CN101787112B - Carbazole polymer fluorescent sensing material for detecting TNT nitro explosive - Google Patents
Carbazole polymer fluorescent sensing material for detecting TNT nitro explosive Download PDFInfo
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000002360 explosive Substances 0.000 title claims abstract description 31
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- 239000000015 trinitrotoluene Substances 0.000 description 31
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Abstract
本发明属于荧光传感技术领域，具体涉及一类以2，7-咔唑为主链，以较大刚性基团构筑侧链的咔唑类聚合物荧光传感材料，及该类材料在用于检测TNT硝基类爆炸物方面的应用。该聚合物的主链为2，7咔唑，通过9位连接的苯环与一个大的侧链基团相连，该类聚合物的结构式如下所示。用于检测TNT硝基类爆炸物的传感发光薄膜是通过旋涂的方法制备的，从而制备得到了结构简单、发光效率高、灵敏度强的薄膜，其在TNT气氛中，1分钟内荧光强度下降了73％，接近文献报道的最好水平，是一类较好的传感材料，并具有广阔的应用前景。
The invention belongs to the field of fluorescent sensing technology, and specifically relates to a class of carbazole-based polymer fluorescent sensing materials with 2,7-carbazole as the main chain and side chains constructed with relatively large rigid groups, and the use of such materials Application in the detection of TNT nitro explosives. The main chain of the polymer is 2,7 carbazole, and the benzene ring connected at the 9-position is connected to a large side chain group. The structural formula of this type of polymer is shown below. The sensing luminescent film used to detect TNT nitro explosives is prepared by spin coating, so that a film with simple structure, high luminous efficiency and strong sensitivity is prepared. In the TNT atmosphere, the fluorescence intensity within 1 minute It has decreased by 73%, which is close to the best level reported in the literature. It is a kind of better sensing material and has broad application prospects.
Description
Technical field
The invention belongs to the fluorescence sense technical field, being specifically related to a class is main chain with 2,7-carbazole, constructs the carbazole polymer fluorescent sensing material of side chain with larger rigid radical, and such material is in the application aspect the TNT nitro explosive.
Background technology
How to detect, destroy the land mine that is dispersed throughout all over the world, detecting the explosive substance of concealing on luggage, mail, aircraft and suspect's health has become a global problem.Research is found, is all contained TNT (2，4，6-trinitrotoluene) in 21 kinds of compounds relevant with explosive substance.Therefore the detection of explosive substance is mainly concentrated in the detection to TNT.Present detection means mainly contains infrared spectroscopy, vapor-phase chromatography, mass spectroscopy, ion mobility spectrometry method etc.Yet these methods all exist certain limitation,, the problems such as fallout ratio high, poor stability, complicated operation lower such as detectability.
The nitro explosive substances such as sensor method detection TNT are compared with other method and are had an enormous advantage.Its principle changes into analyzable other signals such as fluorescence for " chemical signal " with nitro-compound.In various types of sensors, best with the susceptibility of fluorescence chemical sensor, fluorescent polymer sensing technology especially.This technology is based on special " the molecular wire effect " that conjugated polymers shows.The nitro explosive substance sensing technologies such as fluorescent polymer TNT are based on nitro explosive substance molecule to the Fluorescence quenching effect of some special fluorescent polymers, and its ultimate principle is for detecting thing with the intermolecular charge transfer of the explosive substances such as TNT.
There have been in the world some research institutions to carry out the work of fluorescent polymer 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 present sensitivity of reporting (J.AM.Chem.Soc.Vol.120, No.46,1998,11867).With respect to the fluorescent sensing material of other film morphology, the most outstanding characteristics of this class material are exactly the microvoid structure that material is had by molecular designing, can be so that the explosive substance molecules such as TNT be diffused into wherein effectively, however the synthetic more complicated of this class material.
Summary of the invention
The purpose of this invention is to provide a class with the carbazole polymer fluorescent sensing material of large rigid side substituted radical, and such material is in the application aspect the TNT nitro explosive.
