CN100520371C

CN100520371C - Preparation method of pyrene functionalized sensing film and its application in nitryl arene detection

Info

Publication number: CN100520371C
Application number: CNB2006100427252A
Authority: CN
Inventors: 房喻; 张淑娟; 吕凤婷; 高莉宁; 丁立平
Original assignee: Shaanxi Normal University
Current assignee: Shaanxi Normal University
Priority date: 2006-04-25
Filing date: 2006-04-25
Publication date: 2009-07-29
Anticipated expiration: 2026-04-25
Also published as: CN1837793A

Abstract

This invention relates to a preparation method of pyrene functionalized sensing film and its application in nitryl arene detection, which comprises: substrate-lotion-activated substrate-silanizated substrate-trichoromethane solution for four pyrene sulfamoyl derivatives-target. This design is reasonable and practical, and the product has well stability, long lifetime and high sensitivity.

Description

The preparation method of pyrene functionalized sensing film and the application in nitro-aromatic detects

Technical field

The invention belongs to and use fluorescent small molecule to prepare the technical field of fluorescence sense film material, be specifically related to contain application in the nitro-aromatic compound steam to the preparation method of the fluorescence sense film that contains nitro-aromatic class microscratch amount explosive vapor sensitive and in detection.

Background technology

Gas sensor is as the core of gas detecting system, and its research has obtained paying attention to more and more widely.Wherein as the research of gas sensor gas sensitive breakthrough has been arranged in recent years with fluorescence sense film.Fluorescence sense film is output signal with fluorescence, in sensing class material, have highly sensitive, selectivity good, long service life, be easy to many incomparable advantages such as device.It is based on before and after analysans occurs, the fluorescence intensity of fluorescence species, fluorescence spectrum shape, lifetime of excited state, and basic photophysical property such as fluorescence polarization or fluorescence anisotropy this principle that changes realizes technology that test substance is detected.In recent years, the report that the fluorescence sense film technology is applied to microscratch amount explosive detection constantly occurs, and shows good application prospects.According to the The Nomenclature Composition and Structure of Complexes of selected sensing element, can be divided into inorganic semiconductor class, fluorescence polymer class and fluorescent small molecule class to the fluorescence sense film material.The permeability of analysans in sense film with and with the binding ability of sensing element molecule be decision fluorescence sense film response speed, sensitivity and reversible principal element.Consider the influence of permeability to the sense film response speed, in recent years, people attempt that fluorescent small molecule is fixed in solid surface and obtain sensing element molecule and directly be exposed to sense film material in the system to be measured.Wherein chemical fixation especially comes into one's own owing to fixation.The prerequisite of chemical fixationization is to introduce reactive group in stromal surface, and reactive group is mainly introduced in the mode of self-assembled monolayer (SAM).More about fluorescent small molecule class fluorescence sense film preparation methods and performance study at present, the research that still this type of film is applied to gas sensing is less.The research group at the present inventor place is devoted to the preparation and the performance study of this type of sense film material in recent years always.Result of study shows, long-armed to be chemically bonded to stromal surface such as glass be a kind of effective method for preparing the fluorescence sense film material through flexibility with fluorescent small molecule, by the preparation-obtained fluorescence sense film of this method, highly sensitive except having, selectivity good, do not pollute system to be measured, be easy to the advantages such as device, also have characteristics such as stable in properties, long service life, and the nitro-aromatic compound steam table is revealed high detection sensitivity and selectivity.

At present, have only several laboratories few in number in the world in the research of being engaged in the fluorescence sense film of nitro-aromatic compound vapor sensitive.Wherein with the tool representative of the Swager group of Massachusetts Institute Technology.This group introduces bulky group on macromolecular chain, in the hope of form the molecular channel in the film of preparation, improve the permeability of analyte in film, improve the sensing capabilities of film, realized that to 2,4 6-trinitro-toluene etc. contains the sensitive sensing of nitro-aromatic compound steam.Trogler group is silicon atom with the main chain, and the inorganic conjugated fluorescence polymer that side chain has palycyclic aromatic is a material, makes sense film, has realized the sensing to nitro arene explosive substance.Gulino group arrives silicon chip surface with a kind of derivant of porphyrin through the silylating reagent chemical bond, has realized the sensing to nitrogen dioxide gas.But the derivant of fluorescent small molecule pyrene through the long-armed glass matrix surface that is covalently bound to of flexibility, is realized yet there are no report to containing the research of the fluorescence sense film material that microscratch amount nitro-aromatic compound steam detects in the air.

Summary of the invention

A technical matters to be solved by this invention be to provide a kind of reasonable in design, feasible process, easy and simple to handle, reaction conditions is gentle to containing the fluorescence sense film preparation method of nitro-aromatic compound vapor sensitive.

Another technical matters to be solved by this invention is to adopt the application of pyrene functionalized sensing film in nitro-aromatic compound detects of above-mentioned preparation method's preparation.

Solving the problems of the technologies described above the technical scheme that is adopted is that this preparation method comprises the steps:

1, tailors substrate

Glass plate is cut into 0.9 * 2.5cm ²The rectangular glass sheet of size.

2, preparation washing lotion

The sulfuric acid of 30% hydrogen peroxide and 98% is mixed and made into washing lotion by the 7:3 volume ratio.

3, preparation activation substrate

Elder generation's water, ethanol cleaning glass sheet are put into washing lotion after drying up, and 80～100 ℃ were heated 1～2 hour down, and natural cooling with pure redistilled water cleaning glass sheet, is washed the washing lotion of remained on surface off, dries up with hair-dryer, makes the activation substrate.

4, preparation silanization substrate

Utilize the capillary action of water, the one side of activation substrate is closed with glass sheet is bonding, with this activation substrate and sealing activate substrate to put into the volume ratio of 3-diglycidyl propyl ether base trimethoxy silane and toluene solution respectively be the solution of 3:500, soaked 12～48 hours down at 40～60 ℃, take out substrate, wash with toluene solution earlier, wash with chloroform soln again, wash 3-diglycidyl propyl ether base trimethoxy silane of remained on surface off, hair-dryer dries up, one side is made lateral silicon alkanisation substrate with the activation substrate of the bonding sealing of glass sheet, and sealing activation substrate is not made two-sided silanization substrate.

5, the chloroform soln of four kinds of amino pyrene sulfonyl derivatives of preparation

The pyrene sulfonic acid chloride is dissolved in the chloroform soln that is made into 0.01mol/L pyrene sulfonic acid chloride in the methenyl choloride, this solution is poured in the constant pressure funnel, get again with pyrene sulfonic acid chloride mol ratio be that 5～10 ethylenediamine or propane diamine or butanediamine or Diethylenetriamine are dissolved in the methenyl choloride, be made into the ethylenediamine of 0.05～0.10mol/L or the chloroform soln of propane diamine or butanediamine or Diethylenetriamine, and this solution is put into there-necked flask.Under 0 ℃ of stirring condition, with the speed feeding N of 0.6～0.8ml/s ₂, the chloroform soln of pyrene sulfonic acid chloride is added drop-wise in the chloroform soln of ethylenediamine in the there-necked flask or propane diamine or butanediamine or Diethylenetriamine, dropwise the back and continued stirring reaction 1～2 hour.Then reactant liquor is poured in the separating funnel, water and concentration are that 5%NaCl solution is washed till chloroform soln repeatedly and is neutral, add anhydrous magnesium sulfate drying, filter, and make the chloroform soln of four kinds of amino pyrene sulfonyl derivatives.

6, the fluorescence sense film of the different densities of four kinds of amino mediations of preparation

The chloroform soln of four kinds of amino pyrene sulfonyl derivatives of step 5 preparation is diluted to 0.00025～0.005mol/L concentration, single or double silanization substrate is put into the chloroform soln of four kinds of amino pyrene sulfonyl derivatives of 0.00025～0.005mol/L, reflux 6～14 hours, take out single or double silanization substrate respectively, wash with methenyl choloride, use acetone and second distillation water washing again, wash the residue of the unreacted amino pyrene sulfonyl derivative in surface off, make the fluorescence sense film of the different densities of four kinds of amino mediations, put into secondary water and preserve.

In preparation method's of the present invention processing step 5, to be that 5～9 ethylenediamine or propane diamine or butanediamine or Diethylenetriamine are dissolved in the methenyl choloride with pyrene sulfonic acid chloride preferred molar ratio, be made into the ethylenediamine that preferred concentration is 0.05～0.09mol/L or the chloroform soln of propane diamine or butanediamine or Diethylenetriamine, in processing step 6, it is 0.00025～0.004mol/L that the chloroform soln of four kinds of amino pyrene sulfonyl derivatives of step 5 preparation is diluted to preferred concentration, single or double silanization substrate is put into the chloroform soln of four kinds of amino pyrene sulfonyl derivatives of 0.00025～0.004mol/L, and the preferred time of reflux is 10～14 hours.

