CN107417681B - Fluorescent probe compound containing coumarin-thiadiazole Schiff base and preparation method and application thereof - Google Patents
Fluorescent probe compound containing coumarin-thiadiazole Schiff base and preparation method and application thereof Download PDFInfo
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- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 63
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- 238000001514 detection method Methods 0.000 claims abstract description 24
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- 238000000034 method Methods 0.000 claims description 14
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- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 4
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- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
The invention discloses a fluorescent probe compound containing coumarin-thiadiazole Schiff base, a preparation method and application thereof, wherein the structural formula of the fluorescent probe compound containing coumarin-thiadiazole Schiff base is as follows:
the fluorescent probe compound has multiple functions, and can realize the effect of Cu by an ultraviolet-visible spectrophotometry and a fluorescence spectrometry2+And Hg2+The ion identification and quantitative detection have good anti-interference performance, high selectivity and sensitivity under the condition of the existence of other ions.
Description
Technical Field
The invention relates to a fluorescent probe compound containing coumarin-thiadiazole Schiff base, a preparation method and application thereof, and belongs to the field of metal ion detection and fluorescent molecular probes.
Background
Heavy metal ion contamination has become a very serious and urgent problem worldwide, since some heavy metal ions, even at very low concentrations, can be potentially harmful to the environment and human body. In recent years, with the rapid development of chemical sensors, fluorescent probe research has attracted more and more attention in many fields such as chemistry, biology, medicine and environment, and is a major research hotspot at present. Fluorescent probe technology is widely used for detecting various metal ions because of its advantages of good selectivity, high sensitivity, simplicity, rapidness and no need of expensive instruments. The ion can be quantitatively or qualitatively analyzed by utilizing the relation between the ultraviolet/fluorescence performance and the ion concentration, and the method is convenient and quick, has higher selectivity and sensitivity, and is very suitable for real-time or in-situ detection of the heavy metal ions.
Copper is an important trace element and essential nutrient in living systems. Copper toxicity is small, but copper deficiency can lead to disturbances in growth and metabolism. Alteration of copper balance in cells leads to inhibition of neurological diseases such as Menkes 'syndrome, Wilson's disease, familial hereditary sclerosing of the spinal cord, Alzheimer's disease, and Prion's disease, among others. The distribution of copper in cells is tightly controlled, precisely because of its importance for life. Copper has a variable valence state, and participates in a series of processes such as electron transfer, oxidation reduction and the like in a living body, and direct research and simulation of copper protein and cuprase are always hot spots of research of scientists. Therefore, it is necessary to establish a simple and sensitive method for detecting copper ions.
Mercury is an important heavy metal element, widely exists in the nature, and is one of the most threatening heavy metal elements to the human body and the nature, so that a method for quickly and accurately detecting mercury ions is found, and the method has important theoretical and practical values for environmental pollution, food safety detection and the like. At present to Hg2+The research of the measuring method has been reported, but the method also has the defects of expensive instrument, high analysis cost and the like. The fluorescence detection method has the advantages of high sensitivity, specificity in selectivity, short response time and the like, and is favored by people in recent years.
In recent years, research and application of fluorescent probes have been greatly advanced. The fluorescent probe realizes the identification and detection of the target substance by utilizing the change of the fluorescent property before and after the combination of the probe and the target substance, and has the advantages of good selectivity, high sensitivity, real-time in-situ detection, simple and convenient operation method and the like.
Disclosure of Invention
The invention aims to provide a fluorescent probe compound containing coumarin-thiadiazole Schiff base and a preparation method and application thereof. Because the identification performance of the fluorescent probe is related to the space structure of a probe molecule, the invention designs and synthesizes the Schiff base derivative with the C-N structure based on the C-N isomerization mechanism by taking coumarin aldehyde as a fluorescent chromophore parent, and meanwhile, the molecule contains coordination atoms of O, S, N and the like, so that the Schiff base derivative can form coordination molecules with some metal ions to generate specific ultraviolet and fluorescence phenomena.
The coumarin-thiadiazole Schiff base-containing fluorescent probe compound has a structural formula shown in the following formula 1:
the invention relates to a preparation method of a coumarin-thiadiazole Schiff base-containing fluorescent probe compound, which is a product obtained by condensation reaction of coumarin-based aldehyde and 5-amino-1, 3, 4-thiadiazole-2-thiol.
