CN102702558A - 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 PDF

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CN102702558A
CN102702558A CN2012102141630A CN201210214163A CN102702558A CN 102702558 A CN102702558 A CN 102702558A CN 2012102141630 A CN2012102141630 A CN 2012102141630A CN 201210214163 A CN201210214163 A CN 201210214163A CN 102702558 A CN102702558 A CN 102702558A
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film
tocn
conjugated polymer
fluorescent
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CN102702558B (en
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吴文辉
牛庆媛
杨博
穆瑞花
洪东峰
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Beijing Institute of Technology BIT
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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

Based on Mierocrystalline cellulose nanometer fento film is the fluorescent optical sensor and the application of matrix
Technical field
The present invention relates to a kind of highly sensitive fluorescent conjugated polymer chemical sensor, specially refer to preparation method the responsive fluorescent conjugated polymer film of nitro-aromatic explosive substance.
Background technology
Got into since 21 century, reliably and exactly explosive detection has become one of major issue of international concern.The ultra-trace of chemical explosive detect to safeguard national security, the control and the forensic science of environmental pollution all have important effect.Because the increase that international terrorism threatens, the novel method of seeking highly sensitive, highly selective explosive detection becomes the domestic and international research focus.
In recent years, use fluorescent conjugated polymer detection ultra-trace nitro-aromatic explosive substance and received people's very big concern.When one of them major reason is the matter interaction of fluorescent conjugated polymer and electron deficiency of electron rich; The photoinduction charge transfer impels electron rich to produce the quenching of fluorescence effect to body; The delocalization exciton that generates is along the polymer chain transmission, thereby causes the amplification of " ultra 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 under solid film, to use, but when solid-state use; The self quenching that pi-pi accumulation causes fluorescence takes place between the fluorescence chromophore; Can the sensitivity of explosive detection be had a negative impact, low excessively fluorescence intensity is subject to detecting instrument itself and detects the interference of thing background doped signal, the accuracy that influence detects when detecting.
The autofluorescence conjugated polymers as sensing material since, Chinese scholars aspect the rapid diffusion, has been done some research work with raising explosive substance vapour molecule suppressing material fluorescence self quenching in film.Swager seminar has mainly synthesized the polyparaphenylene's acetylene equiconjugate polymkeric substance [J.Am.Chem.Soc.1998,120,5321-5322] that contains the butterfly thiazolinyl.They are incorporated into main polymer chain with three-dimensional butterfly alkene structure, and main chain is isolated, and avoid the interchain pi-pi accumulation, and then suppress the fluorescence self quenching; Also increase the fractional free volume of polymeric film, formed in " molecule hole ", helped 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 that obtains through the physical adsorption quantum dot indicates test paper under the UV-irradiation of 365nm; Can detect surperficial TNT residual [J.Am.Chem.Soc.2011,133,8424-8427].
Spin-coating method is the domestic method of preparation conjugated polymers sense film; But traditional spin coating thin films and process, its application in reality that had some disadvantages affect, restive like film thickness; Not portable as the sheet glass of carrier, quartz plate etc.; Also have chemicalstability and thermal stability problems, use is prone to break or is dissolved in organic solution 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 of oxidation style preparation is a matrix, the preparation method of the fluorescence chemical sense film of the detected trace nitro-aromatic explosive substance of grafting conjugated polymer, and this method technology is simple, reaction conditions is gentle.The fluorescence sense film that makes is easy to carry about with one, and under uv lamp, can realize on-the-spot, quick, visual detection to the nitro-aromatic explosive substance.
The objective of the invention is to realize through following technical proposals:
A kind of is the preparation method of the highly sensitive fluorescent optical sensor of matrix based on Mierocrystalline cellulose nanometer fento film, and concrete steps are following:
(1) preparation TOCN film
The ultrasonic deaeration of TOCN aqeous suspension is got 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, leave standstill 10min～1h after, put into 30～70 ℃ of baking oven 6～10h, treat solvent after evaporating fully the TOCN film.
