CN100559167C - Preparation method of monomolecular layer polysilane fluorescent sensing film sensitive to nitroaromatics - Google Patents
Preparation method of monomolecular layer polysilane fluorescent sensing film sensitive to nitroaromatics Download PDFInfo
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- CN100559167C CN100559167C CNB2007100177232A CN200710017723A CN100559167C CN 100559167 C CN100559167 C CN 100559167C CN B2007100177232 A CNB2007100177232 A CN B2007100177232A CN 200710017723 A CN200710017723 A CN 200710017723A CN 100559167 C CN100559167 C CN 100559167C
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- toluene
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- 229920000548 poly(silane) polymer Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 106
- 239000000758 substrate Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 16
- 239000006210 lotion Substances 0.000 claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 165
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 40
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 35
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 31
- 229910052708 sodium Inorganic materials 0.000 claims description 31
- 239000011734 sodium Substances 0.000 claims description 31
- 238000010992 reflux Methods 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 18
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical class Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 2
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 claims 1
- 238000000944 Soxhlet extraction Methods 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000012153 distilled water Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 125000001624 naphthyl group Chemical group 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 125
- 238000001514 detection method Methods 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 239000010409 thin film Substances 0.000 abstract description 5
- 230000035699 permeability Effects 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001348 alkyl chlorides Chemical class 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000010410 layer Substances 0.000 abstract 2
- 206010070834 Sensitisation Diseases 0.000 abstract 1
- 229920001109 fluorescent polymer Polymers 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 239000002356 single layer Substances 0.000 abstract 1
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 104
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 35
- 229920006395 saturated elastomer Polymers 0.000 description 27
- 229920000642 polymer Polymers 0.000 description 19
- 238000005516 engineering process Methods 0.000 description 18
- 239000002994 raw material Substances 0.000 description 18
- 230000021615 conjugation Effects 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 15
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 14
- KTRCLLBEAXBTIH-UHFFFAOYSA-N C[SiH2]c1cccc2ccccc12 Chemical compound C[SiH2]c1cccc2ccccc12 KTRCLLBEAXBTIH-UHFFFAOYSA-N 0.000 description 13
- 238000002444 silanisation Methods 0.000 description 13
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 12
- 230000004913 activation Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- CIJMVTHFBDSTSK-UHFFFAOYSA-N CC1=CC=C(C=C1)[SiH2]C2=CC=CC3=CC=CC=C32 Chemical compound CC1=CC=C(C=C1)[SiH2]C2=CC=CC3=CC=CC=C32 CIJMVTHFBDSTSK-UHFFFAOYSA-N 0.000 description 9
- -1 nitro arene Chemical class 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- NKRGRHUUEKJCDY-UHFFFAOYSA-N C[Si](CC1=CC=CC2=CC=CC=C21)(Cl)Cl Chemical group C[Si](CC1=CC=CC2=CC=CC=C21)(Cl)Cl NKRGRHUUEKJCDY-UHFFFAOYSA-N 0.000 description 7
- 239000004305 biphenyl Substances 0.000 description 7
- 238000002189 fluorescence spectrum Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- 230000003595 spectral effect Effects 0.000 description 7
- 239000000015 trinitrotoluene Substances 0.000 description 7
- GCKXWRZSEYRRDR-UHFFFAOYSA-N dichloro-(4-methylphenyl)-naphthalen-1-ylsilane Chemical group CC1=CC=C(C=C1)[Si](C2=CC=CC3=CC=CC=C32)(Cl)Cl GCKXWRZSEYRRDR-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 235000013399 edible fruits Nutrition 0.000 description 5
- 239000002304 perfume Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 229950002929 trinitrophenol Drugs 0.000 description 5
- 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 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- ACPGXPKYDGIYLE-UHFFFAOYSA-N hexyl(methyl)silane Chemical compound CCCCCC[SiH2]C ACPGXPKYDGIYLE-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- TZPUFQUQYUYVQC-UHFFFAOYSA-N phenylsilylmethanamine Chemical compound NC[SiH2]C1=CC=CC=C1 TZPUFQUQYUYVQC-UHFFFAOYSA-N 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- OASAGXUWNYOMED-UHFFFAOYSA-N (4-methylphenyl)silane Chemical compound CC1=CC=C([SiH3])C=C1 OASAGXUWNYOMED-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RMBFBMJGBANMMK-UHFFFAOYSA-N 2,4-dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RMBFBMJGBANMMK-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000012491 analyte Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002284 excitation--emission spectrum Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 0 BC(*OC(*)*C(C(*C(*)CC*CC1)O)*#C)C(*)CC1N=C Chemical compound BC(*OC(*)*C(C(*C(*)CC*CC1)O)*#C)C(*)CC1N=C 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- KKRMHVJQWMXYBZ-UHFFFAOYSA-N dichloro-hexyl-methylsilane Chemical compound CCCCCC[Si](C)(Cl)Cl KKRMHVJQWMXYBZ-UHFFFAOYSA-N 0.000 description 1
- MRUIMSDHOCZKQH-UHFFFAOYSA-N dichloro-methyl-(4-methylphenyl)silane Chemical compound CC1=CC=C([Si](C)(Cl)Cl)C=C1 MRUIMSDHOCZKQH-UHFFFAOYSA-N 0.000 description 1
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 1
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- 239000002070 nanowire Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种对硝基芳烃敏感的单分子层聚硅烷荧光传感薄膜的制备方法，包括裁制基片、制备洗液、制备活化基片、制备硅烷化基片、制备聚硅烷、制备单分子层聚硅烷荧光传感薄膜工艺步骤。本发明将末端带有氯功能团的硅烷化试剂单层组装到玻璃基片表面，利用末端带锂的聚硅烷与烷基氯的表面化学反应，将其化学结合到基片表面，将共轭荧光高分子引入传感薄膜中，实现了薄膜传感器超灵敏化，解决了固体荧光传感器稳定性和通透性问题。采用本发明制备的荧光传感薄膜具有稳定性好、使用寿命长、灵敏度高等优点，可在检测含硝基芳烃类化合物的传感器或检测硝基芳烃类化合物的检测仪器上使用，还可将该荧光传感膜感受硝基芳烃类化合后直接用荧光仪器进行检测。
A method for preparing a monomolecular layer polysilane fluorescent sensing film sensitive to nitroaromatics, comprising tailoring a substrate, preparing a lotion, preparing an activated substrate, preparing a silanized substrate, preparing polysilane, and preparing a monomolecular layer Process steps of polysilane fluorescent sensing thin film. In the present invention, a monolayer of silylating reagents with chlorine functional groups at the ends is assembled on the surface of a glass substrate, and the surface chemical reaction between the polysilanes with lithium at the ends and alkyl chlorides is used to chemically bond them to the surface of the substrate, and the conjugated Fluorescent polymers are introduced into the sensing film to achieve ultra-sensitization of the film sensor and solve the stability and permeability problems of the solid fluorescent sensor. The fluorescent sensing film prepared by the present invention has the advantages of good stability, long service life, high sensitivity, etc., and can be used on sensors for detecting nitroaromatic compounds or detection instruments for detecting nitroaromatic compounds. Fluorescence sensing membrane senses the combination of nitroaromatics and detects directly with a fluorescence instrument.
