CN113336779B - Rare earth luminescent material, preparation method thereof and fluorescent sensing application - Google Patents
Rare earth luminescent material, preparation method thereof and fluorescent sensing application Download PDFInfo
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Abstract
The invention discloses a rare earth ternary complex luminescent material, wherein the molecular formula of the complex is Eu (TTolB)3(Phen) wherein ttolB is 4,4, 4-trifluoro-1- (p-tolyl) -1, 3-butanedione; phen is 1, 10-phenanthroline. The compound is prepared by the coordination reaction of europium nitrate, three times of equivalent of TTolB and one time of equivalent of Phen ligand. The luminescent material has good luminescent property, and can quickly present fluorescence quenching sensing response characteristics after being placed in an atmosphere containing organic amine; the luminescent material has selective response to organic amine and high sensitivity; the material has good solubility and stability, is easy to prepare a paper-based or quartz glass sheet-based fluorescence sensing film, can rapidly show fluorescence quenching response capable of being observed by naked eyes in the atmosphere containing organic amine, shows fluorescence sensing performance of rapid response and sensitive identification, can flexibly manufacture test paper into various required specifications, and can be used as a portable fluorescence sensing test paper device for applying organic amine detection.
Description
Technical Field
The invention relates to the technical field of rare earth luminescent materials, in particular to the field of fluorescent sensing application of luminescent materials.
Background
China is the world with the most abundant and widely distributed rare earth resources, the resource reserves account for about 80% of the world reserves, the preparation and research application of the rare earth luminescent material are deeply developed, and the practical application of the rare earth luminescent material in the industries of agriculture, medicine and pharmacology and other high and new technology industries is very important. Due to the unique electronic layer structure of the rare earth ions, the luminescent complex of the rare earth ions has the characteristics of long fluorescence life, high quantum yield, narrow emission band, large stokes shift and the like, and has wide application prospects in the aspects of fluorescence imaging and luminescent materials, particularly fluorescence sensors and fluorescence probes applied to the fields of biological systems and biomedicine. With the development of science and technology, the reaction type fluorescent probe attracts more and more research workers due to the advantages of specific selectivity, high sensitivity and rapid detection.
At present, in the aspect of environmental pollution, the pollution of amine organic matters cannot be ignored. Amine organic matters are extremely harmful pollutants, most of which have the characteristics of high toxicity, high fluidity, durability, biological accumulation and the like, and have great adverse effects on the environment and public health. Some amine organic substances have a fishy smell or a pungent smell of ammonia gas, and have a great stimulation effect on skin, respiratory tract, mucous membrane, eyes and the like. For example, methylamine mixed with air forms an explosive mixture that causes pharyngitis, which people may die from pulmonary edema and respiratory distress syndrome after inhalation (environmental science and technology, 2014,37(07):145- "152). Therefore, if the organic amine waste gas is directly discharged without being treated, environmental pollution and serious harm to human beings and other organisms can be caused. How to reasonably and effectively control the emission of amine compounds and treat the pollutants is a great problem to be solved at present.
Nowadays, a very important research direction is how to limit the concentration of organic amine atmosphere in the environment and make a quick and accurate determination thereof. Currently, there are many conventional detection techniques for measuring the atmosphere of organic amines in the environment, including spectrophotometry, ion chromatography, and gas chromatography. With the development of sensing detection technology, various optical sensors are also gradually developed and applied to the detection of organic amine compounds. Although the chromatographic analysis method can realize higher accuracy and sensitivity and has lower detection limit, compared with the sensing detection technology, the chromatographic analysis method has the defects of long analysis time, expensive equipment, high cost, complex operation and the like. In future, the detection of organic amine pollutants is developed towards miniaturization, intellectualization, generalization, simplified processing process, increased selectivity and improved detection precision, and the optical thin film sensing technology has the advantages of simple operation, good reproducibility, high sensitivity, fast response speed, good selectivity, rich signal acquisition and the like, and probably has great hope of meeting the expectation of the detection of the organic amine pollutants in the future (Gao, M.; et al., ACS Sensors, 2016, 1(2): 179-184.).