(2) preparation bromophenyl TOCN film
Under the effect of condensing agent 1-(3-dimethyl aminopropyl)-3-ethyl carbon diamines/N-maloyl imines; Carboxyl and the aminated compounds reaction 0.5～40h that contains bromophenyl with C-6 position on the TOCN film surface; Use zero(ppm) water and acetone repetitive scrubbing; After vacuum-drying, but process TOCN film with Suzuki reactive behavior site.
(3) preparation fluorescent conjugated polymer (CP)
Under the nitrogen protection, with tetrakis triphenylphosphine palladium ((PPh 4) 3Pd) be catalyzer, but the monomer of Suzuki reaction is reacted 12～56h under reflux temperature.After reaction finishes, use methyl alcohol, water repetitive scrubbing product, after vacuum-drying, process fluorescent conjugated polymer.
(4) preparation fluorescent conjugated polymer film (TOCN-CP film)
Under the nitrogen protection, get fluorescent conjugated polymer and be dissolved in the THF, add the K of 1～3mol/L 2CO 3The aqueous solution, wherein THF and K 2CO 3The volume ratio of the aqueous solution 3: 2.At N 2Protection adds catalyzer (PPh down 4) 3Pd (2mol%), reflux temperature be reaction 8～15h down.Reaction is used methyl alcohol after finishing, and THF, water are docile and obedient preface and are repeatedly washed, and no fluorescent substance occurs in solution, after the drying, gets the TOCN-CP film.
Beneficial effect
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 had the C-6 position that bromophenyl is chemically bonded to the TOCN film surface; Utilize " grafting to " technology that fluorescent conjugated polymer is incorporated into the TOCN film surface through forming the method for stablizing covalent linkage; Realized suppressing the pi-pi accumulation of conjugated polymer chain; Interchain also can form passage simultaneously; Help the diffusion of quencher molecule, this fluorescence sense film is insoluble in multiple solvent, do not pollute system to be measured, advantage such as can reuse and be easy to carry, and overcomes the defective the 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.
The quenching of fluorescence principle of can utilizing the fluorescence sense film of 2 the present invention preparation detects the nitro-aromatic explosive substance of solution state and steam-like easily, can also be under uv lamp the nitro-aromatic explosive substance of visual detection solution state and steam-like.
Description of drawings
2 of accompanying drawing 1 different concns, 4-DNT solution is to the influence of TOCN-CP film fluorescence intensity.
Accompanying drawing 2 is 2, exposes the variation of TOCN-CP film fluorescence intensity behind the different time in the 4-DNT steam.
Accompanying drawing 3TOCN-CP film quencher efficient and 2, the relation curve of exposure duration in the 4-DNT steam.
Accompanying drawing 4 is under ultra violet lamp, to detect 2, the visual photo of 4-DNT.
Embodiment
Below in conjunction with specific embodiment the present invention is further specified.
Embodiment 1
(1) takes by weighing 0.1gTEMPO and 1gNaBr and add in the 500mL deionized water, at room temperature fully stir; After treating that TEMPO and NaBr dissolve fully, in reaction system, add the wet wood pulp cellulose (cellulosic massfraction is 20.15%) of 10g; After treating that Mierocrystalline cellulose is uniformly dispersed, in system, add 20gNaClO solution again, the pH value of controlling reaction system simultaneously is in 10～10.5 scopes; After treating that NaClO solution dropwises, through the continuous pH value that drips the NaOH solution maintenance system of 0.5mol/L, until no longer consuming NaOH solution, reaction finishes; In sand core funnel, filter, and wash 3～5 times, promptly prepare SURGICEL; With the SURGICEL excusing from death that makes, centrifugal, get supernatant liquid, promptly obtain TOCN solution.The ultrasonic deaeration of TOCN aqeous suspension is got film-casting liquid, and wherein the massfraction of TOCN is 0.2%～0.3%; The film-casting liquid of gained is poured into by in the tetrafluoroethylene mould, leave standstill 10min～1h after, put into 30～70 ℃ of baking oven 6～10h, treat solvent after evaporating fully the TOCN film.
(2) the TOCN film being put into pH is 4～7 morpholino b acid damping fluid, adds condensing agent 1-(3-dimethyl aminopropyl)-3-ethyl carbon diamines/N-maloyl imines, and its mol ratio is 2: 1.The DMF solution that adds para-bromoaniline behind the 30mi n.Behind the reaction 16h, water, ethanol are washed repeatedly, but washing gained film is through being had the TOCN active film of Suzuki reaction after the vacuum-drying.
(3) the molar ratio of 1:1 3,6 - dibromo-carbazole and 9,9 - dihexyl-2 ,7 - two knit the brows acid pinacol ester is dissolved in tetrahydrofuran, adding 1 ~ 3mol / L of K 2 CO 3 solution, which tetrahydrofuran and K 2 CO 3 3:2 volume ratio of the aqueous solution.Logical nitrogen adds catalyzer (PPh after for some time 4) 3Pd (2mol%), reflux temperature be reaction 36～56h down.With the order washing several of reaction solution with methyl alcohol, zero(ppm) water.Solid after washing vacuum-drying 12～24h under the room temperature in vacuum drying oven obtains fluorescent conjugated polymer.