The carbazole polymer TNT sensing material that we adopt among the present invention goes out to send the sensing capabilities that improves material from electronic property and two aspects of microscopic appearance of material.At first, because the backbone structure of the strong electron donation of carbazole itself and conjugation can improve the electron transfer efficiency between the nitro explosives such as itself and TNT, thereby reach the purpose of quick its fluorescence of quencher.Secondly, construct suitable large rigid side substituted radical by molecular designing and can realize the opening structure of material under solid-state.This structure can stop the gathering between the aromatic molecules of planar rigidity effectively, effectively reduces intermolecular π-π effect, improves the material fluorescence efficiency.And because the existence of larger side-chain radical, so that intermolecular accumulation produces microvoid structure, this structure can make nitro-compound fast diffusion in film effectively, and then the sensitivity that significantly improves sensing.And this class material is synthetic relatively simple.Utilize carbazole polymer of the present invention, the fluorescence sense of TNT has been reached quencher 73% in 60 seconds, close to quencher 75% in present 60 seconds of reporting.
1. carbazole polymer fluorescent sensing material
Carbazole polymer fluorescent sensing material of the present invention is that a class is with 2, the 7-carbazole is main chain, fluorescent material take larger rigid radical as side chain, thereby because the strong electron donation of carbazole itself can improve and the nitro explosive such as TNT between electron transfer efficiency reach the purpose of quick its fluorescence of quencher.And construct its opening structure under solid-state by the suitable side substitution group of molecular designing, can reach the purpose that stops intermolecular gathering, thereby reduce the quenching of fluorescence that is caused by gathering, and provide effective diffusion path for TNT etc.The general structure of carbazole polymer fluorescent sensing material of the present invention is as follows:
Wherein n is natural number, n=2～100.
The main chain of polymkeric substance is 2 among the present invention, the 7-carbazole, the X of functional group, Y can be respectively H, alkyl chain (straight chain, side chain or loop chain, the C atomicity is 1～16), oxygen base chain (straight chain, side chain or loop chain, the O atomicity is 1～5), oxyalkyl chain (straight chain, side chain or loop chain, the C atomicity is 1～16), the ester group chain (can be determined by the number of carbon or oxygen by the length of chain, the C atomicity is 1～16, the O atomicity is 1～5), carbazole, thiodiphenylamine, benzene, biphenyl, terphenyl, thiophene, the pyrroles, ethene, acetylene, aniline, pentanoic, triphenylamine, fluorenes, naphthalene, anthracene, and interconnect formed derivative.
Radicals X and Y can also be respectively alkyl chain (straight chain, side chain or loop chain, the C atomicity is 1～16), oxygen base chain (straight chain, side chain or loop chain, the O atomicity is 1～5), oxyalkyl chain (straight chain, side chain or loop chain, the C atomicity is 1～16), the ester group chain (can be determined by the number of carbon or oxygen by the length of chain, the C atomicity is 1～16, the O atomicity is 1～5), carbazole, thiodiphenylamine, benzene, biphenyl, terphenyl, aniline, pentanoic, triphenylamine, fluorenes, naphthalene, anthracene, with and interconnect formed derivative.
Further, the structural formula of radicals X and Y is as follows:
H=1～16 wherein;
R is C or Si, connects with the direct key of group Z, and its structure can be:
Group Z is alkyl chain (straight chain, side chain or loop chain, the C atomicity is 1～16), oxygen base chain (straight chain, side chain or loop chain, the O atomicity is 1～5), oxyalkyl chain (straight chain, side chain or loop chain, the C atomicity is 1～16), the ester group chain (can be determined by the number of carbon or oxygen by the length of chain, the C atomicity is 1～16, the O atomicity is 1～5), benzene, biphenyl, terphenyl, carbazole, thiodiphenylamine, thiophene, pyrroles, ethene, acetylene, aniline, pentanoic, triphenylamine, fluorenes, naphthalene, and interconnect formed derivative etc.
Group Z can also be alkyl chain (straight chain, side chain or loop chain, the C atomicity is 1～16), oxygen base chain (straight chain, side chain or loop chain, the O atomicity is 1～5), oxyalkyl chain (straight chain, side chain or loop chain, the C atomicity is 1～16), ester group chain (length of chain can be determined by the number of carbon or oxygen, and the C atomicity is 1～16, the O atomicity is 1～5), benzene, biphenyl, terphenyl, carbazole, thiodiphenylamine, pyrroles, aniline, pentanoic, triphenylamine, fluorenes, naphthalene, anthracene and interconnect formed derivative etc.
