CN108774241B

CN108774241B - Probe and preparation and application thereof

Info

Publication number: CN108774241B
Application number: CN201810592759.1A
Authority: CN
Inventors: 曾晞; 田雁; 许万里; 廖贤; 方浚安; 牟兰
Original assignee: Guizhou University
Current assignee: Guizhou University
Priority date: 2018-06-11
Filing date: 2018-06-11
Publication date: 2021-07-13
Anticipated expiration: 2038-06-11
Also published as: CN108774241A

Abstract

The invention discloses a probe and preparation and application thereof, wherein the chemical name of the probe is as follows: tris [2, 2' -bis [ (4-benzothiazol-2-yl) -2, 5-dihydroxybenzaldehyde]Aminoethyl-2- "-rhodamine carboxamidoethyl]An amine; the compound is prepared by taking tris (2-aminoethyl) amine, rhodamine B and benzothiazole aldehyde as main raw materials. The probe can realize single-probe multi-target detection, namely can be simultaneously used for detecting Hg²⁺、Al³⁺And/or H₂And O, the detection cost is low, and the detection efficiency is high. And facilitates the analysis of complex microscopic systems.

Description

Probe and preparation and application thereof

Technical Field

The invention relates to a probe and preparation and application thereof, in particular to a probe for multi-target ion detection and preparation and application thereof.

Background

The fluorescent probe is used as an important analysis and detection technology due to the characteristics of simplicity, convenience, high sensitivity, real-time and visual detection and the like, and is widely applied to the fields of chemistry, biology and environmental science. There have been many reports of fluorescent probe studies for detecting important metal ions and anions relevant to life and environment.

Hg²⁺As toxic heavy metal ions which are most concerned by the environment, the existence and ultralow content detection method research of the toxic heavy metal ions have important significance for environmental protection, biological safety and the like. As one of widely used metallic materials, Al³⁺The research of rapid and sensitive analysis methods for detection and quality monitoring in environment, food, drug addition and packaging materials is also very meaningful. Micro and constantThe detection of water relates to a plurality of fields, and has application value to the research of a simple, low-cost and rapid analysis method. The multi-target detection fluorescent probe has the advantages of low development and test cost, simple sample treatment, quick determination method and excellent performance, and has development and application values. Due to the structural limitation of various fluorescent probes, the functions of the fluorescent probes in analysis application are single, the application range is limited, and other limitations exist. At present, most of fluorescent probes can only be used for detecting metal ions or acid radical anions, and the fluorescent probes which can be simultaneously used for detecting specific metal ions and water are not reported.

Disclosure of Invention

The invention aims to provide a probe, and preparation and application thereof²⁺、Al³⁺And H₂And O, the detection cost is low, and the detection efficiency is high. And facilitates the analysis of complex microscopic systems.

The technical scheme of the invention is as follows: a probe having a chemical name: tris [2, 2' -bis [ (4-benzothiazol-2-yl) -2, 5-dihydroxybenzaldehyde ] aminefhyl-2- "-rhodamine carboxamidoethyl ] amine; the chemical structural formula of the probe is as follows:

among the aforementioned probes, the aforementioned probe; is synthesized according to the following route:

the preparation method of the probe is characterized in that the probe is prepared by taking tri (2-aminoethyl) amine, rhodamine B and benzothiazole aldehyde as main raw materials.

The method for preparing the probe comprises the following steps:

(1) weighing 27.36mmol of tris (2-aminoethyl) amine in a 100mL three-neck flask under the protection of nitrogen, weighing 20mL of absolute ethanol, stirring, heating, refluxing, weighing 3.42mmol of rhodamine B, dissolving in 40mL of absolute ethanol, adding into a constant pressure funnel, slowly dropwise adding into the three-neck flask, refluxing for 36h after dropwise adding, decompressing, evaporating ethanol, extracting with dichloromethane, drying an organic phase with anhydrous sodium sulfate overnight, evaporating a solvent, obtaining a red viscous substance, separating by silica gel column chromatography, wherein an eluent is a mixture of methanol, chloroform and triethylamine in a volume ratio of 9: 1: 1 to obtain 1.63g of a colorless viscous intermediate a;

