CN102702558B - Fluorescent sensor based on cellulose nanometer micro-fiber (TOCN) film serving as substrate and application thereof - Google Patents
Fluorescent sensor based on cellulose nanometer micro-fiber (TOCN) film serving as substrate and application thereof Download PDFInfo
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- CN102702558B CN102702558B CN201210214163.0A CN201210214163A CN102702558B CN 102702558 B CN102702558 B CN 102702558B CN 201210214163 A CN201210214163 A CN 201210214163A CN 102702558 B CN102702558 B CN 102702558B
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Abstract
The invention relates to a fluorescent chemical sensor for detecting a nitro-aromatic explosive in an ultra-trace way. A fluorescent conjugated polymer is chemically grafted by taking a cellulose nanometer micro-fiber (TOCN) film as a carrier. A preparation method of the sensor comprises the following steps of: preparing a TOCN film of which the C-6 bit is carboxyl by oxidizing cellulose with a 2,2,6,6-tetramethyl piperidine oxide; chemically bonding an amine compound of which the terminal is provided with bromophenyl onto the surface of the film; and introducing a prepared fluorescent conjugated polymer onto the surface of the film through a 'grafting to' technology. According to the invention, hypersensitization of the film sensor is realized, the problems of stability and permeability of the film sensor are solved, and the diffusion pore diameter is up to 97.4 percent. A fluorescent sensing film prepared with the method has the advantages of high mechanical property, high flexibility, easiness for carrying, environment friendliness, renewability and the like, can be used for conveniently detecting nitro-aromatic explosives, and can be used for visually detecting nitro-aromatic explosives under an ultraviolet lamp.
Description
Technical field
The present invention relates to a kind of highly sensitive fluorescent conjugated polymer chemical sensor, specially refer to the preparation method to the fluorescent conjugated polymer film of nitro-aromatic explosive substance sensitivity.
Background technology
Since entering 21 century, reliably and exactly explosive detection has become one of major issue of international concern.The ultra-trace of chemical explosive detects safeguarding national security, control and the forensic science of environmental pollution all have important effect.Due to the increase that international terrorism threatens, the novel method of finding highly sensitive, highly selective explosive detection becomes study hotspot both domestic and external.
In recent years, the application fluorescent conjugated polymer detects the very big concern that ultra-trace nitro-aromatic explosive substance has been subject to people.When one of them major reason is the matter interaction of the fluorescent conjugated polymer of electron rich and electron deficiency, Photoinduced Charge shifts and impels electron rich to produce Fluorescence quenching effect to body, the delocalization exciton generated is along the polymer chain transmission, thereby causes the amplification of " super quencher ".According to this principle, can be applicable to quick, accurate, the supersensitive detection of nitro-aromatic explosive substance.
But, for the fluorescent conjugated polymer sensing material that detects nitro-aromatic based on quenching of fluorescence, most of fluorescent conjugated polymers are to use under solid film, but when solid-state use, the self quenching that pi-pi accumulation causes fluorescence occurs between fluorescence chromophore, can the sensitivity of explosive detection be had a negative impact, too low fluorescence intensity is subject to detecting instrument itself and detects the interference of thing background doped signal, the accuracy that impact detects when detecting.
The autofluorescence conjugated polymers as sensing material since, Chinese scholars is suppressing the material Fluorescence self-quenching and raising explosive substance vapour molecule aspect rapid diffusion, has been done some research work in film.Swager seminar has mainly synthesized the polyparaphenylene's acetylene equiconjugate polymkeric substance [J.Am.Chem.Soc.1998,120,5321-5322] containing the butterfly thiazolinyl.They are incorporated into main polymer chain by three-dimensional butterfly alkene structure, make the main chain isolation, avoid the pi-pi accumulation of interchain, and then the Fluorophotometry self quenching; Also increase the fractional free volume of polymeric film, formed in " molecule hole ", be conducive to infiltration and the diffusion of tested molecule on film, improved response sensitivity.
