CN103940794A - Symtriazine biochemical modified glass surface sensor, manufacturing method and application of sensor - Google Patents
Symtriazine biochemical modified glass surface sensor, manufacturing method and application of sensor Download PDFInfo
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Abstract
The invention relates to a symtriazine biochemical modified glass surface sensor, a manufacturing method of the sensor and application of the sensor in detection of nitro-aromatics. The preparation method of the sensor comprises the following steps: hydroxylating and silanizing a glass sheet, soaking the processed glass sheet in a methylbenzene solution containing symtriazine derivatives and sodium hydride, reacting for 5-20 hours at the temperature of 30-80 DEG C, taking the glass sheet out of the methylbenzene solution, ultrasonically washing the glass sheet in ethanol and tetrahydrofuran to remove the symtriazine derivatives which are adsorbed on the glass sheet. The symtriazine derivatives are bonded on the surface of the glass sheet through a plurality of sites of a molecule, so that the molecule surface is parallel to the surface of the glass sheet. Compared with a comb-grafting monomolecular film, the sensor has the advantages that a flat grafting manner is capable of greatly reducing the probability of forming Pi-Pi accumulation on the side surface between fluorophores. The symtriazine biochemical modified glass surface sensor is applicable to a fluorescence sensor, excellent in quenching response reversibility and high in response speed.
Description
Technical field
The present invention relates to a kind of Striazine derivative chemical modification glass surface sensor, be particularly related to Striazine derivative chemical modification glass surface sensor and preparation method thereof and the application in nitro-aromatic detects, belong to sensor preparation and fluorescent sensing material technical field.
Background technology
Nitro-aromatic compound (NACs), as TNT (TNT), 2,4-dinitrotoluene (DNT) (DNT) etc., are the Main Ingredients and Appearances of various explosives.Realization to nitro-aromatic fast, Sensitive Detection to the safety detection of public place, industrial process control, environmental monitoring etc., all have great importance.At present, adopt X-ray diffractometer, ion mobility spectrometries etc. with airport majority at the train station.Yet these detecting devices are expensive and heavier, are not easy to be prepared into portable detector and detect in real time for scene.
In recent years, fluorescent optical sensor, having demonstrated the superiority such as highly sensitive, simple to operate, with low cost aspect the micro-trace explosive of detection, has caused people's research interest.Conventional sensing material is various conjugated compounds, as palycyclic aromatic, conjugated polymer etc.People generally prepare thin film sensor by the alloy of sensing material solution or itself and certain polymer substrate by the method for spin coating.Yet, spin-coating film have following several respects drawbacks limit its application: 1) conjugated compound easily forms pi-pi accumulation in film, causes Fluorescence self-quenching phenomenon; 2) because spin-coating film has certain thickness, this regular hour that just means nitro-aromatic needs spreads in film, makes inner sensor molecules fluorescent quenching, so response speed is slow, fluorescent quenching rate is low; 3) because sensing material and substrate surface have chemical bond, be not connected, easily cause the loss of sensing material, reduced the serviceable life of thin film sensor.In order to overcome the shortcoming of above spin-coating film sensor, people start fluorescence sense molecule to graft on solid matrix surface by a certain functional group reactions, form the unimolecular film fluorescent optical sensor of pectination.Yet in the unimolecular film structure of this pectination, fluorophor is all positioned at the end of flexible grafted chain, between fluorophore, easily mutually near pi-pi accumulation from the side, produces Fluorescence self-quenching and cause fluorescence intensity to reduce.Therefore, develop the sensitive fluorescent sensing material of response and novel graft reaction mode, for obtaining, the good unimolecular film fluorescent optical sensor of optical property and sensing capabilities is significant.
Summary of the invention
The object of the invention is to overcome above-mentioned deficiency, a kind of Striazine derivative chemical modification glass surface sensor and preparation method thereof is provided.
Another object of the present invention is to provide the application of this kind of sensor in DNT detects.