(2) weighing 0.87mmol of the intermediate a and 1.31mmol of benzothiazole aldehyde in a 100mL three-necked flask, dissolving in 60mL dry ethanol, refluxing and reacting for 4 hours under the protection of nitrogen, evaporating the solvent under reduced pressure to obtain a yellow-green solid, and separating by silica gel column chromatography, wherein an eluent is dichloromethane, n-hexane and diethylamine in a volume ratio of 60: 40: 2 to obtain 362mg of yellow-green solid, namely the probe.

Application of the probe for detecting Hg²⁺、Al³⁺And/or H₂O。

In the application of the probe, the probe is used for detecting Hg²⁺、Al³⁺And/or H₂O comprises:

(1) trace Hg is detected by fluorescence spectrometry with probe as reagent²⁺、Al³⁺Detecting;

(2) micro Hg is treated by ultraviolet-visible absorption spectrometry with a probe as a reagent²⁺、Al³⁺Detecting;

(3) using a probe-Hg²⁺probe-Al³⁺Or probe-Zn²⁺Fluorescence spectrometry for H with complex as reagent₂Detecting O;

(4) using a probe-Hg²⁺probe-Al³⁺Or probe-Zn²⁺Visual colorimetry for H by taking complex as reagent₂And (4) detecting O.

In the application of the probe, the probe is used as a reagent for carrying out fluorescence spectrometry on trace Hg²⁺、Al³⁺The detection of (a) is;

trace Hg is detected by fluorescence spectrometry with probe as reagent²⁺The detection of (a) is; in a volume ratio of 97/3 of 1, 4-dioxane/H₂Dissolution of OIn the solution, metal ions are added into the probe solution and are placed for 1 hour, 360nm is used as an excitation wavelength, and the fluorescence intensity and Hg of the probe at 585nm are²⁺The concentration is in a linear relation; hg detection by calibration curve method²⁺The other coexisting metal ion is Al³⁺，Li⁺，Na⁺，K⁺，Mg²⁺，Ba²⁺，Ca²⁺，Sr²⁺，Zn²⁺，Cd²⁺，Ni²⁺，Co²⁺，Pb²⁺，Cr³⁺，Ag⁺，Cu²⁺，Mn²⁺One, concentration and Hg²⁺At the same time, other above metal ion pairs Hg²⁺The measurement is not interfered;

trace Al is subjected to fluorescence spectrometry by taking probe as reagent³⁺The detection of (a) is; in a volume ratio of 97/3 of 1, 4-dioxane/H₂Adding metal ions into the probe solution, standing for 1 hour, taking 360nm as excitation wavelength, and measuring the fluorescence intensity of the probe at 585nm and Al³⁺The concentration is in a linear relation, and other metal ions do not interfere with detection; detection of Al by calibration Curve method³⁺The other coexisting metal ion is Hg²⁺，Li⁺，Na⁺，K⁺，Mg²⁺，Ba²⁺，Ca²⁺，Sr²⁺，Zn²⁺，Cd²⁺，Ni²⁺，Co²⁺，Pb²⁺，Cr³⁺，Fe³⁺，Ag⁺，Cu²⁺，Mn²⁺One of, in concentration and Al³⁺In the same way, other above-mentioned ion pairs Al³⁺The measurement of (2) is not interfered.

