CN102899031B - Electro-polymeric organic fluorescent material and application of material in TNT detection - Google Patents
Electro-polymeric organic fluorescent material and application of material in TNT detection Download PDFInfo
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Abstract
The invention belongs to the fluorescent sensing technical field and specifically relates to a high-efficiency organic fluorescent material and application of the material in TNT (trinitrotoluene) detection. The structural formula of the high-efficiency organic fluorescent material provided by the invention is Ar2-Ar1-Ar-Ar1-Ar2, wherein Ar1-Ar-Ar1 forms a light-emitting unit; the light-emitting center Ar can be spirofluorene, benzene, carbazole (alkyl chains different in length can be connected at No.9 site) or fluorene (alkyl chains different in length can be connected at No.9 site); Ar1 can be fluorene, biphenyl or difluorene; and electric-active unit Ar2 can be furan, pyrrole, thiophene, carbazole, diphenylamine or triphenylamine. An electro-polymeric thin film formed from the material through electrochemical polymerization is characterized in that intermolecular aggregation in the electrochemical polymerization process can be effectively reduced, the fluorescence efficiency of the electro-polymeric thin film is improved, and the electro-polymeric thin film is capable of effectively transferring charges with TNT molecules to quench fluorescent light, and therefore, effective detection on TNT is realized.
Description
Technical field
The invention belongs to fluorescence sense technical field, be specifically related to the application aspect detection TNT of the high efficiency electropolymerization organic fluorescence materials of a class and such material.
Background technology
How explosive detection has become a global problem.Research is found, is all contained TNT(2,4,6-trotyl in 21 kinds of compounds relevant to explosive substance).Therefore the detection of explosive substance is mainly concentrated in the detection of TNT.Current detection means mainly contains infrared spectroscopy, vapor-phase chromatography, mass spectroscopy, ion mobility spectrometry method etc.Yet these methods all exist certain limitation, as lower in detectability, the problem such as fallout ratio is high, poor stability, complicated operation.
Sensor method detects the nitro explosive substances such as TNT and compares and have an enormous advantage with other method.Its principle is for to change into analyzable other signals such as fluorescence by " chemical signal " of nitro-compound.In various types of sensors, best with the susceptibility of fluorescence chemical sensor.This technology is based on detecting thing with the intermolecular generation charge transfer of the explosive substances such as TNT, causing quenching of fluorescence.
There have been in the world some research institutions to carry out the work of fluorescence TNT explosive substance sensing, wherein more representational be that U.S. T.M.Swager research group reports a series of have a rigid three-dimensional space structure pentiptycene base polymer material, this is one of the highest material of the current sensitivity of reporting (J.AM.Chem.Soc.Vol.120, No.46,1998,11867).But macromolecular solution spin coating is a dynamic process, because phase structure is difficult, control the stability that affects film forming.The thickness homogeneity of film is a problem that is difficult to avoid.The meeting of spin coating simultaneously causes a large amount of waste of material.
Electrochemical polymerization is because its pattern is easy to control, thereby the microstructure that simultaneously can control by changing electrochemical conditions its polymer thin film inherence improves the responding ability of TNT greatly, and becomes a kind of effective fluoroscopic examination means.In addition, electrochemical polymerization is easy to industry preparation and stronger stability also makes this technology be expected to be dropped in future practical application.
Summary of the invention
The object of the present invention is to provide the high efficiency electropolymerization organic fluorescence materials of a class, and the application to TNT context of detection in gas phase and water of the fluorescence sense film of this organic fluorescence materials of preparing by electrochemical polymerization.
1. the organic fluorescence materials that contains electroactive group
High-level efficiency organic fluorescence materials of the present invention, its structural formula is as follows
Ar
2-Ar
1-Ar-Ar
1-Ar
2
Ar
1-Ar-Ar
1form luminescence unit, wherein luminescence center Ar can be spiral shell fluorenes, benzene, carbazole (No. 9 positions can connect the alkyl chain of different lengths) and fluorenes (No. 9 positions can be connected the alkyl chain of different lengths); Ar
1can be fluorenes, biphenyl and difluorene, and their mutual keys connect and form.Electroactive unit Ar
2can be furans, pyrroles, thiophene, carbazole, pentanoic or triphenylamine.