In preparation method's of the present invention processing step 5, to be that 5 ethylenediamine or propane diamine or butanediamine or Diethylenetriamine are dissolved in the methenyl choloride with pyrene sulfonic acid chloride optimum mole ratio, be made into the ethylenediamine that optium concentration is 0.05mol/L or the chloroform soln of propane diamine or butanediamine or Diethylenetriamine, in processing step 6, it is 0.00025mol/L that the chloroform soln of four kinds of amino pyrene sulfonyl derivatives of step 5 preparation is diluted to optium concentration, single or double silanization substrate is put into the chloroform soln of four kinds of amino pyrene sulfonyl derivatives of 0.00025mol/L, and the Best Times of reflux is 14 hours.

Adopt the application of pyrene functionalized sensing film in nitro-aromatic compound detects of method for preparing.

The form that pyrene functionalized sensing film is used in nitro-aromatic compound detects comprises this class sensing membrane is prepared into sensor that using method is used by the detection method of the detecting instrument that uses sensor; Also this class sensing membrane can be installed on the detecting instrument that utilizes the fluorescence principle to detect nitro-aromatic compound and use, using method is used by the detection method of the detecting instrument that detects nitro-aromatic compound; Directly detect after also this class sensing membrane can being experienced nitro-aromatic class chemical combination, as single photon counting time resolution fluorescence spectral instrument or other similar optical detecting instruments of FLS920 model with fluorescent instrument.

The present invention adopts self-assembling method that the silylating reagent individual layer that end has the epoxy radicals functional group is assembled into glass substrate surface, utilize the surface chemical reaction of fluorescent small molecule pyrene and epoxy radicals, its chemical bond is arrived substrate surface, obtain the fluorescence sense film through the long-armed connection of flexibility, having solved polymeric membrane is the fluorescence sense film poor stability of matrix, the problem that lack serviceable life.By the length of regulating linking arm, the modes such as structure that change linking arm, enlarged the kind of fluorescence sense film, improved the sensing capabilities of fluorescence sense film.Advantages such as that the present invention has is reasonable in design, feasible process, easy and simple to handle, reaction conditions gentleness.Adopt the fluorescence sense film of the present invention's preparation to have advantages such as good stability, long service life, sensitivity height, can contain in the nitro-aromatic compound in detection and use.

Description of drawings

Fig. 1 is the static fluorescence excitation-emission spectrum of the two-sided fluorescence sense film of high density under dry state through the mediation of butanediamine linking arm.

Fig. 2 is the static fluorescence excitation-emission spectrum of the two-sided fluorescence sense film of high density under dry state through the mediation of propane diamine linking arm.

Fig. 3 is the static fluorescence excitation-emission spectrum of the two-sided fluorescence sense film of high density under dry state through the mediation of ethylenediamine linking arm.

Fig. 4 is the static fluorescence excitation-emission spectrum of the two-sided fluorescence sense film of high density under dry state through the mediation of Diethylenetriamine linking arm.

Fig. 5 be the two-sided fluorescence sense film of high density through butanediamine linking arm mediation in time by 2,4, the fluorescence emission spectrogram of 6-trinitro-toluene steam quencher.

Fig. 6 be the two-sided fluorescence sense film of high density through butanediamine linking arm mediation in time by 2,4, the quencher efficiency diagram of 6-trinitro-toluene steam quencher.

Fig. 7 be the two-sided fluorescence sense film of high density through butanediamine linking arm mediation in time by 2, the fluorescence emission spectrogram of 4-dinitrotoluene (DNT) steam quencher.

Fig. 8 be the two-sided fluorescence sense film of high density through butanediamine linking arm mediation in time by 2, the quencher efficiency diagram of 4-dinitrotoluene (DNT) steam quencher.

Fig. 9 is that the two-sided fluorescence sense film of high density through butanediamine linking arm mediation is in time by the fluorescence emission spectrogram of paradinitrobenzene steam quencher.

Figure 10 is that the two-sided fluorescence sense film of high density through butanediamine linking arm mediation is in time by the quencher efficiency diagram of paradinitrobenzene steam quencher.

Figure 11 is that the two-sided fluorescence sense film of high density through butanediamine linking arm mediation is in time by the fluorescence emission spectrogram of meta-dinitro-benzent steam quencher.

Figure 12 is that the two-sided fluorescence sense film of high density through butanediamine linking arm mediation is in time by the quencher efficiency diagram of meta-dinitro-benzent steam quencher.

Figure 13 is that the two-sided fluorescence sense film of high density through butanediamine linking arm mediation is in time by the fluorescence emission spectrogram of para-nitrotoluene steam quencher.

Figure 14 is that the two-sided fluorescence sense film of high density through butanediamine linking arm mediation is in time by the quencher efficiency diagram of para-nitrotoluene steam quencher.

Figure 15 is that the two-sided fluorescence sense film of high density through butanediamine linking arm mediation is in time by the fluorescence emission spectrogram of paranitrochlorobenzene steam quencher.

Figure 16 is that the two-sided fluorescence sense film of high density through butanediamine linking arm mediation is in time by the quencher efficiency diagram of paranitrochlorobenzene steam quencher.

Figure 17 is that the two-sided fluorescence sense film of high density through butanediamine linking arm mediation is in time by the fluorescence emission spectrogram of nitrobenzene vapor quencher.

Figure 18 is that the two-sided fluorescence sense film of high density through butanediamine linking arm mediation is in time by the quencher efficiency diagram of nitrobenzene vapor quencher.

Figure 19 mediates the two-sided fluorescence sense film of high density in time by 2,4 through the butanediamine linking arm, the fluorescence emission spectrogram of 6-trinitro-toluene steam quencher.

Figure 20 be the two-sided fluorescence sense film of high density through propane diamine linking arm mediation in time by 2,4, the fluorescence emission spectrogram of 6-trinitro-toluene steam quencher.

Figure 21 be the two-sided fluorescence sense film of high density through ethylenediamine linking arm mediation in time by 2,4, the fluorescence emission spectrogram of 6-trinitro-toluene steam quencher.

Figure 22 be the two-sided fluorescence sense film of high density through Diethylenetriamine linking arm mediation in time by 2,4, the fluorescence emission spectrogram of 6-trinitro-toluene steam quencher.

Figure 23 be the two-sided fluorescence sense film of high density through ethylenediamine (EDA), propane diamine (DAP), butanediamine (DAB), the mediation of Diethylenetriamine (DETA) linking arm by 2,4, the quencher efficiency diagram of 6-trinitro-toluene TNT steam quencher.

Figure 24 is that the two-sided fluorescence sense film of high density through butanediamine linking arm mediation is in time by the fluorescence emission spectrogram of para-nitrotoluene steam quencher.

Figure 25 is that the two-sided fluorescence sense film of high density through propane diamine linking arm mediation is in time by the fluorescence emission spectrogram of para-nitrotoluene steam quencher.

Figure 26 is that the two-sided fluorescence sense film of high density through ethylenediamine linking arm mediation is in time by the fluorescence emission spectrogram of para-nitrotoluene steam quencher.

Figure 27 is that the two-sided fluorescence sense film of high density through Diethylenetriamine linking arm mediation is in time by the fluorescence emission spectrogram of para-nitrotoluene steam quencher.

Figure 28 is that four kinds of two-sided fluorescence sense films of high density through ethylenediamine (EDA), propane diamine (DAP), butanediamine (DAB), the mediation of Diethylenetriamine (DETA) linking arm are by the quencher efficiency diagram of para-nitrotoluene steam quencher.

Figure 29 is that the two-sided fluorescence sense film of high density through butanediamine linking arm mediation is in time by the fluorescence emission spectrogram of nitrobenzene vapor quencher.

Figure 30 is that the two-sided fluorescence sense film of high density through propane diamine linking arm mediation is in time by the fluorescence emission spectrogram of nitrobenzene vapor quencher.

Figure 31 is that the two-sided fluorescence sense film of high density through ethylenediamine linking arm mediation is in time by the fluorescence emission spectrogram of nitrobenzene vapor quencher.

Figure 32 is that the two-sided fluorescence sense film of high density through Diethylenetriamine linking arm mediation is in time by the fluorescence emission spectrogram of nitrobenzene vapor quencher.

Figure 33 is that the two-sided fluorescence sense film of high density through ethylenediamine (EDA), propane diamine (DAP), butanediamine (DAB), the mediation of Diethylenetriamine (DETA) linking arm is by the quencher efficiency diagram of nitrobenzene vapor quencher.

Figure 34 is through the static fluorescence spectrum figure of the two-sided fluorescence sense film of fluorescence sense film, the fluorescence sense film of middle density single face, high density of the low-density single face of propane diamine linking arm mediation when no analyte exists under dry state.

Figure 35 is that the fluorescence sense film (Film1) through the low-density single face of propane diamine linking arm mediation is exposed to 2,4, the fluorescence emission spectrogram of 6-trinitro-toluene saturated vapor different time.