In the visual context of detection of explosive substance, Zhang Zhongping seminar is immersed in common middling speed specification filter paper in two emissive quantum dots ratio fluorescent probe solutions of preparation, the TNT Indicator Paper obtained by the physical adsorption quantum dot is under the UV-irradiation of 365nm, can detect the residual [J.Am.Chem.Soc.2011 of surperficial TNT, 133,8424-8427].
Spin-coating method is the common method for preparing the conjugated polymers sense film, but traditional spin-coating method prepares film and process, its application in practice that had some disadvantages affect, as restive as film thickness, not portable as the sheet glass of carrier, quartz plate etc., also have chemical stability and thermal stability problems, in organic solution, use is easily broken or is dissolved especially, pollutes system to be measured etc.
Summary of the invention
The object of the present invention is to provide a kind of reproducible by TEMPO (2 based on green, 2,6,6-tetramethyl piperidine oxide compound) Mierocrystalline cellulose nanometer fento (TOCN) film that prepared by oxidation style is matrix, the preparation method of the fluorescence chemical sense film of the detected trace nitro-aromatic explosive substance of grafting conjugated polymer, the method technique is simple, reaction conditions is gentle.The fluorescence sense film made is easy to carry about with one, and under ultraviolet lamp, can realize on-the-spot, quick, visual detection to the nitro-aromatic explosive substance.
The objective of the invention is to realize by following technical proposals:
A kind of preparation method of the highly sensitive fluorescent optical sensor that is matrix based on Mierocrystalline cellulose nanometer fento film, concrete steps are as follows:
(1) prepare the TOCN film
The ultrasonic deaeration of TOCN aqeous suspension is obtained to film-casting liquid, and wherein the massfraction of TOCN is 0.2%～0.3%; The film-casting liquid of gained is poured in the tetrafluoroethylene mould, after standing 10min～1h, puts into 30～70 ℃ of baking oven 6～10h, obtains the TOCN film after solvent evaporates fully.
(2) prepare bromophenyl TOCN film
Under the effect of condensing agent 1-(3-dimethyl aminopropyl)-3-ethyl carbon diamines/N-maloyl imines, the carboxyl of C-6 position on the TOCN film surface is reacted to 0.5～40h with the aminated compounds containing bromophenyl, use distilled water and acetone repetitive scrubbing, after vacuum-drying, but make the TOCN film with Suzuki reactive behavior site.
(3) prepare fluorescent conjugated polymer (CP)
Under nitrogen protection, with tetrakis triphenylphosphine palladium ((PPh
4)
3pd) be catalyzer, but the monomer of Suzuki reaction is reacted to 12～56h under reflux temperature.After reaction finishes, use methyl alcohol, water repetitive scrubbing product, after vacuum-drying, make fluorescent conjugated polymer.
(4) prepare fluorescent conjugated polymer film (TOCN-CP film)
Under nitrogen protection, get fluorescent conjugated polymer and be dissolved in tetrahydrofuran (THF), add the K of 1～3mol/L
2cO
3the aqueous solution, wherein tetrahydrofuran (THF) and K
2cO
3the volume ratio of the aqueous solution 3: 2.At N
2add catalyzer (PPh under protection
4)
3pd (2mol%), react 8～15h under reflux temperature.Reaction is used methyl alcohol after finishing, and tetrahydrofuran (THF), water is repeatedly washing in order, until occur without fluorescent substance in solution, after drying, obtains the TOCN-CP film.
Beneficial effect
The advantages such as that the TOCN film that 1 the present invention uses has is pliable and tough, light weight, cheapness, renewable, the activated carboxyl in C-6 position.End is chemically bonded to the C-6 position of TOCN film surface with bromophenyl, " grafting to " technology of utilization is incorporated into the TOCN film surface by fluorescent conjugated polymer by forming the method for stablizing covalent linkage, realized suppressing the pi-pi accumulation of conjugated polymer chain, interchain also can form passage simultaneously, be conducive to the diffusion of quencher molecule, this fluorescence sense film is insoluble in multi-solvents, do not pollute system to be measured, advantages such as can reusing and be easy to carry, overcome the defect in existing research from design, solve some problems of the prepared fluorescence sense film existence of method such as physics spin coating, further improve the speed of response and the detection sensitivity of fluorescence sense film.