Electroactive unit and luminescence unit what be connected can be alkyl chain, oxygen base chain or oxyalkyl chain, also can directly be connected.The length of chain can be determined by the number of carbon or oxygen, has nothing to do with the concrete electroactive unit of selecting and luminescence unit, if number is 0, directly with singly-bound, is connected.We design molecular structure main purpose is like this in electrochemical polymerization process, to avoid the impact on luminous host molecule as far as possible.
Wherein n, p, m are less than 10 positive integer;
Further, we have synthesized compound TCPC and OCPC:
The prepared organic fluorescence materials of the present invention can be applied detecting aspect TNT, is further organic fluorescence materials is prepared into after electropolymerization film for TNT context of detection.
Take TCPC and OCPC as example, and TCPC and OCPC be take spiral shell fluorenes as luminescence center, can effectively lower intermolecular gathering in electropolymerization process, thereby improve the fluorescence efficiency of electropolymerization film, simultaneously can be effectively with TNT molecule generation charge transfer quench fluorescence.And above-mentioned two kinds of compounds all contain carbazole group, can in electropolymerization process, can there is crosslinked action, this being cross-linked can make the glomerate micro nano structure of above-mentioned molecule shape (as shown in Figure 3), particle diameter is between 200～400nm), this micro nano structure both can increase molecule with the specific surface area of TNT molecule contact.On the other hand, the opening structure forming between micro-nano, also can be conducive to the diffusion of TNT molecule, improves its fluorescence response efficiency.Thereby realize the detection to TNT.
2, the preparation of electropolymerization film
The preparation of electropolymerization film of the present invention completes in electrolyzer, referring to patent (200810051197.6), and this electrolyzer simple structure, technique is convenient, is easy to realize large-scale mass production.Electrolyzer consists of working electrode, supporting electrode, reference electrode, electrolyte solution etc.
2.1 working electrode
The working electrode using is redox noble electrode, and it can stably work in mensuration current potential region.The electrode materials using can be that gold, platinum, lead and titanium etc. are the metal electrode of representative, can be also graphite, glass carbon etc. is the non-metal electrode of representative and the tin indium oxide ITO translucent optics electrode that is representative.
2.2 supporting electrode
Supporting electrode Main Function is to form the loop of a conducting with working electrode, redox inertia and the electrode that do not react with solution medium all can, for example gold, platinum, lead, titanium and Graphite Electrodes.
2.3 reference electrode
Reference electrode used in the present invention can be used " silver-silver ion electrode ", " silver-silver chloride electrode " or " saturated calomel electrode " to determine the electropotential of operating potential, with upper electrode material, all can buy and obtain with the form of commodity.
2.4 electrolyte solution
Electrolyte solution is comprised of electroanalysis solvent and supporting electrolyte.
2.5 electroanalysis solvent
The electroanalysis solvent that the present invention uses is N,N-dimethylacetamide, DMF, acetonitrile, trichloromethane, methylene dichloride or pyridine, or their mixed solvent.
2.6 supporting electrolyte
Being applicable to negatively charged ion of the present invention can be perchlorate, tetrafluoroborate ion, hexafluorophosphoricacid acid ions, hexafluoroarsenate radical ion, tetraphenyl borate radical ion; Positively charged ion can be potassium ion, lithium ion, tetramethyl ammonium, tetraethyl ammonium ion, tetra-n-butyl ammonium ion.Negatively charged ion and cationic arbitrary combination just can be used as supporting electrolyte, as tetra n butyl ammonium perchlorate, sodium perchlorate, sodium sulfate etc.
Applying of 2.7 electrochemical depositions---electrode voltage
The method adopting can be direct electrolysis method, electromotive force step method, cyclic voltammetry or pulse voltammetry.
The positive potential of the signal that working electrode is applied (current potential 1) scope is 0.5V～1.2V, and the negative potential of signal (current potential 2) scope is-1.5V～-0.5V that the waveform of signal is square wave or choppy sea.
The aftertreatment of 2.8 electropolymerization films
When working electrode takes out from electrolytic solution, owing to carrying out the compound of electrochemical reaction in solution, be not attached on electropolymerization film, so will clean electropolymerization film.