Figure 36 is that the fluorescence sense film (Film2) through the middle density single face of propane diamine linking arm mediation is exposed to 2,4, the fluorescence emission spectrogram of 6-trinitro-toluene saturated vapor different time.

Figure 37 is exposed to 2,4, the fluorescence emission spectrogram of 6-trinitro-toluene saturated vapor different time through the two-sided fluorescence sense film (Film3) of high density that the propane diamine linking arm mediates.

Figure 38 be through the two-sided fluorescence sense film of fluorescence sense film, the fluorescence sense film of middle density single face, the high density of the low-density single face of propane diamine linking arm mediation with the difference of exposure duration by 2,4, the quencher efficiency diagram of 6-trinitro-toluene steam quencher.

Figure 39 be low-density single face fluorescence sense film through propane diamine linking arm mediation to 2,4, the reversibility of 6-trinitro-toluene saturated vapor sensing is figure as a result.

Embodiment

The present invention is described in more detail below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.

Embodiment 1

With preparation through the low-density of propane diamine linking arm mediation (

Containing 12 following pyrene sensor molecules) the single face fluorescence sense film is example, its preparation methods steps is as follows:

1, tailors substrate

Glass plate is cut into 0.9 * 2.5cm ²The rectangular glass sheet of size.

2, preparation washing lotion

3, preparation activation substrate

4, preparation silanization substrate

Utilize the capillary action of water, the one side of activation substrate is closed with glass sheet is bonding, the volume ratio that this activation substrate is put into 3-diglycidyl propyl ether base trimethoxy silane and toluene solution is the solution of 3:500, soaked 12 hours down at 50 ℃, take out substrate, wash with toluene solution earlier, wash with chloroform soln again, wash 3-diglycidyl propyl ether base trimethoxy silane of remained on surface off, hair-dryer dries up, and makes lateral silicon alkanisation substrate.

5, the chloroform soln of preparation propane diamine base pyrene sulfonyl derivative

The pyrene sulfonic acid chloride is dissolved in the chloroform soln that is made into 0.01mol/L pyrene sulfonic acid chloride in the methenyl choloride, this solution is poured in the constant pressure funnel, get again with pyrene sulfonic acid chloride mol ratio be that 5 propane diamine is dissolved in the methenyl choloride, be made into the chloroform soln of the propane diamine of 0.05mol/L, and this solution is put into there-necked flask.0 ℃ of stirring, with the speed feeding N of 0.6～0.8ml/s ₂The chloroform soln of pyrene sulfonic acid chloride is added drop-wise in the chloroform soln of the propane diamine in the there-necked flask, dropwise the back and continued stirring reaction 2 hours, reactant liquor is poured in the separating funnel, water and concentration are that 5% NaCl solution is washed till chloroform soln repeatedly and is neutral, add anhydrous magnesium sulfate drying, filter, make the chloroform soln of propane diamine base pyrene sulfonyl derivative.

6, the fluorescence sense film of the middle density of preparation propane diamine base linking arm mediation

The chloroform soln of the propane diamine base pyrene sulfonyl derivative of step 5 preparation is diluted to 0.00025mol/L concentration, lateral silicon alkanisation substrate is put into the chloroform soln of the propane diamine base pyrene sulfonyl derivative of 0.00025mol/L, reflux 14 hours, take out lateral silicon alkanisation substrate respectively, wash with methenyl choloride, use acetone and second distillation water washing again, wash the residue of surperficial unreacted propane diamine base pyrene sulfonyl derivative off, make low-density single face fluorescence sense film, put into secondary water and preserve through the mediation of propane diamine base linking arm.

Embodiment 2

With preparation through the middle density of propane diamine linking arm mediation (

Containing 17～25 pyrene sensor molecules) the single face fluorescence sense film is example, its preparation methods steps is as follows:

Prepare in the chloroform soln processing step 5 of propane diamine base pyrene sulfonyl derivative at present embodiment, the pyrene sulfonic acid chloride is dissolved in the chloroform soln that is made into 0.01mol/L pyrene sulfonic acid chloride in the methenyl choloride, this solution is poured in the constant pressure funnel, get again with pyrene sulfonic acid chloride mol ratio be that 8 propane diamine is dissolved in the methenyl choloride, be made into the chloroform soln of the propane diamine of 0.08mol/L, and this solution is put into there-necked flask.Under 0 ℃ of stirring condition, with the speed feeding N of 0.6～0.8ml/s ₂, the chloroform soln of pyrene sulfonic acid chloride is added drop-wise in the chloroform soln of the propane diamine in the there-necked flask, dropwise the back and continued stirring reaction 1～2 hour.Then reactant liquor is poured in the separating funnel, water and concentration are that 5%NaCl solution is washed till chloroform soln repeatedly and is neutral, add anhydrous magnesium sulfate drying, filter, and make the chloroform soln of the amino pyrene sulfonyl derivative of propane diamine.

Present embodiment is in the fluorescence sense film processing step 6 of preparation propane diamine base linking arm mediation, the chloroform soln of the propane diamine base pyrene sulfonyl derivative of step 5 preparation is diluted to 0.0005mol/L concentration, lateral silicon alkanisation substrate is put into the chloroform soln of the propane diamine base pyrene sulfonyl derivative of 0.0005mol/L, reflux 10 hours, take out lateral silicon alkanisation substrate respectively, wash with methenyl choloride, use acetone and second distillation water washing again, wash the residue of surperficial unreacted propane diamine base pyrene sulfonyl derivative off, make fluorescence sense film, put into secondary water and preserve through the middle density single face of propane diamine base linking arm mediation.Other processing step is identical with embodiment 1.

Embodiment 3

With preparation through the high density of propane diamine linking arm mediation (

Containing 40～50 pyrene sensor molecules) the single face fluorescence sense film is example, its preparation methods steps is as follows:

Prepare in the chloroform soln processing step 5 of propane diamine base pyrene sulfonyl derivative at present embodiment, the pyrene sulfonic acid chloride is dissolved in the chloroform soln that is made into 0.01mol/L pyrene sulfonic acid chloride in the methenyl choloride, this solution is poured in the constant pressure funnel, get again with pyrene sulfonic acid chloride mol ratio be that 10 propane diamine is dissolved in the methenyl choloride, be made into the chloroform soln of the propane diamine of 0.10mol/L, and this solution is put into there-necked flask.Under 0 ℃ of stirring condition, with the speed feeding N of 0.6～0.8ml/s ₂, the chloroform soln of pyrene sulfonic acid chloride is added drop-wise in the chloroform soln of the propane diamine in the there-necked flask, dropwise the back and continued stirring reaction 1 hour.Then reactant liquor is poured in the separating funnel, water and concentration are that 5%NaCl solution is washed till chloroform soln repeatedly and is neutral, add anhydrous magnesium sulfate drying, filter, and make the chloroform soln of the amino pyrene sulfonyl derivative of propane diamine.

Present embodiment is in the fluorescence sense film processing step 6 of preparation propane diamine base linking arm mediation, the chloroform soln of the propane diamine base pyrene sulfonyl derivative of step 5 preparation is diluted to 0.005mol/L concentration, lateral silicon alkanisation substrate is put into the chloroform soln of the propane diamine base pyrene sulfonyl derivative of 0.005mol/L, reflux 6 hours, take out lateral silicon alkanisation substrate respectively, wash with methenyl choloride, use acetone and second distillation water washing again, wash the residue of surperficial unreacted propane diamine base pyrene sulfonyl derivative off, make fluorescence sense film, put into secondary water and preserve through the high density single face of propane diamine base linking arm mediation.Other processing step is identical with embodiment 1.

Embodiment 4

Is example with preparation through the basic, normal, high density single face fluorescence sense film of ethylenediamine linking arm mediation, and its preparation methods steps is as follows:

In the present embodiment, with among the above embodiment 1～3, propane diamine replaces to ethylenediamine, is prepared into the basic, normal, high density single face fluorescence sense film through the mediation of ethylenediamine linking arm.

Embodiment 5

Is example with preparation through the basic, normal, high density single face fluorescence sense film of butanediamine linking arm mediation, and its preparation methods steps is as follows:

In the present embodiment, with among the above embodiment 1～3, propane diamine replaces to butanediamine, is prepared into low-density, middle density, high density single face fluorescence sense film through the mediation of butanediamine linking arm.

Embodiment 6

Is example with preparation through the basic, normal, high density single face fluorescence sense film of Diethylenetriamine linking arm mediation, and its preparation methods steps is as follows:

In the present embodiment, with among the above embodiment 1～3, propane diamine replaces to Diethylenetriamine, is prepared into low-density, middle density, high density single face fluorescence sense film through the mediation of Diethylenetriamine linking arm.

