CN112920175A - Coumarin-based palladium ion fluorescent probe compound and preparation method thereof - Google Patents
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Abstract
The invention relates to a coumarin-based palladium ion fluorescent probe compound and a preparation method thereof, belonging to the technical field of organic small molecule fluorescent probes. The palladium ion fluorescent probe compound has the following structural formula:
the preparation method comprises the steps of adding diethyl malonate, glacial acetic acid and piperidine into ethanol solution of 4- (diethylamino) -salicylaldehyde 1, purifying, adding hydrazine hydrate, heating and the like. The palladium ion probe prepared by the invention is fluorescence-enhanced, has high sensitivity and low detection limit of 4.45x10‑8(ii) a The probe shows high selectivity to palladium ions and strong anti-interference performance.
Description
The technical field is as follows:
the invention belongs to the technical field of organic small-molecule fluorescent probes, and particularly relates to a coumarin-based palladium ion fluorescent probe compound and a synthesis method thereof.
Background art:
in modern industrial synthesis methods, heavy metals are widely used in the preparation of compounds and polymer materials in different fields, wherein palladium (Pd) is the most widely used metal-supported catalyst and is particularly commonly used. In addition, palladium is also an indispensable key material in the industries of electronic products, jewelry, aerospace, medical instruments, fuel cells and the like. The palladium discharged in industrial production pollutes soil and water resources, and poses serious threats to ecological systems and human health. Therefore, it is essential to develop an efficient method for detecting the palladium content in industrial, pharmaceutical and environmental samples.
Besides the method of detecting palladium content by using an instrument, the atomic absorption spectrometry is also commonly used as an inductively coupled plasma atomic emission spectrometry, an inductively coupled plasma mass spectrometry, a solid-phase microextraction high performance liquid chromatography, a time-of-flight resonance ionization mass spectrometry, capillary zone electrophoresis and X-ray fluorescence. Fluorescence spectroscopy has attracted attention because of its short response time, high sensitivity, and ease of operation. The coumarin fluorescent dye has the advantages of high molar extinction coefficient, high fluorescence quantum yield, easiness in chemical modification, adjustable absorption emission wavelength, high photo-thermal stability and the like, and is widely applied to detection of various ions and small molecules and bioluminescence imaging. In recent years, many palladium ion fluorescent probes based on different fluorophores such as rhodamine B, fluorescein, cyanine dye, Perylene Diimide (PDI) and the like have been reported in the literature, but the number of the palladium ion fluorescent probes based on coumarin is not large at present.
In view of the harm of palladium ions to the environment and an ecological system and the limitation of the reported probe at present, the coumarin-based palladium ion fluorescent probe with high sensitivity and high selectivity is designed and prepared by combining the excellent photo-physical and chemical properties of coumarin dye molecules, and has research value and application prospect.
The invention content is as follows:
the invention aims to solve the problems in the prior art and provides a coumarin-based palladium ion fluorescent probe compound CCB and a synthesis method thereof.
The technical scheme of the invention is as follows:
a coumarin-based palladium ion fluorescent probe compound has the following structural formula:
a preparation method of a coumarin-based palladium ion fluorescent probe compound comprises the following steps:
(1) adding a compound 2, glacial acetic acid and piperidine into an ethanol solution of the compound 1, and separating and purifying after the reaction is finished to obtain a product, namely a compound 3; the compound 1 is 4- (diethylamino) -salicylaldehyde, and the compound 2 is diethyl malonate;
(2) adding a compound 4 into the methanol solution of the compound 3 obtained in the step (1), and after the reaction is finished, separating and purifying to obtain a product which is marked as a compound 5; said compound 4 is hydrazine hydrate;
(3) under the protection of nitrogen, adding the compound 5 obtained in the step (2) into a methanol solution of a compound 6, heating to 95 ℃, and separating and purifying to obtain a coumarin-based palladium ion fluorescent probe compound; the compound 6 is 4-chloro-2-pyridinecarbaldehyde.
