CN102911386B - Fluorescent polymer brush film, preparation method of fluorescent polymer brush film and application of fluorescent polymer brush film in detecting explosives with high sensitivity - Google Patents
Fluorescent polymer brush film, preparation method of fluorescent polymer brush film and application of fluorescent polymer brush film in detecting explosives with high sensitivity Download PDFInfo
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- CN102911386B CN102911386B CN201210407808.2A CN201210407808A CN102911386B CN 102911386 B CN102911386 B CN 102911386B CN 201210407808 A CN201210407808 A CN 201210407808A CN 102911386 B CN102911386 B CN 102911386B
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- 229920001109 fluorescent polymer Polymers 0.000 title claims abstract description 37
- 239000002360 explosive Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 230000035945 sensitivity Effects 0.000 title abstract description 4
- 239000000758 substrate Substances 0.000 claims abstract description 60
- 229920000642 polymer Polymers 0.000 claims abstract description 45
- 238000001514 detection method Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 50
- 229910052757 nitrogen Inorganic materials 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- -1 propyl group amine Chemical class 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N N,N-Diethylethanamine Substances CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 229920001002 functional polymer Polymers 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical group Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical group CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 230000031709 bromination Effects 0.000 claims description 4
- 238000005893 bromination reaction Methods 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- 229940045803 cuprous chloride Drugs 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- MONMFXREYOKQTI-UHFFFAOYSA-N 2-bromopropanoic acid Chemical compound CC(Br)C(O)=O MONMFXREYOKQTI-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 3
- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 3
- PWYVVBKROXXHEB-UHFFFAOYSA-M trimethyl-[3-(1-methyl-2,3,4,5-tetraphenylsilol-1-yl)propyl]azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC[Si]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PWYVVBKROXXHEB-UHFFFAOYSA-M 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- XZKFBZOAIGFZSU-UHFFFAOYSA-N 1-bromo-4-methylpentane Chemical compound CC(C)CCCBr XZKFBZOAIGFZSU-UHFFFAOYSA-N 0.000 claims description 2
- BHWUCEATHBXPOV-UHFFFAOYSA-N 2-triethoxysilylethanamine Chemical compound CCO[Si](CCN)(OCC)OCC BHWUCEATHBXPOV-UHFFFAOYSA-N 0.000 claims description 2
- QHQNYHZHLAAHRW-UHFFFAOYSA-N 2-trimethoxysilylethanamine Chemical compound CO[Si](OC)(OC)CCN QHQNYHZHLAAHRW-UHFFFAOYSA-N 0.000 claims description 2
- YJADROSYDFWBOK-UHFFFAOYSA-N C1(=CC=CC=C1)C=1C(=C(S(C1)(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C=1C(=C(S(C1)(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1 YJADROSYDFWBOK-UHFFFAOYSA-N 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- VMBJJCDVORDOCF-UHFFFAOYSA-N prop-2-enyl 2-chloroacetate Chemical compound ClCC(=O)OCC=C VMBJJCDVORDOCF-UHFFFAOYSA-N 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 230000033444 hydroxylation Effects 0.000 claims 2
- 238000005805 hydroxylation reaction Methods 0.000 claims 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical group CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims 1
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 abstract description 45
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- UTEBVBBGZIBAGZ-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxypentane-1,5-diamine Chemical compound NCCC[Si](OC)(OC)OC(CCN)CCN UTEBVBBGZIBAGZ-UHFFFAOYSA-N 0.000 description 2
- XGWIFMLYKDVQCZ-UHFFFAOYSA-N C(C)(C)(C)C(C(=O)O)=C.C(C=C)(=O)OC(C)(C)C Chemical compound C(C)(C)(C)C(C(=O)O)=C.C(C=C)(=O)OC(C)(C)C XGWIFMLYKDVQCZ-UHFFFAOYSA-N 0.000 description 2
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention belongs to the field of polymer, and relates to a fluorescent polymer brush film, a preparation method of the fluorescent polymer brush film and an application of the fluorescent polymer brush film in detecting explosives with high sensitivity. The method comprises the steps of synthesizing a polymer brush film with a controlled thickness from nanometer to micrometer on the substrate, and compositing an organic molecule with fluorescence and the brush film to obtain the fluorescent polymer brush film. The fluorescent polymer brush film can be used for intelligently detecting trinitrotoluene (TNT) through an electron transfer effect between the explosive TNT molecule and fluorescent molecule, wherein due to the electronic transfer effect, fluorescence can be quenched, and further the fluorescent intensity of the polymer brush film is reduced. The fluorescent polymer brush film with the function of TNT detection exploits the responsive material system of the polymer, and has an important significance in applications in the fields of optical material, environment monitoring, safety check, counter-terrorism and the like.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of fluorescent polymer molecular brush film, preparation method and for highly sensitive explosive detection.