(4) under the nitrogen protection, get fluorescent conjugated polymer and be dissolved in the THF, add the K of 1～3mol/L 2CO 3The aqueous solution, wherein THF and K 2CO 3The volume ratio of the aqueous solution 3: 2.Nitrogen protection adds catalyzer (PPh down 4) 3Pd (2mol%), reflux temperature be reaction 8～15h down.Reaction is used methyl alcohol after finishing, THF, water repetitive scrubbing, and no fluorescent substance occurs in solution, after the drying, gets the TOCN-CP film.
(5) the TOCN-CP film is immersed in certain density 2, in the 4-DNT solution, takes out the variation that detects its fluorescence intensity at once after for some time, The typical result is seen accompanying drawing 1.
Embodiment 2
(1) the ultrasonic deaeration of TOCN aqeous suspension is got film-casting liquid, wherein the massfraction of TOCN is 0.2%～0.3%; The film-casting liquid of gained is poured in the mould by tetrafluoroethylene system, leave standstill 10min～1h after, put into 30～70 ℃ of baking oven 6～10h, treat solvent after evaporating fully the TOCN film.
(2) the TOCN film being put into pH is 4～7 morpholino b acid damping fluid, adds condensing agent 1-(3-dimethyl aminopropyl)-3-ethyl carbon diamines/N-maloyl imines, and its mol ratio is 2: 1.The DMF solution that adds para-bromoaniline behind the 30min.Behind the reaction 16h, water, ethanol are washed repeatedly, but washing gained film is through being had the TOCN active film of Suzuki reaction after the vacuum-drying.
(3) the molar ratio of 1:1 3,6 - dibromo-carbazole and 9,9 - dihexyl-2 ,7 - two knit the brows acid pinacol ester is dissolved in tetrahydrofuran, adding 1 ~ 3mol / L of K 2 CO 3 solution, which tetrahydrofuran and K 2 CO 3 solution volume ratio 3:2.Logical nitrogen adds catalyzer (PPh after for some time 4) 3Pd (2mol%), reflux temperature be reaction 36～56h down.With the order washing several of reaction solution with methyl alcohol, zero(ppm) water.Solid after washing vacuum-drying 12～24h under the room temperature in vacuum drying oven obtains fluorescent conjugated polymer.
(4) under the nitrogen protection, get fluorescent conjugated polymer and be dissolved in the THF, add the K of 1～3mol/L 2CO 3The aqueous solution, wherein THF and K 2CO 3The volume ratio of the aqueous solution 3: 2.Nitrogen protection adds catalyzer (PPh down 4) 3Pd (2mol%), reflux temperature be reaction 8～15h down.Reaction is used methyl alcohol after finishing, THF, water repetitive scrubbing, and no fluorescent substance occurs in solution, after the drying, gets the TOCN-CP film.
(5) the TOCN-CP film is exposed to 2, in the 4-DNT steam, takes out the variation that detects its fluorescence intensity at once after for some time, The typical result is seen accompanying drawing 2, accompanying drawing 3.
Embodiment 3
(1) the ultrasonic deaeration of TOCN aqeous suspension is got film-casting liquid, wherein the massfraction of TOCN is 0.2%～0.3%; The film-casting liquid of gained is poured in the mould by tetrafluoroethylene system, leave standstill 10min～1h after, put into 30～70 ℃ of baking oven 6～10h, treat solvent after evaporating fully the TOCN film.
(2) the TOCN film being put into pH is 4～7 morpholino b acid damping fluid, adds condensing agent 1-(3-dimethyl aminopropyl)-3-ethyl carbon diamines/N-maloyl imines, and its mol ratio is 2: 1.The DMF solution that adds para-bromoaniline behind the 30min.Behind the reaction 16h, water, ethanol are washed repeatedly, but washing gained film is through being had the TOCN active film of Suzuki reaction after the vacuum-drying.
(3) the molar ratio of 1:1 3,6 - dibromo-carbazole and 9,9 - dihexyl-2 ,7 - two knit the brows acid pinacol ester is dissolved in tetrahydrofuran, adding 1 ~ 3mol / L of K 2 CO 3 solution, which tetrahydrofuran and K 2 CO 3 3:2 volume ratio of the aqueous solution.Logical nitrogen adds catalyzer (PPh after for some time 4) 3Pd (2mol%), reflux temperature be reaction 36～56h down.With the order washing several of reaction solution with methyl alcohol, zero(ppm) water.Solid after washing vacuum-drying 12～24h under the room temperature in vacuum drying oven obtains fluorescent conjugated polymer.
(4) under nitrogen atmosphere, get fluorescent conjugated polymer and be dissolved in the THF, add the K of 1～3mol/L 2CO 3The aqueous solution, wherein THF and K 2CO 3The volume ratio of the aqueous solution 3: 2.Nitrogen protection adds catalyzer (PPh down 4) 3Pd (2mol%), reflux temperature be reaction 8～15h down.Reaction is used methyl alcohol after finishing, THF, water repetitive scrubbing, and no fluorescent substance occurs in solution, after the drying, gets the TOCN-CP film.
(5) the TOCN-CP film is exposed to 2, in the 4-DNT steam, takes out after for some time and under uv lamp, observe colour-change, The typical result is seen accompanying drawing 4.