For cleaning the solution of electropolymerization film, can be that purity is 80%～99% N, a kind of in N-N,N-DIMETHYLACETAMIDE, acetonitrile, toluene, methylene dichloride, hexanaphthene, pyridine, benzyl cyanide, or the mixed solvent of above-mentioned solvent, scavenging period is 20 seconds～10 minutes.
2.9 electropolymerization film preparation processes after are preferably as follows:
2.9.1 the preparation of supporting electrolyte solution
In electrolyte solution, TCPC concentration is 0.5 mg/ml, and supporting electrolyte is hexafluorophosphate, and concentration is 0.1 mol/L, and electroanalysis solvent is the mixing solutions of acetonitrile and methylene dichloride, and volume ratio is 3:2.
2.9.2 the use of electrode
Working electrode is ITO(indium tin oxide) electrode, area is 1 square centimeter～2 square centimeters.Supporting electrode is titanium plate, and area is 4 square centimeters.Reference electrode is silver-silver ion electrode, and the solution in reference electrode is the acetonitrile solution containing hexafluorophosphate (0.1 mol/L) of Silver Nitrate (0.01 mol/L), for determining the current potential of working electrode.
2.9.3 galvanic deposit applies current potential
The electrochemical apparatus using is the Shanghai CHI660C of Chen Hua company electrochemical workstation, and cyclic voltammetric parameter is set to the surface sweeping number of turns 8 circles, and take-off potential is-and 0.9V is to 0.9V, and surface sweeping speed is 200mV/s.
2.9.4 the cleaning of electrochemical deposition film
The compound using solubleness in acetonitrile poor and in methylene dichloride solvability better, and the solvability of supporting electrolyte in methylene dichloride be also than good in acetonitrile, thus we adopt acetonitrile with methylene chloride volume than the mixed solvent of 2:3 as eluent.
3. such electropolymerization film application to the fluoroscopic examination aspect of the nitro explosives such as TNT:
3.1 electropolymerization films are for the fluorescence vapor detection method of TNT
We are bonded at the electropolymerization film preparing on ITO on the lid of quartz colorimetric utensil, regulate light path, make exciting light (RE5301) effectively see through cuvette and are radiated at the center of film, and collect stable spectrum.Regulate after light path, take out film, TNT powder is placed in to the bottom of cuvette, and standing 1 hour, make its vapour pressure that reaches capacity (25 ℃ of 10PPT).Then film is placed in to cuvette, the lid of quartz colorimetric utensil is covered, the emmission spectrum of recording sheet is situation over time.
3.2 electropolymerization films are for the fluorescence water detection method of TNT
The electropolymerization film preparing is placed in to quartz colorimetric utensil, regulates light path to make excitation light irradiation at the center of film.In quartz colorimetric utensil, add deionized water 3mL to make membranes submerged, test its spectrum (RF5301).Then to the tetrahydrofuran solution (0.1mol/L) that drips 3 μ L TNT in cuvette, gather spectroscopic data.
The thickness of 3.3 electropolymerization films is with the variation of polymerizing condition and for the fluorescence response of TNT
Under cyclic voltammetric pattern, we control electropolymerization sweep velocity (200mV/s) scans the number of turns (Scan sweep) by change and obtains the film of different thickness, and it is detected for TNT.
The scanning number of turns is respectively 6,8,12,16,20 circles, and its thickness increases with the increase of the number of turns.After tested, 8 when circle its fluorescence response effect for TNT the most obvious.
3.4 electropolymerization film morphology are for the impact of its fluorescence response
We change by the gated sweep number of turns (8 circle) the electropolymerization film that sweep velocity (50mV/s, 100mV/s, 200mV/s) obtains different-shape.
After characterizing, atomic force microscope obtained the film of different-shape.We find, along with the reduction of sweep velocity, it is smooth that film is tending towards, and its compactness extent also increases thereupon.And along with the densification of film can cause the reduction of its fluorescence response ability.Therefore, select the film in response that faster prepared by sweep velocity (200mV/s) better.
Feature based on electropolymerization film, the molecule of a series of fluorescence electrochemical activities that we are designed and synthetic, this quasi-molecule has following feature:
(1) these molecules all contain fluorenes or spiral shell fluorenes, and have higher fluorescence efficiency and have higher electron donation simultaneously, these be conducive to and TNT between charge transfer.
