CN101787112A - 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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Abstract
The invention belongs to the technical field of fluorescent sensing and particularly relates to a carbazole polymer fluorescent sensing material which adopts 2, 7-carbazole as a main chain and utilizes a high-rigidity group to build a side chain. The invention further provides the application of the carbazole polymer fluorescent sensing material in the aspect of detecting a TNT nitro explosive. The 2, 7-carbazole is adopted as the main chain of a polymer, the main chain is connected with a large side chain group by a 9-position connected benzene ring, and the structural formula of the polymer is shown below. A sensing luminous film for detecting the TNT nitro explosive is prepared through spin coating, and the prepared sensing luminous film has the characteristics of simple structure, high luminous efficiency and high sensitivity. In TNT atmosphere, the fluorescence intensity can be reduced by 73% in 1 minute and is close to the best level in literature reports. Therefore, the fluorescent sensing material is good and has broad application prospect.
Description
Technical field
The invention belongs to the fluorescence sense technical field, be specifically related to a class with 2, the 7-carbazole is a main chain, constructs the carbazole polymer fluorescent sensing material of side chain with big rigid radical, and such material is in the application that is used to detect 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.Discover, all contain TNT (2) 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,, problems such as fallout ratio high, poor stability, complicated operation lower as detectability.
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 transmitters, 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.Nitro explosive substance sensing technologies such as fluorescent polymer TNT are based on the quenching of fluorescence effect of nitro explosive substance molecule to some special fluorescent polymers, and its ultimate principle is for detecting thing with the intermolecular charge transfer of explosive substances such as TNT.
There have been some research institutions to carry out the work of fluorescent polymer TNT explosive substance sensing in the world, wherein more representational be that U.S. T.M.Swager research group is reported 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 being reported (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 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 the carbazole polymer fluorescent sensing material that a class has big rigid side substituted radical, and such material is in the application that is used to detect 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 strong electron donation of carbazole itself and conjugated backbone structure 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 big 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, reduces intermolecular π-π effect effectively, improves the material fluorescence efficiency.And because the existence of bigger side-chain radical makes intermolecular accumulation produce microvoid structure, this structure can make nitro-compound diffusion fast in film effectively, and then the sensitivity that significantly improves sensing.And this class material is synthetic simple relatively.Utilize carbazole polymer of the present invention, the fluorescence sense of TNT has been reached quencher 73% in 60 seconds, quencher 75% in approach to be reported at present 60 seconds.
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 a main chain, with big rigid radical is the fluorescent material of side chain, thereby because the strong electron donation of carbazole itself can improve and 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 and stop intermolecular accumulative purpose, thereby reduce the quenching of fluorescence that causes 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 a 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 a 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 philosophy 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 valid approach for the diffusion of 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 made up of carbazole group.On No. 9 positions of carbazole group, to be connected with phenyl, in the contraposition of this phenyl, be connected with big inflexible side-chain radical, the substituting group Z that is connected with in the periphery of this big side-chain radical.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 small molecule materials such as TNT provides valid 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 that has big rigid side substituted radical of the present invention's preparation can be used for the fluorescence sense of nitro explosives such as TNT is detected.Further, be in substrate, to utilize spin coating method to prepare the fluorescence response layer of nitro explosives such as TNT, after carbazole polymer fluorescent sensing material of the present invention is scattered in organic or inorganic material such as systems such as carbon nanotube, molecular sieve, in substrate, carry out spin coating, 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 the above-mentioned materials of modifying through physical treatment, chemical surface.Nitro explosives such as described TNT comprise explosive substances such as the aromatics that contains nitro, pannonit class, nitric ether.
2. use spin coating method to prepare polymeric film
Synthetic polymer PC D of the present invention is stable amorphous state at normal temperatures.PCD is dissolved in the organic solvent with certain concentration, is spin-coated on the quartz substrate, obtain smooth film (thickness changes with the spin coating condition, does not wait from 5nm～200nm) with certain rotating speed.
In preferred embodiment, organic solvent can be N, N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, 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 N, dinethylformamide, 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, and the rotating speed of sol evenning machine is 1000～4000 commentaries on classics/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 nitro explosives such as TNT
The carbazole polymkeric substance 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 the step instrument and is respectively 5nm, 8nm, 13nm, 28nm, 37nm, 50nm, 67nm.At first measure the fluorescence intensity of carbazole polymeric film, then the TNT powder is placed cuvette bottom, leave standstill and treated (8PPb, 25 ℃) after its vapour pressure that reaches capacity in 2 hours, film is placed TNT atmosphere, write down its fluorescence intensity over time.Write down the thickness of different carbazole polymeric 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 of Fig. 1: PCD and emmission spectrum;
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 change curve in time 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.Every synthetic thought or synthetic route that has the polycarbazole class luminescent material of big rigid side group, and use it for 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 ℃ slowly drip nitrosonitric acid 46mL down in the middle of reaction system, and initial feed is dissolved gradually, is reflected to carry 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, and obtaining white powder is 2,7-dibromo carbazole (productive rate: 60%).