Preferably, the specific steps of step (1) are: adding a compound 2, glacial acetic acid and piperidine into an ethanol solution of the compound 1 in sequence to obtain a reaction solution, reacting the reaction solution at 80 ℃ for 12 hours, and separating and purifying after the reaction is finished to obtain a compound 3, wherein the molar ratio of the compound 1 to the compound 2 to the piperidine to the glacial acetic acid is 1:3.4:0.05: 0.18; the separation and purification method comprises adding water quenching, reacting, extracting with ethyl acetate, and purifying the obtained crude product with petroleum ether/ethyl acetate as eluent by silica gel chromatography column.
Preferably, the specific steps of step (2) are: dropwise adding a compound 4 into an ethanol solution of a compound 3, reacting the reaction solution at room temperature for 12min, and separating and purifying after the reaction is finished to obtain a compound 5, wherein the molar ratio of the compound 3 to the compound 4 is 1: 4; the separation and purification method comprises the steps of freezing after the reaction is finished, carrying out suction filtration, and carrying out vacuum drying on the crude product to obtain a compound 5.
Preferably, the molar ratio of the compound 5 to the compound 6 in the step (3) is 1: 1.1; dissolving a compound 5 in methanol, adding a compound 6 to obtain a reaction solution, and reacting at 95 ℃ for 12 hours; and the separation and purification method comprises the steps of freezing after the reaction is finished, carrying out suction filtration, and carrying out vacuum drying on the crude product to obtain the coumarin-based palladium ion fluorescent probe compound CCB.
The coumarin-based palladium ion fluorescent probe compound CCB prepared by the method can be applied to palladium ion detection.
The invention has the beneficial effects that:
1. the palladium ion fluorescent probe provided by the invention has high sensitivity and low detection limit of 4.45x10-8mol/L is the lowest value of the coumarin-based palladium ion fluorescent probe reported in the literature at present; the palladium ion fluorescent probe has high selectivity on palladium ions and has no obvious response on other 19 interference metal cations; a significant change in the color of the solution was observed with the naked eye.
2. The synthesis method of the palladium ion fluorescent probe is efficient, simple in post-treatment and has practical application prospects.
Description of the drawings:
FIG. 1 shows the preparation of a palladium ion fluorescent probe compound CCB prepared in example 31H NMR spectrum (solvent deuterated chloroform);
FIG. 2 shows the preparation of a palladium ion fluorescent probe compound CCB prepared in example 313C NMR spectrum (solvent deuterated chloroform);
FIG. 3 is a diagram showing the UV-VIS absorption and fluorescence emission spectra of the compound CCB of the fluorescent probe for palladium ions in example 4, wherein the CCB concentration is 5 μ M, the test solvent is tetrahydrofuran, and the excitation wavelength is 444 nm;
FIG. 4 is a time-dependent spectrum of fluorescence quenching of the fluorescent probe for palladium ions after palladium ions are added in example 5, wherein the test solvent is THF/buffer solution, the concentration of CCB is 5 μ M, the concentration of palladium ions is 7 μ M, the excitation wavelength is 444nm, and the emission wavelength is 486 nm;
FIG. 5 shows that in example 5, after palladium ions are added, the test solvent is THF/buffer solution, the CCB concentration is 5 μ M, the palladium ion concentration is 7 μ M, and the water content is 10% -90% under the condition of different water contents;
FIG. 6 is a fluorescence emission spectrum of the palladium ion fluorescent probe of example 7 in the presence of palladium ions of different concentrations, wherein the concentration of the palladium ion fluorescent probe CCB is 5 μ M, and the concentration of the palladium ions is 0-9 μ M;
FIG. 7 is a graph showing the change of fluorescence at 486nm of the fluorescent probe of example 7 in the presence of different concentrations of palladium ions, wherein the concentration of the palladium ion fluorescent probe CCB is 5 μ M, and the concentration of the palladium ions is 0-9 μ M;
FIG. 8 is a fluorescence emission spectrum of the fluorescent probe CCB of example 8 after mixing with different metal cations;
FIG. 9 is a bar graph comparing the fluorescence emission intensity at 486nm of the fluorescent probe CCB of example 8 mixed with different metal cations;
FIG. 10 is a histogram of fluorescence quenching at 486nm of the fluorescent probes CCB of example 8 mixed with 7 μ M palladium ions after adding 70 μ M of different metal cations
FIG. 11 is a photograph showing a comparison of the response of the probe solution of example 8 to palladium ions.