Embodiment 7

Containing 12 following pyrene sensor molecules) two-sided fluorescence sense film is example, its preparation methods steps is as follows:

Prepare in the chloroform soln processing step 5 of propane diamine base pyrene sulfonyl derivative at present embodiment, the pyrene sulfonic acid chloride is dissolved in the chloroform soln that is made into 0.01mol/L pyrene sulfonic acid chloride in the methenyl choloride, this solution is poured in the constant pressure funnel, get again with pyrene sulfonic acid chloride mol ratio be that 5 propane diamine is dissolved in the methenyl choloride, be made into the chloroform soln of the propane diamine of 0.05mol/L, and this solution is put into there-necked flask.0 ℃ of stirring, with the speed feeding N of 0.6～0.8ml/s ₂The chloroform soln of pyrene sulfonic acid chloride is added drop-wise in the chloroform soln of the propane diamine in the there-necked flask, dropwise the back and continued stirring reaction 2 hours, reactant liquor is poured in the separating funnel, water and concentration are that 5%NaCl solution is washed till chloroform soln repeatedly and is neutral, add anhydrous magnesium sulfate drying, filter, make the chloroform soln of propane diamine base pyrene sulfonyl derivative.

In the fluorescence sense film processing step 6 of the middle density that preparation propane diamine base linking arm mediates, the chloroform soln of the propane diamine base pyrene sulfonyl derivative of step 5 preparation is diluted to 0.00025mol/L concentration, two-sided silanization substrate is put into the chloroform soln of the propane diamine base pyrene sulfonyl derivative of 0.00025mol/L, reflux 14 hours, take out two-sided silanization substrate respectively, wash with methenyl choloride, use acetone and second distillation water washing again, wash the residue of surperficial unreacted propane diamine base pyrene sulfonyl derivative off, make the two-sided fluorescence sense film of low-density, put into secondary water and preserve through the mediation of propane diamine base linking arm.Other processing step is identical with embodiment 1.

Embodiment 8

Containing 17～25 pyrene sensor molecules) two-sided fluorescence sense film is example, its preparation methods steps is as follows:

Prepare in the chloroform soln processing step 5 of propane diamine base pyrene sulfonyl derivative at present embodiment, the pyrene sulfonic acid chloride is dissolved in the chloroform soln that is made into 0.01mol/L pyrene sulfonic acid chloride in the methenyl choloride, this solution is poured in the constant pressure funnel, get again with pyrene sulfonic acid chloride mol ratio be that 8 propane diamine is dissolved in the methenyl choloride, be made into the chloroform soln of the propane diamine of 0.08mol/L, and this solution is put into there-necked flask.Under 0 ℃ of stirring condition, with the speed feeding N of 0.6～0.8ml/s ₂, the chloroform soln of pyrene sulfonic acid chloride is added drop-wise in the chloroform soln of the propane diamine in the there-necked flask, dropwise the back and continued stirring reaction 1～2 hour.Then reactant liquor is poured in the separating funnel, water and concentration are that 5% NaCl solution is washed till chloroform soln repeatedly and is neutral, add anhydrous magnesium sulfate drying, filter, and make the chloroform soln of the amino pyrene sulfonyl derivative of propane diamine.

Present embodiment is in the fluorescence sense film processing step 6 of preparation propane diamine base linking arm mediation, the chloroform soln of the propane diamine base pyrene sulfonyl derivative of step 5 preparation is diluted to 0.0005mol/L concentration, two-sided silanization substrate is put into the chloroform soln of the propane diamine base pyrene sulfonyl derivative of 0.0005mol/L, reflux 10 hours, take out two-sided silanization substrate respectively, wash with methenyl choloride, use acetone and second distillation water washing again, wash the residue of surperficial unreacted propane diamine base pyrene sulfonyl derivative off, make the two-sided fluorescence sense film of middle density, put into secondary water and preserve through the mediation of propane diamine base linking arm.Other processing step is identical with embodiment 1.

Embodiment 9

Containing 40～50 pyrene sensor molecules) two-sided fluorescence sense film is example, its preparation methods steps is as follows:

Prepare in the chloroform soln processing step 5 of propane diamine base pyrene sulfonyl derivative at present embodiment, the pyrene sulfonic acid chloride is dissolved in the chloroform soln that is made into 0.01mol/L pyrene sulfonic acid chloride in the methenyl choloride, this solution is poured in the constant pressure funnel, get again with pyrene sulfonic acid chloride mol ratio be that 10 propane diamine is dissolved in the methenyl choloride, be made into the chloroform soln of the propane diamine of 0.10mol/L, and this solution is put into there-necked flask.Under 0 ℃ of stirring condition, with the speed feeding N of 0.6～0.8ml/s ₂, the chloroform soln of pyrene sulfonic acid chloride is added drop-wise in the chloroform soln of the propane diamine in the there-necked flask, dropwise the back and continued stirring reaction 1～2 hour.Then reactant liquor is poured in the separating funnel, water and concentration are that 5%NaCl solution is washed till chloroform soln repeatedly and is neutral, add anhydrous magnesium sulfate drying, filter, and make the chloroform soln of the amino pyrene sulfonyl derivative of propane diamine.

Present embodiment is in the low-density fluorescence sense film processing step 6 of preparation propane diamine base linking arm mediation, the chloroform soln of the propane diamine base pyrene sulfonyl derivative of step 5 preparation is diluted to 0.005mol/L concentration, two-sided silanization substrate is put into the chloroform soln of the propane diamine base pyrene sulfonyl derivative of 0.005mol/L, reflux 6 hours, take out two-sided silanization substrate respectively, wash with methenyl choloride, use acetone and second distillation water washing again, wash the residue of surperficial unreacted propane diamine base pyrene sulfonyl derivative off, make the two-sided fluorescence sense film of high density, put into secondary water and preserve through the mediation of propane diamine base linking arm.Other processing step is identical with embodiment 1.

Embodiment 10

Is example with preparation through the two-sided fluorescence sense film of basic, normal, high density of ethylenediamine linking arm mediation, and its preparation methods steps is as follows:

In the present embodiment, the propane diamine among the above embodiment 7～9 is replaced to ethylenediamine, be prepared into the two-sided fluorescence sense film of basic, normal, high density through the mediation of ethylenediamine linking arm.

Embodiment 11

Is example with preparation through the two-sided fluorescence sense film of basic, normal, high density of butanediamine linking arm mediation, and its preparation methods steps is as follows:

In the present embodiment, with among the above embodiment 7～9, propane diamine replaces to butanediamine, is prepared into low-density, middle density, the two-sided fluorescence sense film of high density through the mediation of butanediamine linking arm.

Embodiment 12

Is example with preparation through the two-sided fluorescence sense film of basic, normal, high density of Diethylenetriamine linking arm mediation, and its preparation methods steps is as follows:

In the present embodiment, with among the above embodiment 7～9, propane diamine replaces to Diethylenetriamine, is prepared into low-density, middle density, the two-sided fluorescence sense film of high density through the mediation of Diethylenetriamine linking arm.

Adopt the basic, normal, high density single or double fluorescence sense film of above embodiment 1～12 preparation of the present invention, to containing nitro-aromatic class microscratch amount explosive steam very high susceptibility is arranged, above-mentioned fluorescence sense film can be used as and detects the application that contains in the nitro-aromatic compound steam.

In order to verify beneficial effect of the present invention, what the inventor adopted the embodiment of the invention 1～2 preparation is the sensing element with the fluorescent small molecule pyrene, low through propane diamine (DAB) linking arm mediation, middle single face fluorescence sense film, what embodiment 9～12 prepared is the sensing element with the fluorescent small molecule pyrene, through butanediamine (DAP), propane diamine (DAB), the two-sided fluorescence sense film of high density of ethylenediamine (EDA) and the mediation of Diethylenetriamine (DETA) linking arm is in the fluorescence spectrum situation of change that contains sense film in the presence of the steam of nitro-aromatic compound, and 2,4, there be following restorative experiment the to the behavior of fluorescence sense film sensing in 6-trinitro-toluene steam.Various experiment situations are as follows:

Optical viewer: Edinburgh Instruments FLS920 single photon counting time resolution fluorescence spectral instrument, produce by Britain Edinburgh instrument company.

Observe article: through the two-sided fluorescence sense film of high density of butanediamine (DAP), propane diamine (DAB), ethylenediamine (EDA) and the mediation of Diethylenetriamine (DETA) linking arm, through low, the middle density single face fluorescence sense film of propane diamine linking arm mediation.