Europium complexes have strong luminescent properties, can form multi-coordination, and are combined with proper ligands to have unique luminescent properties (university chemistry, 2016,31(07): 65-71). Europium complexes have been used as fluorescent materials for a long time, but are only rarely applied to VOC detection at present. Therefore, the fluorescent sensor for developing the europium complex has wide development potential in the aspect of detection. The europium complex is used as a fluorescent probe to be manufactured into a paper-based portable fluorescent sensing film device, is used for sensing and detecting harmful gases in the environment such as organic amine and the like, and has great practical application value.
Disclosure of Invention
The invention aims to provide a rare earth complex luminescent material with selective response to organic amine and high sensitivity, a preparation method thereof and fluorescent sensing application. The europium complex luminescent material with good luminescent property and thermal stability is conveniently and cheaply prepared by the coordination reaction of europium ions and ligands in a solution, the red fluorescence luminescent intensity of the europium complex luminescent material is high, the stability of the europium complex luminescent material is good, and the fluorescent film prepared by the europium complex luminescent material has obvious fluorescence quenching effect on the response of organic amine and can be used for detecting the organic amine in the environment.
One of the technical schemes of the invention is to provide a novel rare earth complex luminescent material, which is obtained by sequentially carrying out coordination reaction on Eu (NO3)3 and a ligand, and has a molecular structure of Eu (TTolB)3(Phen), wherein TTolB is 4, 4, 4-trifluoro-1- (p-tolyl) -1, 3-butanedione; wherein Phen is neutral heterocyclic ligand 1, 10-phenanthroline.
The rare earth complex luminescent material is a triclinic system, P-1 space group (No. 2), unit cell parameters a =11.218(5), b =17.526(5) a, c =25.792(8) a, α =77.299(10) °, β =82.047(17) °, γ =87.019(13) °, V =4898(3) a 3, Z =2, DC =1.500 g/cm3, the crystal color of the material being pale pink near colorless; the structure of the material is expressed as a mononuclear neutral complex, wherein Eu3+ is positioned at the center of a coordination environment, 3 trifluoromethyl substituted beta-diketone ligands TTolB and 1 Phen ligand are chelated around the Eu3+, and four ligands are uniformly distributed around the Eu3 +; the Eu3+ ion adopts an eight-coordination mode, and six coordination atoms O and two coordination atoms N form a dodecahedron configuration; the molecular structure is shown as formula (I):
According to the rare earth complex luminescent material, the Eu atom is located at the center of the coordination polyhedron, the ligand contains the rigid benzene ring and the aromatic heterocycle, the rigidity and the stability of the main structure are enhanced, the compound is favorable for realizing high-efficiency luminescence through an antenna effect, and the fluorine-containing beta-diketone ligand has a good sensitization effect on europium ions. The luminescent material can emit strong red light by taking 610nm as the maximum emission peak under the excitation of ultraviolet light with different wavelengths, and can be used as a red light photoluminescence material or a luminescent layer material in a multilayer electroluminescent device.
The second technical scheme of the invention is to provide a fluorescent sensing application based on rare earth complex luminescent material Eu (TTolB)3 (Phen). The rare earth complex luminescent material has obvious fluorescence quenching response to organic amine, the red fluorescence intensity of the rare earth complex luminescent material is reduced along with time after the rare earth complex luminescent material is placed in an environment with the existence of the organic amine, and the higher the concentration of the organic amine is, the stronger quenching response effect is shown, so that the rare earth complex luminescent material can be used as a fluorescence sensing material for detecting the organic amine. After the paper-based fluorescent film of the rare earth complex luminescent material is placed in an environment with organic amine, the red fluorescence intensity of the paper-based fluorescent film can also be rapidly reduced along with time, and the higher the concentration of the organic amine is, the stronger quenching response effect is shown, and the fluorescence sensing performance of quick response and sensitive identification is shown, so that the paper-based fluorescent film can be used as a portable fluorescence sensing test paper device for detecting the organic amine.
The third technical scheme of the invention is to provide a preparation method of a rare earth complex luminescent material Eu (TTolB)3 (Phen). The preparation method is realized by mixing europium nitrate with solutions of ligands TTolB and Phen to perform a coordination reaction and finally separating out a product of crystal powder. The specific implementation scheme is divided into five steps:
(1) eu (NO3) 3.6H 2O powder was dissolved in acetonitrile at room temperature;
(2) dissolving TTolB and sodium hydroxide powder in a mixed solvent of acetonitrile and water at room temperature;
(3) mixing the two solutions, and stirring to make them fully react to obtain a clear solution A;
(4) dissolving Phen powder in acetonitrile at room temperature, adding into the solution A, mixing and stirring to fully perform coordination reaction to obtain a turbid solution and a large amount of yellow pasty precipitates;
(5) filtering, washing filter residues and then drying to obtain a crystalline powder product; the molar ratio Eu (NO3) 3: TTolB: Phen of the three reactants is 1: 3: 1.