The specific implementation mode is as follows:
the present invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In practice, the technical personnel according to the invention make improvements and modifications, which still belong to the protection scope of the invention.
The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art.
The synthesis route of the coumarin-based palladium ion fluorescent probe compound CCB is as follows:
example 1: preparation of Compound 3
To a solution of 4- (diethylamino) salicylaldehyde (0.193g,1mmol) in ethanol (5mL) was added diethyl malonate (0.52mL,3.4 mmol). To the reaction solution were added 50. mu.L and two drops of glacial acetic acid in 4mL of ethanol. The reaction was stirred at 80 ℃ for 24h, and water (30mL) was added to the system, followed by extraction with ethyl acetate (3X 20 mL). The combined organic phases were washed successively with water, saturated brine and dried over anhydrous sodium sulfate. The crude product obtained after spin drying of the solvent was chromatographed on silica gel using petroleum ether/ethyl acetate as eluent to afford compound 3 as a yellow solid (0.323g, 78%).
1H NMR(400MHz,DMSO-d6)δ8.55(s,1H),7.63(d,J＝9.0Hz,1H),6.77(dd,J＝9.0,2.4Hz,1H),6.53(d,J＝2.4Hz,1H),4.23(q,J＝7.1Hz,2H),3.48(q,J＝7.0Hz,4H),1.28(t,J＝7.1Hz,3H),1.14(t,J＝7.0Hz,6H).13C NMR(101MHz,DMSO)δ163.85,158.51,157.50,153.27,149.69,132.22,110.24,107.81,107.44,96.26,60.79,44.81,40.58,40.37,40.16,39.96,39.75,39.54,39.33,14.69,12.79.
Example 2: preparation of Compound 5
Compound 3(0.29g,1mmol) obtained in example 1 was dissolved in 15mL of methanol, hydrazine hydrate (240. mu.L, 4mmol, 80%) was added to the system, and after stirring at room temperature for 12min, the system was frozen in a refrigerator and filtered with suction to obtain a yellow solid. The crude product was dried under vacuum for 12h to afford compound 5(0.22g, 80%).
1H NMR(400MHz,Chloroform-d)δ9.72(t,J＝4.3Hz,1H),8.68(s,1H),7.43(d,J＝8.9Hz,1H),7.27(s,0H),6.65(dd,J＝8.9,2.5Hz,1H),6.49(d,J＝2.4Hz,1H),4.13(d,J＝4.3Hz,2H),3.46(q,J＝7.1Hz,4H),1.24(t,J＝7.1Hz,7H).13C NMR(101MHz,CDCl3)δ163.90,162.13,157.65,152.69,148.05,131.16,110.01,109.12,108.25,96.62,77.35,77.03,76.72,45.12,12.42.
Example 3: preparation of palladium ion fluorescent probe compound CCB
Compound 5(55mg,0.2mmol) obtained in example 2 was dissolved in 20mL of methanol under nitrogen, 4-chloro-2-pyridinecarbaldehyde (28mg,0.2mmol) was added, and the mixture was refluxed for 12 hours. And (5) putting the system into a refrigerator for freezing, and performing suction filtration to obtain a yellow solid. The crude product was dried under vacuum for 12 hours to obtain a palladium ion fluorescent probe compound CCB (64mg, 80%). Of the product1H NMR spectrum and13the C NMR spectra are shown in FIG. 1 and FIG. 1, respectively.