Observation project: through the two-sided fluorescence sense film of high density exciting in the dry state-emission spectrum of butanediamine (DAP), propane diamine (DAB), ethylenediamine (EDA) and the mediation of Diethylenetriamine (DETA) linking arm; 2,4,6-trinitro-toluene, 2, the steam of 4-dinitrotoluene (DNT), paradinitrobenzene, meta-dinitro-benzent, para-nitrotoluene, paranitrochlorobenzene and nitrobenzene exist down, through the fluorescence emission spectrum and the quencher efficiency diagram of the two-sided fluorescence sense film of high density of butanediamine linking arm mediation; Adopt pump gas method of testing, 2,4,6-trinitro-toluene steam, para-nitrotoluene steam and nitrobenzene vapor exist down, through the fluorescence emission spectrum and the quencher efficiency diagram of four kinds of two-sided fluorescence sense films of high density of butanediamine, propane diamine, ethylenediamine and the mediation of Diethylenetriamine linking arm; 2,4,6-trinitro-toluene steam exists down, through low, the single face of middle density of propane diamine linking arm mediation and the fluorescent emission intensity spectrum and the quencher efficiency diagram of the two-sided fluorescence sense film of high density; 2,4,6-trinitro-toluene steam exists down, restorative through the low-density single face fluorescence sense film Film1 of propane diamine linking arm mediation.

Observation procedure: the method for operating by single photon counting time resolution fluorescence spectral instrument is observed.

1, detects the static fluorescence excitation-emission spectrum of four kinds of two-sided fluorescence membranes of high density under dry state

Adopt the two-sided fluorescence sense film of high density of the propane diamine base linking arm mediation of the embodiment of the invention 9～12 preparations, the two-sided fluorescence sense film of high density through the mediation of ethylenediamine linking arm, the two-sided fluorescence sense film of high density through the mediation of butanediamine linking arm, the two-sided fluorescence sense film of high density through the mediation of Diethylenetriamine linking arm sticks to fluorescence cuvette inwall respectively, at ambient temperature, excitation source is faced on high density fluorescence membrane surface, adopt the front surface reflection method, with the static fluorescence excitation-emission spectrum of four kinds of two-sided fluorescence membranes of high density of single photon counting time resolution fluorescence spectral instrument test, test result is seen Fig. 1～4.

As can be seen from the figure, the fluorescence sense micromolecule is fixed on the glass matrix surface, and is evenly distributed.

2, the two-sided fluorescence sense film of high density in order to the mediation of butanediamine linking arm detects seven kinds of steams that contain nitro-aromatic compound

(1) use the two-sided fluorescence sense film of high density to detect 2,4,6-trinitro-toluene steam through the mediation of butanediamine linking arm

To adhere to fluorescence cuvette inwall through the two-sided fluorescence sense film of high density of butanediamine linking arm mediation, with 2 of less than 0.1 gram, 4,6-trinitro-toluene solid places one jiao of cuvette bottom, seals with being about to the cuvette mouth, allow 2,4, the spontaneous evaporation in time in cuvette of 6-trinitro-toluene steam, 2,4, the saturated vapour pressure of 6-trinitro-toluene is 8.02 * 10 ^-625 ℃ of mmHg.At ambient temperature, film surface in the face of excitation source, is adopted the method for front surface reflection, use single photon counting time resolution fluorescence spectral instrument immediately, the static fluorescence emission spectrum of a sense film of per two minutes records.Experimental result is seen Fig. 5.In time by 2,4, the quencher efficiency diagram of 6-trinitro-toluene steam quencher is seen Fig. 6 through the two-sided fluorescence sense film of high density of butanediamine linking arm mediation.

From Fig. 5,6 as can be seen, along with 2,4, the spontaneous evaporation in cuvette of 6-trinitro-toluene steam, the fluorescence emission spectral intensity of fluorescence sense film constantly descends, and this sense film is described to 2,4, and the response of 6-trinitro-toluene steam is responsive.

(2) use the two-sided fluorescence sense film of high density to detect 2,4-dinitrotoluene (DNT) steam through the mediation of butanediamine linking arm

To adhere to fluorescence cuvette inwall through the two-sided fluorescence sense film of high density of butanediamine linking arm mediation, simultaneously with 2 of less than 0.1 gram, 4-dinitrotoluene (DNT) solid places one jiao of cuvette bottom, seal with being about to the cuvette mouth, allow 2, the spontaneous evaporation in time in cuvette of 4-dinitrotoluene (DNT) steam, 2, the saturated vapour pressure of 4-dinitrotoluene (DNT) DNT is 1.74 * 10 ^-125 ℃ of mmHg.At ambient temperature, film surface in the face of excitation source, is adopted the method for front surface reflection, use single photon counting time resolution fluorescence spectral instrument immediately, the static fluorescence emission spectrum of a sense film of per two minutes records, experimental result is seen Fig. 7.In time by 2, the quencher efficient of 4-dinitrotoluene (DNT) steam quencher is seen Fig. 8 through the two-sided fluorescence sense film of high density of butanediamine linking arm mediation.

From Fig. 7,8 as can be seen, along with 2, the spontaneous evaporation in time in cuvette of 4-dinitrotoluene (DNT) steam, the fluorescence emission spectral intensity of this sense film constantly descends in time, this sense film is described to 2,4-dinitrotoluene (DNT) steam response is responsive, and apparently higher than to 2,4, the quencher efficient of 6-trinitro-toluene steam.

(3) use the two-sided fluorescence sense film of high density to detect the paradinitrobenzene steam through the mediation of butanediamine linking arm

The two-sided fluorescence sense film of high density of butanediamine linking arm mediation is adhered to fluorescence cuvette inwall, paradinitrobenzene solid with less than 0.1 gram places one jiao of cuvette bottom simultaneously, seal with being about to the cuvette mouth, allow the spontaneous evaporation in time in cuvette of paradinitrobenzene steam, the saturated vapour pressure of paradinitrobenzene is 2.4 * 10 ^-525 ℃ of mmHg.At ambient temperature, film surface in the face of excitation source, is adopted the method for front surface reflection, use single photon counting time resolution fluorescence spectral instrument immediately, the static fluorescence emission spectrum of a sense film of per two minutes records, experimental result is seen Fig. 9.The two-sided fluorescence sense film of high density through the mediation of butanediamine linking arm is seen Figure 10 by the quencher efficient of paradinitrobenzene steam quencher in time.

From Fig. 9,10 as can be seen, along with the spontaneous evaporation in time in cuvette of paradinitrobenzene steam, the fluorescence emission spectral intensity of this sense film constantly descends in time, explanation is responsive to the response of paradinitrobenzene steam through the two-sided fluorescence sense film of high density of butanediamine linking arm mediation, and apparently higher than to 2,4, the quencher efficient of 6-trinitro-toluene steam.

(4) use through the two-sided fluorescence sense film detection of the high density of butanediamine linking arm mediation meta-dinitro-benzent steam and will adhere to fluorescence cuvette inwall through the two-sided fluorescence sense film of high density of butanediamine linking arm mediation, meta-dinitro-benzent solid with less than 0.1 gram places one jiao of cuvette bottom simultaneously, seal with being about to the cuvette mouth, allow the spontaneous evaporation in time in cuvette of meta-dinitro-benzent steam, the saturated vapour pressure of meta-dinitro-benzent is 8.8 * 10 ^-425 ℃ of mmHg.At ambient temperature, film surface in the face of excitation source, is adopted the method for front surface reflection, use single photon counting time resolution fluorescence spectral instrument immediately, the static fluorescence emission spectrum of a sense film of per two minutes records, experimental result is seen Figure 11.The two-sided fluorescence sense film of high density through the mediation of butanediamine linking arm is seen Figure 12 by the quencher efficient of meta-dinitro-benzent steam quencher in time.

From Figure 11,12 as can be seen, along with the spontaneous evaporation in time in cuvette of meta-dinitro-benzent steam, fluorescence emission spectral intensity through the two-sided fluorescence sense film of high density of butanediamine linking arm mediation constantly descends in time, illustrate that this sense film is responsive to the response of meta-dinitro-benzent steam, and apparently higher than to 2,4, the quencher efficient of 6-trinitro-toluene steam.

(5) use the two-sided fluorescence sense film of high density to detect the para-nitrotoluene steam through the mediation of butanediamine linking arm

To adhere to fluorescence cuvette inwall through the two-sided fluorescence sense film of high density of butanediamine linking arm mediation, para-nitrotoluene solid with less than 0.1 gram places one jiao of cuvette bottom simultaneously, seal with being about to the cuvette mouth, allow the spontaneous evaporation in time in cuvette of para-nitrotoluene steam, the saturated vapour pressure of para-nitrotoluene is 1.64 * 10 ^-125 ℃ of mmHg.At ambient temperature, film surface in the face of excitation source, is adopted the method for front surface reflection, use single photon counting time resolution fluorescence spectral instrument immediately, the static fluorescence emission spectrum of a sense film of per two minutes records, experimental result is seen Figure 13.The two-sided fluorescence sense film of high density through the mediation of butanediamine linking arm is seen Figure 14 by the quencher efficient of para-nitrotoluene steam quencher in time.

From Figure 13,14 as can be seen, along with the spontaneous evaporation in time in cuvette of para-nitrotoluene steam, fluorescence emission spectral intensity through the two-sided fluorescence sense film of high density of butanediamine linking arm mediation obviously descends in time, illustrate that this sense film is responsive to the response of para-nitrotoluene steam, and apparently higher than to 2,4, the quencher efficient of 6-trinitro-toluene steam.