Fluorescence sense film prepared by 2 the present invention can utilize Fluorescence Quenching Principle to detect easily the nitro-aromatic explosive substance of solution state and steam-like, can also be under ultraviolet lamp the nitro-aromatic explosive substance of visual detection solution state and steam-like.
The accompanying drawing explanation
2 of accompanying drawing 1 different concns, the impact of 4-dinitrotoluene (DNT) solution on TOCN-CP film fluorescence intensity.
Accompanying drawing 2 exposes the variation of TOCN-CP film fluorescence intensity after different time in 2,4-dinitrotoluene (DNT) steam.
The relation curve of open-assembly time in accompanying drawing 3TOCN-CP film quencher efficiency and 2,4-dinitrotoluene (DNT) steam.
Accompanying drawing 4 is for to detect 2 under ultra violet lamp, the visual photo of 4-dinitrotoluene (DNT).
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
(1) take 0.1gTEMPO and 1gNaBr and add in the 500mL deionized water, at room temperature fully stir; After TEMPO and NaBr dissolve fully, to adding the 10g wood pulp cellulose (cellulosic massfraction is 20.15%) that wets in reaction system; After Mierocrystalline cellulose is uniformly dispersed, then add 20gNaClO solution in system, control the pH value of reaction system simultaneously in 10～10.5 scopes; After NaClO solution dropwises, by the continuous pH value that drips the NaOH solution maintenance system of 0.5mol/L, until no longer consume NaOH solution, reaction finishes; Filtered in sand core funnel, and washed 3～5 times, prepared SURGICEL; By the SURGICEL that makes excusing from death, centrifugal, get supernatant liquid, obtain TOCN solution.The ultrasonic deaeration of TOCN aqeous suspension is obtained to film-casting liquid, and wherein the massfraction of TOCN is 0.2%～0.3%; The film-casting liquid of gained is poured in the tetrafluoroethylene mould, after standing 10min～1h, puts into 30～70 ℃ of baking oven 6～10h, obtains the TOCN film after solvent evaporates fully.
(2) the TOCN film is put into to the morpholino b acid damping fluid that pH is 4～7, added condensing agent 1-(3-dimethyl aminopropyl)-3-ethyl carbon diamines/N-maloyl imines, its mol ratio is 2: 1.The DMF solution that adds para-bromoaniline after 30mi n.After reaction 16h, make respectively water, ethanol repeatedly be washed, but washing gained film is had the TOCN active film of Suzuki reaction after vacuum-drying.
(3) by mol ratio, be 1: 13,6-dibromo carbazole and 9,9-dihexyl fluorenes-2, which alcohol ester of 7-hypoboric acid Knit-the-brows is dissolved in tetrahydrofuran (THF), adds the K of 1～3mol/L
2cO
3the aqueous solution, wherein tetrahydrofuran (THF) and K
2cO
3the volume ratio of the aqueous solution 3: 2.Logical nitrogen, after for some time, adds catalyzer (PPh
4)
3pd (2mol%), react 36～56h under reflux temperature.Order washing several by reaction solution with methyl alcohol, distilled water.Solid after washing vacuum-drying 12～24h under room temperature in vacuum drying oven, obtain fluorescent conjugated polymer.
(4) under nitrogen protection, get fluorescent conjugated polymer and be dissolved in tetrahydrofuran (THF), add the K of 1～3mol/L
2cO
3the aqueous solution, wherein tetrahydrofuran (THF) and K
2cO
3the volume ratio of the aqueous solution 3: 2.Add catalyzer (PPh under nitrogen protection
4)
3pd (2mol%), react 8～15h under reflux temperature.Reaction is used methyl alcohol after finishing, and tetrahydrofuran (THF), water repetitive scrubbing, until occur without fluorescent substance in solution, after drying, obtain the TOCN-CP film.
(5) the TOCN-CP film is immersed in certain density 2, in 4-dinitrotoluene (DNT) solution, takes out the variation that detects at once its fluorescence intensity after for some time, typical test result is shown in accompanying drawing 1.