1H NMR(400MHz,Chloroform-d)δ12.10(s,1H),8.84(s,1H),8.50(d,J＝5.4Hz,1H),8.26(d,J＝2.9Hz,2H),7.48(d,J＝8.9Hz,1H),7.28(dd,J＝5.3,1.9Hz,1H),6.69(dd,J＝9.0,2.5Hz,1H),6.52(d,J＝2.5Hz,1H),3.48(q,J＝7.1Hz,4H),1.26(t,J＝7.1Hz,6H).13C NMR(101MHz,Chloroform-d)δ162.74,160.24,157.95,154.78,153.17,150.19,149.48,147.16,144.65,131.55,124.38,121.26,110.39,108.58,108.49,96.60,45.23,12.44.HRMS(ESI Positive)calc.for C20H20ClN4O3 +,[M]+399.1218,
Example 4
And (3) testing the photophysical properties of the fluorescent probe:
a stock solution of the palladium ion fluorescent probe compound CCB obtained in example 3 was prepared in a concentration of 0.5mM in acetone. 30 mu L of the palladium ion fluorescent probe compound CCB stock solution is diluted in 3ml of THF (concentration of 5 mu M), and ultraviolet-visible absorption and fluorescence emission spectra are tested. In fluorescence emission spectroscopy, the excitation wavelength was 444 nm.
The experimental results are as follows: as can be seen from FIG. 3, the maximum absorption wavelength of the palladium ion probe compound was 444nm and the maximum emission wavelength was 486 nm.
Example 5: fluorescent probe response time test
The solvent of the palladium chloride stock solution is H2And O. The test solvent was THF/buffered solution (buffer/THF-1/1, v/v, pH 4.0) at a concentration of 5 μ M for the palladium ion fluorescent probe compound and 7 μ M for the palladium ion. After the addition of palladium ions, the fluorescence emission of the mixture was recorded every 5 s.
The experimental results are as follows: as can be seen from FIG. 4, the addition of palladium ions to the probe solution immediately caused fluorescence quenching; the fluorescence tends to stabilize within three minutes, with the probe fluorescence in the "OFF" state. The fluorescent probe has rapid response to target detection object palladium ions, and the fluorescence change before and after is obvious, thereby being very beneficial to judgment.
Example 6: quenching efficiency of probe compounds at different water contents
The test solvent was THF/buffer solution (pH 4.0) at a ratio of 10% to 90%, wherein the concentration of the palladium ion fluorescent probe compound was 5 μ M and the concentration of palladium ion was 7 μ M.
The experimental results are as follows: as can be seen from FIG. 5, with the increase of the water content, the quenching efficiency of the palladium ion fluorescent probe is highest when the water content is 20%. In order to ensure that the metal ions have better solubility, 50% water content with better quenching effect is selected as a test system.
Example 7: titration test of a solution of a fluorescent probe with palladium ions
The test solvent was THF/buffer solution (buffer solution/THF 1/1, v/v, pH 4.0), the concentration of the palladium ion fluorescent probe compound was 5 μ M, 0 to 10 μ M of palladium ion was added dropwise, and after waiting five minutes, the fluorescence emission spectrum of the mixed solution was recorded with an excitation wavelength of 444 nm. As shown in FIGS. 6 to 8.
The experimental results are as follows: with the addition of palladium ions, the fluorescence emission of the palladium ion fluorescent probe gradually weakens, linearly decreases, and then changes slowly. The palladium ions can coordinate with nitrogen atoms and oxygen atoms of fluorescent probe molecules, so that intramolecular charge transfer is carried out, the fluorescence of the probe is quenched, and the fluorescence is gradually weakened with the addition of the palladium ions.
Detection limit of fluorescent probe:
based on the results of the fluorescence titration test, the decrease in fluorescence Δ I at 486nm of the probe was plotted against the palladium ion concentration (0-9 μ M). The change of the fluorescence intensity and the concentration of the palladium ions are in a linear relationship, and the detection limit of the probe to the palladium ions can be determined by the formula: the limit of detection is calculated as 3x σ/K, where σ is the standard variance value of the blank sample and K is the slope of the line. The detection limit of the fluorescent probe for palladium ions is calculated to be as low as 4.45x10-8，。
Example 8: selectivity of fluorescent probes for palladium ions
Experiments have selected 19 metal cations that are susceptible to interference with palladium ion detection, including: pd2+,Pt2+,Cr6+,As3+,Ag+,Ca2+,Na+,Mg2+,Al3+,K+,Fe3+,Co2+,Ni2+,Cu2+,Zn2+,Hg2+,Cd2+,Pd2+,Mn2+And Mo2+. The concentration of each metal cation was 20. mu.M. The test solvent is THF/buffer solution (buffer solution/THF ═ 1-1, v/v, pH 4.0), the concentration of the probe compound was 5 μ M, and after adding metal ions, the mixture was mixed well and left to stand for five minutes, and the fluorescence emission spectrum of the solution was measured.
