secondThe electrostatic spinning film of alkene doped polymer P, fiber bunchiness pearlitic texture (diameter of pearl is at 5 microns-15 microns) fiberDiameter is distributed in 200 nanometer left and right. Can from the diameter scatter diagram of Fig. 4 d, find out, bottom is one deck GLE, due to its gelatinSo fibre diameter is thicker and intensity is used as more by force sensor construction support. In addition, GLE layer provides a large amount of poroid knotsStructure, allows nitro-aromatic molecule to spread up and down at p-ps electrostatic spinning film. Obviously, these duplicatures of P-PS/GLE show ratioThe advantage that traditional electrostatic spinning film is larger, because traditional nano-fiber film is to be in direct contact with on glass substrate and nitroAromatic hydrocarbons is only diffused into below from top. For the sensing layer of same thickness, this double-decker can accelerate to transmit DNT steamSpeed, therefore also solved to a certain extent sensor thickness to the far-reaching problem of cancellation rate.
The sensing capabilities of experimental example 3 duplicature P-PS/GLE
P-PS/GLE duplicature sensor to the research of DNT sensing capabilities in, sensor is placed on to the saturated vapor of DNTIn pressure, test. As shown in Fig. 5 a～Fig. 5 b, the fluorescence intensity of sensor is along with the prolongation of time for exposure in DNT steamAnd reduce, (Fig. 5 a and Fig. 5 are b). As shown in Figure 5 c, in 5 minutes two sensors quencher rate showing and increasing, then increaseSpeed slowly increases until reach balance after 40 minutes. In 40 minutes, compare traditional individual layer P-PS sensor, duplicatureP-PS/GLE shows higher quencher efficiency. In Fig. 5 d, the I0/I-1 of double-deck sensor change in time in DNT gasChange 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. Can from above resultWith find out sensor P-PS/GLE to the sensing capabilities of DNT will be stronger this mainly by following reason form (I) due toGelatin layer contains a large amount of amino and hydroxyl can effectively make DNT molecule be enriched on sensor surface by hydrogen bond action, increasesTouch opportunity between many nitro-aromatics and sensor. (II) gelatin can enter one as the stephanoporate framework of the bottom at duplicatureStep improves the permeability of sensor. Therefore sensor P-PS/GLE shows higher quencher rate.
Experimental example 4P-PS/GLE film is selective to nitro-aromatic
The quenching mechanism of conjugated polymer sensor is generally considered electronics and supplies receptor mechanism to determine, fluorophorAs electron donor, nitro-aromatic is as electron acceptor, and electronics is transferred to nitro-aromatic from fluorophor. In principle, this machineSystem allows the electron-defect compound of sensor in response to several types. But fluorescent quenching is to be determined by many factors, asVapour pressure, reduction potential, and also the binding constant of analyte (KB) also can affect sensing capabilities.
P-PS/GLE electrostatic spinning film has carried out sensing capabilities test to four kinds of different nitro explosives, comprises DNP,DNT, PA and TNT. Operating process is as follows: at room temperature double-deck sensor is put into saturated nitro-aromatic steam. After 40 minutesRecord its quencher rate. As shown in Figure 6, electrostatic spinning film has significantly different sudden result to four kinds of nitro-aromatic explosivesThe rate of going out. The size order of quencher efficiency is DNT > DNP > TNT > PA. In 30 minutes, sensor reaches the quencher rate of DNT70%, sensor will be much larger than the quencher rate of other nitro-aromatic to the quencher rate of DNT. Although the oxidation-reduction potential of DNT (1.0V) little than TNT (0.7V), but its saturated vapour pressure is TNT 18 times, this may have DNT higherOne of reason of quencher rate. DNT has similar vapour pressure with DNP, but compares DNP, and DNT still demonstrates higher quencherRate. This may be because the hydroxyl of DNP exists, and makes DNP have lower reduction potential. PA has minimum quencher efficiency, and this canDouble action owing to hydroxyl: be on the one hand that electric drive effect makes the redox potential of PA less, be on the other hand pointBetween son, hydrogen bond action reduces the saturated vapour pressure of PA.
The invertibity that experimental example 5P-PS/GLE electrostatic film detects nitro-aromatic
In the practical application of sensor, invertibity is an important parameter. In to invertibity test experiments, DNT is selectedSelect as analyte, by DNT Molecular Detection being checked to the invertibity of Static Spinning film, result is as (Fig. 7). P-PS/GLEElectrostatic spinning film is placed in DNT steam, in the time that quencher is thorough, takes out sensor and is immersed in methanol solution 1 hour, to wash offAbsorb DNT steam, then in 30 DEG C of vacuum drying ovens, be dried 2 hours. By above process, the fluorescence intensity of this film almost canRecover. Repeat after five circulations, the signal strength signal intensity of electrostatic spinning film is not decreased significantly, and this shows, this sensor has goodGood invertibity. This conclusion is significant to the manufacture of sensor.