The technical scheme that the present invention takes is:
A preparation method for Striazine derivative chemical modification glass surface sensor, comprises that step is as follows:
(1) hydroxylation of glass sheet is processed
Glass sheet is removed to surperficial organic impurities at 400～600 ℃ of calcining 2～6h, then clean with ultrapure water, the mixed liquor of then putting into the concentrated sulphuric acid and hydrogen peroxide soaks, and with a large amount of distilled water, cleans glass sheet, and the glass sheet after cleaning is at dustless drying box inner drying;
(2) silanization of glass sheet is processed
Hydroxylated glass sheet is immersed in the mixed liquor of toluene and 3-chloropropyl triethoxysilane (CPTS), 30～80 ℃ are soaked 5～20 hours, after cool to room temperature, with ethanol, clean, remove unnecessary toluene and 3-chloropropyl triethoxysilane, be immersed in ethanol, preserve stand-by;
(3) Striazine derivative is in the grafting of glass sheet surface
Getting Striazine derivative is dissolved in toluene, and add sodium hydride, after stirring, the glass sheet that silanization is processed is soaked in above-mentioned solution, in 30～80 ℃ of reactions 5～20 hours, with the reacted glass sheet of alcohol flushing, put into respectively the ultrasonic concussion of ethanol and tetrahydrofuran and remove the Striazine derivative of physisorption on glass sheet and get final product.
Glass sheet after grafting is kept in ethanol stand-by.
Above-mentioned Striazine derivative (Compound I I), structural formula is as follows:
The described immersion of above-mentioned steps (1) is 50～150 ℃ of immersions in the mixed liquor the concentrated sulphuric acid and hydrogen peroxide (30%) volume ratio are 7:3 1 hour.Described is dried as 100 ℃ of dry 1h in dustless drying box.
In the mixed liquor of the middle toluene of above-mentioned steps (2) and 3-chloropropyl triethoxysilane, the volume ratio of toluene and 3-chloropropyl triethoxysilane is 10:1.
In above-mentioned steps (3), the mass ratio of Striazine derivative and sodium hydride is 1:10～40, and the consumption of toluene is every gram of Striazine derivative 500-5000ml.
Sensor prepared by said method.Syntheti c route is shown in Fig. 1.Fig. 2 is shown in by the 3D model of sensor, the application of described sensor in DNT detects.
Sensor of the present invention uses take three compounds that s-triazine is core, OH by three side chain terminal reacts with the Cl on silanization back glass sheet surface, make this derivative molecular be bonded to glass substrate surface and planes of molecules is parallel to glass surface, thereby prepared a kind of novel monomolecular film sensor, for the detection of nitro-aromatic.The present invention proposes a kind of novel grafting method that fluorophor is grafted on to glass sheet surface, thereby a plurality of sites that are about to molecule are bonded in glass sheet surface and make planes of molecules be parallel to glass sheet surface.Compare with the unimolecular film of pectination grafting, the mode of this calm grafting can reduce the probability that forms from the side pi-pi accumulation between fluorophore widely.In concentration, be 2 * 10
-5with 2 * 10
-3in the tetrahydrofuran solution of the DNT of mol/L, the cancellation rate of this sensor has reached respectively 68.7% and 89.3%.Even if this sensor is reused after 10 times, fluorescence intensity still can return to 77.4% of initial fluorescence intensity, this means that the cancellation process of this sensor has good reversibility.In saturated DNT steam, sensor can reach cancellation balance (cancellation balance 95%) moment.And the current common thin film sensor of being prepared by spin-coating method needs the regular hour just can reach cancellation balance conventionally.Visible, the unimolecular film sensor that grafts on glass surface prepared by the present invention is compared with common spin-coated thin film sensor, has significant advantage in response speed.
Accompanying drawing explanation
The syntheti c route of Fig. 1 sensor.
Fig. 2 grafts on the three-dimensional model (lateral plan) of glass sheet surface Striazine derivative.
Fig. 3 is the ultraviolet-visible absorption spectroscopy of the glass sheet of the compounds of this invention grafting and the THF solvent that soaked thereof.
Fig. 4 is (a) and with the water contact angle of (b) after Striazine derivative grafting after glass surface hydroxylation.
Fig. 5 is that glass sheet sensor is at the XPS spectrum figure of the different phase of preparation process.
Fig. 6 is the fluorescence spectrum of Striazine derivative in the tetrahydrofuran solution of different DNT concentration.
Fig. 7 is the glass sheet sensor of the Striazine derivative grafting fluorescence spectrum in the tetrahydrofuran solution of different DNT concentration
Fig. 8 is the cancellation reversibility of heat conduction process (C of the glass sheet of Striazine derivative grafting to DNT
dNT=2 * 10
-3mol/L).
Fig. 9 glass sheet sensor is in the Kinetics of Dynamic Quenching research to gas phase DNT.