Description
Technical field
The invention belongs to conjugation fluorescence polymer fluorescence sense film material technology field, be specifically related to preparation method the unimolecular layer polysilane fluorescence sense film of nitro-aromatic sensitivity.
Background technology
In recent years, along with the increase of demands such as anti-terrorism, anti-CB weapons, nonmetallic mine detection, environmental quality monitoring, countries in the world are more and more paid attention to the research of all kinds of high performance thin film sensors.With respect to homogeneous phase (solution) sensor, that thin film sensor has is reusable, do not pollute system to be measured substantially, be easy to advantages such as device, therefore, enjoys people to pay attention to.Mostly existing in the optical sensing film is semiconductive thin film, fluorescence polymer film, and dye adulterated (or dyestuff modification) macromolecule or sull etc.Wherein with fluorescence polymer, particularly the conjugation fluorescence polymer enjoys people to pay attention to as the research of sensing element.As the sensing element, the conjugation fluorescence polymer has a series of outstanding advantages.For example: molar extinction coefficient can reach 10
6M
-1Cm
-1, have very strong light collecting light ability; Because of whole molecular backbone is a conjugated structure, allow the optical excitation electronics on chain, to flow rapidly, have so-called " molecular wire effect ", measured molecule is shown as " some contact, multiple spot response ", present significant signal enlarge-effect; It is a ultrafast process that the photoinduction electron transfer of conjugation fluorescence polymer or energy shift, and generally can finish in hundreds of femtoseconds, than fast 4 orders of magnitude of normal radiative decay, therefore does the time spent with quencher, can show as " super quencher ".Based on these characteristics of conjugation fluorescence polymer, can set up efficient, highly sensitive analysis sensing platform, and use it for genetic test, protein enzyme assay, antigen-antibody identification and bacteria-measuring etc.To this, conjugation fluorescence polymer research pioneer, Heeger etc. have given high evaluation.The conjugation fluorescence polymer being fixed in stromal surface, realizing that colorimetric sensor filmsization or granulating are the key points that solves sensor repeated use, array, chipization, also is an important directions of conjugation fluorescence polymer Application in Sensing research.With regard to the stromal surface immobilization of conjugation fluorescence polymer, what people taked all is physical methods such as spin coating, layer assembly and Langmuir-Blodgett film, does not appear in the newspapers as yet with the research of covalent bonds.In general, the film with the physical method preparation all exists chemical stability and thermal stability problems, is easy to leak, pollutes system to be measured when using in solution.Particularly also there be the permeability problem of analyte in film in use with spin-coating method and layer assembly method prepared film.The research group at the present inventor place is devoted to the preparation and the performance study of this type of sense film material in recent years always.Result of study shows, the conjugation fluorescence polymer being chemically bonded on the stromal surface such as glass is a kind of effective method for preparing conjugation fluorescence polymer sense film material, by the preparation-obtained fluorescence sense film of this method, except having characteristics such as the distinctive super quencher of conjugation fluorescence polymer, also have highly sensitive, selectivity good, do not pollute system to be measured, stable in properties, long service life, be easy to advantages such as device, and the nitro-aromatic compound steam table revealed high detection sensitivity and selectivity.
At present, have only several laboratories few in number being engaged in the conjugation fluorescence polymer in the world as of the preparation and the research of sensing element to the film of nitro-aromatic compound vapor sensitive.Wherein with the tool representative of the Swager group of Massachusetts Institute Technology, this group introduces bulky group on the organic polymer chain, in the hope of in the film of preparation, reducing the pi accumulation and the self-quenching of conjugation fluorescence polymer self, and in film, form the molecular channel, improve the permeability of analyte in film, improve the sensing capabilities of film, realized 2,4,6-trinitro-toluene etc. contains the sensitive sensing of nitro-aromatic compound steam.Trogler group is silicon atom with the main chain, and the inorganic conjugated fluorescence polymer that side chain has palycyclic aromatic is a material, makes sense film, has improved the anti-interference of film, has realized the sensing to nitro arene explosive substance.Fujiki group is silicon atom with the main chain, and the inorganic conjugated fluorescence polymer that side chain has the alkoxy fluorine is a material, makes sense film, and nitro-aromatic compound has been realized Sensitive Detection.But the conjugation fluorescence polymer is covalently bound to the glass matrix surface, realizes the research of the fluorescence sense film material that contains the detection of microscratch amount nitro-aromatic compound steam be yet there are no report.
Summary of the invention
A technical matters to be solved by this invention be to provide a kind of reasonable in design, feasible process, easy and simple to handle, reaction conditions is gentle to the preparation method of the unimolecular layer polysilane fluorescence sense film of nitro-aromatic sensitivity.
Solving the problems of the technologies described above the technical scheme that is adopted is that chemical structural formula is
Polysilane, in the structural formula (1), R
1, R
2A kind of in phenyl ring, the naphthalene nucleus or derivatives thereof, R
1, R
2Can be identical or different, R
1, R
2Be preferably phenyl ring; R
3, R
4Be C
1-C
7Alkyl, C
6-C
14Aryl or aralkyl, R
3, R
4Be preferably C
1-C
6Alkyl, C
6-C
10Aryl, R
3, R
4Can be identical or different, n is 5～20, is preferably 8～12 that m is 0～20, is preferably 0～10 that its preparation method comprises the steps:
1, tailors substrate
Glass plate is cut into 0.9 * 2.5cm
2The rectangular glass sheet of size.
2, preparation washing lotion
With the sulfuric acid of 30% hydrogen peroxide and 98% is to be mixed and made into washing lotion at 7: 3 by volume.