Further, group Z is alkyl chain (straight chain, side chain or loop chain, C atomicity are 1～16), oxygen base chain (straight chain, side chain or loop chain, O atomicity are 1～5), oxyalkyl chain (straight chain, side chain or loop chain, C atomicity are 1～16), ester group chain (length of chain can be determined by the number of carbon or oxygen, and the C atomicity is 1～16, the O atomicity is 1～5), benzene, carbazole, thiodiphenylamine, aniline, pentanoic, triphenylamine, naphthalene and interconnective derivative thereof etc.
Highly preferred, the structural formula of group Z is as follows:
Peripheral group Z1 is H, alkyl chain (straight chain, side chain or loop chain, the C atomicity is 1～16), oxygen base chain (straight chain, side chain or loop chain, the O atomicity is 1-5), oxyalkyl chain (straight chain, side chain or loop chain, the C atomicity is 1～16), the ester group chain (can be determined by the number of carbon or oxygen by the length of chain, the C atomicity is 1～16, the O atomicity is 1～5), benzene, biphenyl, terphenyl, carbazole, thiodiphenylamine, thiophene, the pyrroles, ethene, acetylene, aniline, pentanoic, triphenylamine, fluorenes, naphthalene, anthracene, carbazole, thiophene, pyrene etc., and interconnect formed derivative.
Peripheral group Z1 can also be alkyl chain (straight chain, side chain or loop chain, the C atomicity is 1～16), oxygen base chain (straight chain, side chain or loop chain, the O atomicity is 1～5), oxyalkyl chain (straight chain, side chain or loop chain, the C atomicity is 1～16), the ester group chain (can be determined by the number of carbon or oxygen by the length of chain, the C atomicity is 1～16, the O atomicity is 1～5), benzene, carbazole, thiodiphenylamine, aniline, pentanoic, triphenylamine, fluorenes etc., and interconnect formed derivative.
Further again, the structural formula of group Z1 is as follows:
M=1-16 wherein.
Main design idea of the present invention is exactly to go out to send the sensing capabilities that improves material from the electronic property of material and two aspects of microscopic appearance, reduce intermolecular accumulation as far as possible and form opening structure, thereby improve the material fluorescence efficiency, and provide effective approach for the diffusion of the explosive substance molecules such as TNT.Therefore be the very potential material of a class.
Polycarbazole class material involved in the present invention can be synthetic by preferred YAMAMOTO polymerisation process, and concrete synthesis step is seen the embodiment part.Wherein main chain is comprised of carbazole group.Be connected with phenyl with No. 9 positions at carbazole group, be connected with the side-chain radical of large rigidity, the substituting group Z that is connected with in the periphery of this large side-chain radical in the contraposition of this phenyl.The main purpose that we design molecular structure like this is the reduction that the opening structure of construction material reduces the fluorescence efficiency that is caused by polymer buildup, and for the diffusion of the small molecule materials such as TNT provides effective approach, thereby improve its response efficiency.
Further, the high molecular structure of the preferred a kind of explosive substance fluorescence sense of the present invention is as follows:
The carbazole polymer fluorescent sensing material with large rigid side substituted radical of the present invention's preparation can be used for the fluorescence sense of the nitro explosives such as TNT is detected.Further, to utilize spin coating method to prepare the fluorescence response layer of the nitro explosives such as TNT in substrate, after carbazole polymer fluorescent sensing material of the present invention is scattered in organic or inorganic material such as the systems such as carbon nanotube, molecular sieve, carry out spin coating in substrate, and then the fluorescence response layer of preparation nitro explosive.The substrate that is used for spin coating can be quartzy, glass or flexiplast, and through the above-mentioned materials of physical treatment, Chemical modification.The nitro explosives such as described TNT comprise the explosive substances such as the aromatics that contains nitro, pannonit class, nitric ether.
2. use spin coating method to prepare polymeric film
The polymer PC D that the present invention synthesizes is stable amorphous state at normal temperatures.PCD is dissolved in the organic solvent with certain concentration, is spin-coated on the quartz substrate with certain rotating speed, obtain smooth film (thickness changes with the spin coating condition, does not wait from 5nm～200nm).
In preferred embodiment, organic solvent can be N, N-N,N-DIMETHYLACETAMIDE, DMF, acetonitrile, toluene, chlorobenzene, dichlorobenzene, methylene dichloride, trichloromethane, tetrahydrofuran (THF), hexanaphthene, pyridine, propylene carbonate, ethyl acetate, benzyl cyanide, ether or sherwood oil.
