CN113045538B - Salicylol thiol fluorescent probe and preparation method and application thereof - Google Patents
Salicylol thiol fluorescent probe and preparation method and application thereof Download PDFInfo
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- CN113045538B CN113045538B CN202110310214.9A CN202110310214A CN113045538B CN 113045538 B CN113045538 B CN 113045538B CN 202110310214 A CN202110310214 A CN 202110310214A CN 113045538 B CN113045538 B CN 113045538B
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Abstract
The invention belongs to the field of fluorescent probes, and particularly relates to a salicylaldehyde thiol fluorescent probe as well as a preparation method and application thereof. The structural formula of the fluorescent probe is as follows:
the salicylaldehyde thiol fluorescent probe provided by the invention is used for detecting Hg2+Has strong selectivity and specificity, higher detection sensitivity, is suitable for trace detection and has important significance in the aspect of chemical analysis and detection.
Description
Technical Field
The invention belongs to the field of fluorescent probes, and particularly relates to a salicylaldehyde thiol fluorescent probe as well as a preparation method and application thereof.
Background
Mercury is a heavy metal which seriously harms human health, and is one of the most interesting environmental pollutants in the world at present due to the permanence, easy mobility and high biological enrichment. At present, the industries for generating mercury-containing waste in China comprise calcium carbide-process PVC production, non-ferrous metal smelting (copper, lead and zinc), coal-fired power plants, cement production, natural gas production, battery production and the like, wherein the waste residue and smoke dust generated in the smelting process possibly contain mercury due to the associated metal mercury contained in the concentrate, and the mercury is also contained in the by-product sulfuric acid, the discharged tail gas and the waste water as well as the waste residue generated in an electrolysis workshop.
The mercury-containing waste is generally managed according to dangerous solid waste, but can be managed according to the common solid waste after metal recovery or mercury removal treatment, so that the production cost of enterprises is reduced. Therefore, the rapid and accurate detection of the mercury in the mercury-containing waste can effectively improve the accurate management of the solid waste.
The traditional mercury ion detection method has the problems of expensive instrument, long analysis period, complex sample pretreatment, high detection cost and the like, and is difficult to adapt to the requirements of convenience, rapidness, sensitivity and the like of rapid detection of mercury ions. The fluorescence analysis probe method is widely applied to the fields of life science, environmental science and the like as a mercury ion detection method with high selectivity and high sensitivity, and is an important development direction in the field of mercury ion detection research. The fluorescent molecular probe prepared by utilizing the fluorescence characteristic of a substance and the selection specificity of mercury ions can better realize the rapid and simple detection of the mercury ions.
Hg2+There are two main types of small molecule fluorescent probes: (1) a coordination-type probe; (2) a reaction type probe. Both probes can cause the corresponding change of the fluorescence spectrum so as to achieve the purpose of detecting Hg2+The purpose of (1). The coordination type fluorescent probe has low selectivity, large background interference, strong solvation effect in water and the like, so that the application of the fluorescent probe in the aspect of environment is greatly limited. Chemometrics based on the mechanism of mercury ion-induced specific chemical reaction, such probes consisting of Hg only for fluorescence and colorimetric signal output2+Promotes specific chemical reaction, thereby avoiding the negative effects of light signal output induced by other similar chemical ions, and the fluorescent probe is usually used for detecting Hg2+Provides high selectivity and high sensitivity and is widely concerned by researchers.
Disclosure of Invention
The invention aims to provide a salicylaldehyde thiol fluorescent probe for Hg2+Has extremely strong selectivity and specificity.
The second object of the present invention is to provide a method for preparing the above-mentioned salicylaldehyde thiol fluorescent probe.
The third purpose of the invention is to provide the application of the salicylaldehyde thiol fluorescent probe.
In order to realize the purpose, the technical scheme of the salicylaldehyde thiol fluorescent probe is as follows:
a salicylaldehyde thiol fluorescent probe has a structural formula as follows:
the salicylaldehyde thiol fluorescent probe disclosed by the invention is used for detecting Hg2+Has strong selectivity and specificity, higher detection sensitivity, is suitable for trace detection and has important significance in the aspect of chemical analysis and detection.
The technical scheme of the preparation method of the salicylaldehyde thiol fluorescent probe provided by the invention is as follows:
the preparation method of the salicylaldehyde thiol fluorescent probe comprises the following steps: 4-diethylamino salicylaldehyde and 1, 3-propanedithiol react in a solvent in the presence of a catalyst, and the product is purified and then treated.
The preparation method of the salicylaldehyde thiol fluorescent probe synthesizes the fluorescent probe through one-step reaction, the raw materials are easy to obtain, and the synthesis process is simple.
