Dye/metal-organic framework composite material with second-order and third-order nonlinear optical properties and preparation method and application thereof

A third-order non-linear, optical performance technology, applied in the field of dyes/gold, can solve the problems of inapplicability, achieve the effects of increasing biocompatibility, avoiding fluorescence quenching, and improving luminous efficiency

Active Publication Date: 2020-05-19
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Traditional thermocouples and thermometers are not suitable for applicat

Method used

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  • Dye/metal-organic framework composite material with second-order and third-order nonlinear optical properties and preparation method and application thereof
  • Dye/metal-organic framework composite material with second-order and third-order nonlinear optical properties and preparation method and application thereof
  • Dye/metal-organic framework composite material with second-order and third-order nonlinear optical properties and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Synthesis of metals by solvothermal method using zinc nitrate and 4,4'-[[2,2-bis[(4-carboxyphenoxy)methyl]-1,3-propanediyl]bis(oxy)benzoic acid -Organic framework material, its specific synthetic route is as follows:

[0034] 1mmol of zinc nitrate and 1mmol of 4,4'-[[2,2-bis[(4-carboxyphenoxy)methyl]-1,3-propanediyl]bis(oxy)benzoic acid, 15mg cation The dye 4-(4-(dimethylamino)styryl)-1-ethylpyridine was dissolved in 4 mL DMF, 4 mL ethanol and 4 mL H 2 O mixed solvent, then the solution was packaged in a 20mL polytetrafluoroethylene reactor, and placed in an oven at 130°C for 5 days. Cool to room temperature and wash with DMF three times to obtain a two-photon dye-containing metal-organic framework material with a dye content of 8.45 wt%.

[0035] Under the excitation of 1064nm laser, the peak of the obtained emission spectrum is located at 532,599nm. As the temperature increases, the intensity ratio increases ( image 3 ). It can be fitted with the following formul...

Embodiment 2

[0043] Using zinc nitrate and 4',4"-[[2,2-bis[(4'-carboxy[1,1'-biphenyl]-4-yl)oxy]methyl]-1,3-propanediol] Bis(oxygen)]-bis-[1,1'-biphenyl]-4-carboxylic acid is used to synthesize metal-organic framework materials by solvothermal method, and its specific synthetic route is as follows:

[0044] 1 mmol of zinc nitrate and 1 mmol of 6,6'-[[2,2-bis[(6-carboxy-2-naphthyl)oxy]methyl]-1,3-propanediol]bis(oxygen)]-bis -2-Naphthoic acid, 15mg cationic dye 4-(4-(dimethylamino)styryl)-1-ethylpyridine dissolved in 4mL DMF, 4mL ethanol and 4mL H 2 O mixed solvent, then the solution was packaged in a 20mL polytetrafluoroethylene reactor, and placed in an oven at 130°C for 5 days. After cooling to room temperature, washing with DMF three times, the metal-organic framework material containing two-photon dye was obtained.

[0045] When the material is excited by a 1064nm laser, the peak of the emission spectrum is located at 532,599nm, and the intensity ratio increases with the increase of t...

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Abstract

The invention discloses a dye/metal-organic framework composite material with second-order and third-order nonlinear optical properties and a preparation method and self-calibration temperature sensing application thereof. The chemical formula is [M(L)x(G)y].(R)n, M is a metal ion, L is a flexible symmetrical organic ligand containing a carboxylic acid group, G is a solvent molecule, and R represents a dye molecule in a pore channel. Under the excitation of 900-1300 nm, the metal-organic framework generates second harmonics which are not sensitive to temperature; and two-photon fluorescence generated by the dye is quenched due to high-temperature fluorescence of the dye, so that the intensity is reduced along with temperature rise. The ratio of the two signal peaks is in linear relation with the temperature, the cycle performance is good, and the sensor can be effectively applied to physiological temperature sensing. The quantum efficiency and the thermal stability of the loaded dye are obviously improved, and the dye has high stability and good biocompatibility in aqueous solutions with different pH/temperatures and PBS physiological buffer solutions. The physiological temperaturesensing is realized by utilizing two nonlinear optical signals reported for the first time.

Description

technical field [0001] The invention relates to a dye / metal-organic framework composite material with second-order and third-order nonlinear optical properties. Under the excitation of 900-1300nm, metal-organic framework (MOFs) crystals can generate second harmonics ( SHG) and the intensity ratio of the signal peak of the two-photon fluorescence produced by the dye change with the increase of temperature, and there is a linear relationship, which can be effectively applied to physiological temperature sensing. And the material has excellent chemical stability. Background technique [0002] Compared with traditional sensing methods, optical-based sensors have attracted extensive attention from researchers due to their advantages such as fast response, high sensitivity, and low interference to strong electromagnetic fields. Compared with single-emission fluorescence, dual-emission fluorescence based on optical intensity has many advantages, such as being unaffected by probe c...

Claims

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Application Information

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IPC IPC(8): C09K11/02C09K11/06C08G83/00G01N21/64
CPCC08G83/008C09K11/02C09K11/06C09K2211/1007C09K2211/1014C09K2211/1029G01N21/6428G01N2021/6432G01N2021/6439
Inventor 崔元靖万雅婷钱国栋杨雨
Owner ZHEJIANG UNIV
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