Embodiment 2
(1) the ultrasonic deaeration of TOCN aqeous suspension is obtained to film-casting liquid, wherein the massfraction of TOCN is 0.2%～0.3%; The film-casting liquid of gained is poured in the mould of tetrafluoroethylene system, after standing 10min～1h, puts into 30～70 ℃ of baking oven 6～10h, obtains the TOCN film after solvent evaporates fully.
(2) the TOCN film is put into to the morpholino b acid damping fluid that pH is 4～7, added condensing agent 1-(3-dimethyl aminopropyl)-3-ethyl carbon diamines/N-maloyl imines, its mol ratio is 2: 1.The DMF solution that adds para-bromoaniline after 30min.After reaction 16h, make respectively water, ethanol repeatedly be washed, but washing gained film is had the TOCN active film of Suzuki reaction after vacuum-drying.
(3) by mol ratio, be 1: 13,6-dibromo carbazole and 9,9-dihexyl fluorenes-2, which alcohol ester of 7-hypoboric acid Knit-the-brows is dissolved in tetrahydrofuran (THF), adds the K of 1～3mol/L
2cO
3the aqueous solution, wherein tetrahydrofuran (THF) and K
2cO
3the volume ratio of the aqueous solution 3: 2.Logical nitrogen, after for some time, adds catalyzer (PPh
4)
3pd (2mol%), react 36～56h under reflux temperature.Order washing several by reaction solution with methyl alcohol, distilled water.Solid after washing vacuum-drying 12～24h under room temperature in vacuum drying oven, obtain fluorescent conjugated polymer.
(4) under nitrogen protection, get fluorescent conjugated polymer and be dissolved in tetrahydrofuran (THF), add the K of 1～3mol/L
2cO
3the aqueous solution, wherein tetrahydrofuran (THF) and K
2cO
3the volume ratio of the aqueous solution 3: 2.Add catalyzer (PPh under nitrogen protection
4)
3pd (2mol%), react 8～15h under reflux temperature.Reaction is used methyl alcohol after finishing, and tetrahydrofuran (THF), water repetitive scrubbing, until occur without fluorescent substance in solution, after drying, obtain the TOCN-CP film.
(5) the TOCN-CP film is exposed in 2,4-dinitrotoluene (DNT) steam, takes out the variation that detects at once its fluorescence intensity after for some time, typical test result is shown in accompanying drawing 2, accompanying drawing 3.
Embodiment 3
(1) the ultrasonic deaeration of TOCN aqeous suspension is obtained to film-casting liquid, wherein the massfraction of TOCN is 0.2%～0.3%; The film-casting liquid of gained is poured in the mould of tetrafluoroethylene system, after standing 10min～1h, puts into 30～70 ℃ of baking oven 6～10h, obtains the TOCN film after solvent evaporates fully.
(2) the TOCN film is put into to the morpholino b acid damping fluid that pH is 4～7, added condensing agent 1-(3-dimethyl aminopropyl)-3-ethyl carbon diamines/N-maloyl imines, its mol ratio is 2: 1.The DMF solution that adds para-bromoaniline after 30min.After reaction 16h, make respectively water, ethanol repeatedly be washed, but washing gained film is had the TOCN active film of Suzuki reaction after vacuum-drying.
(3) by mol ratio, be 1: 13,6-dibromo carbazole and 9,9-dihexyl fluorenes-2, which alcohol ester of 7-hypoboric acid Knit-the-brows is dissolved in tetrahydrofuran (THF), adds the K of 1～3mol/L
2cO
3the aqueous solution, wherein tetrahydrofuran (THF) and K
2cO
3the volume ratio of the aqueous solution 3: 2.Logical nitrogen, after for some time, adds catalyzer (PPh
4)
3pd (2mol%), react 36～56h under reflux temperature.Order washing several by reaction solution with methyl alcohol, distilled water.Solid after washing vacuum-drying 12～24h under room temperature in vacuum drying oven, obtain fluorescent conjugated polymer.