(2) carbazole molecule is very easy to form dimer by electrochemical oxidation coupling, and dimeric structure is clear and definite, is easy to control, and redox property is stable, and the reticulated film simultaneously forming is stable, the application after being convenient under physical condition.
(3) the luminous main chain that light emitting molecule contains rigidity and flexible alkyl carbazole side chain.This quasi-molecule is conducive to control pattern in electropolymerization process, a plurality of carbazole units have increased crosslink sites, so both can obtain smooth modified electrode by controlling electrochemical conditions, also can obtain the modified electrode that contains micro-nano mechanism, thereby the diffusion that is easy to TNT molecule is greatly carried and is carried on fluorescence response.
(4) between luminescence center and carbazole unit, with the alkyl chain of inertia, be connected, guaranteed that electropolymerization process can not exert an influence to luminescence center, the oxidizing potential of luminescence center is higher than the oxidizing potential of carbazole, and in the situation that not affecting luminescence center, carbazole just electrochemical polymerization can occur.
The fluorescence membrane of preparing with additive method is compared, and its tool of electropolymerization film of electrochemical polymerization has the following advantages:
(1) pattern is easy to change, without carrying out the complex operations such as the doping of template and removal.Only need to change the film that electrochemical conditions can obtain different-shape.
(2) film forming by electrochemical polymerization can form cross-linked network, and the film forming with other modes is compared, and this reticulated structure is conducive to the diffusion of TNT molecule.
(3) electropolymerization film, by change condition, can obtain the microstructure of column, and this structure can effectively improve the contact area of same TNT, further mentions its fluorescence response ability that improves.
(4) the electropolymerization film producing through electrochemical polymerization has superpower fluorescent stability, and its (toluene, tetrahydrofuran (THF), dichloro, acetone, Virahol) fluorescence in conventional organic reagent keeps stable after tested.In 48 hours, its fluorescence does not change.Even in the hydrochloric acid soln of pH=1, and in the sodium hydroxide solution of pH=14, soak 48 hours, its fluorescence does not almost change yet.The application in real life from now on to it of this superpower fluorescent stability, and the equal important role of the steady operation under various environment.
(5) fluorescence membrane of preparing with other modes is compared, and electrochemical polymerization is less for the waste of material, and is easy to suitability for industrialized production, has high industrial prospect.
Accompanying drawing explanation
Fig. 1: electropolymerization film preparation device figure;
The electropolymerization multi-turn cyclic voltammetry curve of Fig. 2: TCPC, OCPC;
Fig. 3: TCPC electropolymerization film atomic force microscope images (AFM);
Fig. 4: TCPC is quenching of fluorescence temporal evolution curve under TNT atmosphere;
Fig. 5: TCPC electropolymerization film fluorescence for TNT in water is identified and Ksv curve.
As shown in Figure 1, each component names is: electrochemical workstation 1; Supporting electrode 2; Electrolyte solution 3; Reference electrode 4; Working electrode 5; Amperometer 6; Voltmeter 7; Organic fluorescence materials 8 solution that can electrochemical deposition.
Embodiment
Embodiment 1: compound TCPC's is synthetic:
The two bromine fluorenes of 2,7-
6g (36mmol) fluorenes, 92mg (1.6mmol) iron trichloride, 4ml bromine lucifuge in dichloromethane solvent is reacted 12 hours.The solid filtering producing, then with ethyl alcohol recrystallization, obtain white solid product, productive rate 75%.
1h NMR (500MHz, CDCl
3): δ 7.66 (s, 2H, Ar-H), δ 7.60-7.59 (d, 2H, Ar-H), δ 7.51-7.49 (d, 2H, Ar-H), δ 3.87 (s, 2H, Ar-H-Ar) mass spectrum (m/z) 323.9 ultimate analyses: calculated value: C
13h
8br
2: C, 48.19; H, 2.49 test values: C, 48.54; H, 2.51
Two bromo-9 Fluorenones of 2,7-
1.3g (4mmol) 2, methanol solution vigorous stirring in pyridine solvent of the two bromine fluorenes of 7-and 0.1ml tetrabutyl oxyammonia passes into oxygen simultaneously, after a large amount of solids to be generated, injects a large amount of water, filters and obtains yellow solid product, productive rate 95%.