3, preparation activation substrate
Elder generation's water, ethanol cleaning glass sheet are put into washing lotion after drying up, and 80～100 ℃ were heated 1～2 hour down, and natural cooling with redistilled water cleaning glass sheet, is washed the washing lotion of remained on surface off, dries up with hair-dryer, makes the activation substrate.
4, preparation silanization substrate
The volume ratio that the activation substrate is put into 3-r-chloropropyl trimethoxyl silane and toluene is 1: 100～120 solution, refluxed 3～6 hours, take out substrate, use earlier toluene wash, wash with tetrahydrofuran again, wash the 3-r-chloropropyl trimethoxyl silane of remained on surface off, dry up, make the silanization substrate with hair-dryer.
5, preparation polysilane
In the 500mL three-neck flask of magnetic stirrer, reflux condensing tube and constant pressure funnel is housed, under 0.6～0.8mL/s argon gas condition, add toluene, sodium, the weight ratio of toluene and sodium is 20～30: 1, be heated to 110 ℃, reflux, be 1800 rev/mins with the magnetic stirrer rotating speed and stirred 1 hour; To be that 1: 2 at least a disubstituted dichlorosilane mixes with toluene with the sodium mol ratio, the weight ratio of toluene and sodium is 20～30: 1, under the lucifuge condition, evenly splash into disubstituted dichlorosilane and toluene mixed solution in the three-neck flask, dripping speed is 1～2 droplet/second, 110 ℃ were refluxed 8～24 hours, and chemical equation is as follows:
Room temperature cooling, suction filtration separates polysilane in filter residue or filtrate, purify, 30～40 ℃ under the pressure of 3000Pa dry 2～3 hours, the pure product of polysilane.
6, preparation unimolecular layer polysilane fluorescence sense film
Under 0.6～0.8mL/s argon gas condition, get the pure product of polysilane and be dissolved in the tetrahydrofuran, in the 50mL round-bottomed flask, prepare 2 * 10
-3～3 * 10
-3The solution of g/mL stirred 10 minutes for 1000 rev/mins with magnetic stirrer, added 3～6 butyl lithiums, after 5 minutes, the silanization substrate is put into flask, after 5 minutes, take out substrate, with tetrahydrofuran flushing 5～10 times, change in the apparatus,Soxhlet's, with tetrahydrofuran extracting 4 hours again, take out, dry up with hair-dryer, make unimolecular layer polysilane fluorescence sense film, sealing is preserved.
Of the present invention in preparation silanization substrate processing step (4), the preferred volume ratio that the activation substrate is put into 3-r-chloropropyl trimethoxyl silane and toluene solution is 1: 100～110 solution, preferably refluxes 3～5 hours.In preparation polysilane processing step (5), in the 500mL three-neck flask of electromagnetic agitation, reflux condensing tube and constant pressure funnel is housed, 0.6 under～0.8mL/s argon gas the condition, add toluene, sodium, the preferred weight ratio of toluene and sodium is 23～27: 1, be heated to 110 ℃, reflux, stirred 1 hour for 1800 rev/mins with the magnetic stirrer rotating speed; To be that 1: 2 at least a disubstituted dichlorosilane mixes with toluene with the sodium mol ratio, the preferred weight ratio of toluene and sodium is 23～27: 1, under the lucifuge condition, evenly splash into disubstituted dichlorosilane and toluene mixed solution in the three-neck flask, dripping speed is 1～2 droplet/second, 110 ℃ of preferred backflows 10～14 hours.In the preparation unimolecular layer polysilane fluorescence sense film processing step (6), under 0.6～0.8mL/s argon gas condition, get polysilane and be dissolved in tetrahydrofuran, the preparation preferred concentration is 2 * 10 in the 50mL round-bottomed flask
-3～3 * 10
-3The solution of g/mL.
Of the present invention in preparation silanization substrate processing step (4), the optimum volume ratio that the activation substrate is put into 3-r-chloropropyl trimethoxyl silane and toluene solution is 1: 110 a solution, best backflow 4 hours.In preparation polysilane processing step (5), electromagnetic agitation is being housed, in the 500mL three-neck flask of reflux condensing tube and constant pressure funnel, 0.6 under～0.8mL/s argon gas the condition, add toluene, sodium, the optimum weight ratio of toluene and sodium is 26: 1, be heated to 110 ℃, reflux, stirred 1 hour for 1800 rev/mins with the magnetic stirrer rotating speed, to be that 1: 2 disubstituted dichlorosilane mixes with toluene with the sodium mol ratio, the optimum weight ratio of toluene and sodium be 26: 1, evenly splashes into disubstituted dichlorosilane and toluene mixed solution in the three-neck flask under the lucifuge condition, dripping speed is 1～2 droplet/second, 110 ℃ of best backflows 13 hours.In the preparation unimolecular layer polysilane fluorescence sense film processing step (6), under 0.6～0.8mL/s argon gas condition, get polysilane and be dissolved in tetrahydrofuran, being mixed with optium concentration in the 50mL round-bottomed flask is 2.5 * 10
-3The solution of g/mL.
The present invention is assembled into glass substrate surface with the silylating reagent individual layer that end has the chlorine functional group, utilize the polysilane of terminal band lithium and the surface chemical reaction of alkyl chloride, its chemical bond is arrived substrate surface, the conjugation fluorescence polymer is introduced in the sense film, realize the thin film sensor hypersensitization, solved solid fluorescence sensor stability and permeability problem.Advantages such as that the present invention has is reasonable in design, feasible process, easy and simple to handle, reaction conditions gentleness.Adopt the fluorescence sense film of the present invention's preparation to have advantages such as good stability, long service life, sensitivity height, can in containing the sensor of nitro-aromatic compound, detection use, also this class fluorescence sense film can be installed on the detecting instrument that utilizes the fluorescence principle to detect nitro-aromatic compound and use, directly detect after also this class fluorescence sense film can being experienced nitro-aromatic class chemical combination, as single photon counting time resolution fluorescence spectral instrument or other similar optical detecting instruments of FLS920 model with fluorescent instrument.
Description of drawings
Fig. 1 is the fluorescence emission spectrogram that the raw materials used proportioning of preparation silanization substrate is respectively 1: 75,1: 100,1: 120 prepared unimolecule strata diphenyl silane fluorescence sense film.
Fig. 2 is the fluorescence emission spectrogram that the reaction time of preparation unimolecule strata diphenyl silane is respectively 1,3,6,9 hour prepared unimolecule strata diphenyl silane fluorescence sense film.
