Preparation method of fluorescent sensing film and film sensor for gas phase detection
阅读说明：本技术 一种荧光传感薄膜的制备方法和气相检测用薄膜传感器 (Preparation method of fluorescent sensing film and film sensor for gas phase detection ) 是由 付艳艳 程建功 李可可 贺庆国 于 2019-11-07 设计创作，主要内容包括：本申请提供一种荧光传感薄膜的制备方法和气相检测用薄膜传感器,该制备方法包括以下步骤：获取荧光传感材料和透明高分子材料；将荧光传感材料和透明高分子材料按照设定比例掺杂获得混合材料；将混合材料溶解于有机良溶剂中获得荧光传感溶液；将荧光传感溶液通过溶液成膜方法在透明基底上制备形成荧光传感薄膜；荧光传感薄膜能够用于气相检测。如此,通过这种荧光传感材料和透明高分子材料掺杂的制备办法能够获得多孔结构的荧光传感薄膜,可以有效降低荧光传感材料的聚集态荧光淬灭现象,使其可以在薄膜态发出较强荧光,同时多孔的荧光传感薄膜有利于被检测气体穿透,提升检测效果。(The application provides a preparation method of a fluorescent sensing film and a film sensor for gas phase detection, wherein the preparation method comprises the following steps: obtaining a fluorescent sensing material and a transparent high polymer material; doping the fluorescent sensing material and the transparent high polymer material according to a set proportion to obtain a mixed material; dissolving the mixed material in an organic good solvent to obtain a fluorescence sensing solution; preparing a fluorescent sensing solution on a transparent substrate by a solution film forming method to form a fluorescent sensing film; the fluorescence sensing film can be used for gas phase detection. Therefore, the fluorescent sensing film with the porous structure can be obtained by the preparation method for doping the fluorescent sensing material and the transparent high polymer material, the aggregation state fluorescent quenching phenomenon of the fluorescent sensing material can be effectively reduced, the fluorescent sensing material can emit stronger fluorescence in a film state, meanwhile, the porous fluorescent sensing film is beneficial to penetration of the detected gas, and the detection effect is improved.)
1. A preparation method of a fluorescence sensing film is characterized by comprising the following steps:
obtaining a fluorescent sensing material and a transparent high polymer material;
doping the fluorescent sensing material and the transparent high polymer material according to a set proportion to obtain a mixed material;
dissolving the mixed material in an organic good solvent to obtain a fluorescence sensing solution;
preparing the fluorescent sensing solution on a transparent substrate by a solution film forming method to form the fluorescent sensing film;
the fluorescence sensing film can be used for gas phase detection.
2. The method of claim 1, wherein the organic fluorescent sensing material comprises a first compound, a second compound, or a third compound;
the first compound has the structural formula:
the structural formula of the second compound is:
the structural formula of the third compound is:
3. the method of claim 2, wherein the transparent polymer material comprises polystyrene, polymethyl methacrylate, polycarbonate, or polyvinyl chloride.
4. The method for preparing a fluorescence sensing film according to claim 3, wherein the doping ratio of the fluorescence sensing material to the polymer material is 1:5-1: 500.
5. The method of claim 1, wherein the good organic solvent comprises tetrahydrofuran, dichloromethane, chloroform, toluene or acetone.
6. The method of claim 1, wherein the concentration of the fluorescence sensing solution is 0.5mg/mL to 50 mg/mL.
7. The method of claim 1, wherein the transparent substrate comprises a glass substrate, a quartz substrate, an organic polymer solid carrier substrate, a transparent substrate, or a composite substrate composed of ultra-thin metal oxides.
8. The method for preparing a fluorescence sensing thin film according to claim 1, wherein the solution film forming method includes a spin-on film forming method, a drop-on film forming method, or a pull-up film forming method.