In further preferred embodiment, organic solvent can be DMF, toluene, chlorobenzene, dichlorobenzene, methylene dichloride, trichloromethane, tetrahydrofuran (THF) or ether.
In preferred implementation further, organic solvent can be methylene dichloride, trichloromethane, tetrahydrofuran (THF), toluene, chlorobenzene or dichlorobenzene.
The concentration of PCD is 1～50mg/ml in the preferred organic solvent, and the rotating speed of sol evenning machine is 1000～4000 to turn/min during the spin coating of PCD solution.
3. spin coating method prepares the aftertreatment of polymeric film
Film after the spin coating preparation is heat-treated under 30 ℃～200 ℃ temperature condition in vacuum drying oven, and heat treatment time is 0.5～24 hour, and heat treatment time is 2～5 hours in further optimization is implemented, and thermal treatment temp is at 40 ℃～60 ℃.
4. polymkeric substance is to the fluoroscopic examination of the nitro explosives such as TNT
The carbazole polymer quartz plate of different film thicknesses of preparation is placed quartz colorimetric utensil (gas sensing pond), its spin coating concentration is respectively 0.25mg/L, 0.5mg/L, 1mg/L, 2mg/L, 3mg/L, 4mg/L and 5mg/L, tests its thickness through step instrument and is respectively 5nm, 8nm, 13nm, 28nm, 37nm, 50nm, 67nm.At first measure the fluorescence intensity of carbazole polymer film, then the TNT powder is placed the cuvette bottom, leave standstill 2 hours after it reaches capacity vapour pressure (8PPb, 25 ℃), film is placed TNT atmosphere, record its fluorescence intensity over time.Record the thickness of different carbazole polymer films, to the fluorescence response of TNT gas molecule, i.e. its fluorescence intensity situation about reducing in time.Through preferred, we select low strength of solution (0.5mg/mL) to prepare spin-coated thin film.
Description of drawings
The Absorption and emission spectra of Fig. 1: PCD;
Fig. 2: the atomic force microscope images of PCD spin-coated thin film (AFM);
Fig. 3: the transmission image of PCD spin-coated thin film (TEM);
Fig. 4: PCD is quenching of fluorescence temporal evolution curve under TNT atmosphere;
Fig. 5: PCD quenching of fluorescence curve in time in TNT and DNT atmosphere.
Embodiment
Although describe the present invention in conjunction with the preferred embodiments, but the present invention is not limited to following embodiment, should be appreciated that under the present invention conceives guiding, those skilled in the art can carry out various modifications and improvement, and claims have been summarized scope of the present invention.
Embodiment 1:
Polymer PC D's is synthetic, and only with the example that synthesizes of following structural compounds, the present invention will be described, rather than limitation of the present invention for we.Synthetic thought or the synthetic route of every polycarbazole class luminescent material with large rigid side group, and use it for the nitro explosive substance fluorescence senses such as TNT all in design philosophy scope of the present invention.
1. product (1) 4,4 '-two bromo-2 nitro biphenyls synthetic
With 10g 4,4 '-'-dibromobiphenyl (32mmol) adds in the 150mL Glacial acetic acid, and 100 ℃ of lower nitrosonitric acid 46mL that slowly drip are in the middle of reaction system, and initial feed is dissolved gradually, and reaction was carried out under 100 ℃ 1 hour.After the cooling, have yellow pasty solid to separate out, this solid filtering is collected, recrystallization obtains yellow powder (9.91g, productive rate 89%), i.e. 4,4 '-two bromo-2 nitro biphenyls for twice in ethanol.Fusing point: 124 ℃
1H?NMR(CDCl
3，500MHz)：δ8.04(s，1H)，7.77-7.76(d，1H)，7.58-7.56(d，2H)，7.30-7.29(d，2H)，7.17-7.15(d，1H).
2. product (2) 2,7-dibromo carbazoles is synthetic:
With 5g 4,4 '-two bromo-2 nitro biphenyls (10mmol) are dissolved in the 20mL triethyl-phosphite, under the nitrogen protection, and reflux 24 hours.Then remaining triethyl-phosphite underpressure distillation is removed, residue black mucus uses 20: 1 sherwood oil of volume ratio and ethyl acetate to carry out column chromatography for separation as developping agent, obtains i.e. 2, the 7-dibromo carbazole (productive rate: 60%) of white powder.