(6) use the two-sided fluorescence sense film of high density to detect the paranitrochlorobenzene steam through the mediation of butanediamine linking arm

To adhere to fluorescence cuvette inwall through the two-sided fluorescence sense film of high density of butanediamine linking arm mediation, paranitrochlorobenzene solid with less than 0.1 gram places one jiao of cuvette bottom simultaneously, seal with being about to the cuvette mouth, allow the spontaneous evaporation in time in cuvette of paranitrochlorobenzene steam, the saturated vapour pressure of paranitrochlorobenzene is 9.0 * 10 ^-225 ℃ of mmHg.At ambient temperature, film surface in the face of excitation source, is adopted the method for front surface reflection, use single photon counting time resolution fluorescence spectral instrument immediately, the static fluorescence emission spectrum of a sense film of per two minutes records, experimental result is seen Figure 15.The two-sided fluorescence sense film of high density through the mediation of butanediamine linking arm is seen Figure 16 by the quencher efficient of paranitrochlorobenzene steam quencher in time.

As can be seen from the figure, along with the spontaneous evaporation in time in cuvette of paranitrochlorobenzene steam, fluorescence emission spectral intensity through the two-sided fluorescence sense film of high density of butanediamine linking arm mediation constantly descends in time, illustrate that this sense film is responsive to the response of paranitrochlorobenzene steam, and apparently higher than to 2,4, the quencher efficient of 6-trinitro-toluene steam.

(7) use the two-sided fluorescence sense film of high density to detect nitrobenzene vapor through the mediation of butanediamine linking arm

To adhere to fluorescence cuvette inwall through the two-sided fluorescence sense film of high density of butanediamine linking arm mediation, the nitrobenzene solution that 3-4 is dripped is added dropwise in the cuvette simultaneously, immediately the cuvette mouth is sealed, allow nitrobenzene vapor volatilize naturally in time in cuvette, the saturated vapour pressure of nitrobenzene is 2.7 * 10 ^-125 ℃ of mmHg.At ambient temperature, film surface in the face of excitation source, is adopted the method for front surface reflection, use single photon counting time resolution fluorescence spectral instrument immediately, the static fluorescence emission spectrum of a sense film of per two minutes records.Experimental result is seen Figure 17.Fluorescence sense film through the mediation of butanediamine linking arm is seen Figure 18 by the quencher efficient of nitrobenzene vapor quencher in time.

As can be seen from the figure, along with nitrobenzene vapor volatilization naturally in time in cuvette, fluorescence emission spectral intensity through the two-sided fluorescence sense film of high density of butanediamine linking arm mediation obviously descends in time, illustrates that this sense film p-nitrophenyl steam response is responsive.

3, relatively through the two-sided fluorescence sense film of high density of ethylenediamine, propane diamine, butanediamine, the mediation of Diethylenetriamine linking arm to 2,4, the efficient that 6-trinitro-toluene steam detects

With 2,4 of 5～6g, 6-trinitro-toluene solid is put into the storage tank of teflon, makes 2,4, and 6-trinitro-toluene steam is saturated in storage tank, pumps in the cuvette with pump and tests.To adhere to fluorescence cuvette inwall through the two-sided substrate fluorescence sense film of high density of butanediamine linking arm mediation, cuvette links by conduit and air pump, opens air pump switch, and 2,4,6-trinitro-toluene steam pumps in the cuvette, at ambient temperature, film surface is faced excitation source, adopt the method for front surface reflection, use single photon counting time resolution fluorescence spectral instrument immediately, the static fluorescence emission spectrum of a sense film of per two minutes records, experimental result is seen Figure 19.

As can be seen from the figure, along with 2,4,6-trinitro-toluene steam is pumped in the cuvette, obviously constantly descends in time through the fluorescence emission spectral intensity of the two-sided fluorescence sense film of high density of butanediamine linking arm mediation.

(2) use the two-sided fluorescence sense film of high density to detect 2,4,6-trinitro-toluene steam through the mediation of propane diamine linking arm

To adhere to fluorescence cuvette inwall through the two-sided fluorescence sense film of high density of propane diamine linking arm mediation, method of testing detects 2 with the two-sided substrate fluorescence sense film of high density through the mediation of butanediamine linking arm, 4,6-trinitro-toluene steam, experimental result is seen Figure 20.

As can be seen from the figure, along with trinitro-first steam is pumped in the cuvette, obviously constantly descend in time through the fluorescence emission spectral intensity of the two-sided fluorescence sense film of high density of propane diamine linking arm mediation.

(3) use the two-sided fluorescence sense film of high density to detect 2,4,6-trinitro-toluene steam through the mediation of ethylenediamine linking arm

To adhere to fluorescence cuvette inwall through the two-sided fluorescence sense film of high density of ethylenediamine linking arm mediation, method of testing detects 2,4 with the two-sided fluorescence sense film of high density through the mediation of butanediamine linking arm, 6-trinitro-toluene steam, and experimental result is seen Figure 21.

As can be seen from the figure, along with 2,4,6-trinitro-toluene steam is pumped in the cuvette, constantly descends in time through the fluorescence emission spectral intensity of the two-sided fluorescence sense film of high density of ethylenediamine linking arm mediation.

(4) use the two-sided fluorescence sense film of high density to detect 2,4,6-trinitro-toluene steam through the mediation of Diethylenetriamine linking arm

To adhere to fluorescence cuvette inwall through the two-sided fluorescence sense film of high density of Diethylenetriamine linking arm mediation, method of testing detects 2 with the two-sided fluorescence sense film of high density through the mediation of butanediamine linking arm, 4,6-trinitro-toluene steam, experimental result is seen Figure 22.

As can be seen from the figure, along with 2,4,6-trinitro-toluene steam is pumped in the cuvette, constantly descends in time through the fluorescence emission spectral intensity of the two-sided fluorescence sense film of high density of butanediamine linking arm mediation.

Relatively through four kinds of two-sided fluorescence sense films of high density of ethylenediamine, propane diamine, butanediamine, the mediation of Diethylenetriamine linking arm in time by 2,4, the experimental result of 6-trinitro-toluene steam quencher is seen Figure 23.

Through the two-sided fluorescence sense film of high density of propane diamine linking arm mediation quencher efficient height, respond the most responsive as seen from the figure than other three kinds of two-sided fluorescence sense films of high density.

4, the efficient that relatively the para-nitrotoluene steam is detected through the two-sided fluorescence sense film fluorescence sense film of four kinds of high density of ethylenediamine, propane diamine, butanediamine, the mediation of Diethylenetriamine linking arm

(1) use the two-sided fluorescence sense film of high density to detect the para-nitrotoluene steam through the mediation of butanediamine linking arm

The para-nitrotoluene solid of 5～6g is put into the storage tank of teflon, in advance that the para-nitrotoluene steam is saturated at this.During experiment, the para-nitrotoluene steam of saturation pumped in the cuvette with pump test.To adhere to fluorescence cuvette inwall through the two-sided fluorescence sense film of high density of butanediamine linking arm mediation, cuvette is connected on the air pump, open air pump switch, the para-nitrotoluene steam is pumped in the cuvette, at ambient temperature, film surface is faced excitation source, adopt the method for front surface reflection, use single photon counting time resolution fluorescence spectral instrument immediately, the static fluorescence emission spectrum of a sense film of per two minutes records, experimental result is seen Figure 24.

As can be seen from the figure, along with the para-nitrotoluene steam is pumped in the cuvette, obviously constantly descend in time through the fluorescence emission spectral intensity of the two-sided fluorescence sense film of high density of butanediamine linking arm mediation.

(2) use the two-sided fluorescence sense film of high density to detect the para-nitrotoluene steam through the mediation of propane diamine linking arm

To adhere to fluorescence cuvette inwall with the two-sided fluorescence sense film of high density of propane diamine linking arm mediation, method of testing detects the para-nitrotoluene steam with the two-sided fluorescence sense film of high density through the mediation of butanediamine linking arm, and experimental result is seen Figure 25.

As can be seen from the figure, along with the para-nitrotoluene steam is pumped in the cuvette, obviously constantly descend in time through the fluorescence emission spectral intensity of the two-sided fluorescence sense film of high density of propane diamine linking arm mediation.

(3) use the two-sided fluorescence sense film of high density to detect the para-nitrotoluene steam through the mediation of ethylenediamine linking arm

To adhere to fluorescence cuvette inwall through the two-sided fluorescence sense film of high density of ethylenediamine linking arm mediation, method of testing detects the para-nitrotoluene steam with the two-sided fluorescence sense film of high density through the mediation of butanediamine linking arm.Experimental result is seen Figure 26.