The quencher rate of the glass sheet sensor of Figure 10 nitro-aromatic grafting to various electron acceptor compounds.
Embodiment
Below in conjunction with embodiment, further illustrate.
The synthetic of 2,4,6-trimethyl s-triazine is according to the method for document [H.G.Elias, E.Greth, Makromol.Chem.1969 (123) 203-208.] report, also can be commercial.4-Fluorobenzaldehyde, chloropropyl triethoxysilane (CPTS), 2-ethylaminoethanol and cetyl trimethyl ammonium bromide (CTAB) are all purchased from Tianjin Ke Miou reagent company limited, without being further purified.The solvent that optic test is used is all process distillations before super-dry and use substantially.
The test of 1HNMR spectrogram is recorded by the German Bruker AVANCE of company II 400 type nuclear magnetic resonance spectrometers.Ultra-violet absorption spectrum is to record with UV-2550PC spectrophotometer.(1486.6eV) that the ESCALAB250 spectrometer of test Shi You Thermo Fischer Scient Inc. of XPS spectrum figure records under Al K α line.The test of contact angle is measured by DSA100 contact angle instrument.Ultimate analysis is to be completed by Vario EL III elemental analyser.
The fluorometric investigation of Striazine derivative and functional glass sheet thereof records by the F-4500 of Hitachi type fluorospectrophotometer.Cancellation dynamics research in the aerial fluorescence spectrum of this detecting device and DNT steam is completed by Edinburg FLS920 fluorescence spectrophotometer.During detection, glass sheet is inserted in fluorescence pond along diagonal line, and glass sheet and incident light are 45 ° of angles.
The preparation of Striazine derivative:
(1) 4-(N-ethyl-N hydroxyethyl) aminobenzaldehyde (I) is synthetic:
1:1.0～3.0:0.001～0.1:5～20 take 4-Fluorobenzaldehyde, 2-(ethylamino-in mass ratio) ethanol, cetyl trimethyl ammonium bromide (CTAB), K
2cO
3then be dissolved in DMSO, magnetic agitation 15～30h in 80～120 ℃ of oil baths, then mixed liquor is poured in distilled water, use again dichloromethane extraction 1～3 time, merge organic layer and with after anhydrous magnesium sulfate drying, with Rotary Evaporators, remove desolventizing, by gained silica gel chromatography (ethyl acetate: sherwood oil=1:5～1:10), obtain yellow oily Compound I for residue; Described DMSO consumption is every gram of K
2cO
3with 10 milliliters, the volume ratio of DMSO and distilled water, methylene chloride is 1:1～5:1～5.
1H?NMR(CDCl3,400MHz)：δ(ppm)1.18(t,3H,J=6.8Hz),3.54(t,2H,J=5.6Hz),3.51-3.46(m,2H,J=7.2Hz),3.81(t,2H,J=5.6Hz),4.28(t,1H),6.71(d,2H,J=8.4Hz),7.62(d,2H,J=8.4Hz),9.60(s,1H).Calcd?for?C
11H
15NO
2:C,68.37;H,7.82;N,7.25;O:16.56.Found:C,67.82;H,7.61;N,7.18;O,17.39.
(2) 2,4,6-tri-[4-(N-ethyl-N-2-hydroxyethyl) styryl] s-triazine (II) synthetic
By 2,4,6-trimethyl s-triazine and KOH join in alcohol solvent, at 60～110 ℃, stir after 30min, slowly drip again the ethanolic solution of Compound I, after adding, at 60～110 ℃, continue reaction 15～30 hours, with Rotary Evaporators, remove desolventizing, by gained for residue silica gel chromatography (ethyl acetate: sherwood oil=1:5～1:10, obtains Compound I I; The mass ratio of 2,4,6-trimethyl s-triazine, KOH and Compound I is 1:1.0～3.0:2.0～10.0.
Described alcohol solvent consumption is every gram 2,4, and 6-trimethyl s-triazine adds 50～150 milliliters.The ethanolic solution concentration of Compound I is 0.05g/ml.
1H?NMR(CDCl
3,400MHz)：δ（ppm）1.10（t,9H,J=7.2Hz）,3.45-3.40（m,6H,J=7.6Hz）,3.55（t,6H,J=5.6Hz）,4.74(t,6H,J=5.2Hz),6.73（d,6H,J=8.4Hz）,6.82（d,3H,J=15.6Hz）,7.58（d,3H,J=8.8Hz），8.06(d,6H,J=16Hz).Calcd?for?C
39H
48N
6O
3:C,72.19;H,7.46;N,12.95;O:7.40.Found:C,71.39;H,7.61;N,13.07;O,7.93.