The fourth technical scheme of the invention is to provide a preparation method of a film-based fluorescence sensing film based on a rare earth complex luminescent material Eu (TTolB)3 (Phen). The preparation method is realized by dissolving Eu (TTolB)3(Phen) crystal powder and coating cellulose film or glass sheet with the solution. The specific implementation scheme comprises six steps:
(1) Preparing a dichloromethane solution A with a certain concentration of Eu (TTolB)3(Phen) according to the quantity concentration of substances;
(2) adding a proper amount of methylene dichloride solution of PMMA into the solution A, and uniformly mixing to obtain a solution B;
(3) and coating the solution B on a cellulose film (namely test paper base paper) or a glass sheet in a dip-coating mode and the like, and drying to obtain the paper-based or glass-based fluorescent sensing film device.
The rare earth complex luminescent material Eu (TTolB)3(Phen) provided by the invention has the beneficial effects that an anionic beta-diketone ligand and a neutral phenanthroline ligand are well combined, the luminescent efficiency and the thermal stability of the material are effectively improved through the synergistic effect of the two ligands, the material presents strong narrow-band red light emission characteristics under the excitation of ultraviolet light, and the technical support is provided for the further application of the luminescent material in the fields of organic electroluminescence and the like.
The invention has the beneficial effects that in the sensing application of the rare earth complex luminescent material Eu (TTolB)3(Phen), the complex has good fluorescence property, and very small amount of material powder can emit strong fluorescence, so that only a small amount of fluorescent powder is needed in practical application, the application cost is conveniently reduced, and the doping way which is easy to operate also provides convenience for the control of the application cost; after the materials prepared by the same process are placed in an organic amine atmosphere, the sensing response characteristic of fluorescence quenching can be quickly observed; and the solubility and the stability of the fluorescent sensing material are good, so that the fluorescent sensing material is convenient to use.
The paper-based or glass-based fluorescent film based on the rare earth complex luminescent material Eu (TTolB)3(Phen) has the beneficial effects that the paper-based fluorescent film is used for sensing organic amine, the use of the paper-based fluorescent film is as simple and convenient as that of a common gas detection test paper, and when the paper-based fluorescent film is used specifically, after the paper-based fluorescent film is placed in an environment with organic amine for a short time, an ultraviolet light source is used for irradiating the film, the red fluorescent intensity of the paper-based fluorescent film can be observed to be rapidly reduced along with the time, and the higher the concentration of the organic amine is, the stronger quenching response effect is shown, and the fluorescence sensing performance of rapid response and sensitive identification is shown, so that the paper-based or glass-based fluorescent film can be used for detecting the organic amine as a portable fluorescent sensing test paper device; the fluorescent sensing film can be flexibly manufactured into various required shapes, has light weight, is very convenient to carry and easy to prepare, and provides technical support for further application of luminescent materials. Glass-based fluorescent films also have very similar sensing properties. And the sensor film can be easily compounded with a fluorescent reference substance to prepare a ratio type sensing film.
The preparation method has the beneficial effects that the preparation method of the rare earth complex-based luminescent material Eu (TTolB)3(Phen) and the paper-based and glass-based fluorescent sensing film has the advantages of simple and convenient process, simple used equipment, simple and easily obtained raw materials, low production cost, capability of obtaining a large amount of products in a short time, easiness in popularization and the like.
Drawings
FIG. 1 is a single crystal structure diagram of a rare earth complex luminescent material Eu (TTolB)3(Phen) molecule.
FIG. 2 is a stacking diagram of rare earth complex luminescent material Eu (TTolB)3(Phen) molecules in a unit cell and a space around the unit cell.
FIG. 3 is a graph showing an ultraviolet-visible absorption spectrum of a rare earth complex luminescent material Eu (TTolB)3(Phen), wherein a concentration of a dichloromethane solution is 4.5 x 10-6 mol/L, a horizontal axis represents a wavelength, and a vertical axis represents an absorbance.