Fig. 3 is that preparation unimolecule strata diphenyl silane fluorescence sense film raw material proportioning is respectively 1.5 * 10
-3G/mL, 2 * 10
-3G/mL, 2.5 * 10
-3G/mL, 3 * 10
-3The fluorescence emission spectrogram of the unimolecule strata diphenyl silane fluorescence sense film of g/mL preparation.
Fig. 4 is the static fluorescence excitation-emission spectrum of unimolecule strata diphenyl silane fluorescence sense film under dry state.
Fig. 5 be unimolecule strata diphenyl silane fluorescence sense film in time by 2,4, the fluorescence emission spectrogram of 6-trinitro-toluene saturated vapor quencher.
Fig. 6 be unimolecule strata diphenyl silane fluorescence sense film in time by 2, the fluorescence emission spectrogram of 4-dinitrotoluene (DNT) saturated vapor quencher.
Fig. 7 be unimolecule strata diphenyl silane fluorescence sense film in time by 2,4, the fluorescence emission spectrogram of 6-trinitrophenol saturated vapor quencher.
Fig. 8 is that unimolecule strata diphenyl silane fluorescence sense film is in time by the fluorescence emission spectrogram of nitrobenzene saturated vapor quencher.
Fig. 9 be unimolecule strata diphenyl silane fluorescence sense film in time by 2,4, the efficiency diagram of 6-trinitro-toluene saturated vapor quencher.
Figure 10 be unimolecule strata diphenyl silane fluorescence sense film in time by 2, the efficiency diagram of 4-dinitrotoluene (DNT) saturated vapor quencher.
Figure 11 be unimolecule strata diphenyl silane fluorescence sense film in time by 2,4, the efficiency diagram of 6-trinitrophenol saturated vapor quencher.
Figure 12 is that unimolecule strata diphenyl silane fluorescence sense film is in time by the efficiency diagram of nitrobenzene saturated vapor quencher.
Figure 13 is that unimolecule strata diphenyl silane fluorescence sense film is in time by the fluorescence emission spectrogram of benzene saturated vapor quencher.
Figure 14 is that unimolecule strata diphenyl silane fluorescence sense film is in time by the fluorescence emission spectrogram of perfume saturated vapor quencher.
Figure 15 is that unimolecule strata diphenyl silane fluorescence sense film is in time by the fluorescence emission spectrogram of fruit aroma gases saturated vapor quencher.
Embodiment
The present invention is described in more detail below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
Used sodium metal raw material 3g is an example with preparation unimolecule strata diphenyl silane fluorescence sense film of the present invention, and its preparation method is as follows:
1, tailors substrate
Glass plate is cut into 0.9 * 2.5cm
2The rectangular glass sheet of size.
2, preparation washing lotion
With the sulfuric acid of 30% hydrogen peroxide and 98% is to be mixed and made into washing lotion at 7: 3 by volume.
3, preparation activation substrate
Elder generation's water, ethanol cleaning glass sheet are put into washing lotion after drying up, and 80～100 ℃ were heated 1～2 hour down, and natural cooling with redistilled water cleaning glass sheet, is washed the washing lotion of remained on surface off, dries up with hair-dryer, makes the activation substrate.
4, preparation silanization substrate
The volume ratio that the activation substrate is put into 3-r-chloropropyl trimethoxyl silane and toluene solution is 1: 110 a solution, refluxed 4 hours, take out substrate, use earlier toluene wash, wash with tetrahydrofuran again, wash the 3-r-chloropropyl trimethoxyl silane of remained on surface off, dry up, make the silanization substrate with hair-dryer.
5, the poly-diphenyl silane of preparation
In the 500mL three-neck flask of magnetic stirrer, reflux condensing tube and constant pressure funnel is housed, under 0.6～0.8mL/s argon gas condition, add 3g sodium, 78g toluene is heated to 110 ℃, refluxes, and stirs 1 hour for 1800 rev/mins with the magnetic stirrer rotating speed; The 16.51g diphenyl dichlorosilane is mixed with 78g toluene, the mol ratio that is diphenyl dichlorosilane and sodium is 1: 2, under the lucifuge condition, evenly splash into disubstituted dichlorosilane and toluene mixed solution in the three-neck flask, dripping speed is 1～2 droplet/second, 110 ℃ were refluxed 13 hours, and chemical equation is as follows:
N=10 in the following formula, the room temperature cooling, suction filtration, filter residue 120mL secondary water washing 3～5 times, suction filtration, filter residue is washed 3～5 times with 120mL ethanol, and suction filtration, filter residue are washed 3 times with the 120mL cyclohexane again, suction filtration, the gained solid 30 ℃ under the pressure of 3000Pa dry 2 hours, must gather diphenyl silane, the molecular weight of prepared poly-diphenyl silane is 1880.
6, preparation unimolecular layer polysilane fluorescence sense film
Under 0.6～0.8mL/s argon gas condition, get polysilane and be dissolved in the tetrahydrofuran, in the 50mL round-bottomed flask, prepare 2.5 * 10
-3The suspending liquid of g/mL stirred 10 minutes for 1000 rev/mins with magnetic stirrer, added 3～6 butyl lithiums, after 5 minutes, the silanization substrate is put into flask, after 5 minutes, take out substrate, with tetrahydrofuran flushing 5～10 times, change in the apparatus,Soxhlet's, with tetrahydrofuran extracting 4 hours again, take out, dry up with hair-dryer, make unimolecule strata diphenyl silane fluorescence sense film, sealing is preserved.Prepared unimolecule strata diphenyl silane fluorescence sense film, the static fluorescence excitation-emission spectrum under dry state is seen Fig. 4.