The coumarin-based aldehyde is 3-aldehyde-7-N, N-diethylamino coumarin.
The preparation method of the coumarin-thiadiazole Schiff base-containing fluorescent probe compound comprises the following steps:
weighing 1.0mmol of 3-aldehyde-7-N, N-diethylamino coumarin and 1.1mmol of 5-amino-1, 3, 4-thiadiazole-2-thiol, respectively dissolving in 10mL of absolute ethanol, stirring for dissolving, mixing in a reactor, adding a drop of glacial acetic acid as a catalyst, heating to 75 ℃, and carrying out reflux reaction for 6 hours; and after the reaction is finished, cooling, performing suction filtration, recrystallizing with absolute ethyl alcohol, performing suction filtration, washing and drying to obtain the target product.
The synthetic route of the target product of the invention is as follows:
the invention relates to an application of a fluorescent probe compound containing coumarin-thiadiazole Schiff base in qualitative or quantitative Cu detection2+Can be used as detection reagent.
The invention relates to an application of a fluorescent probe compound containing coumarin-thiadiazole Schiff base, which is characterized in that ultraviolet-visible absorption spectrum determination is carried out in a water-containing medium, and the color of a solution is changedTo Cu2+And (4) qualitative detection.
The aqueous medium is acetonitrile and water according to the volume ratio of 1: 1, and (b) a mixed solution.
The invention relates to an application of a fluorescent probe compound containing coumarin-thiadiazole Schiff base, which is used for carrying out ultraviolet-visible absorption spectrum determination in a water-containing medium to realize the determination of Cu2+And (4) carrying out quantitative detection.
The aqueous medium is acetonitrile and water according to the volume ratio of 1: 1, and (b) a mixed solution.
The invention relates to an application of a fluorescent probe compound containing coumarin-thiadiazole Schiff base in qualitative or quantitative Hg detection2+Can be used as detection reagent.
The application of the coumarin-thiadiazole Schiff base-containing fluorescent probe compound is to perform fluorescence spectrum determination in a water-containing medium and realize Hg by the change of fluorescence intensity2+Qualitative or quantitative detection of (a).
The aqueous medium is acetonitrile and water according to the volume ratio of 1: 1, and (b) a mixed solution.
The target product of the invention has a C-N structure and contains thiadiazole Schiff base derivatives of substituted coumarin groups, and the molecular structure of the thiadiazole Schiff base derivatives is characterized in that the Schiff base compounds contain hydrophilic sulfhydryl groups in the structure, and simultaneously contain coordination atoms of O, S, N and the like in molecules, so that the thiadiazole Schiff base derivatives can be combined with some metal ions in an aqueous medium to form coordination molecules to generate specific ultraviolet and fluorescence phenomena.
The fluorescent probe compound can be used for Cu2+The identification and detection of ions have strong anti-interference capability on various metal ions, and the fluorescent probe compound and Cu of the invention2+The phenomenon of obvious color change generated by ion mixing can realize naked eye identification and colorimetric analysis; the fluorescent probe compound can also identify Hg2+Ions.
The invention has the beneficial effects that:
the fluorescent probe compound has multiple functions, and can realize the aim of Cu respectively by an ultraviolet-visible spectrophotometry and a fluorescence spectrometry2+And Hg2+Recognition of ionsOtherwise. Selective identification of Cu by ultraviolet-visible spectrophotometry2+Ions, selective identification of Hg by fluorescence spectroscopy2+Ions. The fluorescent probe compound can be used for treating Cu in a medium containing water2 +Or Hg2+Fast ion identification, quantitative detection, and Cu detection2+Or Hg2+The ion identification has higher selectivity and better anti-interference capability, and the obvious color change phenomenon can realize naked eye identification and colorimetric analysis.
Drawings
FIG. 1 shows the volume ratio of acetonitrile to water of a fluorescent probe compound L of the present invention is 1: 1, adding ultraviolet absorption spectra of different metal ions into the mixed solution, and adding Cu into the mixed solution2+The color of L changes.
FIG. 2 shows the addition of Cu2+The volume ratio of the ionic fluorescent probe compound L in acetonitrile to water is 1: 1 ultraviolet-visible absorption spectrum titration spectrogram.
