CN100559167C - Preparation method to the unimolecular layer polysilane fluorescence sense film of nitro-aromatic sensitivity - Google Patents
Preparation method to the unimolecular layer polysilane fluorescence sense film of nitro-aromatic sensitivity 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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Abstract
A kind of preparation method of the unimolecular layer polysilane fluorescence sense film to the nitro-aromatic sensitivity comprises and tailors substrate, preparation washing lotion, preparation activation substrate, preparation silanization substrate, preparation polysilane, preparation unimolecular layer polysilane fluorescence sense film processing step.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.Adopt the fluorescence sense film of the present invention's preparation to have advantages such as good stability, long service life, sensitivity height, can contain the sensor of nitro-aromatic compound or detect on the detecting instrument of nitro-aromatic compound and use in detection, directly detect after also this fluorescence sense film can being experienced nitro-aromatic class chemical combination with fluorescent 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.
Claims (4)
1, a kind of preparation method of the unimolecular layer polysilane fluorescence sense film to the nitro-aromatic sensitivity, this poly-silicon
The chemical structural formula of alkane is
(1)
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
3, R
4Be C
1-C
7Alkyl, C
6-C
14Aryl or aralkyl, R
3, R
4Can be identical or different, n is 5～20, and m is 0～20, and 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 and 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: 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 and 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 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.
2, according to the preparation method of the described unimolecular layer polysilane fluorescence sense film to the nitro-aromatic sensitivity of claim 1, it is characterized in that: in the chemical structural formula of polysilane (1), R
1, R
2Wherein be phenyl ring, R
3, R
4Wherein be C
1-C
6Alkyl, C
6-C
10Aryl, R
3, R
4Can be identical or different, n wherein is 8～12, m wherein is 0～10.
3, according to the preparation method of the described unimolecular layer polysilane fluorescence sense film to the nitro-aromatic sensitivity of claim 1, it is characterized in that: in preparation silanization substrate processing step (4), the volume ratio that the activation substrate is put into 3-r-chloropropyl trimethoxyl silane and toluene solution wherein is 1: 100～110 solution, refluxes 3～5 hours; In preparation polysilane processing step (5), in the 500mL three-neck flask of magnetic stirrer, reflux condensing tube and constant pressure funnel is housed, 0.6 under～0.8mL/s argon gas the condition, add toluene and sodium, toluene and sodium weight ratio wherein are 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 disubstituted dichlorosilane mixes with toluene with the sodium mol ratio, the weight ratio of toluene and sodium wherein 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, and 110 ℃ were wherein refluxed 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 the pure product of polysilane and be dissolved in tetrahydrofuran, being mixed with concentration in the 50mL round-bottomed flask wherein is 2.5 * 10
-3～3 * 10
-3The solution of g/mL.
4, according to the preparation method of the described unimolecular layer polysilane fluorescence sense film to the nitro-aromatic sensitivity of claim 1, it is characterized in that: of the present invention in preparation silanization substrate processing step (4), the volume ratio that the activation substrate is put into 3-r-chloropropyl trimethoxyl silane and toluene solution wherein is 1: 110 a solution, refluxes 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 and sodium, the weight ratio of toluene and sodium wherein 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 weight ratio of toluene and sodium wherein 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, and 110 ℃ were wherein refluxed 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 concentration in the 50mL round-bottomed flask wherein is 2.5 * 10
-3The solution of g/mL.
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