In above-mentioned research process, synthesize novel double-layer nanometer tunica fibrosa sensor also by electrostatic spinning techniqueBe used for testing Nitro-aromatic Compounds in Different, the P-PS layer on upper strata detects nitro-aromatic and the gelatin of bottom as master reference materialSkeleton has following several functions, improves the sensing capabilities of this bilayer sensor: I) gelatin has a large amount of amino and hydroxyl baseGroup, between nitro-aromatic and gelatin, carry out enrichment nitro-aromatic by interaction of hydrogen bond power, make Nitro-aromatic Compounds in Different poly-Thereby collection reaches the effect that improves quencher rate at P-PS sensing layer. II), it is as in the stephanoporate framework below P-PS layer, brightGlue-line can allow nitro-aromatic molecule in the diffusion simultaneously up and down of P-PS layer, greatly improves the permeability of P-PS layer. Therefore, compareP-PS/GLE in the double-deck sensor of individual layer P-PS film shows nitro-aromatic sensing capabilities better.
Experimental example 6
Spin-coating film: in order comparing, identical mixed liquor to be spin-coated on and to make film on slide. 0.4 milligram of polymer PBe dissolved in 4 milliliters of mixed solutions (DMF:THF=3:1) with 0.4g polystyrene, then stir 24 hours. Use spinner KW-Under 4A instrument and spin rate 2000rpm, prepare the spin-coating film of (10 × 20 × 1 millimeter) on slide. This film vacuum drying. With ringThe thickness of border SEM (SEM) film is confirmed as 50 nanometers.
Through experimental verification, spin-coating film effect is effective not as static spinning membrane detection nitro-aromatic.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned, not the present invention is protected to modelThe restriction of enclosing, one of ordinary skill in the art should be understood that, on the basis of technical scheme of the present invention, those skilled in the art are notNeed to pay various amendments that creative work can make or distortion still in protection scope of the present invention.
Claims (10)
1. the double-deck electrostatic spinning film sensor application in nitro-aromatic class material detects.
2. application as claimed in claim 1, is characterized in that: described double-deck electrostatic spinning film sensor is by double membrane structureComposition, its bottom is gelatin electrostatic spinning film (GEL), this layer is placed in glass sheet surface as casing play; Top layer is with polyphenyl secondAlkene is as carrier, and fluorescence sense polymer P carries out blending and is prepared into electrostatic spinning film (PS-P), and this layer is sensing layer.
3. application as claimed in claim 2, is characterized in that: the gelatin fiber in described gelatin electrostatic spinning film (GEL)Diameter is 20～35 microns, and described electrostatic spinning film (PS-P) is the Static Spinning of polystyrene doping fluorescent sensing polymer PSilk film, fiber bunchiness pearlitic texture, the diameter of described pearlitic texture is 5～15 microns, the diameter of fiber be 180nm～220nm。
4. application as claimed in claim 1, is characterized in that, the preparation method of double-deck electrostatic spinning film sensor, comprise asLower step:
(1) prepare gelatin electrostatic spinning film: gelatin is dissolved in the mixed solution of 2,2,2-trifluoroethanol and THF, stirs,The solution obtaining is carried out to electrostatic spinning, be used for receiving the film of electrostatic spinning taking sheet glass as carrier, make and load on glassGelatin film on sheet;
(2) fluorescence sense polymer P and polystyrene (PS) are dissolved in DMF and THF mixed solution, stir, by what obtainSolution carries out electrostatic spinning, is used for receiving the film of electrostatic spinning with the sheet glass of the covering gelatin film in step (1), and spinning completesAfter, be dried, obtain double-deck electrostatic spinning film sensor.
5. application as claimed in claim 4, is characterized in that, in step (1) and (2), the condition of described electrostatic spinning is: acceptDistance be 20～30cm, voltage 15～25kV, the flow velocity of solution by syringe pump with 1mLH-1Constant rate of speed control.
6. application as claimed in claim 2 or claim 3, is characterized in that, described fluorescence sense polymer P is fluorescent conjugated polymer.
7. application as claimed in claim 6, is characterized in that, the structural formula of described fluorescence sense polymer P is suc as formula 1:
Wherein x:(0.1～2), y:(0.1～2), z:(0.1～2).
8. application as claimed in claim 7, is characterized in that, the preparation method of described fluorescence sense polymer P comprises following stepRapid:
Bromo-9 with 2,5-dibromo thiophene, polyphenylacetylene support base polymer and 2,7-bis-, 9-diphenylfluorene is raw material, carry out polymerization systemStructural formula suc as formula 1 polymer; Wherein, the structural formula of described polyphenylacetylene support base polymer is suc as formula 2:
9. application as claimed in claim 1, is characterized in that: nitro-aromatic class material is TNT (TNT), 2,4-dinitrotoluene (DNT) (DNT), picric acid (PA), 2,4-DNP (DNP) or derivatives thereof.
10. application as claimed in claim 1, is characterized in that, the method that sensor detects nitro-aromatic class material is:
First when measuring nitro-aromatic class material and not existing, the fluorescence intensity F0 of sensing material, then measures nitro-aromatic class materialThe fluorescence intensity F of sensing material while existence, make fluorescence intensity and the working curve of time, and it is thin to draw out double-deck electrostatic spinningThe comparison diagram of film sensors to different nitro-aromatic class materials.
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