As can be seen from the figure, along with the para-nitrotoluene steam is pumped in the cuvette, obviously constantly descend in time through the fluorescence emission spectral intensity of the two-sided fluorescence sense film of high density of ethylenediamine linking arm mediation.

(5) use the two-sided fluorescence sense film of high density to detect the para-nitrotoluene steam through the mediation of Diethylenetriamine linking arm

To adhere to fluorescence cuvette inwall through the two-sided fluorescence sense film of high density of Diethylenetriamine linking arm mediation, method of testing detects the para-nitrotoluene steam with the two-sided fluorescence sense film of high density through the mediation of butanediamine linking arm, and experimental result is seen Figure 27.

As can be seen from the figure, along with the para-nitrotoluene steam is pumped in the cuvette, obviously constantly descend in time through the fluorescence emission spectral intensity of the two-sided fluorescence sense film of high density of Diethylenetriamine linking arm mediation.

Relatively seen Figure 28 by the experimental result of para-nitrotoluene steam quencher in time through four kinds of two-sided fluorescence sense films of high density of ethylenediamine, propane diamine, butanediamine, the mediation of Diethylenetriamine linking arm.

As can be seen from the figure, respond the most responsive through the two-sided fluorescence sense film of high density of propane diamine linking arm mediation quencher efficient height than other three kinds of two-sided fluorescence sense films of high density.

5, comparison is through the efficient of the two-sided fluorescence sense film p-nitrophenyl steam detection of four kinds of high density of ethylenediamine, propane diamine, butanediamine, the mediation of Diethylenetriamine linking arm

(1) use the two-sided fluorescence sense film of high density to detect nitrobenzene vapor through the mediation of butanediamine linking arm

To adhere to fluorescence cuvette inwall through the two-sided fluorescence sense film of high density of butanediamine linking arm mediation, glass tube with internal diameter 4mm, long 20mm adheres to one jiao of fluorescence cuvette inwall again, the nitrobenzene solution of 0.5mL is injected in the glass tube, immediately the cuvette mouth is sealed.At ambient temperature, film surface in the face of excitation source, is adopted the method for front surface reflection, use single photon counting time resolution fluorescence spectral instrument immediately, the static fluorescence emission spectrum of a sense film of per two minutes records, experimental result is seen Figure 29.

As can be seen from the figure, along with the quick volatilization of nitrobenzene vapor in cuvette, obviously descend fast in time through the fluorescence emission spectral intensity of the two-sided fluorescence sense film of high density of butanediamine linking arm mediation.

(2) use the two-sided fluorescence sense film of high density to detect nitrobenzene vapor through the mediation of propane diamine linking arm

To adhere to fluorescence cuvette inwall through the two-sided fluorescence sense film of high density of propane diamine linking arm mediation, method of testing detects nitrobenzene vapor with the two-sided fluorescence sense film of high density through the mediation of butanediamine linking arm, and experimental result is seen Figure 30.

As can be seen from the figure, along with the quick volatilization of nitrobenzene vapor in cuvette, obviously descend fast in time through the fluorescence emission spectral intensity of the two-sided fluorescence sense film of high density of propane diamine linking arm mediation.

(3) use the two-sided fluorescence sense film of high density to detect nitrobenzene vapor through the mediation of ethylenediamine linking arm

To adhere to fluorescence cuvette inwall through the two-sided fluorescence sense film of high density of ethylenediamine linking arm mediation, method of testing detects nitrobenzene vapor with the two-sided fluorescence sense film of high density through the mediation of butanediamine linking arm, and experimental result is seen Figure 31.

As can be seen from the figure, along with the quick volatilization of nitrobenzene vapor in cuvette, obviously descend in time through the fluorescence emission spectral intensity of the two-sided fluorescence sense film of high density of ethylenediamine linking arm mediation.

(4) use the two-sided fluorescence sense film of high density to detect nitrobenzene vapor through the mediation of Diethylenetriamine linking arm

To adhere to fluorescence cuvette inwall through the two-sided fluorescence sense film of high density of Diethylenetriamine linking arm mediation, method of testing detects nitrobenzene vapor with the two-sided fluorescence sense film of high density through the mediation of butanediamine linking arm, and experimental result is seen Figure 32.

As can be seen from the figure, along with the quick volatilization of nitrobenzene vapor in cuvette, obviously descend in time through the fluorescence emission spectral intensity of the two-sided fluorescence sense film of high density of Diethylenetriamine linking arm mediation.

Relatively seen Figure 33 by the experimental result of nitrobenzene vapor quencher in time through four kinds of two-sided fluorescence sense films of high density of ethylenediamine, propane diamine, butanediamine, the mediation of Diethylenetriamine linking arm.

6, use the two-sided fluorescence sense film of fluorescence sense film, the fluorescence sense film of middle density single face, high density of the low-density single face that mediates through the propane diamine linking arm to detect 2,4,6-trinitro-toluene steam

(1) through the mensuration of the two-sided static fluorescence spectrum of fluorescence sense film of fluorescence sense film, the fluorescence sense film of middle density single face, the high density of the low-density single face of propane diamine linking arm mediation

To adhere to fluorescence cuvette inwall respectively through the two-sided fluorescence sense film of fluorescence sense film, the fluorescence sense film of middle density single face, high density of the low-density single face of propane diamine linking arm mediation, again the cuvette mouth be sealed.At ambient temperature, excitation source is faced on the fluorescence sense film surface of three kinds of different densities, adopted the method for front surface reflection, test the static fluorescence emission spectrum of the fluorescence sense film of three kinds of different densities with single photon counting time resolution fluorescence spectral instrument.The static fluorescence spectrum figure under dry state of the fluorescence sense film of three kinds of different densities sees Figure 34.

As can be seen from the figure, the fluorescence spectrum of the fluorescence sense film of low-density single face (Film1) mainly exists with the form at monomer peak; The existing monomer of the fluorescence spectrum peak of the fluorescence sense film (Film2) of middle density single face has the excimer peak again; The fluorescence spectrum of the fluorescence sense film (Film3) that high density is two-sided mainly exists with the form at excimer peak.

(2) use low-density single face fluorescence sense film (Film1) to detect 2,4,6-trinitro-toluene steam through the mediation of propane diamine linking arm

Getting 10 volumes is 5mL plastic seal bottle, and with 2,4 of 2～3 grams, 6-trinitro-toluene solid is put into bottle, puts a fritter cotton yarn thereon, the sealing bottleneck.During test, to be positioned in the different bottles respectively successively through the low-density single face fluorescence sense film Film1 of propane diamine linking arm mediation, make film be exposed to 2,4, in the 6-trinitro-toluene saturated vapor, the variation of fluorescence intensity behind the record exposure different time, this sense film is adhered to fluorescence cuvette inwall fixed position, at ambient temperature, excitation source is faced on this sense film surface, adopt the method for front surface reflection, with the static fluorescence emission spectrum of single photon counting time resolution fluorescence spectral instrument record sense film.Take off this sense film then, it is positioned in the bottle, be exposed to 2,4 successively, 6-trinitro-

toluene steam

1,3,5,10,30 minutes writes down the static fluorescence emission spectrum of this sense film successively, and experimental result is seen Figure 35.

As can be seen from the figure, along with through the low-density single face fluorescence sense film of propane diamine linking

arm mediation

2,4, exposure in the 6-trinitro-toluene steam, the fluorescence emission spectral intensity of fluorescence sense film obviously constantly descends, this sense film is described to 2,4, the response of 6-trinitro-toluene steam is very responsive.

(3) use middle density single face fluorescence sense film (Film2) to detect 2,4,6-trinitro-toluene steam through the mediation of propane diamine linking arm

Method of testing detects 2,4 with the low-density single face fluorescence sense film (Film1) that mediates through the propane diamine linking arm, and the method for testing of 6-trinitro-toluene steam is identical.Experimental result is seen Figure 36.

arm mediation

2,4, exposure in the 6-trinitro-toluene steam, the fluorescence emission spectral intensity of fluorescence sense film obviously constantly descends, this sense film is described to 2,4, the response of 6-trinitro-toluene steam is responsive.

(4) the two-sided fluorescence sense film of high density (Film3) in order to the mediation of propane diamine linking arm detects 2,4,6-trinitro-toluene steam

Method of testing detects 2,4 with the low-density single face fluorescence sense film (Film1) that mediates through the propane diamine linking arm, and the method for testing of 6-trinitro-toluene steam is identical.Be exposed to 2,4 successively, 6-trinitro-

toluene steam

1,3,5,10,20,30 minutes writes down the static fluorescence emission spectrum of this sense film successively.Experimental result is seen Figure 37.

arm mediation

Through the two-sided fluorescence sense film of fluorescence sense film, the fluorescence sense film of middle density single face, the high density of the low-density single face of propane diamine linking arm mediation with the difference of exposure duration by 2,4, the quencher efficiencies of 6-trinitro-toluene steam quencher is seen Figure 38.