FIG. 4 is a chart of an infrared absorption spectrum of a rare earth complex luminescent material Eu (TTolB)3(Phen), in which the abscissa represents wave number and the ordinate represents transmittance.
FIG. 5 is an emission spectrum of crystalline powder of rare earth complex luminescent material Eu (TTolB)3(Phen), with an excitation wavelength of 365nm and a maximum emission peak at 610 nm; the abscissa is wavelength and the ordinate is intensity.
FIG. 6 shows an emission spectrum of a rare earth complex luminescent material Eu (TTolB)3(Phen) paper-based film, wherein the excitation wavelength is 365nm, and the maximum emission peak is located at 610 nm; the abscissa is wavelength and the ordinate is intensity.
FIG. 7 shows an emission spectrum of a rare earth complex luminescent material Eu (TTolB)3(Phen) quartz glass substrate film, wherein an excitation wavelength is 365nm, and a maximum emission peak is located at 610 nm; the abscissa is wavelength and the ordinate is intensity.
FIG. 8 shows fluorescence emission spectra (main peaks) of a paper-based sensing film of rare earth complex luminescent material Eu (TTolB)3(Phen) after responding to different times in diisopropylamine atmosphere; the abscissa is wavelength and the ordinate is intensity.
FIG. 9 shows fluorescence emission spectra (main peak) of a paper-based sensing film of rare earth complex luminescent material Eu (TTolB)3(Phen) after responding to different times in aniline atmosphere; the abscissa is wavelength and the ordinate is intensity.
FIG. 10 shows fluorescence emission spectra (main peaks) of a quartz glass sheet-based sensing film of a rare earth complex luminescent material Eu (TTolB)3(Phen) after response for different times in a methylamine atmosphere; the abscissa is wavelength and the ordinate is intensity.
Detailed Description
The implementation process and the performance of the material of the invention are illustrated by the examples:
example 1
The preparation of rare earth complex luminescent material Eu (TTolB)3(Phen) can be realized by the following steps:
A. weighing: weighing 0.223g of Eu (NO3) 3.6H 2O, 0.352 g of 4, 4, 4-trifluoro-1- (p-tolyl) -1, 3-butanedione, 0.0625g of NaOH and 0.099g of Phen (o-phenanthroline);
B. dissolving: europium nitrate is dissolved in 5ml of deionized water, and the mixture is stirred at room temperature until the europium nitrate is completely dissolved, so that the solution is colorless and transparent; dissolving 4, 4, 4-trifluoro-1- (p-tolyl) -1, 3-butanedione and NaOH in 3ml of deionized water and 5ml of acetonitrile mixed solution, and fully stirring to obtain a light yellow solution; dissolving Phen (phenanthroline) in 5ml of acetonitrile, and stirring at room temperature until the solution is completely dissolved, wherein the solution is a colorless transparent solution;
C. Importing: slowly dripping a mixed solution of light yellow 4, 4, 4-trifluoro-1- (p-tolyl) -1, 3-butanedione and NaOH into a europium nitrate aqueous solution one drop by one drop to ensure that the solution is subjected to full coordination reaction, and stirring for 15min, wherein the solution is light yellow and slightly turbid; slowly dripping Phen (o-phenanthroline) acetonitrile solution into the mixed solution one drop by one drop, and stirring at room temperature for 10min to obtain light milky turbid solution with yellow pasty precipitate at the bottom;
D. and (3) filtering: after fully stirring and reacting, filtering to obtain transparent clear filtrate and yellow precipitate, wherein the yellow precipitate has strong luminescence;
E. and (3) drying: drying the yellow precipitate in a drying oven at 80 deg.C for 15 min; cooling to room temperature, and emitting strong red light by an ultraviolet lamp; the precipitate was triturated and collected and weighed to give 0.431g of yellow powder; the yield of the powder product, calculated as Eu (TTolB)3(Phen), was about 70.3;
example 2
The preparation of rare earth complex luminescent material Eu (TTolB)3(Phen) single crystal can be realized by the following steps:
A. weighing: weighing 0.033g of powder synthesized by the method of example 1;
B. dissolving and filtering: dissolving the powder in 3ml of dichloromethane, fully stirring and dissolving at room temperature until the solution is clear, and then filtering;
C. and (3) crystallization: placing the light-colored filtrate obtained by filtering into a clean test tube, adding n-hexane as a precipitator into the upper layer, sealing, standing and crystallizing;
D. Selecting a crystal test structure: after three days, a large number of light-colored crystals grow in the test tube, the crystals are taken out, crystals with the size of 0.45mm multiplied by 0.35mm multiplied by 0.29mm are selected for X-ray single crystal diffraction test, and the crystal structure of Eu (TTolB)3(Phen) is obtained through analysis. The crystal structure is shown in fig. 1 and fig. 2.
