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Rate type difunctional fluorescence molecular probe for detecting HSO4- ions, SO2 and derivatives thereof

A fluorescent molecular probe, SO2 technology, applied in the field of analytical chemistry, can solve the problems of difficult separation and purification, slow development of multifunctional probes, and high preparation costs

Inactive Publication Date: 2017-03-22
HUNAN NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Among the reported papers and patents, the SO 2 The detection methods of derivatives are in the majority (synthesis and fluorescence properties research of coumarin bisulfite ion probe, Peng Mengjiao, Guo Yuan. Fine Chemical Industry, 2011., Chinese patent CN104804729 A, Chinese patent CN 104262287 A), and patent Reported detection of HSO 4 - However, the method is rare, such as Chinese patent CN 102746452 A, but its synthesis steps are many, separation and purification are difficult, and the preparation cost is high
Among the reported fluorescence analysis methods, the ratiometric fluorescent probes that are less affected by the concentration and can effectively eliminate the influence of microenvironmental changes are only a minority, and the detection of HSO 4 - and SO 2 Different analysis methods or different single-functional fluorescent probes should be used for detection of its derivatives. Multi-functional fluorescent probes refer to the use of one kind of fluorescence to specifically identify different objects and generate different fluorescent signals. Up to now, the development of multifunctional probes has been slow, and few reports have been reported, while the ratiometric detection of HSO based on the same probe 4 - and SO 2 And its derivatives and non-interfering bifunctional probes have not been reported

Method used

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  • Rate type difunctional fluorescence molecular probe for detecting HSO4- ions, SO2 and derivatives thereof
  • Rate type difunctional fluorescence molecular probe for detecting HSO4- ions, SO2 and derivatives thereof
  • Rate type difunctional fluorescence molecular probe for detecting HSO4- ions, SO2 and derivatives thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Example 1 Synthesis of 3-ethyl-1,1,2-trimethyl-1H-benzo[e]indol-3-ium iodide.

[0031] Add 10 g (47.78 mmol) of 1,1,2-trimethyl-1H-benzo[e]indole and 8.94 g (57.34 mmol) of ethyl iodide in a 100 mL round bottom flask, 40 mL of acetonitrile, and load Reflux the condenser, heat and stir to reflux for 20 hours; cool the reaction solution to room temperature, filter, wash the filter cake with ether, and dry in vacuo to obtain 3-ethyl-1,1,2-trimethyl-1H-benzo[e ] Indol-3-ium iodide 14.6 g (83.7% yield).

Embodiment 2

[0032] Example 2 Synthesis of 3-ethyl-2-(4-hydroxystyryl)-1,1-dimethyl-1H-benzo[e]indol-3-ium iodide

[0033] Into a 25 mL round bottom flask was added 3.0 g (8.21 mmol) 3-ethyl-1,1,2-trimethyl-1H-benzo[e]indol-3-ium iodide and 1.2 g (9.86 mmol) Dissolve p-hydroxybenzaldehyde in 15 mL of absolute ethanol, add 3-4 drops of piperidine or pyrrolidine, and stir at room temperature for 12 hours; filter the reaction solution, wash with ethanol, and dry in vacuum to obtain the fluorescent molecular probe compound 2.98 of the present invention. g (77.2% yield). 1 H NMR (500 MHz, DMSO- d 6 ) δ 8.55 - 8.43 (d, J = 16.1Hz, 1H), 8.43 - 8.37 (d, J = 8.5 Hz, 1H), 8.31 - 8.25 (d, J = 9.0 Hz, 1H),8.24 - 8.18 (d, J = 8.2 Hz, 1H), 8.18 - 8.12 (d, J = 8.8 Hz, 2H), 8.11 - 8.03(d, J = 8.9 Hz, 1H), 7.83 – 7.76 (ddd, J = 8.4, 6.9, 1.3 Hz, 1H), 7.73 - 7.66(t, J = 7.5 Hz, 1H), 7.54 - 7.40 (d, J = 16.1 Hz, 1H), 7.00 - 6.89 (d, J =8.4 Hz, 2H), 5.10 - 4.48 (q, J = 7.2 Hz, 2H), 2.2...

Embodiment 3

[0034] Example 3 Dual-functional probes in the detection of HSO 4 - Applications in ions.

[0035] Spectral property experiment of fluorescent molecular probes according to the present invention: dissolving the probes in dimethyl sulfoxide (DMSO) to configure 1 mM probe solutions, and configuring 1 mM NaHSO respectively 4 aqueous solution and Na 2 SO 3 Aqueous solution, and 10 mM interfering ion aqueous solution, all tests are tested at room temperature with a volume ratio of organic phase to aqueous phase of 8:2, the organic phase is dimethyl sulfoxide (DMSO) with 1 mM probe solution and detection The ethanol added at the time, the water phase is HSO 4 - and SO 2 Aqueous solution and deionized water added during detection. The specific test method is: take 20 μL of 1 mM probe solution, 1580 μL of analytical pure ethanol, 20 μL of 1mM NaHSO 4 Water solution and 380 μL deionized water solution were placed in a 2 mL sample tube, and the changes in UV absorption and fluor...

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Abstract

The invention provides a rate type difunctional fluorescence molecular probe for detecting HSO4- ions, SO2 and derivatives thereof. A rate type fluorescence probe can utilize different reaction mechanisms and fluorescence signals under a same detection condition to respectively detect HSO4- ions, SO2 and derivatives thereof; after HSO4- is added, the ultraviolet spectrum blue shift is 99nm, the fluorescence spectrum is in rate type change and the color of the probe solution is changed from red to yellow; after Na2SO3 is added, two new ultraviolet absorption peaks are generated, the fluorescence spectrum is obviously changed and the color of the probe is changed from red to white, so that the distinctive detection for HSO4- ions, SO2 and derivatives thereof is realized. The difunctional probe has ultrahigh sensitivity and ultralow limit of detection for HSO4- ions, SO2 and derivatives thereof; the preparation cost is low; the difunctional fluorescence probe for respectively detecting HSO4- ions, SO2 and derivatives thereof on the basis of different mechanisms of the same probe for different detected objects is rarely reported; the rate type difunctional fluorescence molecular probe has an ultrahigh application value in the fields of biological chemistry, analysis and detection, and the like.

Description

technical field [0001] The invention belongs to the technical field of analytical chemistry, in particular to a ratio-type HSO 4 - and SO 2 Synthesis of bifunctional fluorescent molecular probes and their derivatives, and the differential detection of HSO in the environment and cells by the probes 4 - ions and SO 2 and its derivatives applications. Background technique [0002] Among the many important anions, bisulfate (HSO 4 - ) has been valued because of its important role in biology. This amphiphilic anion can dissociate at high pH to produce toxic and corrosive sulfate anion (SO 4 2- ), strongly irritating and corrosive to eyes, skin, mucous membranes and upper respiratory props (Spectrochimica Acta Part a-Molecular and Biomolecular Spectroscopy.2016. 169. 38-44). Sulfites have been widely used in food and beverage processing as preservatives because of their ability to inhibit microbial growth and prevent discoloration. However, excess sulfites can induce con...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D209/60C09K11/06G01N21/64
CPCC07D209/60C09K11/06C09K2211/1029G01N21/643G01N21/6486
Inventor 尹鹏尹国兴李海涛喻婷曾盈张友玉
Owner HUNAN NORMAL UNIVERSITY
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