As shown in FIGS. 9 to 11, the results of the experiment were as follows: as can be seen from fluorescence emission spectra, the probe shows obvious fluorescence attenuation signal response to palladium ions only, and has high selectivity and strong anti-interference capability. As can be seen from FIG. 11, the color change before and after the addition of the palladium ion to the probe solution is significant, indicating that the probe can realize the visual rapid determination of the palladium ion.
The above detailed description is specific to one possible embodiment of the present invention, which is not intended to be limiting
The scope of the invention is to be determined by the appended claims.
Claims (5)
1. A coumarin-based palladium ion fluorescent probe compound has the following structural formula:
2. a method for synthesizing the coumarin-based palladium ion fluorescent probe compound as claimed in claim 1, comprising the steps of:
(1) adding a compound 2, glacial acetic acid and piperidine into an ethanol solution of the compound 1, and separating and purifying after the reaction is finished to obtain a product, namely a compound 3; the compound 1 is 4- (diethylamino) -salicylaldehyde, and the compound 2 is diethyl malonate;
(2) adding a compound 4 into the methanol solution of the compound 3 obtained in the step (1), and after the reaction is finished, separating and purifying to obtain a product which is marked as a compound 5; said compound 4 is hydrazine hydrate;
(3) under the protection of nitrogen, adding the compound 5 obtained in the step (2) into a methanol solution of a compound 6, heating to 95 ℃, and separating and purifying to obtain a coumarin-based palladium ion fluorescent probe compound; the compound 6 is 4-chloro-2-pyridinecarbaldehyde.
3. The method for synthesizing the coumarin-based palladium ion fluorescent probe compound according to claim 2, wherein the step (1) comprises the following specific steps: adding a compound 2, glacial acetic acid and piperidine into an ethanol solution of the compound 1 in sequence to obtain a reaction solution, reacting the reaction solution at 80 ℃ for 12 hours, and separating and purifying after the reaction is finished to obtain a compound 3, wherein the molar ratio of the compound 1 to the compound 2 to the piperidine to the glacial acetic acid is 1:3.4:0.05: 0.18; the separation and purification method comprises adding water quenching, reacting, extracting with ethyl acetate, and purifying the obtained crude product with petroleum ether/ethyl acetate as eluent by silica gel chromatography column.
4. The method for synthesizing the coumarin-based palladium ion fluorescent probe compound according to claim 2, wherein the step (2) comprises the following specific steps: dropwise adding a compound 4 into an ethanol solution of a compound 3, reacting the reaction solution at room temperature for 12min, and separating and purifying after the reaction is finished to obtain a compound 5, wherein the molar ratio of the compound 3 to the compound 4 is 1: 4; the separation and purification method comprises the steps of freezing after the reaction is finished, carrying out suction filtration, and carrying out vacuum drying on the crude product to obtain a compound 5.