Example 3
Preparing a paper-based fluorescent film of a rare earth complex luminescent material Eu (TTolB)3 (Phen): weigh 0.0015g of Eu (TTolB)3 (Phen); adding the mixture into 5ml of dichloromethane solution, and fully stirring the mixture to fully and completely dissolve the dichloromethane solution to obtain light-colored clear solution; the complex solution is slowly introduced into the PMMA solution, and the solution is light in color, clear and transparent. Then, carrying out micro-spraying on the solution on a test strip prepared in advance to manufacture a sensitive surface of the fluorescence sensor, and obtaining the ratio type fluorescence test strip (paper-based fluorescence film) after drying; the paper-based fluorescence sensing film is very sensitive to the response of organic amine, and fluorescence quenching can occur when a small amount of organic amine exists in the environment.
Example 4
Preparing a paper-based fluorescent film of a rare earth complex luminescent material Eu (TTolB)3 (Phen): weigh 0.0015g of Eu (TTolB)3 (Phen); adding the solution into 5ml of dichloromethane solution, fully stirring the solution to fully and completely dissolve the solution to obtain a light-colored clear solution, soaking a cellulose film test strip prepared in advance into the solution, taking out the test strip after the solution is completely and uniformly soaked, drying the test strip after the test strip is pressed, and waiting for drying to obtain the portable fluorescent test strip (paper-based fluorescent film); the paper-based fluorescence sensing film is very sensitive to the response of organic amine, and fluorescence quenching can occur when a small amount of organic amine exists in the environment.
Example 5
Preparation of quartz glass sheet-based fluorescent film of red fluorescent complex material Eu (TTolB)3 (Phen): weigh 0.0015g Eu (TTolB)3 (Phen); adding the mixture into 5ml of dichloromethane solution, and fully stirring the mixture to fully and completely dissolve the dichloromethane solution to obtain light-colored clear solution; and slowly introducing the complex solution into the PMMA solution, wherein the solution is light in color, clear and transparent. Spin-coated (1200 rad/min) on cleaned quartz plates, dried (70 ℃, 30 min), and then placed in VOC for response, and the fluorescence spectra are tested. The fluorescent sensing film is very sensitive to the response of organic amine, and fluorescence quenching can occur when a small amount of organic amine exists in the environment.
A series of performance tests were performed on phase pure powders of Eu (TTolB)3(Phen) and film samples thereof. The steady-state fluorescence test is carried out on the film, and the result shows that Eu (TTolB)3(Phen) can emit strong red fluorescence under the action of different excitation wavelengths. Therefore, the material can be applied to a luminescent material in an OLED device. And the organic amine VOC response fluorescence test of the material shows that the material has an obvious fluorescence quenching type sensing response phenomenon in the organic amine atmosphere. Therefore, the material can also be applied to a fluorescence sensing material for detecting organic amine. Specific emission spectra are shown in fig. 5, 6, 7, 8, 9 and 10.
Claims (6)
1. A rare earth complex luminescent material is characterized in that: the structural formula of the luminescent material is Eu (TTolB)3(Phen) wherein ttolB is 4, 4, 4-trifluoro-1- (p-tolyl) -1, 3-butanedione; wherein Phen is neutral heterocyclic ligand 1, 10-phenanthroline; the rare earth complex luminescent material is triclinic, a P-1 space group, and has unit cell parameters of a =11.218(5) A, b =17.526(5) A, c =25.792(8) A, α =77.299(10) °, β =82.047(17) °, γ =87.019(13) °, V =4898(3) A3，Z=2，DC=1.500 g/cm3 The crystal color of the material is light powder and nearly colorless; the structure of the material is represented by a mononuclear neutral complex, wherein Eu3+Is positioned in the center of the coordination environment, 3 trifluoromethyl substituted beta-diketone ligands TTolB and 1 Phen ligand are chelated at the periphery, and the four ligands are uniformly distributed in Eu3＋The periphery of (a); eu (Eu)3+The ions adopt an octa-coordination mode, and a dodecahedron configuration is formed by six coordination atoms O and two coordination atoms N; the molecular structure is shown as formula (I):
the luminescent material can emit red light by taking 610nm as the maximum emission peak under the excitation of ultraviolet light with different wavelengths, and can be used as a red light photoluminescence material or a luminescent layer material in a multilayer electroluminescent device.