Claims (5)

1. one kind is the highly sensitive fluorescent optical sensor of matrix based on Mierocrystalline cellulose nanometer fento film; But its characteristic is to introduce Suzuki reactive behavior site at the carboxyl with the reproducible TOCN film surface of snappiness and environmental protection C-6 position, then with the fluorescent conjugated polymer chemical graft to film surface.
2. as claimed in claim 1 is the preparation method of the highly sensitive fluorescent optical sensor of matrix based on Mierocrystalline cellulose nanometer fento film, and its characteristic may further comprise the steps:
(1) preparation TOCN film
The ultrasonic deaeration of TOCN aqeous suspension is got film-casting liquid, and wherein the massfraction of TOCN is 0.2%～0.3%; The film-casting liquid of gained is poured in the mould by tetrafluoroethylene system, leave standstill 10min～1h after, put into 30～70 ℃ of baking oven 6～10h, treat solvent after evaporating fully the TOCN film;
(2) preparation bromophenyl TOCN film
Under the effect of condensing agent 1-(3-dimethyl aminopropyl)-3-ethyl carbon diamines/N-maloyl imines; Carboxyl and the aminated compounds reaction 0.5～40h that contains bromophenyl with C-6 position on the TOCN film surface; Use zero(ppm) water and acetone repetitive scrubbing; After vacuum-drying, but process TOCN film with Suzuki reactive behavior site;
(3) preparation fluorescent conjugated polymer
Under the nitrogen protection, with tetrakis triphenylphosphine palladium ((PPh 4) 3Pd) be catalyzer, but the monomer of Suzuki reaction is reacted 12～56h under reflux temperature.After reaction finishes, use methyl alcohol, water repetitive scrubbing product, after vacuum-drying, process fluorescent conjugated polymer;
(4) preparation fluorescent conjugated polymer film (TOCN-CP film)
The fluorescent conjugated polymer of preparation is dissolved in the mixing solutions of THF and salt of wormwood, puts into there-necked flask, N with bromophenyl TOCN film 2Protection adds (PPh down 4) 3Pd, reflux temperature use methyl alcohol after reacting 2～24h down, THF, water repetitive scrubbing, and no fluorescent substance occurs in solution, after the drying, gets the TOCN-CP film.
3. method according to claim 2 is characterized in that in the step (2) the brominated phenyl group of described amino-complex.
4. method according to claim 2 is characterized in that in the step (3), but the monomer of described Suzuki reaction is the boric acid or the boric acid ester of aryl or thiazolinyl, chlorine, bromine, iodo aromatic hydrocarbons or alkene.
5. method according to claim 2 is characterized in that in the step (3) the end group boronic acid containing of described fluorescent conjugated polymer, boric acid ester.
CN201210214163.0A 2012-06-25 2012-06-25 Fluorescent sensor based on cellulose nanometer micro-fiber (TOCN) film serving as substrate and application thereof Expired - Fee Related CN102702558B (en)