Embodiment 1
The preparation method of Striazine derivative chemical modification glass surface sensor:
(1) hydroxylation of glass sheet is processed
Glass sheet (1.35cm * 2cm * 0.1) is removed to surperficial organic impurities at 500 ℃ of calcining 3h, then clean with ultrapure water.Then put into the concentrated sulphuric acid (V): hydrogen peroxide (30%) (V)=mixed liquor of 7:3,98 ℃ are soaked 1 hour.With a large amount of distilled water, clean glass sheet, the glass sheet after cleaning is dried 1h in dustless drying box at 100 ℃.
(2) silanization of glass sheet is processed
Hydroxylated glass sheet is immersed in the mixed liquor of 10ml toluene and 1ml3-chloropropyl triethoxysilane, at 50 ℃, soak 12 hours, after cool to room temperature, with a large amount of ethanol, clean, remove unnecessary toluene and 3-chloropropyl triethoxysilane, be immersed in ethanol, preserve stand-by.
(3) Striazine derivative is in the grafting of glass sheet surface
Get Striazine derivative 0.01g, be dissolved in 30ml toluene, and add sodium hydride 0.3g.After stirring, the glass sheet of silanization is soaked in above-mentioned solution.At 30 ℃, react after 5 hours, with alcohol flushing, then put into respectively each ultrasonic concussion 0.5h of 20ml ethanol and 20ml tetrahydrofuran, remove the Striazine derivative of physisorption on glass sheet.Glass sheet after grafting is kept in ethanol to be measured.
Embodiment 2
The preparation method of Striazine derivative chemical modification glass surface sensor:
(1) hydroxylation of glass sheet is processed
Glass sheet (1.35cm * 2cm * 0.1) is removed to surperficial organic impurities at 400 ℃ of calcining 6h, then clean with ultrapure water.Then put into the concentrated sulphuric acid (V): hydrogen peroxide (30%) (V)=mixed liquor of 7:3,60 ℃ are soaked 1 hour.With a large amount of distilled water, clean glass sheet, the glass sheet after cleaning is dried 1h in dustless drying box at 100 ℃.
(2) silanization of glass sheet is processed
Hydroxylated glass sheet is immersed in the mixed liquor of 20ml toluene and 2ml3-chloropropyl triethoxysilane, at 80 ℃, soak 6 hours, after cool to room temperature, with a large amount of ethanol, clean, remove unnecessary toluene and 3-chloropropyl triethoxysilane, be immersed in ethanol, preserve stand-by.
(3) Striazine derivative is in the grafting of glass sheet surface
Get Striazine derivative 0.005g, be dissolved in 20ml toluene, and add sodium hydride 0.1g.After stirring, the glass sheet of silanization is soaked in above-mentioned solution.At 80 ℃, react after 20 hours, with alcohol flushing, then put into respectively each ultrasonic concussion 0.5h of 20ml ethanol and 20ml tetrahydrofuran, remove the Striazine derivative of physisorption on glass sheet.Glass sheet after grafting is kept in ethanol to be measured.
Embodiment 3
The preparation method of Striazine derivative chemical modification glass surface sensor:
(1) hydroxylation of glass sheet is processed
Glass sheet (1.35cm * 2cm * 0.1) is removed to surperficial organic impurities at 600 ℃ of calcining 4h, then clean with ultrapure water.Then put into the concentrated sulphuric acid (V): hydrogen peroxide (30%) (V)=mixed liquor of 7:3,150 ℃ are soaked 1 hour.With a large amount of distilled water, clean glass sheet, the glass sheet after cleaning is dried 1h in dustless drying box at 100 ℃.
(2) silanization of glass sheet is processed
Hydroxylated glass sheet is immersed in the mixed liquor of 5ml toluene and 0.5ml3-chloropropyl triethoxysilane, at 30 ℃, soak 20 hours, after cool to room temperature, with a large amount of ethanol, clean, remove unnecessary toluene and 3-chloropropyl triethoxysilane, be immersed in ethanol, preserve stand-by.