5. The method for synthesizing the coumarin-based palladium ion fluorescent probe compound according to claim 2, wherein the molar ratio of the compound 5 to the compound 6 in the step (3) is 1: 1.1; dissolving a compound 5 in methanol, adding a compound 6 to obtain a reaction solution, and reacting at 95 ℃ for 12 hours; and the separation and purification method comprises the steps of freezing after the reaction is finished, carrying out suction filtration, and carrying out vacuum drying on the crude product to obtain the coumarin-based palladium ion fluorescent probe compound.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2680005A1 (en) * | 2012-06-28 | 2014-01-01 | Rheinische Friedrich-Wilhelms-Universität Bonn | Lipid analysis |
| CN104761549A (en) * | 2015-02-12 | 2015-07-08 | 陕西学前师范学院 | Palladium ion probe and preparation and application thereof |
| CN105315264A (en) * | 2015-11-24 | 2016-02-10 | 山西大同大学 | N'-(quinoiline-2-methylene)-7-diethylamine coumarin-3-formylhydrazine and preparation method and application thereof |
| CN105669708A (en) * | 2016-01-18 | 2016-06-15 | 新乡医学院 | Coumarin schiff-base copper ion complex-based fluorescent probe for thiol as well as preparation method and application thereof |
| CN107382935A (en) * | 2017-09-05 | 2017-11-24 | 南京农业大学 | A kind of coumarin fluorescent probe C1 and its preparation method and application |
| CN111253386A (en) * | 2020-02-14 | 2020-06-09 | 中北大学 | Naked eye recognition Cu2+Fluorescent probe and preparation method and application thereof |
| CN111393461A (en) * | 2020-03-17 | 2020-07-10 | 广东省测试分析研究所（中国广州分析测试中心） | Palladium ion fluorescent probe compound based on BODIPY and synthetic method thereof |
| CN111423439A (en) * | 2020-05-18 | 2020-07-17 | 南昌航空大学 | Novel coumarin conjugated heterocyclic fluorescent probe for detecting Fe (III) |
-
2020
- 2020-12-17 CN CN202011491164.0A patent/CN112920175B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2680005A1 (en) * | 2012-06-28 | 2014-01-01 | Rheinische Friedrich-Wilhelms-Universität Bonn | Lipid analysis |
| CN104761549A (en) * | 2015-02-12 | 2015-07-08 | 陕西学前师范学院 | Palladium ion probe and preparation and application thereof |
| CN105315264A (en) * | 2015-11-24 | 2016-02-10 | 山西大同大学 | N'-(quinoiline-2-methylene)-7-diethylamine coumarin-3-formylhydrazine and preparation method and application thereof |
| CN105669708A (en) * | 2016-01-18 | 2016-06-15 | 新乡医学院 | Coumarin schiff-base copper ion complex-based fluorescent probe for thiol as well as preparation method and application thereof |
| CN107382935A (en) * | 2017-09-05 | 2017-11-24 | 南京农业大学 | A kind of coumarin fluorescent probe C1 and its preparation method and application |
| CN111253386A (en) * | 2020-02-14 | 2020-06-09 | 中北大学 | Naked eye recognition Cu2+Fluorescent probe and preparation method and application thereof |
| CN111393461A (en) * | 2020-03-17 | 2020-07-10 | 广东省测试分析研究所（中国广州分析测试中心） | Palladium ion fluorescent probe compound based on BODIPY and synthetic method thereof |
| CN111423439A (en) * | 2020-05-18 | 2020-07-17 | 南昌航空大学 | Novel coumarin conjugated heterocyclic fluorescent probe for detecting Fe (III) |
Non-Patent Citations (7)
| Title |
|---|
| AIMIN REN 等: "Developed a high-performance sensor based on cumarin derivative for rapid and sensitive detection of palladium ion in organic wastewater", 《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》 * |
| RUXIN LIU等: "A turn-on fluorescent probe based on quinoline and coumarin for rapid, selective and sensitive detection of hypochlorite in water samples", 《LUMINESCENCE.》 * |
| XIANG-ZHU CHEN 等: "A coumarin-based colorimetric and fluorescent dual probe for palladium(II) ions that can be used in live cells", 《NEWJ.CHEM.》 * |
| XIANGZHU CHEN 等: "Colorimetric and fluorescent probe for real-time detection of palladium (II) ion in aqueous medium and live cell imaging", 《DYES AND PIGMENTS》 * |
| 任爱民: "新型香豆素酰肼、三氮唑衍生物的合成及其荧光性质的研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 周高 等: "一种新型荧光探针的合成及其对Ｃｕ２＋ 的选择性识别", 《光谱学与光谱分析》 * |
| 赵秀文 等: "基于香豆酰肼的高选择性的铜离子荧光探针", 《发光学报》 * |
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