9. A gas-phase detection thin film sensor comprising the fluorescent sensor thin film produced by the production method according to any one of claims 1 to 8, wherein the gas-phase detection thin film sensor can be used for detecting a gas.
10. The thin film sensor for gas phase detection according to claim 9, wherein the gas comprises an organic amine gas, a hydrogen peroxide gas, a drug gas, a nerve agent gas, a simulant gas, or a trace explosive volatile gas.
Technical Field
The application relates to the technical field of chemical sensors, in particular to a preparation method of a fluorescent sensing film and a film sensor for gas phase detection.
Background
High-sensitivity gas sensors are urgently required in various fields such as public safety, environmental protection, public health and the like. The thin film fluorescence sensor is expected to show a great deal in the aspect of gas sensing due to the advantages of high sensitivity, quick response, easiness in device formation and the like. However, the development of organic thin-film fluorescent sensing materials lags much behind the development of solution-phase fluorescent sensing materials. The types of fluorescent materials and detectable gases that can be used for gas phase detection are much smaller than the types of fluorescent materials and analytes detected in solution phase.
The main reason why the thin film fluorescence sensing research lags behind the solution phase sensing research is that most fluorescence sensing materials have fluorescence aggregation induced quenching phenomenon. Therefore, many materials with good luminescence property and good sensing effect in solution emit very weak luminescence due to aggregation induced quenching effect after being prepared into a thin film, and cannot be used for gas phase detection.
In order to develop a fluorescence sensing material for gas phase detection, some solutions in the prior art are designed to synthesize aggregation-inducing luminescent materials to solve this problem. However, the aggregation-induced emission materials are of few types, and are mostly concentrated in a few limited material structures such as tetraphenylethylene, tetraphenylsilole, salicylaldehyde imine and the like, so that the application of the aggregation-induced emission materials is greatly limited. It would be clear that the development of thin film fluorescence sensors could be greatly facilitated if a method could be found that would allow the application of existing solution phase detectable materials to gas phase detection.
Disclosure of Invention
The method solves the technical problem that the fluorescence sensing material cannot be used for gas phase detection due to weak luminescence caused by aggregation induced quenching effect after being prepared into a film.
In order to solve the above technical problem, an embodiment of the present application discloses a method for preparing a fluorescence sensing thin film, which includes the following steps:
obtaining a fluorescent sensing material and a transparent high polymer material;
doping the fluorescent sensing material and the transparent high polymer material according to a set proportion to obtain a mixed material;
dissolving the mixed material in an organic good solvent to obtain a fluorescence sensing solution;
the fluorescent sensing solution is prepared on the transparent substrate by a solution film forming method to form a fluorescent sensing film, and the fluorescent sensing film can be used for gas phase detection.
Further, the organic fluorescent sensing material comprises a first compound, a second compound or a third compound;
the first compound has the structural formula:
the second compound has the structural formula:
the structural formula of the third compound is:
further, the transparent polymer material includes polystyrene, polymethyl methacrylate, polycarbonate, or polyvinyl chloride.
Furthermore, the doping ratio of the fluorescent sensing material to the high polymer material is 1:5-1: 500.
Further, the good organic solvent includes tetrahydrofuran, dichloromethane, chloroform, toluene or acetone.
Further, the concentration of the fluorescence sensing solution is 0.5mg/mL-50 mg/mL.
Further, the transparent substrate includes a glass substrate, a quartz substrate, an organic polymer solid carrier substrate, a transparent substrate or a composite substrate composed of an ultrathin metal oxide.
Further, the solution film forming method includes a spin-coating film forming method, a drop-coating film forming method, or a pull-coating film forming method.
The application also provides a film sensor for gas phase detection, which comprises the fluorescent sensing film prepared by the preparation method, and the film sensor for gas phase detection can be used for detecting gas.
Further, the gas includes organic amine gas, hydrogen peroxide gas, drug gas, nerve agent gas, simulant gas, or trace explosive volatile gas.