1h NMR (500MHz, CDCl
3): δ 7.78 (s, 2H, Ar-H), δ 7.65-7.63 (d, 2H, Ar-H), δ 7.41-7.39 (d, 2H, Ar-H). mass spectrum (m/z) 337.3. ultimate analysis calculated value C
13h
6br
20:C, 46.20; H, 1.79 test values: C, 46.44; H, 2.02.
Two bromo-9-(2 '-the biphenyl)-9-fluorenols of 2,7-
0.74ml (4.5mmol) 2-bromo biphenyl is dissolved in anhydrous diethyl ether and is added drop-wise in 97mg (4mmol) magnesium rod, usings a little iodine to start grignard reaction as initiator, after question response starts, raw material is slowly dripped, and refluxes 2 hours after dropwising again.By 1.11g (3.3mmol) 2, two bromo-9 Fluorenones of 7-join in the Grignard reagent preparing in batches, and backflow is spent the night.Except desolventizing, add saturated aqueous ammonium chloride to stir 3 hours, chloroform extraction, anhydrous magnesium sulfate drying.Take methylene dichloride and sherwood oil mixed solvent is eluent, and column chromatography obtains white solid, productive rate 83%.
1h NMR (500MHz, CDCl
3): δ 8.41-8.40 (d, 2H, Ar-H), δ 7.57-7.54 (t, 2H, Ar-H), δ 7.38-7.35 (t, 2H, AR-H), δ 7.33-7.32 (m, 8H, Ar-H), δ 7.00-6.98 (m, 4H, Ar-H), δ 6.95-6.94 (d, 2H, Ar-H), δ 6.86-6.83 (t, 2H, Ar-H), δ 6.70-6.66 (t, 4H, Ar-H), δ 6.10-6.09 (d, 2H, Ar-H). mass spectrum: 492.2. ultimate analysis theoretical value C
25h
16br
20:C, 61.00; H, 3.28 actual values: C, 59.54; H, 3.81.
2,7-is two bromo-9,9-xenyl fluorenes
1.15g (2.3mmol) 2, two bromo-9-(2 '-biphenyl)-9 '-fluorenols of 7-are dissolved in the Glacial acetic acid of boiling, add several concentrated hydrochloric acids as dewatering agent back flow reaction 3 hours.Cooling, add large water gaging, to filter, washing obtains white solid product, productive rate 95%.
1h NMR (500MHz, CDCl
3): δ 7.86-7.84 (d, 2H, Ar-H), δ 7.68-7.66 (d, 2H, Ar-H), δ 7.50-7.47 (d, 2H, Ar-H), δ 7.42-7.39 (t, 2H, Ar-H), δ 7.16-7.13 (t, 2H, Ar-H), δ 6.83 (s, 2H, Ar-H), δ 6.73-6.71 (d, 2H, Ar-H). mass spectrum 474.2. ultimate analysis: calculated value C
25h
14br
20:C, 63.32; H, 2.98 test values: C, 63.15; H, 3.06.
2,7-pair-(4,4,5,5-tetramethyl--1,3,2-dioxa boron)-9,9-xenyl fluorenes (1)
Under nitrogen protection, 1ml (2.5mmol) butyllithium is slowly added drop-wise to 0.711g (1.5mmol) 2 under-78 ° of C, and 7-two bromo-9; in the tetrahydrofuran solution of 9 '-xenyl fluorenes; after dropwising, temperature is raised to stirring at room 15 minutes, then is down to-78 ° of C, add fast 1.22ml (6mmol) 2-isopropoxy-4; 4; 5,5-tetramethyl--1,3; 2-dioxa borine, stirring at room 24 hours.Washing, extracted with diethyl ether, anhydrous magnesium sulfate drying, except desolventizing, ethyl alcohol recrystallization obtains white solid product, productive rate 50%.