In the application of the probe, the probe is used as a reagent to treat trace Hg by ultraviolet-visible absorption spectrometry²⁺、Al³⁺The detection of (a) is;

micro Hg is treated by ultraviolet-visible absorption spectrometry with a probe as a reagent²⁺The detection of (a) is; in a volume ratio of 97/3 of 1, 4-dioxane/H₂In the O solution, after the metal ions are added into the probe solution and placed for 1 hour, the absorbance of the probe at 558nm and Hg²⁺The concentration is in a linear relation, and other metal ions do not interfere with detection; by using correction yeastsMethod for detecting Hg by linear method²⁺(ii) a Other coexisting metal ions: al (Al)³⁺，Li⁺，Na⁺，K⁺，Mg²⁺，Ba²⁺，Ca²⁺，Sr²⁺，Zn²⁺，Cd²⁺，Ni²⁺，Co²⁺，Pb²⁺，Cr³⁺，Fe³⁺，Ag⁺，Cu²⁺，Mn²⁺One, concentration and Hg²⁺For the same Hg²⁺The measurement is not interfered;

micro Al is treated by ultraviolet-visible absorption spectrometry by taking a probe as a reagent³⁺The detection of (a) is; in a volume ratio of 97/3 of 1, 4-dioxane/H₂In the O solution, after metal ions are added into the probe solution and placed for 1 hour, the absorbance of the probe at 558nm and Al³⁺The concentration is in a linear relation, and other metal ions do not interfere with detection; detection of Al by calibration Curve method³⁺(ii) a Other coexisting metal ions: hg is a mercury vapor²⁺，Li⁺，Na⁺，K⁺，Mg²⁺，Ba²⁺，Ca²⁺，Sr²⁺，Zn²⁺，Cd²⁺，Ni²⁺，Co²⁺，Pb²⁺，Cr³⁺，Fe³⁺，Ag⁺，Cu²⁺，Mn²⁺One of, in concentration and Al³⁺In the same way, for Al³⁺The measurement of (2) is not interfered.

In the application of the probe, the probe-Hg is used²⁺probe-Al³⁺Or probe-Zn²⁺The complex is a reagent, and H2O is detected by fluorescence spectrometry;

(1) using a probe-Hg²⁺The complex is used as a reagent for detecting water in 1, 4-dioxane by a fluorescence spectrum method: is to detect H₂When O is required, H with different volume ratios is respectively added into the 1, 4-dioxane₂O, standing for 1 hour, and exciting by a wavelength of 360nm to obtain a probe-Hg²⁺The fluorescence peak at 530nm is red-shifted to 585nm along with the change of the volume percentage of water in 1, 4-dioxane, the fluorescence intensity at 585nm is gradually reduced along with the increase of the volume percentage of water, the fluorescence intensity and the water content are in a linear relation when the water content is in the range of 1-10% and 10-20%,detection of H by calibration Curve method₂O；

(2) With a probe-Al³⁺The complex is used as a reagent for detecting water in 1, 4-dioxane by a fluorescence spectrum method: is to detect H₂When O is required, H with different volume ratios is respectively added into the 1, 4-dioxane₂O, standing for 1 hour, exciting at a wavelength of 360nm, and probing with-Al³⁺The fluorescence peak at 530nm is red-shifted to 585nm along with the change of the volume percentage of water in 1, 4-dioxane, the fluorescence intensity at 585nm is gradually reduced along with the increase of the volume percentage of water, the fluorescence intensity and the water content are in a linear relation when the water content is in the range of 1-9 percent, and H is detected by a correction curve method₂O；

(3) With probe-Zn²⁺The complex is used as a reagent for detecting water in 1, 4-dioxane by a fluorescence spectrum method: is to detect H₂When O is required, H with different volume ratios is respectively added into the 1, 4-dioxane₂O, standing for 1 hour, and exciting by a wavelength of 360nm to obtain probe-Zn²⁺The fluorescence peak at 590nm is blue-shifted to 548nm along with the change of the volume percentage of water in 1, 4-dioxane, and when the water content is 1-20 percent, the fluorescence intensity at 548nm is linearly increased; when the water content is 20-50%, the fluorescence intensity tends to be stable; when the water content is 50-70%, the fluorescence intensity is linearly reduced, and H is detected by using a calibration curve method₂O。