Fusing point: 233-234 ℃.
1H?NMR(CDCl
3，500MHz)：δ8.10(s，1H)，7.89-7.87(d，2H)，7.59(s，1H)，7.37-7.35(d，2H).
Synthetic route:
3. product (3) N-(para Toluic Acid's methoxycarbonyl)-2,7-dibromo carbazole synthetic
To react the product of (2) gets 1g (3.08mmol) and adds DMF (15ml) and NaH (148mg; 3.7mmol); stir under the room temperature and add parafluorobenzoic acid methyl esters 0.6ml after 30 minutes; 4.62mmol) and under argon shield 70 ℃ of constant temperature stirred water extraction after the cooling 3 days.Organic phase is filtered after with anhydrous magnesium sulfate drying, and the white solid behind the rotary evaporation obtains white sterling 917mg behind the DMF recrystallization, i.e. N-(para Toluic Acid's methoxycarbonyl)-2,7-dibromo carbazole, productive rate 65%.
1H-NMR (250MHz, CD
2Cl
2): δ 8.37 (d, J=8.52Hz, 2H), 8.21 (d, J=8.2Hz, 2H), 7.86 (d, J=8.52Hz, 2H), 7.62 (d, J=1.27Hz, 2H), 7.51 (d d, J=8.2Hz, J=1.57Hz, 2H), 3.98 (s, 3H)
13C-NMR (75.46MHz, CD
2Cl
2): δ 166.29,142.46,141.49,132.43,130.96,127.72,124.92,123.10,122.66,120.89,113.85,52.43. ultimate analysis (%) C
20H
13Br
2NO
2: calculated value .:C, 52.32; H, 2.85; N, 3.05. actual value: C, 52.21; H, 2.93; N, 3.14.
4. product (4) N-(4-is to two octyloxyphenyl phenylformic acid)-2,7-dibromo carbazole synthetic
Get 4-octyloxy bromobenzene 32.73g (9.58mmol) and be dissolved in the 15ml anhydrous THF solution, be cooled to-78 ℃.Adding 2g (4.35mmol) product 3 is dissolved among the anhydrous THF of 50ml, it is joined in the mentioned solution, and cooling also mixes, and reaction is stirred and spent the night, after finishing, reaction adds water filtration, the organic layer anhydrous magnesium sulfate drying, behind the rotary evaporation solvent, the column chromatography take the hexanaphthene that contains 5% ethyl acetate as developping agent separates, obtain white solid 2.52g, be N-(4-is to two octyloxyphenyl phenylformic acid)-2,7-dibromo carbazole, productive rate 70%.
1H-NMR (250MHz, CD
2Cl
2): δ 7.99 (d, J=8.2Hz, 2H), 7.56 (m, 4H), 7.41 (m, 4H), 7.26 (d, J=8.85Hz, 4H), 6.90 (d, J=8.85Hz, 4H), 3.97 (t, J=6.62Hz, 4H, OCH
2), 2.89 (s, 1H, OH), 1.74 (m, 4H, CH
2), 1.30 (m, 20H, Alkyl), 0.88 (t, J=6.95Hz, 6H, CH
3).
13C-NMR (75.46MHz, CD
2Cl
2): δ 158.92,148.14, and 142.27,139.28,135.44,130.01,129.44,126.54,123.92,122.11,121.87,120.24,114.22,113.49,81.57,68.50,32.21,29.75,29.67,29.63,26.42,23.04,14.24. ultimate analysis (%) C
47H
53Br
2NO
3, calculated value .:C, 67.22; H, 6.36; N, 1.67. actual value: C, 68.09, H, 6.20; N, 1.63.
5. product (5) 4-((4-(2,7-, two bromo-9H-carbazyls) phenyl) two (4-octyloxy) phenyl) methyl) phenol is synthetic:
1.2g product 4 (1.78mmol) and the heating of 3ml Acetyl Chloride 98Min. are mixed backflow 24 hours, and the Acetyl Chloride 98Min. distilled is gone out, and remaining solid carries out drying.Add 1.84g (19.6mmol) phenol mix and blend to this solid, 120 ℃ of reactions of constant temperature 3 days behind the unnecessary phenol of distilled, separate by column chromatography as exhibition comes agent take the hexanaphthene that contains 5% ethyl acetate.Obtain colorless solid 1.07g, i.e. 4-((4-(2,7-, two bromo-9H-carbazyls) phenyl) two (4-octyloxy) phenyl) methyl) phenol, productive rate 66%.