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, constant temperature stirred 3 days the water extraction of cooling back for 70 ℃ 4.62mmol) and under argon shield.Organic phase anhydrous magnesium sulfate drying after-filtration, the white solid behind the rotary evaporation obtain the pure product 917mg of white, i.e. N-(para Toluic Acid's methoxycarbonyl)-2,7-dibromo carbazole, productive rate 65%. behind the DMF recrystallization
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 above-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, is that the column chromatography of developping agent separates with the hexanaphthene that contains 5% ethyl acetate, 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 Acetyl Chloride 98Min. steams and slips out, and remaining solid carries out drying.Mix stirring to this solid adding 1.84g (19.6mmol) phenol, 120 ℃ of reactions of constant temperature 3 days after the steaming slide excessive phenol, serve as that exhibition comes agent to separate by column chromatography with 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. phenyl product (6) 2,7-two bromo-9-(4-(3 (4-hot alkoxyl group) phenyl) methyl))-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, with the hexanaphthene that contains 5% ethyl acetate is that the column chromatography of developping agent separates, and obtains white solid 427mg, promptly 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, the degassing.In addition 13.8mg (0.0973mmol) COD is dissolved among the 0.65ml DMF as in another flask the degassing.Add 35.14mg (0.0973mmol) Ni (COD) in the glove box in monomeric bottle.In the flask of COD, add the 0.7ml dry toluene 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, promptly 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 the chloroformic solution of PCD (concentration is 0.5mg/ml) with 1500 rev/mins rotating speeds on quartz substrate, through the test of step instrument, 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, and the solvent when eliminating spin coating with this has than lower boiling owing to chloroform simultaneously, in volatilization process, easily assemble, and producing the hole that differs in size, size 5～200nm does not wait (see Fig. 3, lighter zone is the hole).The hole that this evaporating solvent brings helps reducing intermolecular effect, more helps the diffusion of nitro-compound molecule in polymeric film, makes the quencher at short notice 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 the detection thing, and the explosive substance that the present invention detected also mainly is example with TNT.We detect the existence of TNT by the quenching of fluorescence phenomenon 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 effect preferably, and quencher 57% in 1 minute.(see figure 5)
Claims (7)
1. carbazole polymer fluorescent sensing material, its structural formula is as follows:
Wherein n is a natural number, n=2～100,
Radicals X and Y be straight chain, side chain or the loop chain of C atomicity 1～16 alkyl chain,
The oxygen base chain of the straight chain of O atomicity 1～5, side chain or loop chain,
The oxyalkyl chain of the straight chain of C atomicity 1～16, side chain or loop chain,
The C atomicity is 1～16, the O atomicity is 1～5 ester group chain,
Carbazole, thiodiphenylamine, benzene, biphenyl, terphenyl, aniline, pentanoic,
Triphenylamine, fluorenes, naphthalene, anthracene or they interconnect formed derivative;
R is C or Si, connects with the direct key of group Z, and its structure is:
Group Z be straight chain, side chain or the loop chain of C atomicity 1～16 alkyl chain,
The oxygen base chain of the straight chain of O atomicity 1～5, side chain or loop chain,
The oxyalkyl chain of the straight chain of C atomicity 1～16, side chain or loop chain,
The ester group chain of C atomicity 1～16, O atomicity 1～5,
Benzene, biphenyl, terphenyl, carbazole, thiodiphenylamine, thiophene, pyrroles, ethene, acetylene, aniline, pentanoic, triphenylamine, fluorenes, naphthalene or they interconnect formed derivative.
2. carbazole polymer fluorescent sensing material as claimed in claim 1 is characterized in that: the structural formula of radicals X and Y is as follows,
H=1～16 wherein.
3. carbazole polymer fluorescent sensing material as claimed in claim 1 is characterized in that: the structural formula of group Z is as follows,
Peripheral group Z1 be H,
The alkyl chain of the straight chain of C atomicity 1～16, side chain or loop chain,
The oxygen base chain of the straight chain of O atomicity 1～5, side chain or loop chain,
The oxyalkyl chain of the straight chain of C atomicity 1～16, side chain or loop chain,
The C atomicity is 1～16, the O atomicity is 1～5 ester group chain,
Benzene, biphenyl, terphenyl, carbazole, thiodiphenylamine, thiophene, pyrroles, ethene, acetylene, aniline, pentanoic, triphenylamine, fluorenes, naphthalene, anthracene, carbazole, thiophene, pyrene or they interconnect formed derivative.
4. carbazole polymer fluorescent sensing material as claimed in claim 3 is characterized in that: the structural formula of group Z1 is as follows,
5. carbazole polymer fluorescent sensing material as claimed in claim 4 is characterized in that: the structural formula of carbazole polymer fluorescent sensing material is as follows,
6. any one described carbazole polymer fluorescent sensing material of claim 1～5 is in the application that is used to detect aspect the TNT nitro explosive.
7. carbazole polymer fluorescent sensing material as claimed in claim 6 is in the application that is used to detect aspect the TNT nitro explosive, and it is characterized in that: the TNT nitro explosive is aromatics, pannonit class explosive substance or the nitrate esters explosive substance that contains nitro.
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