Used sodium metal raw material 3g is an example with preparation unimolecule strata diphenyl silane fluorescence sense film of the present invention, and its preparation method is as follows:
Present embodiment is in preparation silanization substrate 4, and the volume ratio that the activation substrate is put into 3-r-chloropropyl trimethoxyl silane and toluene solution is 1: 100 a solution, refluxes 3 hours, and other technology in this step is identical with embodiment 1.In the poly-silicon diphenyl alkane step 5 of preparation, in the 500mL three-neck flask of magnetic stirrer, reflux condensing tube and constant pressure funnel is housed, under 0.6～0.8mL/s argon gas condition, add 3g sodium, 60g toluene is heated to 110 ℃, reflux, stirred 1 hour for 1800 rev/mins with the magnetic stirrer rotating speed; The 16.51g diphenyl dichlorosilane is mixed with 60g toluene, the mol ratio that is diphenyl dichlorosilane and sodium is 1: 2, under the lucifuge condition, evenly splash into disubstituted dichlorosilane and toluene mixed solution in the three-neck flask, dripping speed is 1～2 droplet/second, 110 ℃ were refluxed 8 hours, other step in this step is identical with embodiment 1, and the molecular weight of prepared poly-silicon diphenyl alkane is 980, i.e. n=5.In the fluorescence sense film step 6 of preparation unimolecule strata diphenyl silane, under 0.6～0.8mL/s argon gas condition, get poly-diphenyl silane and be dissolved in the tetrahydrofuran preparation 2 * 10
-3The suspending liquid of g/mL, other technology in this step is identical with embodiment 1.Other step is identical with embodiment 1.
Used sodium metal raw material 3g is an example with preparation unimolecule strata diphenyl silane fluorescence sense film of the present invention, and its preparation method is as follows:
Present embodiment is in preparation silanization substrate 4, and the volume ratio that the activation substrate is put into 3-r-chloropropyl trimethoxyl silane and toluene solution is 1: 120 a solution, refluxes 6 hours, and other technology in this step is identical with embodiment 1.In the poly-silicon diphenyl alkane step 5 of preparation, in the 500mL three-neck flask of magnetic stirrer, reflux condensing tube and constant pressure funnel is housed, under 0.6～0.8mL/s argon gas condition, add 3g sodium, 90g toluene is heated to 110 ℃, reflux, stirred 1 hour for 1800 rev/mins with the magnetic stirrer rotating speed; The 16.51g diphenyl dichlorosilane is mixed with 90g toluene, the mol ratio that is diphenyl dichlorosilane and sodium is 1: 2, under the lucifuge condition, evenly splash into disubstituted dichlorosilane and toluene mixed solution in the three-neck flask, dripping speed is 1～2 droplet/second, 110 ℃ were refluxed 24 hours, other step in this step is identical with embodiment 1, and the molecular weight of prepared poly-silicon diphenyl alkane is 3700, i.e. n=20.In the fluorescence sense film step 6 of preparation unimolecule strata diphenyl silane, under 0.6～0.8mL/s argon gas condition, get poly-diphenyl silane and be dissolved in the tetrahydrofuran preparation 3 * 10
-3The suspending liquid of g/mL, other step in this step is identical with embodiment 1.Other step is identical with embodiment 1.
Embodiment 4
Used sodium metal raw material 3g is an example with preparation unimolecule strata of the present invention (Alpha-Naphthyl) methyl-monosilane fluorescence sense film, and its preparation method is as follows:
In the poly-diphenyl silane step 5 of the preparation of embodiment 1, diphenyl dichlorosilane is replaced with (Alpha-Naphthyl) dimethyl dichlorosilane (DMCS), the molar weight of (Alpha-Naphthyl) dimethyl dichlorosilane (DMCS) is identical with diphenyl dichlorosilane, after reaction is finished, to gather (Alpha-Naphthyl) methyl-monosilane and separate in filtrate, and purify, other technology in this step is identical with embodiment 1, the molecular weight of prepared poly-(Alpha-Naphthyl) methyl-monosilane is 2600, i.e. n=15.Preparation unimolecule strata (Alpha-Naphthyl) methyl-monosilane fluorescence sense film step 6 is identical with embodiment 1.Other step is identical with embodiment 1.
Used sodium metal raw material 3g is an example with preparation unimolecule strata of the present invention (Alpha-Naphthyl) methyl-monosilane fluorescence sense film, and its preparation method is as follows:
In the poly-diphenyl silane step 5 of preparation in embodiment 2, diphenyl dichlorosilane is replaced with (Alpha-Naphthyl) dimethyl dichlorosilane (DMCS), the molar weight of (Alpha-Naphthyl) dimethyl dichlorosilane (DMCS) is identical with diphenyl dichlorosilane, after reaction is finished, to gather (Alpha-Naphthyl) methyl-monosilane and separate in filtrate, and purify, other technology in this step is identical with embodiment 2, the molecular weight of prepared poly-(Alpha-Naphthyl) methyl-monosilane is 1950, i.e. n=11.Preparation unimolecule strata (Alpha-Naphthyl) methyl-monosilane fluorescence sense film step 6 is identical with embodiment 2.Other step is identical with embodiment 1.
Embodiment 6
Used sodium metal raw material 3g is an example with preparation unimolecule strata of the present invention (Alpha-Naphthyl) methyl-monosilane fluorescence sense film, and its preparation method is as follows:
In the poly-diphenyl silane step 5 of the preparation of embodiment 3, diphenyl dichlorosilane is replaced with (Alpha-Naphthyl) dimethyl dichlorosilane (DMCS), the molar weight of (Alpha-Naphthyl) dimethyl dichlorosilane (DMCS) is identical with diphenyl dichlorosilane, after reaction is finished, to gather (Alpha-Naphthyl) methyl-monosilane and separate in filtrate, and purify, other technology in this step is identical with embodiment 3, the molecular weight of prepared poly-(Alpha-Naphthyl) methyl-monosilane is 3150, i.e. n=18.Preparation unimolecule strata (Alpha-Naphthyl) methyl-monosilane fluorescence sense film step 6 is identical with embodiment 3.Other step is identical with embodiment 1.
Embodiment 7
Used sodium metal raw material 3g is an example with preparation unimolecule strata of the present invention (Alpha-Naphthyl) p-methylphenyl silane fluorescence sense film, and its preparation method is as follows:
In the poly-diphenyl silane step 5 of the preparation of embodiment 1, diphenyl dichlorosilane is replaced with (Alpha-Naphthyl) p-methylphenyl dichlorosilane, the molar weight of (Alpha-Naphthyl) p-methylphenyl dichlorosilane is identical with diphenyl dichlorosilane, after reaction is finished, to gather (Alpha-Naphthyl) p-methylphenyl silane and separate in filtrate, and purify, other technology in this step is identical with embodiment 1, the molecular weight of prepared poly-(Alpha-Naphthyl) p-methylphenyl silane is 3260, i.e. n=13.Preparation unimolecule strata (Alpha-Naphthyl) p-methylphenyl silane fluorescence sense film step 6 is identical with embodiment 1.Other step is identical with embodiment 1.