1H-NMR (250MHz, CD
2Cl
2): δ 7.98 (d, J=8.45Hz, 2H), 7.57 (s, 2H), 7.44 (m, 6H), 7.17 (m, 6H), 6.84 (d, J=9Hz, 6H), 4.9 (s, 1H, OH), 3.95 (t, J=6.57Hz, 4H, OCH
2), 1.77 (m, 20H, Alkyl).
13C-NMR (75.46MHz, CD
2Cl
2): δ 157.74,154.47, and 148.41,142.25,139.26,135.51,134.25,133.06,132.59,132.35,125.95,123.90,122.08,121.84,120.21,114.69,113.72,113.51,81.57,68.50,32.31,29.68,29.65,26.43,23.04,14.27. ultimate analysis (%) C
53H
57Br
2NO
2, calculated value .:C, 69.51; H, 6.27; N, 1.53. actual value: C, 69.55; H, 6.09; N, 1.45.
6. product (6) 2,7-two bromo-9-(4-(3 (4-hot alkoxyl group) phenyl) methyl) phenyl)-carbazole synthetic
400g (0.43mmol) product 5 is dissolved in the 7ml THF solution, and adds 0.084mloctylbromide (0.48mmol) and KOH refluxed 18 hours under argon shield.After the reaction cooling, the water extraction, the organic layer anhydrous magnesium sulfate drying, behind the rotary evaporation solvent, be that the column chromatography of developping agent separates with the hexanaphthene that contains 5% ethyl acetate, obtain white solid 427mg, namely 2,7-two bromo-9-(4-(3 (the hot alkoxyl group of 4-) phenyl) methyl) phenyl)-and carbazole, productive rate 95%.
1H-NMR (250MHz, CD
2Cl
2): δ 7.99 (d, J=5.97Hz, 2H), 7.57 (s, 2H), 7.42 (m, 6H), 7.17 (d, J=6.92Hz, 6H), 6.84 (d, J=6.57Hz, 6H), 3.95 (t, J=6.27Hz, 6H, OCH
2), 1.77 (m, 6H, CH
2), 1.30 (m, 30H, Alkyl), 0.88 (t, J=5.97Hz, 9H, CH
3).
13C-NMR (75.46MHz, CD
2Cl
2): δ 157.73,154.47, and 148.46,142.26,139.30,134.23,133.06,132.34,125.96,123.90,121.84,120.20,113.72,113.70,113.51,68.38,63.26,32.22,29.75,29.71,29.63,26.45,23.04,14.24. ultimate analysis (%) C
61H
73Br
2NO
3, calculated value .:C, 71.27; H, 7.16; N, 1.36. actual value: C, 71.82; H, 7.10; N, 1.27.
7. the poly-9-of product (7) (4-(3 (the hot alkoxyl group of 4-) phenyl) methyl) phenyl)-carbazole synthetic
Negate answers 6 monomer 100mg (0.0973mmol) and pyridine 50mg as in the flask, and is degassed.In addition 13.8mg (0.0973mmol) COD is dissolved among the 0.65ml DMF as in another flask, degassed.Add 35.14mg (0.0973mmol) Ni (COD) in the glove box in the bottle of monomer.Add the 0.7ml dry toluene in the flask of COD and move in the monomer bottle 60 ℃ of activation 30 minutes, in the monomer bottle, add the 4ml dry toluene again, under the nitrogen protection, 80 ℃ of temperature controls, reacting by heating 4 days.After reaction finishes, add the dichloro extraction, be light blue under the solution sunlight, anhydrous magnesium sulfate drying, rotary evaporation is used Al
2O
3Column chromatography separate, separate after product recrystallization in methanol solution, obtain the thread solid of 47mg white, i.e. poly-9-(4-(3 (the hot alkoxyl group of 4-) phenyl) methyl) phenyl)-carbazole, productive rate 47%.