FIG. 3 shows the volume ratio of acetonitrile to water of the fluorescent probe compound L is 1: 1, metal ion selectivity and anti-interference histogram in the mixed solution;
represents L in a volume ratio of acetonitrile to water of 1: 1, adding ultraviolet absorption intensity of different metal ions into the mixed solution;represents a ratio of acetonitrile to water in a volume ratio of 1: 1 adding different metal ions and Cu into the mixed solution2+Ultraviolet absorption intensity (lambda) of ionsmax＝506nm)。
FIG. 4 shows the volume ratio of acetonitrile to water of the fluorescent probe compound L is 1: 1, adding fluorescence spectra (lambda) of different metal ions into the mixed solutionex＝500nm)。
In FIG. 5, the volume ratio of the fluorescent probe compound L in acetonitrile to water is 1: 1 of mixed solution of Hg2+Fluorescence titration spectrum (lambda) of (A)ex＝500nm)。
FIG. 6 shows fluorescent probe compound L in acetonitrileAnd the volume ratio of water is 1: 1, metal ion selectivity and anti-interference histogram in the mixed solution;
representing the fluorescence intensity of different metal ions added into the L acetonitrile solution;
represented in a volume ratio of acetonitrile to water of 1: 1, adding different metal ions and Hg into the mixed solution2+Fluorescence intensity (lambda) of ionem＝568nm)。
Detailed Description
The invention is further illustrated by, but is not limited to, the following examples.
Example 1: synthesis of fluorescent Probe Compound (L) of the present invention
Weighing 0.245g (1.0mmol) of 3-aldehyde-7-N, N-diethylamino coumarin and 0.147g (1.1mmol) of 5-amino-1, 3, 4-thiadiazole-2-thiol, respectively dissolving in 10mL of absolute ethanol, and stirring to fully dissolve; mixing the two materials, adding into a round-bottom flask, adding a drop of glacial acetic acid as a catalyst, heating to 75 ℃, refluxing for 6h, cooling the reaction solution, performing suction filtration, recrystallizing with absolute ethyl alcohol, performing suction filtration, washing and drying to obtain 0.297g of a product, wherein the yield is 82.4%.
FT-IR(KBr，cm-1): 3431(S-H stretching vibration), 2976,2929 (-CH)2and-CH3Stretching vibration), 1738(C ═ O stretching vibration), 1615,1502 (benzene ring stretching vibration), 1348(-C-H bending vibration), 1132(-C-N stretching vibration), 683(-N-H out-of-plane bending vibration).
1H NMR(400MHz,DMSO-d6):1H NMR(400MHz,DMSO):δ(ppm)14.42(s,1H,-SH),8.68(s,1H,-CH＝N-),8.59(s,1H,-CH＝),7.68(d,1H,-CH＝),6.82(dd,1H,-CH＝),6.61(d,1H,-CH＝),3.50(q,4H,-CH2-),1.15(t,6H,-CH3).ESI-MS:m/z 361.08for C16H16N4O2S2.
Example 2: ultraviolet-visible absorption Spectroscopy determination of fluorescent Probe Compound L
Accurate and accurateThe fluorescent probe compound L was weighed to 3.6mg, dissolved and prepared to have a concentration of 1.0X 10-2A mol/L acetonitrile stock solution; using acetonitrile and water in a volume ratio of 1: 1 stock solution was diluted to a concentration of 1.0X 10-5mol/L of the solution to be tested. Taking 3mL of the solution with the concentration of 1.0X 10-5Putting the mol/L solution to be detected into a quartz cuvette (the thickness of the quartz cuvette is 1cm), and then respectively adding 3 mu L of the solution with the concentration of 1.0 multiplied by 10-2mol/L of various metal ions (Na)+，K+，Ag+，Ca2+，Mg2+，Mn2+，Cd2+，Cr3+，Cu2+，Ni2+，Co2+，Fe3+，Fe2+，Hg2+) The solution was shaken up and after 1 minute the UV-Vis absorption spectrum of the solution was determined (see FIG. 1). Before the addition of metal ions, the ultraviolet-visible absorption spectrum of the fluorescent probe compound L shows that a definite absorption peak is formed at 506nm, and when Cu is added2+After the ions are generated, the absorption peak of the fluorescent probe compound L at 506nm is weakened, a new absorption peak appears at 446nm, the color of the solution is changed from yellow brown to yellow green (as shown in an insert in figure 1 of the attached drawing), the solution can be observed by naked eyes, the naked eye identification function is realized, and the fluorescent probe compound L can be used for ultraviolet identification and naked eye identification of Cu2+A colorimetric probe for the ion; and under the same conditions, other metal ions such as: na (Na)+，K+，Ag+，Ca2+，Mg2+，Mn2+，Cd2 +，Cr3+，Zn2+，Ni2+，Co2+，Fe2+，Hg2+The addition of the (B) has no obvious influence on the large-L ultraviolet-visible absorption spectrum, and the color of the solution is basically not changed.