2. The method for preparing the rare earth complex luminescent material according to claim 1, which comprises the steps of:
(1) Eu (NO) at room temperature3)3·6H2Dissolving O powder in acetonitrile;
(2) dissolving TTolB and sodium hydroxide powder in a mixed solvent of acetonitrile and water at room temperature;
(3) mixing the two solutions, and stirring to make them fully react to obtain a clear solution A;
(4) dissolving Phen powder in acetonitrile at room temperature, adding into the solution A, mixing and stirring to allow full coordination reaction to occur, and obtaining a turbid solution and a large amount of yellow pasty precipitate;
(5) filtering, washing filter residue and then drying to obtain a crystalline powder product; molar ratio Eu (NO) of the above three reactants3)3·6H2O, TTolB, Phen is 1: 3: 1.
3. The application of the paper-based rare earth complex fluorescent sensing film with sensitive and selective response to organic amine is characterized in that: the fluorescence sensing film is prepared by mixing rare earth complex luminescent material Eu (TTolB)3(Phen) dissolving and coating on test paper base paper; after the fluorescent sensing film is placed in an environment with organic amine, the red fluorescence intensity of the fluorescent sensing film is rapidly weakened along with time, the higher the concentration of the organic amine is, the stronger quenching response effect is shown, the fluorescent sensing performance of quick response and sensitive identification is shown, and the fluorescent sensing film can be used as a portable fluorescent sensing test paper device to be applied to convenient detection of the organic amine, wherein the organic amine is diisopropylamine, aniline or methylamine; wherein the structural formula of the rare earth complex luminescent material is Eu (TTolB) 3(Phen) wherein TTolB is 4, 4, 4-trifluoro-1- (p-tolyl) -1, 3-butanedione; wherein Phen is neutral heterocyclic ligand 1, 10-phenanthroline; the rare earth complex luminescent material is a triclinic system, P-1 space group, unit cell parameters a =11.218(5) a, b =17.526(5) a, c =25.792(8) a, α =77.299(10) ° β =82.047(17) ° γ =87.019(13) ° V =4898(3) a3，Z=2，DC=1.500 g/cm3 The crystal color of the material is light powder and nearly colorless; the material structure shows mononuclear neutralityComplex compound of which Eu3+Is positioned in the center of the coordination environment, 3 trifluoromethyl substituted beta-diketone ligands TTolB and 1 Phen ligand are chelated at the periphery, and the four ligands are uniformly distributed in Eu3＋The periphery of (a); eu (Eu)3+The ions adopt an octa-coordination mode, and a dodecahedron configuration is formed by six coordination atoms O and two coordination atoms N; the molecular structure is shown as formula (I):
4. the use according to claim 3, wherein the fluorescence sensing film is prepared by a method comprising the steps of:
(1) preparing a certain concentration Eu (TTolB) according to the quantity concentration of the substances3(Phen) in dichloromethane;
(2) adding a proper amount of methylene dichloride solution of PMMA into the solution A, and uniformly mixing to obtain a solution B;
(3) coating the solution B on a cellulose film in a manner of dip coating and the like, or designing the cellulose film into an array sensing film according to the concentration gradient difference, and drying the array sensing film to obtain the fluorescent sensing film device.