Embodiment 8
Used sodium metal raw material 3g is an example with preparation unimolecule strata of the present invention (Alpha-Naphthyl) p-methylphenyl silane fluorescence sense film, and its preparation method is as follows:
In the poly-diphenyl silane step 5 of the preparation of embodiment 2, diphenyl dichlorosilane is replaced with (Alpha-Naphthyl) p-methylphenyl dichlorosilane, the molar weight of (Alpha-Naphthyl) p-methylphenyl dichlorosilane is identical with diphenyl dichlorosilane, after reaction is finished, to gather (Alpha-Naphthyl) p-methylphenyl silane and separate in filtrate, and purify, other technology in this step is identical with embodiment 2, the molecular weight of prepared poly-(Alpha-Naphthyl) p-methylphenyl silane is 1790, i.e. n=7.Preparation unimolecule strata (Alpha-Naphthyl) p-methylphenyl silane fluorescence sense film step 6 is identical with embodiment 2.Other step is identical with embodiment 1.
Embodiment 9
Used sodium metal raw material 3g is an example with preparation unimolecule strata of the present invention (Alpha-Naphthyl) p-methylphenyl silane fluorescence sense film, and its preparation method is as follows:
In the poly-diphenyl silane step 5 of the preparation of embodiment 3, diphenyl dichlorosilane is replaced with (Alpha-Naphthyl) p-methylphenyl dichlorosilane, the molar weight of (Alpha-Naphthyl) p-methylphenyl dichlorosilane is identical with diphenyl dichlorosilane, after reaction is finished, to gather (Alpha-Naphthyl) p-methylphenyl silane and separate in filter is covered, and purify, other technology in this step is identical with embodiment 3, the molecular weight of prepared poly-(Alpha-Naphthyl) p-methylphenyl silane is 3750, i.e. n=16.Preparation unimolecule strata (Alpha-Naphthyl) p-methylphenyl silane fluorescence sense film step 6 is identical with embodiment 3.Other step is identical with embodiment 1.
With preparation unimolecular layer diphenyl silane of the present invention and the used sodium metal raw material 3g of dimethyl-silicon alkyl copolymer fluorescence sense film is example, and its preparation method is as follows:
In the poly-diphenyl silane step 5 of the preparation of embodiment 1, is that 1: 1 mixed liquor is replaced with diphenyl dichlorosilane in molar ratio with diphenyl dichlorosilane and dimethyldichlorosilane, integral molar quantity is identical with diphenyl dichlorosilane, after reaction is finished, in filtrate, diphenyl silane is separated with the dimethyl-silicon alkyl copolymer, purify, the molecular weight of diphenyl silane and dimethyl-silicon alkyl copolymer is 2800, be n=12, m=9, other technology in this step is identical with embodiment 1.Preparation unimolecular layer diphenyl silane is identical with embodiment 1 with dimethyl-silicon alkyl copolymer fluorescence sense film film step 6.Other step is identical with embodiment 1.
Embodiment 11
With preparation unimolecular layer diphenyl silane of the present invention and the used sodium metal raw material 3g of aminomethyl phenyl silane multipolymer fluorescence sense film is example, and its preparation method is as follows:
In the poly-diphenyl silane step 5 of the preparation of embodiment 1, is that 1: 1 mixed liquor is replaced with diphenyl dichlorosilane in molar ratio with diphenyl dichlorosilane and dichloromethyl phenylsilane, integral molar quantity is identical with diphenyl dichlorosilane, after reaction is finished, in filtrate, diphenyl silane is separated with the aminomethyl phenyl silane multipolymer, purify, the molecular weight of diphenyl silane and aminomethyl phenyl silane multipolymer is 2300, be n=7, m=8, other technology in this step is identical with embodiment 1.Preparation unimolecular layer diphenyl silane is identical with embodiment 1 with aminomethyl phenyl silane multipolymer fluorescence sense film step 6.Other step is identical with embodiment 1.
With preparation unimolecular layer diphenyl silane of the present invention and the used sodium metal raw material 3g of methyl hexyl silane multipolymer fluorescence sense film is example, and its preparation method is as follows:
In the poly-diphenyl silane step 5 of the preparation of embodiment 1, is that 1: 2 mixed liquor is replaced with diphenyl dichlorosilane in molar ratio with diphenyl dichlorosilane and methyl hexyl dichlorosilane, integral molar quantity is identical with diphenyl dichlorosilane, after reaction is finished, in filtrate, diphenyl silane is separated with methyl hexyl silane multipolymer, purify, the molecular weight of diphenyl silane and methyl hexyl silane multipolymer is 3900, be n=7, m=20, other technology in this step is identical with embodiment 1.Preparation unimolecular layer diphenyl silane is identical with embodiment 1 with methyl hexyl silane multipolymer fluorescence sense film step 6.Other step is identical with embodiment 1.
Embodiment 13
With preparation unimolecular layer diphenyl silane of the present invention and the used sodium metal raw material 3g of methyl p-methylphenyl silane copolymer fluorescence sense film is example, and its preparation method is as follows:
In the poly-diphenyl silane step 5 of the preparation of embodiment 1, is that 1: 1 mixed liquor is replaced with diphenyl dichlorosilane in molar ratio with diphenyl dichlorosilane and methyl p-methylphenyl dichlorosilane, integral molar quantity is identical with diphenyl dichlorosilane, after reaction is finished, in filtrate, diphenyl silane is separated with methyl p-methylphenyl silane copolymer, purify, the molecular weight of phenyl silane and methyl p-methylphenyl silane copolymer is 2650, be n=9, m=7, other technology in this step is identical with embodiment 1.Preparation unimolecular layer diphenyl silane is identical with embodiment 1 with the fluorescence sense film step 6 of methyl p-methylphenyl silane copolymer.Other step is identical with embodiment 1.
With preparation unimolecular layer diphenyl silane of the present invention and the used sodium metal raw material 3g of (Alpha-Naphthyl) methyl-monosilane multipolymer fluorescence sense film is example, and its preparation method is as follows:
In the poly-diphenyl silane step 5 of the preparation of embodiment 1, is that 1: 1 mixed liquor is replaced with diphenyl dichlorosilane in molar ratio with diphenyl dichlorosilane and (Alpha-Naphthyl) dimethyl dichlorosilane (DMCS), integral molar quantity is identical with diphenyl dichlorosilane, after reaction is finished, in filtrate, diphenyl silane is separated with (Alpha-Naphthyl) methyl-monosilane multipolymer, purify, the molecular weight of diphenyl silane and (Alpha-Naphthyl) methyl-monosilane multipolymer is 2900, be n=7, m=9, other technology in this step is identical with embodiment 1.Preparation unimolecular layer diphenyl silane is identical with embodiment 1 with (Alpha-Naphthyl) methyl-monosilane multipolymer step 6.Other step is identical with embodiment 1.