Background technology
TNT(trotyl) as a kind of common explosive, not only affect public safety but also itself be also a kind of harmful carcinogenic substance, be distributed in water body, air and soil environment is caused to great pollution, affect people's physical and mental health.There is strict limit value various countries to the TNT content of tap water at present, and it is 2ppb that Environmental Protection in America department requires TNT maximum level in tap water.Therefore a kind of short-cut method of How to choose is realized the Sensitive Detection of TNT is seemed to particularly important.
Polymer molecule brush film refers to and to high-density one end of polymer molecular chain is connected on various interfaces or polymer chain and a kind of homopolymer or the multipolymer Polymer Systems that form.The feature of polymer molecule brush is that polymer thickness is even, its structural performance is control and adjustment interface or surperficial physicochemical property well, and can regulate and control the accumulation shape of polymer molecule brush and the distribution of functional group by changing composition, structure and the density of polymkeric substance, realize modification, modification and function nano particle compound of effects on surface, expansion, in the widespread use in polymer materials field, has become study hotspot at present.In recent years, along with scientific and technical development, the successful invention of various controlled radical polymerization technology provides effective approach for preparing the research of polymer molecule brush film.If fluorescence molecule and polymer molecule brush is carried out compound, utilize the stabilization of molecular brush and fluorescence molecule bonding, can obtain the polymer molecule with excellent photoluminescent property and brush film, using it as fluorescence detecting sensor, there is important using value.
Utilize the strong electron-withdrawing power of the nitro explosives such as TNT, fluorescence molecule in itself and polymer molecule brush is interacted, cause the photoluminescent property generation cancellation of fluorescence molecule, thereby can realize fluorescent functional polymer molecule brush film to the intelligence of TNT and Sensitive Detection.
Summary of the invention
The object of this invention is to provide a kind of fluorescent polymer molecular brush film, preparation method and for highly sensitive explosive detection.
First the method synthesizes thickness from nanometer to the controlled polymer molecule brush film of micron in substrate, and then will have the organic molecule (fluorescence molecule) and molecular brush Film laminated of photoluminescent property, and acquisition has the polymer molecule brush film of photoluminescent property.Utilize the transfer transport effect between explosive TNT molecule and fluorescence molecule, cause cancellation fluorescence and the fluorescence intensity of polymer molecule brush film is reduced, realize the Intelligent Measurement of fluorescent polymer molecular brush film to TNT.This photoluminescent property molecular brush thin-film material can be realized and detecting TNT in larger concentration range, and has very high detection sensitivity, and detectability can reach 0.1ppb, far below the 2ppb lowest detection standard of environmental administration's regulation.The fluorescent polymer molecular brush thin-film material of this TNT of having measuring ability has been opened up polymer responsiveness material system, will be in rapid sensitive explosive detection, environmental monitoring, the fields such as airport security, optical material, safety inspection and anti-terrorism have important practical significance and using value.