(3) Striazine derivative is in the grafting of glass sheet surface
Get Striazine derivative 0.002g, be dissolved in 10ml toluene, and add sodium hydride 0.02g.After stirring, the glass sheet of silanization is soaked in above-mentioned solution.At 50 ℃, react after 10 hours, with alcohol flushing, then put into respectively each ultrasonic concussion 0.5h of 20ml ethanol and 20ml tetrahydrofuran, remove the Striazine derivative of physisorption on glass sheet.Glass sheet after grafting is kept in ethanol to be measured.
Performance test
(1) test of ultraviolet spectrum:
Glass sheet sensor after Compound I I grafting is soaked in the THF of 10ml, places after 6h, respectively the ultraviolet-visible absorption spectroscopy of tested glass sheet sensor and the THF that soaked thereof.Result as shown in Figure 3.Can find out, glass sheet sensor has absorption peak at 420nm place, is the absorption peak of Compound I I; And THF solvent does not have absorption peak in the above scope of 325nm, the Compound I I not being dissolved down from glass sheet in solvent is described.This experimental result has confirmed Compound I I, and chemical graft is in glass sheet surface, and glass surface does not exist the Compound I I molecule of physisorption.
(2) test of water contact angle:
The water contact angle of Striazine derivative grafting glass sheet is measured by DSA100 contact angle measurement.Fig. 4 is (a) and with the water contact angle of the glass surface of (b) after Striazine derivative functionalization after glass surface hydroxylation.After hydroxylation is processed, glass sheet surface hydroxyl quantity increases greatly, and the water wettability on surface strengthens, so water contact angle less (27.1 ± 0.2 °).Striazine derivative is grafted on after glass sheet surface, and the hydrophobicity on surface strengthens greatly, so water contact angle enlarges markedly (88.2 ± 0.2 °).This variation of water contact angle has confirmed the successful grafting of Striazine derivative on glass surface.
(3) photoelectron spectroscopy test:
Striazine derivative is grafted in glass sheet surface, and the photoelectron spectroscopy of this glass sheet surface (XPS) is schemed as shown in Figure 5.Can find out, the glass sheet (GS-OH) after the glass sheet (GS-Cl) of modifying with chloropropyl siloxane (CPTS) is processed with hydroxylation is compared, and at 199.75ev place, has occurred Cl2p peak.With the glass sheet after Compound I I grafting, at 400.18ev place, occurred the new peak of N1s, and Cl2p peak intensity greatly reduces.This is that Compound I I successfully grafts on a positive evidence in glass sheet surface.。
(4) Striazine derivative is in the mensuration of the grafting density of glass surface:
The density measure of the fluorophor on Striazine derivative grafting glass sheet is to measure according to the method for document [S.Flink, F.C.J.M.van Veggel, D.N.Reinhoudt, Chem.Commun. (1999) 2229-2230].According to Lambert-Beer's law (ρ=A ε
-1), surface fluorescence groups density (ρ) can obtain by absorbance (A) and molar absorptivity efficiency (ε).In this work, utilized the absorption at 420nm place, and determined that by experiment the molar absorptivity ε of Striazine derivative in THF solution is 143610M
-1cm
-1.From calculating, the density of the fluorophor on Striazine derivative functional glass sheet surface is every
individual molecule.
(5) Compound I I(is Striazine derivative) in tetrahydrofuran solution, the sensing capabilities of DNT is tested:
Method of testing
1) solution preparation: take 90.2mg Compound I I and be dissolved in 10ml THF, preparation 1 * 10
-2the solution of mol/L.Get this solution 5 microlitres, add in 5ml volumetric flask, and be settled to scale with THF, prepare 1 * 10
-5the THF solution of the Compound I I of mol/L.Separately take 91mg DNT and be dissolved in 50mLTHF, preparation 1.0 * 10
-2the DNT solution of mol/L.
2) Compound I I is to DNT sensing capabilities testing procedure: by the THF solution 3ml(concentration of the Compound I I of above-mentioned configuration, be 1 * 10
-5mol/L) pour in 100ml conical flask, add 5 microlitres 1.0 * 10
-2the DNT solution of mol/L, pours into after mixing in fluorescence pond, with the F-4500 of Hitachi type fluorospectrophotometer, tests its fluorescence spectrum (excitation wavelength is 420nm).Record fluorescence peak intensity.In this solution, successively add 5 microlitres 1.0 * 10
-2the DNT solution of mol/L, test adds the fluorescence spectrum after DNT solution at every turn, records corresponding fluorescence peak intensity I.To not add the fluorescence intensity of the Compound I I solution of quencher DNT to be designated as I
0, calculate each quencher rate Q=1-I/I
0.What the fluorescence spectrum of Compound I I in THF solution changed with the increase of DNT concentration the results are shown in Figure 6.