In order to determine the processing step of the best of the present invention, the inventor has carried out a large amount of laboratory study tests, and various test situation are as follows:
Detecting instrument: FLS920 type single photon counting time resolution fluorescence spectral instrument, produce by Britain Edinburgh instrument company.
1, determines the raw materials used proportioning of preparation silanization substrate
The volume ratio that the inventor has investigated 3-r-chloropropyl trimethoxyl silane and toluene solution is respectively 1: 75,1: 100,1: 120,1: 150 four kinds of ratios, under the constant condition of other process conditions, prepares three kinds of membraneous materials.
Detect its fluorescence spectrum with single photon counting time resolution fluorescence spectral instrument, the results are shown in Figure 1.
As seen from Figure 1, under the constant condition of other process conditions, increase along with 3-r-chloropropyl trimethoxyl silane volume ratio, prepared film fluorescence intensity increases, and it is little, more satisfactory that volume ratio is respectively 1: 100,1: 120 film strength difference, volume ratio is that 1: 150 prepared film is because 3-r-chloropropyl trimethoxyl silane concentration is excessive, film leaks easily, and stability is bad, does not provide its fluorescence spectrum.It is 1: 100～120 that the present invention selects the volume ratio of 3-r-chloropropyl trimethoxyl silane and toluene solution, and wherein optimum volume ratio is 1: 110.
2, determine the reaction time of preparation silanization substrate
The volume ratio that the activation substrate is put into 3-r-chloropropyl trimethoxyl silane and toluene is 1: 100 a solution, and return time was got respectively 1,3,6,9 hour.Under the constant condition of other process conditions, prepare four kinds of membraneous materials.
Detect its fluorescence spectrum with single photon counting time resolution fluorescence spectral instrument, the results are shown in Figure 2.
As seen from Figure 2, under the constant condition of other process conditions, the 1 hour prepared fluorescence sense film strength ratio that refluxes a little less than, prepared fluorescence sense film strength ratio was more approaching in 3,6,9 hours.It is 3～6 hours that the present invention selects 3-r-chloropropyl trimethoxyl silane and toluene solution return time, and wherein optimum reacting time is 4 hours.
3, determine the reaction time of the poly-diphenyl silane of preparation
The inventor has investigated diphenyl dichlorosilane and the sodium metal mol ratio is 1: 2, and return time was respectively 6,12,24 hours in the time of 110 ℃.Under the constant condition of other process conditions, make three parts of poly-diphenyl silanes, calculate its productive rate.The results are shown in Table 1.
The reaction time of the poly-diphenyl silane of table 1 preparation and the relation of productive rate
| Reaction time | 6 |
12 hours | 24 hours |
| Productive rate (%) | 5.2 | 9.9 | 10.3 |
By table 1 as seen, under the constant condition of other process conditions, the reaction time is that the productive rate of 6 hours prepared poly-diphenyl silanes is less, and the reaction time is that the productive rate of 12 hours and 24 hours prepared poly-diphenyl silanes is higher, and more approaching.It is 1: 2 that the present invention selects diphenyl dichlorosilane and sodium mol ratio, and return time is 8～24 hours in the time of 110 ℃, and wherein best return time is 13 hours.
4, preparation unimolecule strata diphenyl silane fluorescence sense film raw material proportioning
The tetrahydrofuran solution concentration that the inventor has investigated poly-diphenyl silane is respectively 1.5 * 10
-3G/mL, 2 * 10
-3G/mL, 2.5 * 10
-3G/mL, 3 * 10
-3G/mL, 5 * 10
-3Five kinds of solution of g/mL under the constant condition of other process conditions, prepare five kinds of unimolecule strata diphenyl silane fluorescence sense films.
Detect its fluorescence spectrum with single photon counting time resolution fluorescence spectral instrument, the results are shown in Figure 3.
As seen from Figure 3, under the constant condition of other process conditions, solution concentration is 1.5 * 10
-3The prepared unimolecule strata of g/mL diphenyl silane fluorescence sense film intensity is the most weak, and solution concentration is 5 * 10
-3The unimolecule strata diphenyl silane fluorescence sense film intensity that g/mL makes is the strongest, but prepared unimolecule strata diphenyl silane fluorescence sense film is because poly-diphenyl silane concentration is excessive, unimolecule strata diphenyl silane fluorescence sense film stability is bad, and solution concentration is 2 * 10
-3G/mL, 2.5 * 10
-3G/mL, 3 * 10
-3The prepared unimolecule strata diphenyl silane fluorescence sense film fluorescence intensity of g/mL is more satisfactory, and more stable, and concentration is 5 * 10
-3The instability of the prepared unimolecule strata of g/mL diphenyl silane fluorescence sense film does not provide its fluorescence spectrum.It is 2 * 10 that the present invention selects the tetrahydrofuran solution concentration of poly-diphenyl silane
-3～3 * 10
-3G/mL, wherein optium concentration is 2.5 * 10
-3G/mL.
In order to verify beneficial effect of the present invention, the inventor adopts the unimolecule strata diphenyl silane fluorescence sense film of the embodiment of the invention 1 preparation, the static state of having measured unimolecule strata diphenyl silane fluorescence sense film with single photon counting time resolution fluorescence spectral instrument excites-emission spectrum, 2,4,6-trinitro-toluene, 2,4-dinitrotoluene (DNT), 2,4, the fluorescence spectrum under 6-trinitrophenol, nitrobenzene saturated vapor exist.
Experimental result is as follows:
Observe article: unimolecule strata diphenyl silane fluorescence sense film.
1, experimental technique
Method of operating observation unimolecule strata diphenyl silane fluorescence sense film exciting-emission spectrum by FLS920 type single photon numeration time resolution fluorescence spectral instrument in dry state, 2,4,6-trinitro-toluene, 2,4-dinitrotoluene (DNT), 2,4, under 6-trinitrophenol, nitrobenzene, benzene, perfume, the fruit aroma gases saturated vapor existence condition, the fluorescence emission spectrum of observation unimolecule strata diphenyl silane fluorescence sense film.