1H-NMR(500MHz，CDCl
3)：δ8.23-8.21(m，2H，Ar-H)，δ7.72(S，2H，Ar-H)，δ7.59-7.51(m，4H，Ar-H)，δ7.41(m，2H，Ar-H)，δ7.12-7.10(m，6H，Ar-H)，6.77-6.75(m，6H，Ar-H)，δ3.89(m，6H，OCH
2)，δ1.75-1.72(m，6H，CH
2)，δ1.28-1.24(m，6H，CH
2)，δ0.85-0.83(m，9H，CH
3).
The luminosity of embodiment 2:PCD
The solid film of PCD is luminous at 415nm, is a kind of reasonable blue-light-emitting polymer, and its absorption peak is respectively at 270nm and 395nm (as shown in Figure 1).The solid state fluorescence efficient of PCD film reaches 17%.Thickness 8nm.
Embodiment 3: the spin coating preparation of polymeric film
We carry out spin coating with 1500 rev/mins rotating speeds in quartz substrate with the chloroformic solution of PCD (concentration is 0.5mg/ml), through the step instrument test, obtain the film of mean thickness 8nm.Can be accessed than even curface by shown in Figure 2, this even curface structure is for the luminous effect that outbalance is arranged of polymkeric substance.
Embodiment 4: the aftertreatment of polymer PC D film
Film after the polymer PC D spin coating heated 3 hours under the condition of 45 ℃ in vacuum, solvent when eliminating spin coating with this, have than lower boiling owing to chloroform simultaneously, in volatilization process, easily assemble, and produce the hole differ in size, size 5～200nm does not wait (see Fig. 3, lighter zone is the hole).The hole that this evaporating solvent brings is conducive to reduce intermolecular effect, more is conducive to the diffusion of nitro-compound molecule in polymeric film, makes the at short notice quencher of its fluorescence intensity.
Embodiment 5: polymer PC D film is for the fluorescence response character of nitro explosive substance
Nitro explosive mainly contains the aromatics of nitro, wherein is most widely used with TNT (trotyl) to be used as detecting thing, and the explosive substance that the present invention detects is also mainly take TNT as example.We detect the existence of TNT by the Fluorescence-quenching of comparative polymers film under TNT atmosphere.As shown in Figure 4, quenching of fluorescence 73% in (8PPb, standard atmosphere is depressed, 25 ℃) 1 minute proves that product of the present invention is the extraordinary fluorescent sensing material of a class under saturated TNT atmosphere.We also use this film to detect for other nitro explosives such as DNT (dinitrotoluene (DNT)) simultaneously, find to have equally to respond preferably effect, and quencher 57% in 1 minute.(seeing Fig. 5)
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| CN102965098A (en) * | 2012-11-26 | 2013-03-13 | 南京邮电大学 | Assembly of organic nano rod and application of organic nano rod in fluorescence detection of explosive in aqueous solution |
| CN104956206B (en) * | 2012-12-04 | 2020-05-05 | 昆士兰大学 | Methods of detecting analytes via luminescence quenching |
| CN105133188B (en) * | 2015-07-31 | 2018-06-29 | 南京邮电大学 | Adulterate the polymer nanofiber film and preparation method and application of carbazole derivates |
| CN105153007B (en) * | 2015-09-07 | 2017-10-27 | 北京理工大学 | A kind of fluorescence lights the fluorescent material of type detection explosive, preparation method and application |
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| CN106167500B (en) * | 2016-06-08 | 2018-07-31 | 华中科技大学 | A kind of compound and preparation method thereof for explosive TNT detection and analysis |
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| CN106431805B (en) * | 2016-09-09 | 2019-05-21 | 陕西金士盾警用装备有限公司 | Organic fluorescence small molecule thin-film material and its application in the detection of DNT and TNT steam |
| CN106525789A (en) * | 2016-10-24 | 2017-03-22 | 武汉鹰飞拓光电子有限公司 | Preparation method for detecting explosive sensitive thin-film |
| DE102017103535B4 (en) | 2017-02-21 | 2018-10-31 | Institut Dr. Foerster Gmbh & Co. Kg | Fluorescent silane layers for the detection of explosives |
| CN108489953A (en) * | 2018-05-10 | 2018-09-04 | 长春理工大学 | A kind of preparation method of in-situ modification paper substrate nitro explosive fluorescent sensing material |
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