1H?NMR(500MHz，CDCl
3)：δ7.88-7.83(m，6H，Ar-H)，δ7.37-7.34(t，2H，Ar-H)，δ7.13(s，2H，Ar-H)，δ7.10-7.07(t，2H，Ar-H)，δ6.70-6.68(d，2H，Ar-H)，δ1.22(s，24H，CH
3)。Ultimate analysis: calculated value C
37h
38b
20
4: C, 78.2; H, 6.71 test values: C, 77.66; H, 6.80.
The bromo-hexane of N-(6-)-carbazole
10g (59.8mmol) and 9.48ml (61.4mmol) 1, the two bromohexanes of 6-are dissolved in tetrahydrofuran (THF) and are added drop-wise in the sodium hydride that washes away oxide film, stirring at room 24h.Filter residue sodium hydride, concentrated filtrate.Take methylene dichloride and sherwood oil mixed solvent is eluent, and column chromatography obtains white solid, productive rate 45%.
1h NMR (500MHz, CDCl
3): δ 8.11-8.09 (d, 2H, Ar-H), δ 7.47-7.45 (t, 2H, Ar-H), δ 7.40-7.39 (d, 2H, Ar-H), δ 7.23-7.21 (t, 2H, Ar-H), δ 4.31-4.30 (t, 2H, N-CH
2), δ 3.36-3.35 (t, 2H, Br-H), δ 1.92-1.86 (m, 2H, CH
2), δ 1.84-1.78 (m, 2H, CH
2), δ 1.49-1.44 (m, 2H, CH
2), δ 1.42-1.38 (m, 2H, CH
2). ultimate analysis theoretical value C
18h
20nBr:C, 65.46; H, 6.10; N, 4.24 test values: C, 65.44; H, 6.10; N, 4.12
2-is bromo-9,9-(N-carbazole-hexyl) fluorenes (5)
The tetrahydrofuran solution of 2.03g (6.15mmol) 2-bromo fluorenes is slowly added drop-wise to the bromo-hexane of 0.7g (2.8mmol) N-(6-) in the tetrahydrofuran solution of-carbazole and sodium hydride, back flow reaction 48h.Cooling, filters remaining sodium hydride, concentrated.Take methylene dichloride and sherwood oil mixed solvent is eluent, and column chromatography obtains white solid, productive rate 95%.
1h NMR (500MHz, DMSO): δ 8.12-8.10 (d, 4H, Ar-H-car), δ 7.76-7.75 (d, 1H, Ar-H-flu), δ 7.72-7.71 (d, 1H, Ar-H-flu), δ 7.57 (s, 1H, Ar-H-flu), δ 7.48-7.47 (d, 4H, Ar-H-car), δ 7.42-7.39 (t, 4H, Ar-H-car), δ 7.28-7.25 (m, 4H, Ar-H-flu), δ 7.18-7.15 (t, 4H, Ar-H-car), δ 4.26-4.23 (m, 4H, N-CH
2), δ 1.83-1.82 (m, 4H, CH
2), δ 1.53-1.52 (m, 4H, CH
2), δ 1.01 (m, 8H, CH
2), δ 0.40-0.38 (m, 4H, CH
2). ultimate analysis theoretical value: C
49h
47n
2br:C, 79.12; H, 6.37; N, 3.77 actual values: C, 79.13; H, 7.32; N, 3.18.
9,9,9 ", 9 " bis-(N-carbazole-hexyls)-9 ', 9 '-xenyl trimerization fluorenes (TCPC)
98.1mg(0.17mmol)（1）、257mg(0.34mmol)（5）、5.8mgPd(PPh
3)
4(1％mol)。Building-up process is with (TPPP), productive rate 50%.
