Large Stokes shift and near infrared fluorescence emitting new rhodamine fluorescent dye and synthetic method thereof

A technology of Stokes and fluorescent dyes, which is applied in the field of new rhodamine-based fluorescent dyes and their synthesis, which can solve the problems of complex dye synthesis, staying in the stage of small amount of preparation in the laboratory, and small Stokes shift, and achieve the goal of synthesis The effect of simple steps, cheap raw materials, and easy products

Active Publication Date: 2015-06-17
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] At present, the emission wavelength of commercial rhodamine fluorophores is mostly less than 600nm, and there are few red or near-infrared rhodamine dyes with a fluorescence peak above 600nm in literature reports, and the synthesis of these dyes is relatively complicated, and most of them stay in the laboratory A small amount of preparation stage, and also has the disadvantage of small Stokes shift of traditional xanthene fluorescent dyes (~20nm) (Yuichiro Koide, YasuteruUrano, Kenjiro Hanaoka, Wen Piao, MoriakiKusakabe, Nae Saito, Takuya Terai, Takayoshi Okabe, and Tetsuo Nagano, J. Am. Chem. Soc., 2012, 134(11), 5029-5031)

Method used

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  • Large Stokes shift and near infrared fluorescence emitting new rhodamine fluorescent dye and synthetic method thereof
  • Large Stokes shift and near infrared fluorescence emitting new rhodamine fluorescent dye and synthetic method thereof
  • Large Stokes shift and near infrared fluorescence emitting new rhodamine fluorescent dye and synthetic method thereof

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Effect test

Embodiment 1

[0055] 1. Synthesis of intermediate 4-methoxy-1,2-o-phenylenediamine

[0056]

[0057] 4-Methoxy-2-nitroaniline (16.8g, 0.1mol) was dissolved in 200mL of methanol, 1.68g of palladium carbon and 22mL of hydrazine hydrate were added, and reacted at 60°C for 6 hours to obtain the red oily intermediate 4-methoxy- 1,2-o-phenylenediamine.

[0058] 2. Synthesis of intermediate 6-methoxyquinoxaline

[0059]

[0060] Dissolve 4-methoxy-1,2-o-phenylenediamine in 350mL of acetonitrile, add dropwise 32mL of 40% aqueous solution of glyoxal, react at 60°C for 6 hours, evaporate the solvent, and collect the distillate by vacuum distillation or column chromatography. Yellow needle intermediate 6-methoxyquinoxaline.

[0061] 3. Synthesis of intermediate 1,4-diethyl-6-methoxy-1,2,3,4-tetrahydroquinoxaline

[0062]

[0063] 6-Methoxyquinoxaline (5.5g, 0.034mol) was dissolved in 150mL of anhydrous toluene, sodium borohydride (13.2g, 0.35mol) was slowly added at 5°C, and then glacial a...

Embodiment 2

[0071] Embodiment 2: Spectral properties of rhodamine dyes in different solvents

[0072] 1. Absorption spectra of rhodamine dyes in different solvents

[0073] Take 17.1mg rhodamine dye and dissolve it in 7.07mL DMSO to make a concentration of 5mmol L -1 mother liquor. Pipette 8 μL of mother liquor into a sample bottle, and make 4 mL of solution with different solvents, the concentration is 10 μmol L -1 . Determination of the absorption spectra of rhodamine dyes in different solvents as attached Figure 4 shown. It can be seen from the figure that the rhodamine dye has a large absorbance in polar solvents, and the molar extinction coefficient (ε) of the dye in the aqueous solution is 34486mol -1 ·L·cm -1 .

[0074] 2. Fluorescence emission spectra of rhodamine dyes in different solvents

[0075] Determination of 10μmol·L in different solvents -1 The fluorescence emission spectrum of the rhodamine solution is attached Figure 5 shown. It can be seen from the figure ...

Embodiment 3

[0076] Embodiment 3: Spectral properties of rhodamine dyes in different pH aqueous solutions

[0077] 1. Absorption spectra of rhodamine dyes in different pH aqueous solutions

[0078] Pipette 8 μL to a concentration of 5mmol·L -1 The mother liquor into the sample bottle, made into aqueous solutions with different pH values, the concentration is 10μmol L -1 . Determination of the absorption spectra of rhodamine dyes in different pH solutions as attached Image 6 shown. It can be seen from the figure that the configuration of rhodamine dyes changes when pH=1-3, and the configuration is relatively stable in aqueous solutions with pH≥4.

[0079] 2. Fluorescence emission spectra of rhodamine dyes in different pH aqueous solutions

[0080] Under the irradiation of 578nm excitation light, measure 10 μmol L in different pH solutions -1 The fluorescence emission spectrum of rhodamine dye is attached Figure 7 shown. It can be seen from the figure that pH has little effect on f...

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Abstract

The invention discloses a large Stokes shift shift and near infrared fluorescence emitting new rhodamine fluorescent dye and a synthetic method thereof, an intermediate can be obtained by catalytic hydrogenation reduction, oxalaldehyde condensation, sodium borohydride reduction, Vilsmeier formolation, acid catalyzed demethylation and other reaction, the intermediate is reacted with diphenyl keto acid to obtain the target product rhodamine fluorescent dye. Compared with fluorescent dyes in the prior art, the new rhodamine fluorescent dye prepared by the synthetic method has high light stability, the fluorescence emission wavelength is in the near infrared region (-700 nm), and the new rhodamine fluorescent dye has a large Stokes shift (-100 nm) and higher fluorescence quantum yield (0.28), and can be used in luminescent materials, biological fluorescence probes and fluorescence imaging and other fields.

Description

technical field [0001] The invention belongs to the field of fluorescent dyes, and in particular relates to a novel rhodamine-based fluorescent dye with large Stokes shift and near-infrared fluorescence emission and a synthesis method thereof. Background technique [0002] Fluorescence detection has the characteristics of high sensitivity and high selectivity. It has been developed rapidly in the fields of chemistry, environmental science and biomedicine in the past 20 years, and has become the preferred tool for microenvironment detection in biological and medical research. Compared with radioactive substance tracking methods, fluorescent probes are more friendly to organisms and the environment. Fluorescence detection technology has many advantages and plays an important role in the fields of biotechnology, flow cytometry, drug metabolism research, DNA sequencing and gene analysis. [0003] Rhodamine fluorescent dye is a basic dye based on xanthene. The maximum absorption...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C09B57/00C07D491/052C09K11/06G01N21/64
Inventor 徐兆超尹文婷刘晓刚
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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