A preparation method with the fluorescent polymer molecular brush film of highly sensitive explosive detection function, its step is as follows:
(1) substrate (be generally inorganic substrate, comprise quartz, glass, mica, silicon chip etc.) is put into and filled dense H
2sO
4(98wt%) and H
2o
2in the reactor of mixing solutions (volume ratio 7:3), under 70～95 ℃ of conditions, heat 30～90 minutes, make substrate surface produce oh group, then by deionized water rinse substrate and dry up with nitrogen, then substrate is placed in to 30～60uL and contains amino silane coupling agent (as 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 2-aminoethyl Trimethoxy silane, 2-aminoethyl triethoxyl silane, aminoethyl aminoethyl aminopropyl trimethoxysilane etc.) and react 8～12 hours with 10mL toluene mixing solutions, make substrate surface connect upper amino group, after substrate is dried up with the flushing of methylene dichloride equal solvent, put into and fill 0.1～0.3mL initiator (2-bromine isobutyl acylbromide, 2 bromopropionic acid methyl esters, 2-isobutyl ethyl bromide, vinyl chloroacetate, allyl chloroacetate, 4-brooethyl benzophenone, 4, 4'-dibromo methyldiphenyl ketone, chlor(o)acetamide or azo-bis-isobutyl cyanide etc.), 0.12～0.2mL acid absorber (triethylamine, Tri N-Propyl Amine, n-Butyl Amine 99 or pyridine etc.), in the air-tight bottle of 5～10mL methylene dichloride, under 0 ℃ of condition, react after 1～3 hour, at room temperature react again 15～18 hours, then after the substrate taking-up that is connected to initiator being rinsed respectively with acetone and toluene, with nitrogen, dry up,
(2) surface step (1) being obtained is connected to the substrate of initiator and puts into reactor, add 5～8mL acetone, 1～3mL deionized water, 0.8～2mol polymerization single polymerization monomer 1, after 0.67～0.7mmol part monomer 2, mix, under room temperature, logical high pure nitrogen is after 30～60 minutes, reaction system is warming up to 60～70 ℃, add 0.223～0.278mmol catalyzer monomer 3, mix, under sealing circulating water condensing condition, react 3～6 hours, substrate is taken out with tetrahydrofuran (THF) and carried out after ultrasonic cleaning dries up, being placed in 120～260 ℃ of baking ovens heats 15～90 minutes, with a large amount of deionized water rinsings nitrogen, dry up, on substrate, obtained polymer molecule brush film, its thickness is 20～200nm,
(3) in reactor; the NaOH aqueous solution that substrate with polymer molecule brush film prepared by step (2) is put into pH=7.5～9.0 soaks 15～90 minutes; taking-up dries up; join in 0.1～2mM fluorescence molecule aqueous solution; nitrogen protection lower magnetic force stirs; at 25～35 ℃ of reaction 5～8h, then by distilled water centrifuge washing 3～5 times repeatedly for substrate, obtain being compounded with the fluorescent functional polymer molecule brush film of fluorescence molecule.
In order to test the intelligent detecting function of fluorescent polymer molecular brush film to TNT, by after the TNT solution of different concns and the effect of fluorescent polymer molecular brush film, the fluorescence spectrum of testing film, result shows along with TNT strength of solution increases, the linear reduction of fluorescence intensity of polymer molecule brush film.The minimum detectability of TNT is reached to the highly sensitive level of 0.1ppb, and this polymer molecule brush film can use repeatly, we carried out TNT concentration 0 and 1ppb between reciprocal fluorometric investigation repeatedly, show that fluorescent polymer molecular brush film prepared by the present invention has the reciprocal character of good fluorescence, has realized the Sensitive Detection of fluorescent polymer molecular brush film to TNT.
In aforesaid method, polymerization single polymerization monomer 1 can be tert-butyl acrylate (tert-Butylacrylate), ethyl propenoate (Ethylacrylate), glycidyl methacrylate (GMA) or methyl methacrylate (MMA) etc.;
In aforesaid method, part monomer 2 can be pentamethyl-diethylenetriamine (PMDETA), 2,2-dipyridyl (2,2-Dipyridyl) or three-(2-dimethylaminoethyl) amine (Me6-TREN) etc.;
In aforesaid method, catalyzer monomer 3 can be cuprous bromide (CuBr), cuprous chloride (CuCl) or cuprous iodide (Cul) etc.;
In aforesaid method, fluorescence molecule can be bromination (N, N, N-triethyl-3-(4-(1, 2-phenylbenzene-2-(4-(2-triethylamine) oxyethyl group) vinyl) vinyl) phenyl) propyl group amine (TAPE), 3-(4-(1, 2-phenylbenzene-2-(4-sulfo group oxyethyl group) phenyl) vinyl) propyl group-1-sodium sulfonate (TPE), bromination 2, 2 ', 2 "-(4, 4 ', 4 " propyl group-(2-(4-(3-s triethylamine)) phenyl) 1, 1, 2-triphenyl vinyl three oxygen) three (N, N, N-triethyl ethamine) (TTAPE), Silole (silole) or hexaphenyl thiophene are coughed up (HPS) etc. and derivative thereof.