Can find out, along with the rising of DNT concentration, the fluorescence intensity of Compound I I solution weakens gradually.When DNT concentration is 5 * 10
-5during mol/L, cancellation efficiency (Q) reaches 72%, yet work as DNT concentration, continues to be elevated to 2 * 10
-3mol/L, cancellation efficiency is slowly elevated to 94%.This result has disclosed Compound I I, in lean solution, DNT has been had to higher response sensitivity.Electronics metastasis between confession-acceptor is to cause Compound I I by the main cause of nitro-aromatic quencher, and the electronics in excited state is shifted to electron accepter (DNT) by electron donor (molecule I I)
(6) glass sheet of Compound I I grafting is tested DNT sensing capabilities:
Method of testing
1) solution preparation: take 91mg DNT and be dissolved in 50mL THF, preparation 1.0 * 10
-2the DNT solution of mol/L.
Get appropriate this solution and dilute with THF, making the DNT solution of 9 parts of variable concentrations, concentration range is: 0～200 * 10
-5mol/L.
2) glass sheet of Compound I I grafting is to DNT sensing capabilities testing procedure: glass sheet is inserted in fluorescence pond (angle of glass sheet and incident light is 45 °) along diagonal line, the DNT solution that adds successively variable concentrations, and test its fluorescence spectrum, record fluorescence peak intensity, calculate the quencher rate Q of glass sheet in variable concentrations DNT solution.
Result as shown in Figure 7, along with the concentration of DNT is from 2 * 10
-7mol/L is increased to 2 * 10
-3mol/L, quencher rate raises gradually.When DNT concentration is 5 * 10
-5during mol/L, cancellation efficiency reaches 68.7%, and then DNT concentration continues to be increased to 2 * 10
-3mol/L, cancellation efficiency is just slowly increased to 89.3%.Can find out, when DNT concentration is rarer, this glass sheet sensor has higher response sensitivity.
(7) reversibility of the fluorescent quenching process of the glass sheet sensor of Compound I I grafting
Glass sheet sensor can be measured by following steps by the reversibility of DNT quencher: first at room temperature glass sheet immersion being filled to DNT concentration is 2 * 10
-3in the fluorescence pond of the tetrahydrofuran solution of mol/L, after immersion 5min, test its fluorescence spectrum (excitation wavelength is 420nm).Subsequently, with a large amount of ethanol, clean glass sheet, and with after ethanol supersound washing 30min, measure the fluorescence spectrum that fluorescence recovers back glass sheet.Above fluorescent quenching-recovering step is cycled to repeat 10 times, the fluorescence intensity after recording the fluorescence peak intensity after fluorescent quenching and fluorescence in each repetitive process and recovering.
Test result is listed in Fig. 8.As seen from the figure, from for the second time circulation, the fluorescence intensity of recovery between green strength 77.4% and 82.5% between, cancellation rate is between 85.0% and 92.8%.Clearly, the fluorescent quenching process of sensor demonstrates good reversibility.
(8) the sensing capabilities test of the glass sheet of Compound I I grafting to gas phase DNT:
Method of testing: the glass sheet of Compound I I grafting is carefully inserted to (angle of glass sheet and incident light is 45 °) along fluorescence pond diagonal line, measure the aerial fluorescence intensity of glass sheet sensor situation over time by Edinburg FLS920 fluorescence spectrophotometer.Glass sheet is taken out, and add 100mg DNT powder in fluorescence pond, after sealing, standing 1h under room temperature, reaches capacity DNT steam in fluorescence pond.Then glass sheet sensor is carefully inserted to (angle of glass sheet and incident light is 45 °) along fluorescence pond diagonal line, and measure immediately glass sheet sensor at the airborne fluorescence intensity that contains DNT situation (λ over time
ex/em=410/488nm).Test result as shown in Figure 9.
Can find out, once glass sheet sensor is put into DNT saturated vapour, its fluorescence intensity moment is reduced to the 5%(quencher rate 95% of its fluorescence intensity in air), illustrate that this unimolecular film sensor fluorescence intensity is sensitive to the response of DNT steam, can reach its cancellation response balance moment.And the common thin film sensor of being prepared by spin-coating method often needs the regular hour just can reach quenching effect balance at present.The visible unimolecular film glass sheet sensor by Compound I I grafting is showing obvious advantage aspect response speed.