Example 3: ultraviolet-visible absorption spectrum titration experiment and detection limit determination of fluorescent probe compound L
Taking 3mL of the solution with the concentration of 1.0X 10-5Adding 3, 6, 9, 12, 15, 18, 21, 24, 27 and 30 mul of solution to be detected with the concentration of 1.0 multiplied by 10 into a quartz cuvette according to mol/L-3mol/L of Cu2+Ionic water solution, shaking up, and measuring the violet of solution after balancingExo-visible absorption spectrum (as shown in fig. 2). With Cu2+Upon addition of the ions, the absorbance of fluorescent probe compound L at 446nm gradually increased, while the absorbance at 506nm gradually decreased, and a distinct equivalence point appeared at 469nm, indicating that the ratio of acetonitrile to water by volume was 1: 1 of fluorescent probe compound L and Cu2+Ion-forming stable complexes, Cu2+The ion is at 1.0X 10-6～1.2×10-5In the mol/L range, Cu2+The ion concentration and the variation of the absorbance at 446nm are in a good linear relation (R is 0.98), and the fluorescent probe compound L to Cu is obtained by calculation2+The detection limit of the ions is 1.28X 10-6mol/L。
Example 4: fluorescent probe compounds L vs Cu2+Selectivity and immunity to ion recognition
Taking 3mL of the solution with the concentration of 1.0X 10-5Adding 3 mul of solution to be detected with the concentration of 1.0 multiplied by 10 into a quartz cuvette-2mol/L of Cu2+After ionization, 3. mu.L of the solution was added to the reaction solution at a concentration of 1.0X 10-2mol/L of various metal ions (Na)+，K+Etc.) and shaken, and the uv absorption spectrum (as shown in fig. 3) was measured after 1 minute, and the results showed addition of other metal ions such as: na (Na)+，K+The ultraviolet absorption performance of the fluorescent probe compound L is hardly influenced by the equal amount, which shows that the fluorescent probe compound L has little influence on the Cu2+The ion identification has higher selectivity and better anti-interference capability.
Example 5: fluorescence spectroscopic determination of fluorescent Probe Compound L
Taking 3mL of the solution with the concentration of 1.0X 10-5Putting the mol/L solution to be detected in a quartz cuvette, and then respectively adding 3 mu L of the solution with the concentration of 1.0 multiplied by 10-2mol/L of various metal ions (Na)+，K+，Ag+，Ca2+，Mg2+，Mn2+，Cd2+，Cr3+，Cu2+，Ni2+，Co2+，Fe3+，Hg2+) The solution was shaken up and after 1 minute the fluorescence emission spectrum was measured at an excitation wavelength of lambda 500nm (as shown in figure 4) and showed no addition of goldWhen the compound belongs to ions, the fluorescent probe compound L has a weaker fluorescence peak at the position of lambda 568nm, Hg2+The addition of the ions has obvious fluorescence enhancement effect on the fluorescence peak of the fluorescent probe compound L at 568 nm. Hg is added2 +Then, the fluorescence peak intensity of the fluorescent probe compound L increased by about 5 times; and other metal ions such as: na (Na)+，K+，Ag+，Ca2+And the like have no obvious fluorescence enhancement phenomenon.