In the application of the probe, the probe-Hg is used²⁺probe-Al³⁺Or probe-Zn²⁺The complex is a reagent, and H2O is detected by a visual colorimetry;

(1) probe-Hg under 365nm UV lamp²⁺Adding H with the volume ratio of 0%, 1% and 30% into 1, 4-dioxane solvent of the complex respectively₂O, standing for 1 hour, probe-Al³⁺The fluorescence color of the solution is green, red and fluorescence quenching respectively; with H in 1, 4-dioxane solvent₂Changes in the percent by volume of O, sharp changes in the fluorescence color, and detection of H₂The lower limit of detection of the volume percent of O is 1%;

(2) probe-Al under 365nm UV lamp³⁺The complex is added into 1, 4-dioxane solvent by volume ratio of 0 percent and 1 percent respectively10% of H₂O, standing for 1 hour, probe-Al³⁺The fluorescence color of the solution is green, red and fluorescence quenching respectively; with H in 1, 4-dioxane solvent₂The change of volume percentage of O, the change of fluorescence color is sharp; detection of H₂The lower limit of detection of the volume percent of O is 1%;

(3) under 365nm ultraviolet lamp, probe-Zn²⁺Adding H with volume ratio of 0%, 1% and 40% into 1, 4-dioxane solvent₂O, standing for 1 hour, probe-Zn²⁺The fluorescence colors of the solution are respectively red, fluorescence quenching and yellow; with H in 1, 4-dioxane solvent₂Changes in the percent by volume of O, sharp changes in the fluorescence color, and detection of H₂The lower limit of detection of the volume percentage of O is 1%.

Applicants have conducted extensive research for long-term, and in part:

1. probe concentration of 10. mu.M 1, 4-dioxane/H in a volume ratio of 97/3₂In O solution, no metal ion or 100 μ M of metal ion Hg is added²⁺，Al³⁺，Li⁺，Na⁺，K⁺，Zn²⁺，Mg²⁺，Ca²⁺，Ba²⁺，Sr²⁺，Cr³⁺，Fe³⁺，Co²⁺，Ni²⁺，Cu²⁺，Pb²⁺，Cd²⁺，Ag⁺，Mn²⁺Fluorescence spectra measured after 1 hour of action. Hg is a mercury vapor²⁺、Al³⁺The addition of (2) significantly enhanced the fluorescence intensity of the probe at 585 nm. The fluorescence spectrum and the intensity of the probe are not changed by adding other experimental metal ions, which shows that the probe selectively detects Hg under the condition²⁺、Al³⁺. The excitation wavelength was 360 nm. See in particular fig. 1.

2. Probe concentration of 10. mu.M 1, 4-dioxane/H in a volume ratio of 97/3₂Adding Hg with different concentrations into O solution²⁺Fluorescence spectra were measured after 1 hour of exposure to the probe solution. Fluorescence intensity of the probe at 585nm as a function of Hg²⁺The concentration increases and increases linearly. The excitation wavelength tested was 360 nm.See in particular fig. 2.

3. Probe concentration of 10. mu.M 1, 4-dioxane/H in a volume ratio of 97/3₂Adding Hg with different concentrations into O solution²⁺After 1 hour of action, the fluorescence intensity at a wavelength of 585nm is determined. The ordinate is the fluorescence intensity value and the abscissa is Hg²⁺The concentration of (c). The excitation wavelength was 360 nm. See in particular fig. 3.