Tool of the present invention has the following advantages: 1, the polymer molecule of the composite fluorescence molecule of synthesized brush film has excellent photoluminescent property, this molecular brush has sensitive detection character in larger concentration range to TNT, along with the rising of TNT concentration, the fluorescence intensity of polymer molecule brush reduces gradually, and have repeatedly can duplicate detection performance; 2, the even thickness of this polymer molecule brush film and in nanometer to micro-meter scale, be conducive to quantitatively compound and stable fluorescence molecule, the detection by quantitative of realization to TNT; 3, prepared polymer molecule brush film thickness can carry out controllable adjustment by conditions such as reaction monomers concentration, polymerization reaction times, and its gauge can be controlled between 20nm～200nm; 4, prepared fluorescent polymer molecular brush film has very high detection sensitivity to TNT, detectability can reach 0.1ppb, 2ppb lowest detection standard far below environmental administration's regulation, the Sensitive Detection of realization to TNT, and can expanded application in fields such as rapid sensitive explosive detection, environmental monitoring, airport security, anti-terrorisms.
Accompanying drawing explanation
Fig. 1: be Poly(acrylicacid) atomic force microscope images of polymer molecule brush film; Show that molecular brush film thickness is more even, show smooth; (embodiment 1);
Fig. 2: be TAPE/Poly(acrylicacid) the change in fluorescence spectrogram of fluorescent polymer molecular brush film within the scope of TNT concentration 0～200ppb; At wavelength 472nm punishment sub brush film, have very strong fluorescence peak, under different TNT concentration, molecular brush film fluorescence intensity change is obvious; (embodiment 1)
Fig. 3: be TAPE/Poly(acrylicacid) fluorescent polymer molecular brush film fluorescence intensity is with the variation diagram of TNT concentration, show the increase along with TNT concentration, film fluorescence intensity declines obviously, illustration is under lower TNT concentration (0～0.5ppb), increase along with TNT concentration, film fluorescence intensity presents linear decrease Changing Pattern, illustrates that film can carry out detection by quantitative to TNT; And its detectability is minimum can reach 0.1ppb, lower than the lowest detection standard of national tap water regulation; (embodiment 1);
Fig. 4: be TAPE/Poly(acrylicacid) fluorescent polymer molecular brush film is 0 to carry out repeatedly 10 tests, the reciprocal change curve of its fluorescence intensity with 1ppb to TNT concentration; Illustrate that this fluorescent polymer molecular brush film can carry out test request back and forth, can reuse.(embodiment 1)
Embodiment
Embodiment 1:
1. quartz substrate is put into the H that fills 98wt%
2sO
4and H
2o
2in the reactor of (volume ratio 7:3) mixing solutions, under 95 ℃ of conditions, heat 30 minutes, make substrate surface produce oh group.With after deionized water rinsing 4 times, with nitrogen, dry up.Then 10mL toluene solution quartz substrate being placed in containing 30uL silane coupling agent 3-aminopropyl triethoxysilane (APTES) reacts 8 hours, makes substrate surface connect upper amino group.After substrate is dried up by dichloromethane rinse, put into and fill 0.1mL initiator 2-bromine isobutyl acylbromide, 0.12mL triethylamine, in the air-tight bottle of 10mL methylene dichloride, under 0 ℃ of condition, react after 2 hours, at room temperature react again 15 hours, after then the substrate taking-up that is connected to initiator being rinsed respectively with acetone and toluene, with nitrogen, dry up, stand-by;
2. surface step (1) being obtained is connected to the substrate of initiator and puts into reactor, add 5mL acetone, 2mL deionized water, 0.8mol polymerization single polymerization monomer tert-butyl acrylate (tert-Butylacrylate), 0.67mmol pentamethyl-diethylenetriamine (PMDETA), mix, under room temperature, logical high pure nitrogen is after 30 minutes, reaction system is warming up to 60 ℃, add 0.223mmol catalyzer monomer CuBr, mix, under sealing circulating water condensing condition, react 3 hours, substrate is taken out with tetrahydrofuran (THF) and carried out after ultrasonic cleaning dries up, being placed in 200 ℃ of baking ovens heats 30 minutes, with a large amount of deionized water rinsings nitrogen, dry up, on substrate, obtained polymer molecule brush film [Poly(acrylicacid)], use step instrument to test its thickness for 133nm,
