Compound based on Rhodamine B and thiobisethylamine as well as preparation method and application thereof

A technology of aminoethyl sulfide and compounds, applied to the application of mercury ion probes in the detection of mercury ions, based on the field of rhodamine B and aminoethyl sulfide compounds and their preparation, can solve the problem of irreversible mercury ion reactions, Problems such as rare raw materials and difficult synthesis can achieve the effects of industrial application, mild reaction conditions and wide detection range

Active Publication Date: 2016-08-17
SUZHOU UNIV
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  • Abstract
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AI Technical Summary

Problems solved by technology

[0003] However, the reported rhodamine-based spectral probes have rare raw materials, complex structures, and difficult synthesis, and some can only detect Hg in pure organic solvents (such as absolute ethanol). 2+ , or the anti-interference ability and practicability are not good, and the rhodamine Hg with good comprehensive performance 2+ There are very few spectroscopic probes (see: Xu L, Wang S, Lv YN, Son YA, Cao DR. A highly selective and sensitive photo switchable fluorescent probe for Hg 2+ based on bisthienylethene-rhodamine 6G dyad and for live cells imaging. Spectrochim. Acta Part A 2014; 128: 567-574; Bhalla V, Tejpal R, Kumar M. Rhodamine appended terphenyl: A reversible “off-on” fluorescent chemosensor for mercury ions. Sens. Actuators B 2010; 151: 180-185; Zhang X, Zhu YY. A new fluorescent chemodosimeter for Hg 2+ -selective detection in aqueous solution based on Hg 2+ -promoted hydrolysis of rhodamine-glyoxylic acid conjugate. Sens. Actuators B 2014; 202: 609-614)
In addition, rhodamine Hg 2+ The conversion of the signal of the spectral probe is generally achieved by two methods, one is to add mercury ions, coordinate with the probe and induce the ring opening of the spironolactam, which often responds or delays the reaction to other metal cations; the other Mercury ions activate the thiocarbonyl stoichiometric reaction. The biggest problem is that the reaction of mercury ions is irreversible, so follow-up analysis cannot be performed, probes cannot be reused, and mercury ions cannot be recovered, making it impractical.

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  • Compound based on Rhodamine B and thiobisethylamine as well as preparation method and application thereof
  • Compound based on Rhodamine B and thiobisethylamine as well as preparation method and application thereof
  • Compound based on Rhodamine B and thiobisethylamine as well as preparation method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] Embodiment one: Hg 2+ Preparation of probe RMTE

[0034] According to the ratio of raw materials in Table 1 (molar ratio of rhodamine B and aminoethyl sulfide) and reaction conditions, with dichloromethane as solvent, N,N-diisopropylethylamine as additive, in N 2 Under protection, stir the reaction, cool to room temperature, remove the solvent by rotary evaporation, and separate by column chromatography, the eluent is methanol / chloroform / petroleum ether, 1 / 12 / 2 (v / v / v), dried to obtain Target product RMTE as yellow solid powder.

[0035] NMR, 1 H NMR (400 MHz, CDCl 3 ), δ / ppm: 1.16 ( t , 12H, J=6.8 Hz), 2.23 ( t , 2H, J=8 Hz), 2.50 ( t , 2H, J=6.4 Hz), 2.77 ( t , 2H, J=6.4 Hz), 3.27–2.37 ( m , 10H), 3.66 (s, 2H), 6.27 ( d , 2H, J=6.4 Hz), 6.37 ( d , 2H, J=2.4 Hz), 6.44 ( s , 2H), 7.08–7.10 ( m , 1H), 7.43–7.46 ( m , 2H), 7.89–7.91 ( m , 1H), 13 C NMR (300 MHz, CDCl 3 ), Δ / PPM: 12.35, 29.37, 34.71, 40.24, 40.83, 44.31, 64.69, 97.34, 105.62, 107.96, 122....