2, observations
Observations is seen Fig. 4～15.
In Fig. 4, horizontal ordinate is a wavelength, and ordinate is a fluorescence intensity.As can be seen from Figure 4, unimolecule strata diphenyl silane fluorescence sense film maximum excitation wavelength is 370nm, and maximum emission wavelength is 410nm.
In Fig. 5, horizontal ordinate is a wavelength, and ordinate is a fluorescence intensity.As can be seen from Figure 5, unimolecule strata diphenyl silane fluorescence sense film is 2,4, exposure duration increases in the 6-trinitro-toluene saturated vapor, and fluorescence intensity significantly reduces, and instruction book molecule strata diphenyl silane fluorescence sense film is to 2,4,6-trinitro-toluene steam has good response.
In Fig. 6, horizontal ordinate is a wavelength, and ordinate is a fluorescence intensity.As can be seen from Figure 6, unimolecule strata diphenyl silane fluorescence sense film is 2, and exposure duration increases in the 4-dinitrotoluene (DNT) saturated vapor, and fluorescence intensity significantly reduces, instruction book molecule strata diphenyl silane fluorescence sense film is to 2, and 4-dinitrotoluene (DNT) steam has good response.
In Fig. 7, horizontal ordinate is a wavelength, and ordinate is a fluorescence intensity.As can be seen from Figure 7, unimolecule strata diphenyl silane fluorescence sense film is 2,4, exposure duration increases in the 6-trinitrophenol steam, and fluorescence intensity significantly reduces, and instruction book molecule strata diphenyl silane fluorescence sense film is to 2,4,6-trinitrophenol steam has good response.
In Fig. 8, horizontal ordinate is a wavelength, and ordinate is a fluorescence intensity.As can be seen from Figure 8, unimolecule strata diphenyl silane fluorescence sense film is the exposure duration increase in the nitrobenzene saturated vapor, and fluorescence intensity significantly reduces, and instruction book molecule strata diphenyl silane fluorescence sense film p-nitrophenyl steam has good response.
In Fig. 9, horizontal ordinate be unimolecule strata diphenyl silane fluorescence sense film 2,4, the exposure duration in the 6-trinitro-toluene saturated vapor, ordinate is a quencher efficient.As can be seen from Figure 9, unimolecule strata diphenyl silane fluorescence sense film is to 2,4, and the quencher efficient of 6-trinitro-toluene saturated vapor reaches 95%.
In Figure 10, horizontal ordinate be unimolecule strata diphenyl silane fluorescence sense film 2, the exposure duration in the 4-dinitrotoluene (DNT) saturated vapor, ordinate is a quencher efficient.As can be seen from Figure 10, unimolecule strata diphenyl silane fluorescence sense film is to 2, and the quencher efficient of 4-dinitrotoluene (DNT) saturated vapor reaches 97%.
In Figure 11, horizontal ordinate is the exposure duration of unimolecule strata diphenyl silane fluorescence sense film in nitrobenzene vapor, and ordinate is a quencher efficient.As can be seen from Figure 11, the quencher efficient of unimolecule strata diphenyl silane fluorescence sense film p-nitrophenyl saturated vapor reaches 90%.
In Figure 12, horizontal ordinate be unimolecule strata diphenyl silane fluorescence sense film 2,4, the exposure duration in the 6-trinitro-toluene saturated vapor, ordinate is a quencher efficient.As can be seen from Figure 12, unimolecule strata diphenyl silane fluorescence sense film is to 2,4, and the quencher efficient of 6-trinitro-toluene saturated vapor reaches 95%.
In Figure 13, horizontal ordinate is a wavelength, and ordinate is a fluorescence intensity.As can be seen from Figure 13, the exposure duration increase of unimolecule strata diphenyl silane fluorescence sense film in the benzene saturated vapor, fluorescence intensity does not have significant change, illustrates that the existence of benzene vapor detects noiseless to unimolecule strata diphenyl silane fluorescence sense film.
In Figure 14, horizontal ordinate is a wavelength, and ordinate is a fluorescence intensity.As can be seen from Figure 14, the exposure duration increase of unimolecule strata diphenyl silane fluorescence sense film in the perfume saturated vapor, fluorescence intensity does not have significant change, and it is noiseless to illustrate that the perfume steam exists the detection of unimolecule strata diphenyl silane fluorescence sense film.
In Figure 15, horizontal ordinate is a wavelength, and ordinate is a fluorescence intensity.As can be seen from Figure 15, the exposure duration increase of unimolecule strata diphenyl silane fluorescence sense film in fruit aroma gases saturated vapor, fluorescence intensity does not have significant change, and it is noiseless to illustrate that fruit aroma gases saturated vapor exists the detection of unimolecule strata diphenyl silane fluorescence sense film.
3, experiment conclusion
(1) draws poly-diphenyl silane by the static spectrum of unimolecule strata diphenyl silane fluorescence sense film and be fixed to substrate surface effectively, and evenly distribute.
(2) existence of nitro-aromatic compound in the air, to the fluorescent emission of unimolecule strata diphenyl silane fluorescence sense film have comparatively fast, stronger quenching effect, the ultrasensitiveness that shows the nitro-aromatic compound steam detects.
(3) unimolecule strata diphenyl silane fluorescence sense film does not have obvious response to the volatile matter of article such as benzene, fruit, perfume, illustrates that this sense film is fast to the response speed of nitro-aromatic compound, selectivity good.
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| CN102030484B (en) * | 2010-11-03 | 2012-08-29 | 陕西师范大学 | Preparation method and application of pyrene-containing conjugated polymer fluorescent sensing film |
| CN102304229B (en) * | 2011-04-06 | 2012-10-24 | 杭州师范大学 | Method for preparing optically active poly(alkyl-aryl) silane |
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| CN107022083B (en) * | 2017-04-18 | 2020-11-13 | 齐鲁工业大学 | A kind of silicon-based hyperbranched conjugated polymer and preparation method thereof |
| CN107022082B (en) * | 2017-04-18 | 2020-11-13 | 齐鲁工业大学 | Application of a silicon-based hyperbranched conjugated polymer in the detection of nitroaromatic compounds |
| CN109085145A (en) * | 2018-07-02 | 2018-12-25 | 深圳砺剑防卫技术有限公司 | A kind of fluorescence sense film and preparation method thereof and explosive detection instrument |
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