3. in reactor, substrate with polymer molecule brush film prepared by step (2), the NaOH aqueous solution of putting into pH=7.5 soaks 60 minutes, taking-up dries up, join in the 0.1mM fluorescence molecule TAPE aqueous solution, pass into nitrogen protection lower magnetic force and stir, at 35 ℃ of reaction 5h, with distilled water centrifuge washing 3 times repeatedly, obtain being compounded with the fluorescent functional polymer molecule brush film [TAPE/Poly(acrylicacid)] of fluorescence molecule;
4. by after the TNT solution of different concns and the effect of fluorescent polymer molecular brush film, the fluorescence spectrum of testing film, result shows along with TNT strength of solution increases, there is linear reduction in the fluorescence intensity of polymer molecule brush film.The minimum detectability of TNT is reached to the highly sensitive level of 0.1ppb, and this polymer molecule brush film can be reused, we tested TNT concentration 0 and 1ppb between reciprocal fluorometric investigation repeatedly, polymer molecule brush film has the reciprocal character of good fluorescence.Realized the Sensitive Detection of fluorescent polymer molecular brush film to TNT.
Embodiment 2:
1. quartz substrate is put into the H that fills 98wt%
2sO
4and H
2o
2in the reactor of (volume ratio 7:3) mixing solutions, under 70 ℃ of conditions, heat 90 minutes, make substrate surface produce oh group.With after deionized water rinsing 5 times, with nitrogen, dry up.Then 12mL toluene solution quartz substrate being placed in containing 60uL 3-aminopropyl trimethoxysilane reacts 10 hours, makes substrate surface connect upper amino group.After substrate is dried up by dichloromethane rinse, put into and fill 0.15mL initiator 2 bromopropionic acid methyl esters, 0.16mL Tri N-Propyl Amine, in the air-tight bottle of 5mL methylene dichloride, under 0 ℃ of condition, react after 1 hour, at room temperature react again 18 hours, after then the substrate taking-up that is connected to initiator being rinsed respectively with acetone and toluene, with nitrogen, dry up, stand-by;
2. surface step (1) being obtained is connected to the substrate of initiator and puts into reactor, add 6mL acetone, 1mL deionized water, 1.25mol polymerization single polymerization monomer methyl methacrylate (MMA), 0.7mmol tri--(2-dimethylaminoethyl) amine (Me6-TREN), mix, under room temperature, logical high pure nitrogen is after 60 minutes, reaction system is warming up to 70 ℃, add 0.25mmol catalyzer monomer CuBr, mix, under sealing circulating water condensing condition, react 5 hours, substrate is taken out with tetrahydrofuran (THF) and carried out after ultrasonic cleaning dries up, being placed in 180 ℃ of baking ovens heats 90 minutes, with a large amount of deionized water rinsings nitrogen, dry up, on substrate, obtained polymer molecule brush film [Poly(acrylicacid)], use step instrument to test its thickness for 200nm,
3. in reactor, substrate with polymer molecule brush film prepared by step (2), the NaOH aqueous solution of putting into pH=9.0 soaks 15 minutes, taking-up dries up, join in the 2mM fluorescence molecule HPS aqueous solution, pass into nitrogen protection lower magnetic force and stir, at 25 ℃ of reaction 8h, with distilled water centrifuge washing 5 times repeatedly, obtain being compounded with the fluorescent functional polymer molecule brush film [HPS/Poly(acrylicacid)] of fluorescence molecule;
4. by after the TNT solution of different concns and the effect of fluorescent polymer molecular brush film, the fluorescence spectrum of testing film, result shows along with TNT strength of solution increases, there is linear reduction in the fluorescence intensity of polymer molecule brush film.We tested TNT concentration 0 and 1ppb between reciprocal fluorometric investigation repeatedly, polymer molecule brush film has the reciprocal character of good fluorescence, this polymer molecule brush film can be reused.