To further improve the yield, the preferred molar ratio of 4-diethylamino salicylaldehyde to 1, 3-propanedithiol is 1: 3.2.
Preferably, the catalyst is boron trifluoride diethyl etherate, and the molar ratio of the 4-diethylamino salicylaldehyde to the boron trifluoride etherate is 1: 1.3.
In view of environmental protection and reaction effect, the solvent is preferably dichloromethane.
Preferably, the reaction is carried out at room temperature for 4 h.
Preferably, the purification post-treatment comprises the following steps: adjusting pH to 8-9 with saturated sodium bicarbonate solution, adding dichloromethane for extraction, collecting organic phase, distilling under reduced pressure to remove solvent, and recrystallizing with mixed solvent composed of toluene and cyclohexane. More preferably, the volume ratio of toluene to cyclohexane in the mixed solvent is 1:3. The purification post-treatment mode has simple process and good purification effect.
The technical scheme of the application of the salicylaldehyde thiol fluorescent probe provided by the invention is as follows:
the salicylaldehyde thiol fluorescent probe is used for detecting Hg2+The use of (1).
Experiments prove that the salicylidene thiol fluorescent probe can be prepared in a citric acid buffer solution with the pH value of 6.0: p-Hg in CH3CN ═ 1:1(V: V) solution2+The detection has the advantages of high sensitivity, good selectivity and the like.
Preferably, Hg is detected by fluorescence spectroscopy in a solution containing a salicylaldehyde thiol fluorescent probe2+。
Drawings
FIG. 1 is a high resolution HR-MS chart of the fluorescent probe L identification mechanism validation of the present invention;
FIG. 2 is a graph showing the selective recognition of different metal ions by the fluorescent probe L of the present invention;
FIG. 3 shows Hg recognition by fluorescent probe L in the present invention2+The metal cation interference resistance diagram has an excitation wavelength of 310nm and an emission wavelength of 361 nm;
FIG. 4 is a graph showing a fluorescence titration of a fluorescent probe L in the present invention;
FIG. 5 shows the L pair of Hg fluorescent probes at λ 310nm in the present invention2+Working curve diagram of (2).
Detailed Description
In the invention, the reaction process for preparing the salicylaldehyde thiol fluorescent probe by using the 4-diethylamino salicylaldehyde and the 1, 3-propanedithiol is as follows:
the salicylidene thiol fluorescent probe is prepared by the following steps in a citric acid buffer solution: CH (CH)3To Hg in CN ═ 1:1(V: V) solution2+Has high-efficiency and sensitive specific detection capability.
From the above experimental results such as the fluorescence spectrum study, it is presumed that the probe L recognizes Hg2+The possible mechanism of (a) is shown in the following reaction scheme:
hg is added into the detection solution of the probe L2+Due to Hg2+The product 1 is hydrolyzed into salicylaldehyde derivative 1 by reacting with thiol in molecular structure, quenched by fluorescence, and confirmed by HR-MS (attached figure 1).
The experimental results in FIG. 1 show that the theoretical calculation of molecular weight for Compound 1 is 216.0990, Probe L and Hg2+The HR-MS result of the reaction product of (3) is shown as 216.0992. This data confirms the mechanism of action shown in the above equation.
The following further describes embodiments of the present invention with reference to the drawings and specific examples.
First, specific examples of the salicylaldehyde thiol fluorescent probe of the present invention
Example 1
The salicylaldehyde thiol fluorescent probe of the embodiment has the following structural formula:
second, specific examples of the preparation method of salicylaldehyde thiol fluorescent probe of the present invention
Example 2
The preparation method of the salicylaldehyde thiol fluorescent probe in this example is described as the preparation of the fluorescent probe in example 1, and specifically includes the following steps:
in a 100ml round bottom flask, 4-diethylaminosalicylaldehyde (387mg,2mmol),1, 3-propanedithiol (692mg,6.4mmol,3.2eq) and 50ml of anhydrous dichloromethane were charged and dissolved, boron trifluoride diethyl ether (369mg,2.6mmol,1.3eq) was added with stirring to react at room temperature for 4 hours, after completion of the reaction, the pH was adjusted to 8 to 9 with a saturated sodium bicarbonate solution, extraction was carried out 3 times with dichloromethane, the organic phase was collected, the solvent was distilled off under reduced pressure, and then recrystallization was carried out with a mixed solvent of toluene/cyclohexane (the volume ratio of toluene to cyclohexane was 1:3) to obtain a pale yellow solid (hereinafter referred to as probe L).