As can be seen from the figure, the fluorescence sense film of low-density single face (Film1) quencher is most effective, and to 2,4, the response of 6-trinitro-toluene steam is the most responsive.

7, through the fluorescence sense film fluorescence sense film (Film1) of the low-density single face of propane diamine linking arm mediation to 2,4,6-trinitro-toluene saturated vapor sensing The reversible experiment

Getting 10 volumes is 5mL plastic seal bottle, and with 2,4 of 2～3 grams, 6-trinitro-toluene solid is put into bottle, puts a fritter cotton yarn thereon, and bottleneck is sealed.To adhere to fluorescence cuvette inwall fixed position through the fluorescence sense film fluorescence sense film (Film1) of the low-density single face of propane diamine linking arm mediation, at ambient temperature, excitation source is faced on this sense film surface, adopt the method for front surface reflection, write down the static fluorescence emission spectrum of this sense film with single photon counting time resolution fluorescence spectral instrument, take off this sense film then, it is positioned in the bottle, make it be exposed to 2,4,6-trinitro-toluene steam merges 9 minutes time, takes out, write down the static fluorescence emission spectrum of this sense film immediately with single photon counting time resolution fluorescence spectral instrument, replicate determination 5 times.Then this sense film is taken out and put into ethanolic solution immersion 5 minutes, dry up after the taking-up and carry out replication.Press this step replication 5 times, measurement result is seen Figure 39.

As can be seen from Figure 39, to 2,4, the detection of 6-trinitro-toluene steam is reversible through the low-density single face fluorescence sense film (Film1) of propane diamine linking arm mediation.

8, with the low-density single face fluorescence sense film (Film1) of propane diamine linking arm mediation benzene, toluene, ethanol, perfume steam, flue gas interference are tested

To adhere to fluorescence cuvette inwall through the low-density single face fluorescence sense film (Film1) of propane diamine linking arm mediation, respectively benzene vapor, toluene steam, ethanol steam, perfume steam, fruit smell, flue gas are injected in the cuvette, the cuvette mouth is sealed, at ambient temperature, excitation source is faced on this sense film surface, adopt the method for front surface reflection, use single photon counting time resolution fluorescence spectral instrument immediately, the static fluorescence emission spectrum of a sense film of per two minutes records.Significant change does not take place in spectrum.Test findings shows, and is insensitive to benzene vapor, toluene steam, ethanol steam, perfume steam, flue gas through the low-density single face fluorescence sense film (Film1) of propane diamine linking arm mediation.

9, conclusion

(1) static spectroscopic assay shows that the fluorescent small molecule pyrene has been fixed to substrate surface effectively, and it is more even to distribute.

(2) existence of nitro-aromatic compound in the air, fluorescent emission through the fluorescence sense film of four kinds of different densities of butanediamine, propane diamine, ethylenediamine and the mediation of Diethylenetriamine linking arm all there is stronger quenching effect, shows detection sensitivity the nitro-aromatic compound steam.

(3) compare with three kinds of different densities fluorescence sense films that mediate through butanediamine, ethylenediamine and Diethylenetriamine linking arm through the low-density single face fluorescence sense film of propane diamine linking arm mediation, through the low-density single face fluorescence sense film of propane diamine linking arm mediation to 2,4, the quencher of 6-trinitro-toluene steam is most effective, illustrates that this film is the highest to the sensing sensitivity of nitro-aromatic compound.

(4) through the fluorescence sense film of four kinds of different densities of butanediamine, propane diamine, ethylenediamine and the mediation of Diethylenetriamine linking arm the volatile matter of article such as benzene, toluene, ethanol, cigarette, fruit, perfume there is not obvious response, this type of sense film is described, and not only response is good to nitro-aromatic compound, and the selectivity height.

(5) restorative experiment shows that the fluorescence sense film of the different densities that mediates through butanediamine, propane diamine, ethylenediamine and Diethylenetriamine linking arm is reversible to the nitro-aromatic compound response.

Claims

1, a kind of preparation method of pyrene functionalized sensing film is characterized in that this preparation method comprises the steps:

(1) tailors substrate

Glass plate is cut into 0.9 * 2.5cm ²The rectangular glass sheet of size;

(2) preparation washing lotion

The sulfuric acid of 30% hydrogen peroxide and 98% is mixed and made into washing lotion by the 7:3 volume ratio;

(3) preparation activation substrate

Elder generation's water, ethanol cleaning glass sheet are put into washing lotion after drying up, and 80～100 ℃ were heated 1～2 hour down, and natural cooling with pure redistilled water cleaning glass sheet, is washed the washing lotion of remained on surface off, dries up with hair-dryer, makes the activation substrate;

(4) preparation silanization substrate

Utilize the capillary action of water, the one side of activation substrate is closed with glass sheet is bonding, with this activation substrate and sealing activate substrate to put into the volume ratio of 3-diglycidyl propyl ether base trimethoxy silane and toluene solution respectively be the solution of 3:500, soaked 12～48 hours down at 40～60 ℃, take out substrate, wash with toluene solution earlier, wash with chloroform soln again, wash 3-diglycidyl propyl ether base trimethoxy silane of remained on surface off, hair-dryer dries up, one side is made lateral silicon alkanisation substrate with the activation substrate of the bonding sealing of glass sheet, and sealing activation substrate is not made two-sided silanization substrate;

(5) chloroform soln of four kinds of amino pyrene sulfonyl derivatives of preparation

The pyrene sulfonic acid chloride is dissolved in the chloroform soln that is made into 0.01mol/L pyrene sulfonic acid chloride in the methenyl choloride, this solution is poured in the constant pressure funnel, get again with pyrene sulfonic acid chloride mol ratio be that 5～10 ethylenediamine or propane diamine or butanediamine or Diethylenetriamine are dissolved in the methenyl choloride, be made into the ethylenediamine of 0.05～0.10mol/L or the chloroform soln of propane diamine or butanediamine or Diethylenetriamine, and this solution put into there-necked flask, under 0 ℃ of stirring condition, with the speed feeding N of 0.6～0.8ml/s ₂The chloroform soln of pyrene sulfonic acid chloride is added drop-wise in the chloroform soln of ethylenediamine in the there-necked flask or propane diamine or butanediamine or Diethylenetriamine, dropwise the back and continued stirring reaction 1～2 hour, then reactant liquor is poured in the separating funnel, water and concentration are that 5%NaCl solution is washed till chloroform soln repeatedly and is neutral, add anhydrous magnesium sulfate drying, filter, make the chloroform soln of four kinds of amino pyrene sulfonyl derivatives;

(6) fluorescence sense film of the different densities of four kinds of aminolink mediations of preparation

The chloroform soln of four kinds of amino pyrene sulfonyl derivatives of step (5) preparation is diluted to 0.00025～0.005mol/L concentration, single or double silanization substrate is put into the chloroform soln of four kinds of amino pyrene sulfonyl derivatives of 0.00025～0.005mol/L, reflux 6～14 hours, take out single or double silanization substrate respectively, wash with methenyl choloride, use acetone and second distillation water washing again, wash the residue of the unreacted amino pyrene sulfonyl derivative in surface off, make the fluorescence sense film of the different densities of four kinds of aminolink mediations, put into secondary water and preserve.

2, preparation method according to the described pyrene functionalized sensing film of claim 1, it is characterized in that: in preparation method's of the present invention processing step (5), will with the pyrene sulfonic acid chloride wherein mol ratio be that 5～9 ethylenediamine or propane diamine or butanediamine or Diethylenetriamine are dissolved in the methenyl choloride, being made into wherein, concentration is the ethylenediamine of 0.05～0.09mol/L or the chloroform soln of propane diamine or butanediamine or Diethylenetriamine, in processing step (6), being diluted to the chloroform soln of four kinds of amino pyrene sulfonyl derivatives of step (5) preparation wherein, concentration is 0.00025～0.004mol/L, single or double silanization substrate is put into the chloroform soln of four kinds of amino pyrene sulfonyl derivatives of 0.00025～0.004mol/L, and wherein the reflux time is 10～14 hours.

3, preparation method according to the described pyrene functionalized sensing film of claim 1, it is characterized in that: in preparation method's of the present invention processing step (5), will with the pyrene sulfonic acid chloride wherein mol ratio be that 5 ethylenediamine or propane diamine or butanediamine or Diethylenetriamine are dissolved in the methenyl choloride, being made into wherein, concentration is the ethylenediamine of 0.05mol/L or the chloroform soln of propane diamine or butanediamine or Diethylenetriamine, in processing step (6), being diluted to the chloroform soln of four kinds of amino pyrene sulfonyl derivatives of step (5) preparation wherein, concentration is 0.00025mol/L, single or double silanization substrate is put into the chloroform soln of four kinds of amino pyrene sulfonyl derivatives of 0.00025mol/L, and wherein the time of reflux is 14 hours.

4, adopt the application of pyrene functionalized sensing film in nitro-aromatic compound detects of claim 1 preparation.