1h NMR (500MHz, DMSO): δ 8.16-8.15 (d, 2H, Ar-H-flu), δ 8.09-8.07 (d, 8H, Ar-H-car), δ 7.92-7.91 (d, 2H, Ar-H-flu), δ 7.80-7.78 (d, 2H, Ar-H-flu), δ 7.68-7.65 (t, 4H, Ar-H-flu), δ 7.48 (s, 2H, Ar-H-flu), δ 7.42-7.39 (d, 8H, Ar-H-car), δ 7.36-7.33 (t, 8H, Ar-H-car), δ 7.30-7.27 (m, 4H, Ar-H-flu), δ 7.24-7.17 (m, 6H, Ar-H-flu), δ 7.14-7.11 (t, 8H, Ar-H-car), δ 7.05-7.01 (t, 2H, Ar-H-flu), δ 6.86 (s, 2H, Ar-H-flu), δ 6.69-6.67 (d, 2H, Ar-H-flu), δ 4.18-4.15 (m, 8H, N-CH
2), δ 1.79-1.78 (m, 8H, CH
2), δ 1.46-1.45 (m, 8H, CH
2), δ 0.94 (m, 16H, CH
2), δ 0.45-0.43 (m, 8H, CH
2) .FT-IR (λ, cm
-1): 3048,2929,2852,1595,1483,1463,1451,1347,1323,1228,1152,1119,819,747,723. mass spectrums (M+H)
+1641.8 (100%). ultimate analysis theoretical value C
123h
108n
4: C, 89.96, H, 6.63, N, 3.41 actual values: C, 89.73, H, 6.92, N, 3.36.
Embodiment 2: compound OCPC's is synthetic:
9,9,9 ", 9 " bis-(N-carbazole-hexyls)-9 ', 9 ', 9 ", 9 "-xenyl dimerization bromine fluorenes
Get 2.0 grams, reactant boron fat, 3.12 grams of two bromines add 9 milliliters of dry toluenes, 6 milliliters of 219 milligrams of aqueous sodium carbonates of tetraphenylphosphonium palladium, 90 degree reactions two days.Sherwood oil dichloro (1:1) developping agent column chromatography for separation.Obtain 2.18 grams of products, productive rate 61%
1h NMR (500MHz, CDCl3,25 ° of C, TMS): δ=8.04 (d, J=7.6Hz, 8H; Ar-H), 7.70 (m, 3H; Ar-H), 7.57 (m, 5H; Ar-H), 7.45 (m, 1H; Ar-H), 7.37 (m, 10H; Ar-H), 7.24 (m, 10H; Ar-H), 7.17 (t, J=7.6Hz, 8H; Ar-H), 4.10 (m, 8H; CH
2), 1.90 (m, 8H; CH2), 1.63 (m, 8H; CH
2), 1.07 (m, 16H; CH
2), 0.60ppm (m, 8H; CH
2); 13C NMR (125MHz, CDCl
3, 25 ° of C, TMS): mass spectrum: 1406[M+]; Ultimate analysis theoretical value: C
98h
93brN
4: C, 83.67; H, 6.66; N, 3.98; Test value: C, 83.87; H, 6.45; N, 4.07.
9,9,9 ", 9 " bis-(N-carbazole-hexyls) two-(4,4,5,5-tetramethyl--1,3,2-dioxa boron)-9 ', 9 ', 9 ", 9 "-xenyl dimerization fluorenes
Get M1 quality and be 1 gram and add 221 milligrams of Potassium ethanoates, 14 milligrams of lead chlorides, 6 milliliters of hexanaphthenes.80 degree stirring heating one day.Sherwood oil dichloro (2:3) developping agent column chromatography for separation.648 milligrams of products, productive rate 63%.
1h NMR (500MHz, CDCl3,25 ° of C, TMS): δ=8.03 (m, 8H; Ar-H), 7.84 (d, J=7.3Hz, 1H; Ar-H), 7.73 (m, 5H; Ar-H), 7.59 (m, 4H; Ar-H), 7.35 (m, 9H; Ar-H), 7.24 (m, 10H; Ar-H), 7.15 (m, 8H; Ar ↑ H), 4.19 (t, J=7.6Hz, 8H; CH2), 1.96 (m, 8H; CH
2), 1.61 (m, 8H; CH
2), 1.37 (s, 12H; CH
2), 1.07 (m, 16H; CH
2), mass spectrum: 1453[M+]; Ultimate analysis theoretical value (%) C
104h
105bN
40
2: C, 85.92; H, 7.28; N, 3.85; Test value: C, 85.84; H, 7.25; N, 3.69.