By adopting the technical scheme, the application has the following beneficial effects:
the embodiment of the application forms the fluorescent sensing film by doping the transparent high polymer material and the fluorescent sensing material, can effectively reduce the aggregation state fluorescence quenching phenomenon of the fluorescent sensing material by optimizing the doping proportion, the concentration of the fluorescent sensing solution and selecting different good organic solvents, so that the fluorescent sensing film can emit stronger fluorescence in a film state, and meanwhile, the composite material formed by doping the transparent high polymer material and the fluorescent sensing material has higher viscosity, better film forming property, porous film and better permeability, and is favorable for gas phase detection.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic flow chart illustrating a method for manufacturing a fluorescence sensing film according to an embodiment of the present disclosure;
FIG. 2 is a scanning electron microscope image of an undoped fluorescent sensing thin film and a doped fluorescent sensing thin film in example 1 of the present application;
FIG. 3 is a fluorescent image of an undoped fluorescent sensing film and a doped fluorescent sensing film under an ultraviolet lamp in example 1 of the present application;
FIG. 4 is a graph of the fluorescence intensity of the doped fluorescence sensing film in example 1 of the present application at 618nm of its maximum emission wavelength as a function of time in diethylamine vapor;
FIG. 5 is a graph of the fluorescence intensity of the doped fluorescence sensing film in example 2 of the present application at 618nm of its maximum emission wavelength as a function of time in diethylamine vapor;
FIG. 6 is a graph of the fluorescence intensity of the doped fluorescence sensing film in example 3 of the present application at 618nm of its maximum emission wavelength as a function of time in diethylamine vapor;
FIG. 7 is a graph of the fluorescence intensity of the doped fluorescence sensing film in example 4 of the present application at 618nm of its maximum emission wavelength as a function of time in diethylamine vapor;
FIG. 8 is a scanning electron microscope photograph of an undoped fluorescent sensing thin film and a doped fluorescent sensing thin film in example 5 of the present application;
FIG. 9 is a graph of the fluorescence intensity of the doped fluorescence sensing film in example 5 of the present application at 618nm of its maximum emission wavelength as a function of time in diethylamine vapor;
FIG. 10 is a graph of the fluorescence intensity of the doped fluorescence sensing film in example 6 of the present application at 618nm of its maximum emission wavelength as a function of time in diethylamine vapor;
FIG. 11 is a graph showing the fluorescence intensity of the doped fluorescence sensing film of example 7 with time in diethylamine vapor at 618nm of the maximum emission wavelength;
FIG. 12 is a graph showing the fluorescence intensity of the doped fluorescence sensing film in example 8 with time in hydrogen peroxide vapor at 468nm of the maximum emission wavelength;
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It is to be understood that the embodiments described are only a few embodiments of the present application and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the present application. In the description of the embodiments of the present application, it is to be understood that the terms "upper", "lower", "top", "bottom", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are only for convenience in describing the present application and simplifying the description, and do not indicate or imply that the referred devices or elements must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present application. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. Moreover, the terms "first," "second," and the like are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the application described herein are capable of operation in sequences other than those illustrated or described herein.
Referring to fig. 1, fig. 1 is a method for preparing a fluorescence sensing film according to an embodiment of the present disclosure, the method comprising the following steps:
s1, obtaining a fluorescent sensing material and a transparent high polymer material;
s2, doping the fluorescent sensing material and the transparent high polymer material according to a set proportion to obtain a mixed material;
s3, dissolving the mixed material in an organic good solvent to obtain a fluorescence sensing solution;
s4, preparing the fluorescent sensing solution on a transparent substrate by a solution film forming method to form a fluorescent sensing film;
the fluorescence sensing film prepared by the method can be used for gas phase detection.
