Three europium-terbium co-doped fluorescent probes based on different carboxylic acid ligands and application of film in temperature sensing

A fluorescent probe, europium and terbium technology, applied in the field of temperature sensing, can solve the problems of different fluorescence quenching efficiencies

Active Publication Date: 2020-08-14
烟台希尔德材料科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Therefore, for the co-doped fluorescent probe prepared by using two different lanthanide metals, when the external temperature rises, the energy of the ligands to the different lanthanide metal atoms changes, resulting in different fluorescence quenching efficiencies of the two lanthanide metals.

Method used

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  • Three europium-terbium co-doped fluorescent probes based on different carboxylic acid ligands and application of film in temperature sensing
  • Three europium-terbium co-doped fluorescent probes based on different carboxylic acid ligands and application of film in temperature sensing
  • Three europium-terbium co-doped fluorescent probes based on different carboxylic acid ligands and application of film in temperature sensing

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] 0.00785g (0.0214 mmol) EuCl 3 ·6H 2 O, 0.5521 g (1.478 mmol) of TbCl 3 ·6H 2 O, 0.0646 g (0.25 mmol) of 4,4´-dicarboxydiphenyl ether and 0.8 mL of 1-butyl-3-methylimidazolium iodide ionic liquid were added to a 25 mL Teflon-lined reactor and mixed well , then put the reaction kettle in an oven, react at 180 ℃ for 3 days, cool to room temperature, wash with acetone and ethanol, and obtain a colorless and transparent hexagonal Co-doped fluorescent probes. Such as figure 1 As shown, its structural unit is [Eu 0.0143 Tb 0.9857 (OBA)(H 2 O)Cl], where OBA represents the 4,4´-dicarboxydiphenylether root that has lost protons on the two carboxyl groups. The fluorescent probe belongs to the monoclinic crystal system, and the space group is P 2 1 / n, a = 15.3579Å, b = 11.1607Å, c = 8.4026Å, α = γ = 90°, β = 97.739(1)°, V = 1427.13Å 3 , Z=4.

[0039] The inventors used the solid-state fluorescence detection method to excite the above-mentioned fluorescent probes at 280n...

Embodiment 2

[0042] Fully grind 0.0150g of the 4,4´-dicarboxydiphenyl ether-europium-terbium co-doped fluorescent probe obtained in Example 1, weigh 0.0080g of maltose-modified polylactic acid, put it in a 7mL glass vial, and stir for half an hour After the maltose-modified polylactic acid is completely dissolved, add the ground sample into the maltose-modified polylactic acid solution and continue to stir for ten minutes. Use a dropper to absorb the solution and drop it on a glass plate to dry naturally to obtain Diphenyl ether-europium and terbium co-doped probe films.

Embodiment 3

[0044] Application of 4,4'-dicarboxydiphenyl ether-europium and terbium co-doped fluorescent probe film for temperature sensing in Example 2

[0045] 1. Iron plate simple analog temperature sensor

[0046] The 4,4´-dicarboxydiphenyl ether-europium-terbium co-doped fluorescent probe film was placed on the iron plate to form a simple analog temperature sensor. Use a lighter to heat the fluorescent probe film on the iron plate, and irradiate it with an ultraviolet lamp to observe the luminescent phenomenon of the fluorescent probe film. The initial fluorescent probe film emits relatively strong yellow light. After heating for about 18 seconds, the yellow light emitted by the analog temperature sensor gradually weakens until it finally turns green; then, remove the lighter and continue to use the ultraviolet lamp After irradiation, the green light emitted by the analog temperature sensor on the iron plate slowly returns to the original yellow color. This recovery process takes a...

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Abstract

The invention discloses three europium-terbium co-doped fluorescent probes based on different carboxylic acid ligands and application of a film in temperature sensing. The three probes all have excellent yellow fluorescence properties at normal temperature. The probe 1 is [Eu0. 0143Tb0. 9857 (OBA) (H2O) Cl], and OBA represents 4, 4'-dicarboxyl diphenyl ether radicals without protons on two carboxyl groups. The probe 2 is [Eu0.0167Tb0.0.0.9833 (BDC) (H2O) Cl], and BDC represents terephthalic acid radicals of which two carboxyl groups lose protons. The probe 3 is [PMI] 2 [Eu0.0012Tb0.9988 (BPDC)3Cl2], PMI represents 1-propyl-3-methylimidazole monovalent cations, and BPDC represents 4, 4'-biphenyl dicarboxylate with two carboxyl groups losing protons. When the temperature rises from 25 DEG Cto 200 DEG C, the fluorescence of the probe 1 gradually changes from yellow to green, the fluorescence of the probe 2 gradually changes from yellow to red, and the fluorescence of the probe 3 gradually changes from yellow to red and is finally completely quenched. When the temperature is reduced from 200 DEG C to 25 DEG C, the fluorescence of the probe 1 is recovered from green to yellow, and thefluorescence of the probe 2 is recovered from red to yellow; the fluorescence of the probe 3 is recovered from quenching to yellow. And the sensing film based on the three probes can be used for a visual temperature sensor.

Description

technical field [0001] The invention belongs to the field of temperature sensing, and specifically relates to three kinds of sensors based on 4,4´-dicarboxydiphenyl ether-europium-terbium co-doped, terephthalic acid-europium-terbium co-doped with 4,4´-biphenyl dicarboxylic acid-terbium Europium and terbium co-doped fluorescent probes, and the application of thin films based on three fluorescent probes in temperature sensing. Background technique [0002] Temperature is a fundamental thermodynamic variable and it is one of the most commonly measured physical parameters in many fields. The rapid and accurate measurement of temperature is crucial in all aspects of social life, and high-precision temperature sensing detection has attracted more and more attention, especially in controlled manufacturing, micro-area environmental monitoring and production safety systems. However, traditional physical temperature probes, such as thermocouples and thermometers, have certain limitat...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C09K11/06C07F5/00G01K11/32G01K11/16
CPCC09K11/06C07F5/003G01K11/32C09K2211/182
Inventor 徐玲李鸿刘冰焦桓
Owner 烟台希尔德材料科技有限公司
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