Example 6: fluorescence spectrum titration experiment and detection limit determination of fluorescent probe compound L
Taking 3mL of the solution with the concentration of 1.0X 10-5Adding 3, 6, 9, 12, 15, 18, 21, 24, 27, 30, 33, 36, 39, 42, 45 and 48 mu L of the solution to be detected with the concentration of 1.0 multiplied by 10 into a quartz cuvette with mol/L-3mol/L of Hg2+The fluorescence spectra of the ionic aqueous solutions (FIG. 5) were determined after shaking and equilibration as a function of Hg2+Addition of ions, fluorescent probe compound L at lambdaexThe fluorescence intensity under excitation at 500nm gradually increased. The concentration of the ion was 0.5X 10 as shown by the relationship between the concentration and the fluorescence intensity-6～1.4×10-5In mol/L range, Hg2+The ion concentration and the fluorescence intensity have a better linear relation (R is 0.99), and the fluorescent probe compound L is relative to Hg2+The detection limit of the ions is 2.96 multiplied by 10-7mol/L。
Example 7: fluorescent probe compounds L vs Hg2+Selectivity and immunity to ion recognition
Taking 3mL of the solution with the concentration of 1.0X 10-5Adding 3 mul of solution to be detected with the concentration of 1.0 multiplied by 10 into a quartz cuvette-2mol/L of Hg2+After ionization, 3. mu.L of the solution was added to the reaction solution at a concentration of 1.0X 10-2mol/L of various metal ions (Na)+，K+Etc.) and shaken, and the fluorescence emission spectrum measured after 1 minute at an excitation wavelength of λ 500nm (as shown in fig. 6 of the accompanying drawings) shows the addition of other metal ions such as: na (Na)+，K+The average had little effect on the fluorescence intensity of the fluorescent probe compound L, indicating that the fluorescent probe compound L had little effect on Hg2+Ion recognition is highSelectivity and better anti-interference capability.
Claims (8)
1. A coumarin-thiadiazole Schiff base-containing fluorescent probe compound is characterized by having a structural formula as follows:
2. a method for preparing a coumarin-thiadiazole-based schiff base-containing fluorescent probe compound as claimed in claim 1, which is characterized in that:
the target product is obtained by condensation reaction of aldehyde based on coumarin and 5-amido-1, 3, 4-thiadiazole-2-thiol.
3. The method of claim 2, wherein:
the coumarin-based aldehyde is 3-aldehyde-7-N, N-diethylamino coumarin.
4. The method of claim 2, comprising the steps of:
weighing 1.0mmol of 3-aldehyde-7-N, N-diethylamino coumarin and 1.1mmol of 5-amino-1, 3, 4-thiadiazole-2-thiol, respectively dissolving in 10mL of absolute ethanol, stirring for dissolving, mixing in a reactor, adding a drop of glacial acetic acid as a catalyst, heating to 75 ℃, and carrying out reflux reaction for 6 hours; and after the reaction is finished, cooling, performing suction filtration, recrystallizing with absolute ethyl alcohol, performing suction filtration, washing and drying to obtain the target product.
5. The use of the coumarin-thiadiazole-based schiff base-containing fluorescent probe compound as defined in claim 1, wherein the coumarin-based schiff base-containing fluorescent probe compound comprises the following components: is to qualitatively or quantitatively detect Cu in the course of non-disease treatment and diagnosis2+Or Hg2+Can be used as detection reagent.
6. The coumarin-thiadiazole-group-containing Schiff according to claim 1The application of the alkali fluorescent probe compound is characterized in that: is used for ultraviolet-visible absorption spectrometry in aqueous medium in the treatment and diagnosis of non-diseases, and Cu is obtained by changing the color of solution2+And (4) qualitative detection.
7. The use of the coumarin-thiadiazole-based schiff base-containing fluorescent probe compound as defined in claim 1, wherein the fluorescent probe compound comprises: is used for ultraviolet-visible absorption spectrum measurement in an aqueous medium in the non-disease treatment and diagnosis process to realize the measurement of Cu2+And (4) carrying out quantitative detection.
8. The use of the coumarin-thiadiazole-based schiff base-containing fluorescent probe compound as defined in claim 1, wherein the fluorescent probe compound comprises: is used for fluorescence spectrum determination in aqueous medium in the treatment and diagnosis process of non-diseases, and the Hg is realized by the change of fluorescence spectrum intensity2+Qualitative or quantitative detection of (a).
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