In the embodiment of the application, the organic fluorescent sensing material may be a first compound, a second compound, or a third compound;
wherein the first compound has the
the second compound is known in the art as 5- (2,5-Bis (2-butyloxy) -3, 6-dioxol-4- (5- (4,4,5, 5-tetramethylol-1, 3,2-dioxaborolan-2-yl) thiophen-2-yl) -2, 3, 5, 6-tetrahydrorrolol [3,4-c ] pyrro-1-yl) thiophene-2-carbaldehyde, and in the chinese name 5- (2,5-Bis (2-butyloctyl) -3,6-dioxo-4- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiophen-2-yl) -2, 3, 5, 6-tetrahydropyrrole [3,4-c ] pyrrol-1-yl) thiophen-2-carbaldehyde.
The first compound has the structural formula:
the second compound has the structural formula:
the structural formula of the third compound is:
wherein the first compound and the second compound are commercial products purchased from Suzhou nakai science and technology limited, and the samples are laboratory analytically pure. The preparation method of the third compound is as follows: 742mg of N, N-diphenyl-4- (4,4,5,5-tetramethyl-1, -1,3, 2-boronic acid pinacol ester) aniline is dissolved in 4mL of N, N-dimethylformamide to obtain a first solution, then 2g of phosphorus oxychloride is dropwise added into the first solution at room temperature to obtain a second solution, the second solution is reacted at 90 ℃ for 1 hour to obtain a reaction solution, the reaction solution is cooled to room temperature, then poured into an ice water mixture, and extraction is carried out with dichloromethane. And after the extract liquid is dried, performing column chromatography separation to obtain a bright yellow solid product, namely a third compound.
In the embodiment of the present application, the transparent polymer material may be any one of polystyrene, polymethyl methacrylate, polycarbonate, or polyvinyl chloride.
In the embodiment of the present application, the doping ratio of the fluorescent sensing material and the transparent polymer material is 1:5-1:500, where 1:5 and 1:500 are not two extreme values, and this range is only a reference value, for a specific material, the optimal doping ratio needs to be individually optimized, for example, when the doping amount of the polymer is too small, a uniform thin film may not be formed, the doping amount of the polymer is too large, the solubility is close to saturation, and an excessively thick thin film is formed, which may cause a reduction in the effect, and the doping ratio may be determined according to specific situations.
In the embodiment of the present application, the good organic solvent may be any one of tetrahydrofuran, dichloromethane, chloroform, toluene, or acetone. The mixed material obtained after the fluorescent sensing material and the transparent high polymer material are doped is dissolved in the solvent, the concentration range of the mixed material can be 0.5mg/mL-50mg/mL, and in practical situations, the concentration of the solution can be regulated and controlled according to the respective properties of different materials so as to obtain the optimal performance.
In the embodiment of the present application, the transparent substrate may be any one of a glass substrate, a quartz substrate, an organic polymer solid carrier substrate, a transparent substrate, or a composite substrate composed of ultrathin metal oxides.
In the embodiment of the present application, the solution film forming method includes a spin-on film forming method, a drop-on film forming method, or a pull-up film forming method.
The embodiment of the application forms the fluorescent sensing film by doping the transparent high polymer material and the fluorescent sensing material, can effectively reduce the aggregation state fluorescence quenching phenomenon of the fluorescent sensing material by optimizing the doping proportion, the concentration of the fluorescent sensing solution and selecting different good organic solvents, so that the fluorescent sensing film can emit stronger fluorescence in a film state, and meanwhile, the composite material formed by doping the transparent high polymer material and the fluorescent sensing material has higher viscosity, better film forming property, porous film and better permeability, and is favorable for gas phase detection.
The application also provides a film sensor for gas phase detection, which comprises the fluorescent sensing film prepared by the preparation method, and the film sensor for gas phase detection has high sensitivity to gas and can be used for detecting gas.
In the embodiment of the present application, the gas may be organic amine gas, hydrogen peroxide gas, drug gas, nerve agent gas, simulant gas or trace explosive volatile gas.
Based on the above, several embodiments are described below.
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