9,9,9 ", 9 ", 9 " ', 9 "-tetra-(N-carbazole-hexyls)-9 ', 9 ', 9 ", 9 " the poly-fluorenes (OCPC) of-xenyl five
Get each 1 gram of M1 and M2, synthesis condition is as TCPC, and dichloro sherwood oil (1:1) column chromatography for separation can obtain 1.2 grams of products, productive rate 48%
Nuclear-magnetism
1h NMR (500MHz, CDCl
3, 25 ° of C, TMS): δ=8.03 (m, 16H; Ar-H), 7.95 (d, J=7.9Hz, 2H; Ar-H), 7.68 (m, 20H; Ar-H), 7.33 (m, 24H; Ar-H), 7.17 (m, 36H; Ar-H), 7.07 (t, J=7.6Hz, 2H; Ar-H), 7.01 (s, 2H; Ar-H), 6.85 (d, J=7.6Hz, 2H; Ar-H), 4.16 (m, 16H; CH
2), 1.97 (m, 16H; CH
2), 1.59 (m, 16H; CH
2), 1.05 (m, 32H; CH
2), 0.63ppm (m, 16H; CH
2); Mass spectrum: 2966; Ultimate analysis theoretical value: C
221h
200n
8: C, 89.43; H, 6.79; N, 3.78; Actual value: C, 89.32; H, 6.67; N, 3.89.
Embodiment 3: the preparation of electropolymerization film
Electropolymerization film preparation adopts cyclic voltammetry, the tetra-n-butyl ammonium hexafluorophosphate TPAPF6 of take is ionogen, TCPC or OCPC concentration are 0.5mg/ml, and what two chloromethyl cyanide mixing solutionss (volume ratio 2: 3) often swept that a circle is all accompanied by every one deck electrochemical polymerization film goes doping process.We select 0.89V that the upper limit of sweep limit is set as cyclic voltammetric.In order to improve the performance of adulterating of going of electrochemical polymerization film, the lower limit that we set cyclic voltammetry scan scope is-0.9V, and at this moment setting cyclic voltammetry scan interval is-0.9V～0.89V.It is 200mV/s that sweep velocity is set, and the scanning number of turns is 8 circles.
Embodiment 4: the aftertreatment of electropolymerization film
By acetonitrile and methylene chloride volume, than the mixed solvent that is respectively 2:3, electropolymerization film is cleaned.High pure nitrogen rinses 5 minutes, and 45 ° of C heating of vacuum 4 hours, remove solvent.
Embodiment 5: the fluorescence vapor detection of electropolymerization film to TNT nitro explosive
By (the scanning number of turns under the different condition of preparation, sweep limit, concentration) electropolymerization film is respectively as in quartz colorimetric utensil (gas sensing pond), and in quartz colorimetric utensil, TNT has reached its saturated vapor pressure (8PPb, 25 ° of C), record its fluorescence intensity over time.Record the fluorescence response of electropolymerization film to TNT gas molecule under differing materials different condition, the situation that its fluorescence intensity reduces in time.Through preferred, we select (0.5mg/mL TCPC, sweep velocity: 200mv/s scans the number of turns: 8 enclose, as Fig. 2) is best electropolymerizatioconditions conditions.Its pattern as shown in Figure 3.Its in 1 minute 33.7%, 5 minute quencher 62.0%(of quencher as Fig. 4).
Embodiment 6: electropolymerization film is the fluoroscopic examination in water to TNT
The TCPC film of preparing under above-mentioned condition is placed in to quartz colorimetric utensil, first adds deionized water 3ml, add 3 η L tetrahydrofuran (THF) TNT solution at every turn, observe its change in fluorescence.It also has very high responding ability for TNT in water.When its concentration reaches 0.1mM, its quenching of fluorescence 61.7%(is as Fig. 5).
Claims (5)
1. an electropolymerization organic fluorescence materials, its structural formula is as follows:
2. the application of the electropolymerization organic fluorescence materials of claim 1 aspect detection TNT.
3. electropolymerization organic fluorescence materials as claimed in claim 2, in the application detecting aspect TNT, is characterized in that: be that organic fluorescence materials claimed in claim 1 is prepared into after electropolymerization film for TNT context of detection.
4. the application of electropolymerization organic fluorescence materials as claimed in claim 2 aspect detection TNT, is characterized in that: for the fluorescence vapor detection to TNT.
5. the application of electropolymerization organic fluorescence materials as claimed in claim 2 aspect detection TNT, is characterized in that: for the fluorescence water to TNT, detect.
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