(9) selectivity of the glass sheet of Compound I I grafting to nitro-aromatic
Choose common electron acceptor compound, as 2,4,6-trinitro-toluene (TNT), 2,4-dinitrotoluene (DNT) (DNT), para-nitrotoluene (NT), 2,4,6-trinitrophenol (TNP), 1,4-dinitro benzene (m-DNB), 1,4-benzoquinones (BQ), para-Phthalonitrile (DCNB), 1,4-dichloro-benzenes (DClB), tetrachloroquinone (CA), nitromethane (NM), quencher rate when tested glass sheet sensor reaches quencher balance in the saturated vapour of these electron acceptor compounds.Method of testing: get each electron accepter 100mg(solid) or 100 μ l(liquid), add respectively the bottom in fluorescence pond, seal, place 1 hour.Then glass sensor is inserted in fluorescence pond and placed after 5 minutes along diagonal line, test its fluorescence spectrum, calculate quencher rate.Test result as shown in figure 10.
Can find out, sensor has higher quencher rate to nitro-aromatic compound.Consider that most nitro-aromatic compounds are put into explosive raw material catalogue, therefore this sensor has important value to developing the sensitive nitro-aromatic explosives sensor of response.
Claims (7)
1. a preparation method for Striazine derivative chemical modification glass surface sensor, is characterized in that, comprises that step is as follows:
(1) hydroxylation of glass sheet is processed
Glass sheet is removed to surperficial organic impurities at 400～600 ℃ of calcining 2～6h, then clean with ultrapure water, the mixed liquor of then putting into the concentrated sulphuric acid and hydrogen peroxide soaks, and with a large amount of distilled water, cleans glass sheet, and the glass sheet after cleaning is at dustless drying box inner drying;
(2) silanization of glass sheet is processed
Hydroxylated glass sheet is immersed in the mixed liquor of toluene and 3-chloropropyl triethoxysilane, 30～80 ℃ are soaked 5～20 hours, after cool to room temperature, with ethanol, clean, remove unnecessary toluene and 3-chloropropyl triethoxysilane, be immersed in ethanol, preserve stand-by;
(3) Striazine derivative is in the grafting of glass sheet surface
Getting Striazine derivative is dissolved in toluene, and add sodium hydride, after stirring, the glass sheet that silanization is processed is soaked in above-mentioned solution, in 30～80 ℃, react after 5～20 hours, with alcohol flushing, then put into respectively each the ultrasonic concussion of ethanol and tetrahydrofuran and remove the Striazine derivative of physisorption on glass sheet.
2. the preparation method of a kind of Striazine derivative chemical modification glass surface sensor according to claim 1, is characterized in that, Striazine derivative structural formula is as follows:
3. the preparation method of a kind of Striazine derivative chemical modification glass surface sensor according to claim 1, it is characterized in that, the described immersion of step (1) is 50～150 ℃ of immersions in the mixed liquor the concentrated sulphuric acid and hydrogen peroxide (30%) volume ratio are 7:3 1 hour.
4. the preparation method of a kind of Striazine derivative chemical modification glass surface sensor according to claim 1, it is characterized in that, in the mixed liquor of the middle toluene of step (2) and 3-chloropropyl triethoxysilane, the volume ratio of toluene and 3-chloropropyl triethoxysilane is 10:1.
5. the preparation method of a kind of Striazine derivative chemical modification glass surface sensor according to claim 1, it is characterized in that, in step (3), the mass ratio of Striazine derivative and sodium hydride is 1:10～40, and the consumption of toluene is every gram of Striazine derivative 500-5000ml.
6. the sensor that prepared by method claimed in claim 1.
7. the application of sensor claimed in claim 6 in DNT detects.
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| CN106568760A (en) * | 2016-10-18 | 2017-04-19 | 河南大学 | Method for preparing AFM-TERS tip by in situ reduction method |
| CN110146559A (en) * | 2019-05-05 | 2019-08-20 | 福建九五检测技术服务有限公司 | A kind of soil pollution detection method |
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Cited By (3)
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| CN106568760A (en) * | 2016-10-18 | 2017-04-19 | 河南大学 | Method for preparing AFM-TERS tip by in situ reduction method |
| CN110146559A (en) * | 2019-05-05 | 2019-08-20 | 福建九五检测技术服务有限公司 | A kind of soil pollution detection method |
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