(4) under nitrogen atmosphere, get fluorescent conjugated polymer and be dissolved in tetrahydrofuran (THF), add the K of 1～3mol/L
2cO
3the aqueous solution, wherein tetrahydrofuran (THF) and K
2cO
3the volume ratio of the aqueous solution 3: 2.Add catalyzer (PPh under nitrogen protection
4)
3pd (2mol%), react 8～15h under reflux temperature.Reaction is used methyl alcohol after finishing, and tetrahydrofuran (THF), water repetitive scrubbing, until occur without fluorescent substance in solution, after drying, obtain the TOCN-CP film.
(5) the TOCN-CP film is exposed in 2,4-dinitrotoluene (DNT) steam, after for some time, takes out and observe colour-change under ultraviolet lamp, typical test result is shown in accompanying drawing 4.
Claims (4)
1. the preparation method of the highly sensitive fluorescent optical sensor that is matrix based on Mierocrystalline cellulose nanometer fento film, its feature comprises the following steps:
(1) prepare Mierocrystalline cellulose nanometer fento film
The ultrasonic deaeration of Mierocrystalline cellulose nanometer fento aqeous suspension is obtained to film-casting liquid, and wherein the massfraction of Mierocrystalline cellulose nanometer fento is 0.2%～0.3%; The film-casting liquid of gained is poured in the mould of tetrafluoroethylene system, after standing 10min～1h, puts into 30～70 ℃ of baking oven 6～10h, obtains Mierocrystalline cellulose nanometer fento film after solvent evaporates fully;
(2) prepare bromophenyl Mierocrystalline cellulose nanometer fento film
Under the effect of condensing agent 1-(3-dimethyl aminopropyl)-3-ethyl carbon diamines/N-maloyl imines, the carboxyl of C-6 position on Mierocrystalline cellulose nanometer fento film surface is reacted to 0.5～40h with the aminated compounds containing bromophenyl, use distilled water and acetone repetitive scrubbing, after vacuum-drying, but make the Mierocrystalline cellulose nanometer fento film with Suzuki reactive behavior site;
(3) prepare fluorescent conjugated polymer
Under nitrogen protection, with tetrakis triphenylphosphine palladium ((PPh
3)
4pd) be catalyzer, but the monomer of Suzuki reaction is reacted to 12～56h under reflux temperature, after reaction finishes, use methyl alcohol, water repetitive scrubbing product, after vacuum-drying, make fluorescent conjugated polymer;
(4) prepare the fluorescent conjugated polymer film
The fluorescent conjugated polymer of preparation is dissolved in the mixing solutions of tetrahydrofuran (THF) and salt of wormwood, together with bromophenyl Mierocrystalline cellulose nanometer fento film, puts into there-necked flask, N
2add (PPh under protection
3)
4pd, after reacting 2～24h under reflux temperature, use methyl alcohol, and tetrahydrofuran (THF), water repetitive scrubbing, until occur without fluorescent substance in solution, after drying, obtain Mierocrystalline cellulose nanometer fento-fluorescent conjugated polymer film.
2. method according to claim 1, is characterized in that in step (2) the brominated phenyl group of described aminated compounds.
3. method according to claim 1, is characterized in that in step (3), but boric acid or boric acid ester that the monomer of described Suzuki reaction is aryl or thiazolinyl, chlorine, bromine, iodo aromatic hydrocarbons or alkene.
4. method according to claim 1, is characterized in that in step (3) end group boronic acid containing or the boric acid ester of described fluorescent conjugated polymer.
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| CN106243365B (en) * | 2016-07-29 | 2019-04-05 | 中国人民武装警察部队福州指挥学院 | A kind of preparation method and applications of CNFs, CPFD nano hybridization aeroge |
| CN107200830B (en) * | 2017-05-25 | 2018-12-25 | 南方医科大学 | A kind of ionization containing organic radical polymerization fluorenes and its preparation method and application |
| CN107417952B (en) * | 2017-07-28 | 2020-11-13 | 华北电力大学（保定） | Cellulose fluorescent film and preparation method thereof |
| CN108318462B (en) * | 2017-12-18 | 2020-07-07 | 重庆三峡学院 | Fluorescent probe molecule for pH detection, fluorescent film sensor thereof, preparation method and application |
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