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Cited By (6)

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CN104155275A (en) * 2014-08-12 2014-11-19 南京邮电大学 Method for detecting repeatability of tetraaryl vinyl fluorescent nano fiber on explosive
CN106243365A (en) * 2016-07-29 2016-12-21 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
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CN107417952A (en) * 2017-07-28 2017-12-01 华北电力大学（保定） A kind of cellulose fluorescent film and preparation method thereof
CN108318462A (en) * 2017-12-18 2018-07-24 重庆三峡学院 Fluorescent probe molecule and its fluorescence membrane sensor and preparation method and application for pH detections
WO2021104425A1 (en) * 2019-11-28 2021-06-03 华南理工大学 Nanocellulose-based electro-driven material and preparation method therefor

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011100010A2 (en) * 2009-11-20 2011-08-18 University Of Utah Research Foundation Sensors and methods for detecting peroxide based explosives

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011100010A2 (en) * 2009-11-20 2011-08-18 University Of Utah Research Foundation Sensors and methods for detecting peroxide based explosives

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CN104155275A (en) * 2014-08-12 2014-11-19 南京邮电大学 Method for detecting repeatability of tetraaryl vinyl fluorescent nano fiber on explosive
CN106243365A (en) * 2016-07-29 2016-12-21 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
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
CN107200830A (en) * 2017-05-25 2017-09-26 南方医科大学 A kind of ionization containing organic radical polymerization fluorenes and its preparation method and application
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
CN107417952A (en) * 2017-07-28 2017-12-01 华北电力大学（保定） A kind of cellulose fluorescent film and preparation method thereof
CN107417952B (en) * 2017-07-28 2020-11-13 华北电力大学（保定） Cellulose fluorescent film and preparation method thereof
CN108318462A (en) * 2017-12-18 2018-07-24 重庆三峡学院 Fluorescent probe molecule and its fluorescence membrane sensor and preparation method and application for pH detections
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
WO2021104425A1 (en) * 2019-11-28 2021-06-03 华南理工大学 Nanocellulose-based electro-driven material and preparation method therefor

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