Embodiment 3:
1. quartz substrate is put into the H that fills 98wt%
2sO
4and H
2o
2in the reactor of (volume ratio 7:3) mixing solutions, under 85 ℃ of conditions, heat 60 minutes, make substrate surface produce oh group.With after deionized water rinsing 3 times, with nitrogen, dry up.Then 10mL toluene solution quartz substrate being placed in containing 50uL aminoethyl aminoethyl aminopropyl trimethoxysilane reacts 12 hours, makes substrate surface connect upper amino group.After substrate is dried up by dichloromethane rinse, put into and fill 0.3mL initiator vinyl chloroacetate, 0.2mL pyridine, in the air-tight bottle of 10mL methylene dichloride, under 0 ℃ of condition, react after 3 hours, at room temperature react again 15 hours, after then the substrate taking-up that is connected to initiator being rinsed respectively with acetone and toluene, with nitrogen, dry up, stand-by;
2. surface step (1) being obtained is connected to the substrate of initiator and puts into reactor, add 8mL acetone, 3mL deionized water, 2mol polymerization single polymerization monomer ethyl propenoate (Ethylacrylate), 0.19mmol part monomer 2, 2-dipyridyl (2, 2-Dipyridyl), mix, under room temperature, logical high pure nitrogen is after 50 minutes, reaction system is warming up to 60 ℃, add 0.278mmol catalyzer monomer CuCl, mix, under sealing circulating water condensing condition, react 6 hours, substrate is taken out with tetrahydrofuran (THF) and carried out after ultrasonic cleaning dries up, being placed in 260 ℃ of baking ovens heats 15 minutes, with a large amount of deionized water rinsings nitrogen, dry up, on substrate, obtained polymer molecule brush film [Poly(acrylicacid)], use step instrument to test its thickness for 20nm,
3. in reactor, substrate with polymer molecule brush film prepared by step (2), the NaOH aqueous solution of putting into pH=7.5 soaks 90 minutes, taking-up dries up, join in the 0.2mM fluorescence molecule TAPE aqueous solution, pass into nitrogen protection lower magnetic force and stir, at 30 ℃ of reaction 6.5h, with distilled water centrifuge washing 5 times repeatedly, obtain being compounded with the fluorescent functional polymer molecule brush film [TAPE/Poly(acrylicacid)] of fluorescence molecule;
4. by after the TNT solution of different concns and the effect of fluorescent polymer molecular brush film, the fluorescence spectrum of testing film, result shows along with TNT strength of solution increases, there is linear reduction in the fluorescence intensity of polymer molecule brush film.We tested TNT concentration 0 and 1ppb between reciprocal fluorometric investigation repeatedly, polymer molecule brush film has the reciprocal character of good fluorescence, this polymer molecule brush film can be reused.