5. The application of the rare earth complex doped polymer-based fluorescent sensing film with sensitive and selective response to organic amine is characterized in that: the fluorescence sensing film is prepared by mixing rare earth complex luminescent material Eu (TTolB)3(Phen) dissolving, doping, mixing with polymethyl methacrylate, and coating; after the fluorescent sensing film is placed in an environment with organic amine, the red fluorescence intensity of the fluorescent sensing film is rapidly weakened along with time, the higher the concentration of the organic amine is, the stronger quenching response effect is shown, the fluorescent sensing performance of quick response and sensitive identification is shown, the fluorescent sensing film can be used as a sensitive film in a fluorescent sensor to be applied to the detection of the organic amine, and the optical fiber system is convenient to integrate and utilize, wherein the organic amine is diisopropylamine, aniline and methylamine; wherein the structural formula of the rare earth complex luminescent material is Eu (TTolB)3(Phen) wherein TTolB is 4, 4, 4-trifluoro-1- (p-tolyl) -1, 3-butanedione; wherein Phen is neutral heterocyclic ligand 1, 10-phenanthroline; the rare earth complex luminescent material is triclinic, a P-1 space group, and has unit cell parameters of a =11.218(5) A, b =17.526(5) A, c =25.792(8) A, α =77.299(10) °, β =82.047(17) °, γ =87.019(13) °, V =4898(3) A 3，Z=2，DC=1.500 g/cm3 The crystal color of the material is light powder and nearly colorless; the structure of the material is expressed as a mononuclear neutral complex, wherein Eu3+Is positioned in the center of the coordination environment, 3 trifluoromethyl substituted beta-diketone ligands TTolB and 1 Phen ligand are chelated at the periphery, and the four ligands are uniformly distributed in Eu3＋The periphery of (a); eu (Eu)3+The ions adopt an octa-coordination mode, and a dodecahedron configuration is formed by six coordination atoms O and two coordination atoms N; the molecular structure is shown as formula (I):
6. the use according to claim 5, wherein the method for preparing the fluorescence sensing film comprises the following steps:
(1) dissolving PMMA solid in dichloromethane at room temperature;
(2) at room temperature, mixing rare earth complex Eu (TTolB)3(Phen) powder dissolved in dichloromethane;
(3) mixing the two solutions, and stirring to mix them uniformly to obtain a clear solution A;
(4) and spin-coating the clear solution A on a quartz plate at room temperature, and drying to obtain the fluorescent sensing film.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103063705A (en) * | 2012-12-25 | 2013-04-24 | 华中农业大学 | Trimethylamine gas sensor and preparation method thereof |
| CN103694265A (en) * | 2013-12-31 | 2014-04-02 | 中国计量学院 | Novel light-emitting beta-diketone rare earth complex crystal form material |
| CN103694993A (en) * | 2013-12-31 | 2014-04-02 | 中国计量学院 | Beta-diketone rare earth complex red fluorescent material |
| CN106124466A (en) * | 2016-06-16 | 2016-11-16 | 陕西师范大学 | The application in detection aniline of the p-phthalic acid europium fluorescent probe containing 1 ethyl 3 Methylimidazole. |
| CN107089905A (en) * | 2017-03-14 | 2017-08-25 | 中山大学 | Triethylamine fluorescent optical sensor based on nanometer zeolite L rare-earth beta diketone complex hybrid material and its preparation method and application |
| CN109715618A (en) * | 2016-10-17 | 2019-05-03 | 新生命医药科技有限公司 | Urinary polyamine as prostate cancer detection biomarker |
-
2021
- 2021-06-04 CN CN202110623086.3A patent/CN113336779B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103063705A (en) * | 2012-12-25 | 2013-04-24 | 华中农业大学 | Trimethylamine gas sensor and preparation method thereof |
| CN103694265A (en) * | 2013-12-31 | 2014-04-02 | 中国计量学院 | Novel light-emitting beta-diketone rare earth complex crystal form material |
| CN103694993A (en) * | 2013-12-31 | 2014-04-02 | 中国计量学院 | Beta-diketone rare earth complex red fluorescent material |
| CN106124466A (en) * | 2016-06-16 | 2016-11-16 | 陕西师范大学 | The application in detection aniline of the p-phthalic acid europium fluorescent probe containing 1 ethyl 3 Methylimidazole. |
| CN109715618A (en) * | 2016-10-17 | 2019-05-03 | 新生命医药科技有限公司 | Urinary polyamine as prostate cancer detection biomarker |
| CN107089905A (en) * | 2017-03-14 | 2017-08-25 | 中山大学 | Triethylamine fluorescent optical sensor based on nanometer zeolite L rare-earth beta diketone complex hybrid material and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| A simple photoluminescent strategy for pH and amine vapors detection based on Eu(III)-complex functionalized material;Zhichao Zeng et al.;《RSC Adv.》;20160411;第6卷;第37385-37390页 * |
| Luminescent hybrid composites based on the intercalation of Eu(III) complexes into a-zirconium;Yali Li et al.;《New J. Chem.》;20170926;第41卷;第14103-14108页 * |
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