4. Probe concentration of 10. mu.M 1, 4-dioxane/H in a volume ratio of 97/3₂Adding 100 mu M of metal ion Hg into the O solution respectively²⁺，Al³⁺，Li⁺，Na⁺，K⁺，Zn²⁺，Mg²⁺，Ca²⁺，Ba²⁺，Sr²⁺，Cr³⁺，Fe³⁺，Co²⁺，Ni²⁺，Cu²⁺，Pb²⁺，Cd²⁺，Ag⁺，Mn²⁺Thereafter, the fluorescence intensity at 585nm, Hg, was measured²、Al³⁺The addition of (2) can cause the probe to generate intense fluorescence. Then, the probe-Hg is directed to²⁺After adding 100. mu.M of the above-mentioned other metal ions to the mixed solution, the change in fluorescence intensity at 585mn was measured. Black bars indicate the fluorescence intensity at 585mn after addition of metal ions to the probe solutions, respectively; white bars are indicated in probe-Hg²⁺The mixed solution was added with the other coexisting metal ions, respectively, to change the fluorescence intensity at 585 nm. Indicating the removal of Fe³⁺In addition to a slight effect, the probe detects Hg²⁺The fluorescence intensity of (2) is not affected by the coexistence of the above-mentioned other ions. The excitation wavelength tested was 360nm and the fluorescence emission wavelength was 585 nm. After 1 hour of action, the test is carried out, the ordinate is the fluorescence intensity value and the abscissa is the metal ion. See in particular fig. 4.

5. Probe concentration of 10. mu.M 1, 4-dioxane/H in a volume ratio of 97/3₂Respectively adding Al with different concentrations into the O solution³⁺Fluorescence spectra measured after 1 hour of exposure to the probe solution. Fluorescence intensity of probe at 585nm with Al³⁺The concentration increases and increases linearly. The excitation wavelength tested was 360 nm. See in particular fig. 5.

6. Probes at a concentration of 10. mu.M were used at a volume ratio of 1 of 97/3,4-dioxane/H₂Respectively adding Al with different concentrations into the O solution³⁺The fluorescence intensity at a wavelength of 585nm was determined after 1 hour of action. The ordinate is the fluorescence intensity value and the abscissa is Al³⁺The concentration of (c). The excitation wavelength was 360 nm. See in particular fig. 6.

7. Probe concentration of 10. mu.M 1, 4-dioxane/H in a volume ratio of 97/3₂Adding 100 mu M of metal ion Hg into the O solution respectively²⁺，Al³⁺，Li⁺，Na⁺，K⁺，Zn²⁺，Mg²⁺，Ca²⁺，Ba²⁺，Sr²⁺，Cr³⁺，Fe³⁺，Co²⁺，Ni²⁺，Cu²⁺，Pb²⁺，Cd²⁺，Ag⁺，Mn²⁺Thereafter, the fluorescence intensity at 585nm, Hg, was measured²⁺、Al³⁺The addition of (2) can cause the probe to generate intense fluorescence. Then respectively directing to the probes-Al³⁺After adding 100. mu.M of the above-mentioned other metal ions to the mixed solution, the change in fluorescence intensity at 585mn was measured. Black bars indicate the fluorescence intensity at 585mn after addition of metal ions to the probe solutions, respectively; white bars are shown in Probe-Al³⁺The mixed solution was added with the other coexisting metal ions, respectively, to change the fluorescence intensity at 585 nm. Indicating the removal of Fe³⁺In addition to a slight effect, probe detection of Al³⁺The fluorescence intensity of (2) is not affected by the coexistence of the above-mentioned other ions. The excitation wavelength tested was 360nm and the fluorescence emission wavelength was 585 nm. After 1 hour of action, the test is carried out with fluorescence intensity values on the ordinate and metal on the abscissa. See in particular fig. 7.

8. Probe concentration of 10. mu.M 1, 4-dioxane/H in a volume ratio of 97/3₂In O solution, no metal ion or 100 μ M of metal ion Hg is added²⁺，Al³⁺，Li⁺，Na⁺，K⁺，Zn²⁺，Mg²⁺，Ca²⁺，Ba²⁺，Sr²⁺，Cr³⁺，Fe³⁺，Co²⁺，Ni²⁺，Cu²⁺，Pb²⁺，Cd²⁺，Ag⁺，Mn²⁺UV-Vis test after 1 hour of actionAbsorption spectrum. Hg is a mercury vapor²⁺、Al³⁺The addition of the ions significantly increased the absorbance of the probe at 558nm, while the addition of the other experimental metal ions described above did not change the absorption spectrum and intensity of the probe. Shows that the probe selectively detects Hg under the condition²⁺、Al³⁺. See in particular fig. 8.