Claims (9)
1. a preparation method for fluorescent polymer molecular brush film, its step is as follows:
(1) substrate is carried out to hydroxylation processing, make substrate surface produce oh group, then by deionized water rinse substrate and dry up with nitrogen; Then substrate is placed in to 30～60uL and contains amino silane coupling agent and react 8～12 hours with 10mL toluene mixing solutions, make substrate surface connect upper amino group; After substrate is dried up by dichloromethane rinse, put into the air-tight bottle that fills 0.1～0.3mL initiator, 0.12～0.2mL acid absorber, 5～10mL methylene dichloride, under 0 ℃ of condition, react after 1～3 hour, at room temperature react again 15～18 hours, after then the substrate taking-up that is connected to initiator being rinsed respectively with acetone and toluene, with nitrogen, dry up;
(2) surface step (1) being obtained is connected to the substrate of initiator and puts into reactor, add 5～8mL acetone, 1～3mL deionized water, 0.8～2mol polymerization single polymerization monomer, after 0.67～0.7mmol part monomer, mix, under room temperature, logical high pure nitrogen is after 30～60 minutes, reaction system is warming up to 60～70 ℃, add 0.223～0.278mmol catalyzer monomer, mix, under sealing circulating water condensing condition, react 3～6 hours, substrate is taken out with tetrahydrofuran (THF) and carried out after ultrasonic cleaning dries up, being placed in 120～260 ℃ of baking ovens heats 15～90 minutes, with a large amount of deionized water rinsings nitrogen, dry up, on substrate, obtained polymer molecule brush film, its thickness is 20～200nm, polymerization single polymerization monomer is tert-butyl acrylate, ethyl propenoate, glycidyl methacrylate or methyl methacrylate, part monomer is pentamethyl-diethylenetriamine, 2,2-dipyridyl or three-(2-dimethylaminoethyl) amine, catalyzer monomer is cuprous bromide, cuprous chloride or cuprous iodide,
(3) in reactor, the NaOH aqueous solution that substrate with polymer molecule brush film prepared by step (2) is put into pH=7.5～9.0 soaks 15～90 minutes, taking-up dries up, join in 0.1～2mM fluorescence molecule aqueous solution, nitrogen protection lower magnetic force stirs, at 25～35 ℃ of reaction 5～8h, then by distilled water centrifuge washing 3～5 times repeatedly for substrate, obtain being compounded with the fluorescent functional polymer molecule brush film of fluorescence molecule; Fluorescence molecule is bromination (N, N, N-triethyl-3-(4-(1,2-phenylbenzene-2-(4-(2-triethylamine) oxyethyl group) vinyl) vinyl) phenyl) propyl group amine, 3-(4-(1,2-phenylbenzene-2-(4-sulfo group oxyethyl group) phenyl) vinyl) propyl group-1-sodium sulfonate, bromination 2,2 ', 2 ' '-(4,4 ', 4 ' ' propyl group-(2-(4-(3-s triethylamine)) phenyl) 1,1,2-triphenyl vinyl three oxygen) three (N, N, N-triethyl ethamine), Silole or hexaphenyl thiophene are coughed up.
2. the preparation method of a kind of fluorescent polymer molecular brush film as claimed in claim 1, is characterized in that: substrate is quartz, glass, mica or silicon chip.
3. the preparation method of a kind of fluorescent polymer molecular brush film as claimed in claim 1, is characterized in that: the hydroxylation of substrate is processed, and is that substrate is put into and filled dense H
2sO
4and H
2o
2in the reactor of mixing solutions, under 70～95 ℃ of conditions, heat 30～90 minutes H
2sO
4concentration be 98wt%, H
2sO
4and H
2o
2volume ratio 7:3.
4. the preparation method of a kind of fluorescent polymer molecular brush film as claimed in claim 1, is characterized in that: containing amino silane coupling agent is 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, 2-aminoethyl Trimethoxy silane, 2-aminoethyl triethoxyl silane or aminoethyl aminopropyl trimethoxysilane.
5. the preparation method of a kind of fluorescent polymer molecular brush film as claimed in claim 1, it is characterized in that: initiator is 2-bromine isobutyl acylbromide, 2 bromopropionic acid methyl esters, 2-isobutyl ethyl bromide, vinyl chloroacetate, allyl chloroacetate, 4-brooethyl benzophenone, 4,4'-dibromo methyldiphenyl ketone or chlor(o)acetamide or azo-bis-isobutyl cyanide.
6. the preparation method of a kind of fluorescent polymer molecular brush film as claimed in claim 1, is characterized in that: acid absorber is triethylamine, Tri N-Propyl Amine, n-Butyl Amine 99 or pyridine.
7. the claim 1～6 fluorescent polymer molecular brush film that prepared by method described in any one.
8. fluorescent polymer molecular brush film claimed in claim 7 is for highly sensitive explosive detection.
9. fluorescent polymer molecular brush film as claimed in claim 8, for highly sensitive explosive detection, is characterized in that: for detection of TNT.
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