The nuclear magnetism of the obtained product is characterized as follows:1H NMR(300MHz,CDCl3,δ):l.14(6H,t),l.90(1H,dtt),2.15(1H,dtt),2.89(2H,dt),3.04(2H,brt),5.30(1H,s),6.16-6.78(2H,m)6.35(1H,brs),7.04(1H,dd)；13CNMR(75MHz,CDCl3δ):12.58,24.79,31.78,44.23,47.42,99.77,104.19,109.90,129.88,149.54,155.95.
third, the invention relates to the application of salicylaldehyde thiol fluorescent probe
EXAMPLE 1 specific selectivity test
Preparing a metal inorganic salt solution: accurately weighing the corresponding metal salt KNO3，Na NO3，Ca(NO3)2，Mg(NO3)2，Ba(NO3)2，Zn(NO3)2，Fe(NO3)2，Fe(NO3)2，Mn(NO3)2，Cu(NO3)2，Co(NO3)2，Ni(NO3)2，Hg(NO3)2Dissolving in high-purity water to prepare a solution with the metal ion concentration of 10mM for later use.
1mM probe solution preparation: the corresponding probes L were accurately weighed and dissolved in DMSO to prepare a 1mM fluorescent probe solution for use.
The fluorescence selectivity was tested using a fluorescence spectrometer, as shown in fig. 2, with probe L alone (final concentration controlled at 10 μ M) in citrate buffer (pH 6.0, the same applies below): CH (CH)3CN is 1:1(V: V) solution with certain fluorescence emission intensity when Hg is added2+After (10eq), the fluorescence emission intensity was quenched, but when other metal ions were added (to control the final concentration to 100. mu.M), the fluorescence intensity was not significantly changed. The experimental results show that the probe has good specific selectivity on mercury ions.
Experimental example 2 fluorescence interference Performance experiment
The experimental examples respectively test the interference of metal cations in fluorescence emission spectra. Adding the probe solution to citric acid buffer solution, CH3CN (citric acid buffer solution: CH)3CN 1:1(V: V); probe L final concentration of 10. mu.M), the fluorescence emission intensity (361nm) was measured by adding each metal cation to be tested (100. mu.M), and then 100. mu.M Hg was added to the solution containing each metal ion2+Solution, fluorescence emission intensity was measured, and the results are shown in fig. 3.
As can be seen from FIG. 3, the fluorescence intensity (361nm) obtained when mercury ions were added in the presence of other metal cations was substantially the same as that obtained when mercury ions were added alone, indicating that probe L was responsible for Hg2+The detection has stronger anti-metal cation interference capability.
Experimental example 3 detection sensitivity experiment
In the same manner as in Experimental examples 1 and 2, the buffer solution of citric acid and C was usedH3CN to establish a detection solution containing a probe L (the concentration of the probe is 1X 10)-5mol/L) is added, the mercury ion solution is added, so that the concentration of the mercury ions in the system is 0 and 1 multiplied by 10 respectively-6M、2×10-6M、3×10-6M、4×10-6M、5×10-6M、6×10-6M、7×10-6M、8×10-6M、9×10-6M、1.0×10-5M、1.1×10-5M、1.2×10-5M、1.3×10-5M、1.4×10-5M、1.5×10-5M, different concentrations of Hg2+The fluorescence spectrum response chart of (2) is shown in FIG. 4.
In FIG. 4, the emission wavelength (nm) is plotted on the abscissa, the fluorescence intensity is plotted on the ordinate, and the excitation wavelength is 310 nm. When the concentration of mercury ions is increased from 0 to 1.5X 10-5In the course of mol/L, the fluorescence intensity gradually decreased. The fluorescence spectrum analysis shown in FIG. 5 shows that the concentration of added mercury ions is 0 to 7X 10-6In the mol/L range, the fluorescence intensity and the concentration of the added mercury ions have a good linear relation curve, the quantitative detection of the mercury ions can be realized, and the method has higher detection sensitivity and is suitable for trace detection.
Claims (2)
1. Salicylate thiol fluorescent probe for detecting Hg2+The application of the aspect is characterized in that the structural formula of the salicylidene thiol fluorescent probe is as follows:
2. use according to claim 1, characterized in that Hg is detected by fluorescence spectroscopy in a solution containing a fluorescent probe of the salicylaldehyde thiol group2+。
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3557194A (en) * | 1971-01-19 | 1971-01-19 | Ferro Corp | Hydroxydithioaromatic acids,derivatives thereof and process for their manufacture |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3557194A (en) * | 1971-01-19 | 1971-01-19 | Ferro Corp | Hydroxydithioaromatic acids,derivatives thereof and process for their manufacture |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis of 2-Substituted Benzofurans and Indoles Using Functionalized Titanium Benzylidene Reagents on Solid Phase;Macleod, Calum等;《Journal of Organic Chemistry》;20021203;387-401 * |
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