Embodiment 2

[0038] Embodiment two: RMTE to Hg 2+ the response to

[0039] CH at RMTE 3 Add Hg to CN / HEPES buffer solution (1 / 1, v / v, pH=7.05) 2+ , measure the UV-Vis absorption spectrum and fluorescence spectrum before and after adding ions, the results are shown in Figure 1, solvent: CH 3 CN / HEPES buffer solution (1 / 1, v / v, pH=7.05), concentration: 20 μM (RMTE), 200 μM (Hg 2+ ). Excitation wavelength: 520 nm, slit width: 5 nm. Hg 2+ The addition of a new absorption peak at 560 nm in the UV-Vis absorption spectrum of RMTE (Figure 1 left panel), the fluorescence was significantly enhanced by 33.9 times (Figure 1 right panel).

[0040] CH at RMTE 3 Add Hg to CN / HEPES buffer solution (2 / 8, v / v, pH=7.05) 2+ , measure the UV-Vis absorption spectrum and fluorescence spectrum before and after adding ions, the results are shown in Figure 2, solvent: CH 3 CN / HEPES buffer solution (2 / 8, v / v, pH=7.05), concentration: 20 μM (RMTE), 200 μM (Hg 2+ ). Excitation wavelength: 520 nm, slit width...

Embodiment 3

[0043] Embodiment three: RMTE and Hg 2+ concentration relationship

[0044] Figure 4 shows the samples containing different concentrations of Hg 2+ UV-Vis absorption spectrum (left) and fluorescence spectrum (right) of RMTE solution, solvent: CH 3 CN / HEPES buffer solution (1 / 99, v / v, pH=7.05), concentration: 20 μM (RMTE), Hg 2+ Concentrations from bottom to top are 0, 10, 20, 30, 40, 60, 80, 100, 120, 140, 160, 180 and 200 μM, insets are RMTE absorbance (A) and Hg at 561 nm, respectively 2+ The relationship between concentration and RMTE fluorescence intensity (F) at 578 nm vs. Hg 2+ The relationship between concentration, excitation wavelength: 520 nm, slit width: 5 nm. As can be seen from the left figure of Figure 4, with the Hg 2+ As the concentration increases, the absorbance of RMTE at 561 nm first increases and then tends to be stable. in Hg 2+ In a wide range of concentrations, the absorbance A and Hg 2+ The concentration has a good linear relationship, and the ...

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Abstract

The invention discloses a compound based on Rhodamine B and thiobisethylamine as well as a preparation method and application thereof, in particular to a novel Rhodamine Hg2+colorimetric and fluorescent probe with excellent comprehensive performances and a reversible sensing mechanism. The novel Rhodamine Hg2+ colorimetric and fluorescent probe has the excellent comprehensive performances that raw materials are easy to obtain, a synthetic method is simple, and a molecular structure is simple; the selectivity for Hg2+ is good, the sensitivity is high, the anti-interference ability is strong, and the cytotoxicity is small; the detection can be performed in an almost pure water buffer solution close to neutral; Hg2+ in a pond and a tap water sample can be effectively detected; Hg2+ in HgCl2 can be detected; as a molecule contains an aliphatic primary amino group, the self modification or the modification of other materials can be further performed.

Description

technical field [0001] The invention belongs to the technical field of heavy metal ion probes, in particular to a compound based on rhodamine B and aminoethyl sulfide, a preparation method thereof, and the application of the compound as a mercury ion probe in detecting mercury ions. Background technique [0002] Mercury is the second most common toxic heavy metal. Whether it is elemental mercury, inorganic mercury, or organic mercury, it can damage organs such as the kidney, central nervous system, and brain, leading to cognitive and motor dysfunction, and even cancer. If mercury and its compounds exist in natural water bodies, they can easily pollute the water environment and cause harm to a wide range of people. Hg 2+ The most common form of mercury contamination, it is highly water soluble, so its detection is critical. Spectral probes have attracted much attention due to their advantages of simple operation, rapid detection sensitivity, high selectivity, and low cost. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D491/107C09K11/06G01N21/64G01N21/78
CPCC07D491/107C09K11/06C09K2211/1029C09K2211/1088G01N21/643G01N21/78
Inventor 徐冬梅洪苗苗
Owner SUZHOU UNIV
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