9. Probe concentration of 10. mu.M 1, 4-dioxane/H in a volume ratio of 97/3₂Adding Hg with different concentrations into O solution²⁺UV-VIS absorption spectra measured after 1 hour of exposure to the probe solution. Absorbance of probe at 558nm with Hg²⁺The concentration increases and increases linearly. See in particular fig. 9.

10. Probe concentration of 10. mu.M 1, 4-dioxane/H in a volume ratio of 97/3₂Adding Hg with different concentrations into O solution²⁺The absorbance at 558nm was measured after 1 hour of action. The ordinate is absorbance value and the abscissa is Hg²⁺The concentration of (c). See in particular fig. 10.

11. Probe concentration of 10. mu.M 1, 4-dioxane/H in a volume ratio of 97/3₂Adding 100 mu M of metal ion Hg into the O solution respectively²⁺，Al³⁺，Li⁺，Na⁺，K⁺，Zn²⁺，Mg²⁺，Ca²⁺，Ba²⁺，Sr²⁺，Cr³⁺，Fe³⁺，Co²⁺，Ni²⁺，Cu²⁺，Pb² ⁺，Cd²⁺，Ag⁺，Mn²⁺Thereafter, the absorbance at 558nm, Al, was measured³⁺、Hg²⁺The addition of (2) can cause strong absorption of the probe. Then, the probe-Hg is directed to²⁺After adding 100. mu.M of the above-mentioned other metal ions to the mixed solution, the change in absorbance at 558mn was measured. Black bars indicate the absorbance at 558mn after adding metal ions to the probe solutions, respectively; white bars are indicated in probe-Hg²⁺The mixed solution is added with the other coexisting metal ions respectively, and then the change of the absorbance value at 558nm is realized. Indicating that the probe detects Hg²⁺The absorbance of (b) is not affected by the coexistence of the above ions. The test was carried out after 1 hour of action. The maximum absorption wavelength tested was 558 nm. Ordinate of the curveThe absorbance values are plotted on the abscissa for the metal ions. See in particular fig. 11.

12. Probe concentration of 10. mu.M 1, 4-dioxane/H in a volume ratio of 97/3₂Respectively adding Al with different concentrations into the O solution³⁺UV-VIS absorption spectra measured after 1 hour of exposure to the probe solution. Absorbance of probe at 558nm with Al³⁺The concentration increases and increases linearly. See in particular fig. 12.

13. Probe concentration of 10. mu.M 1, 4-dioxane/H in a volume ratio of 97/3₂Respectively adding Al with different concentrations into the O solution³⁺The absorbance at 558nm was measured after 1 hour of action. The ordinate is absorbance value and the abscissa is Al³⁺The concentration of (c). See in particular fig. 13.

14. Probe concentration of 10. mu.M 1, 4-dioxane/H in a volume ratio of 97/3₂Adding 100 mu M of metal ion Hg into the O solution respectively²⁺，Al³⁺，Li⁺，Na⁺，K⁺，Zn²⁺，Mg²⁺，Ca²⁺，Ba²⁺，Sr²⁺，Cr³⁺，Fe³⁺，Co²⁺，Ni²⁺，Cu²⁺，Pb² ⁺，Cd²⁺，Ag⁺，Mn²⁺Thereafter, the absorbance at 558nm, Al, was measured³⁺、Hg²⁺The addition of (2) can cause strong absorption of the probe. Then respectively directing to the probes-Al³⁺After adding 100. mu.M of the above-mentioned other metal ions to the mixed solution, the change in absorbance at 558mn was measured. Black bars indicate the absorbance at 558mn after adding metal ions to the probe solutions, respectively; white bars are shown in Probe-Al³⁺The mixed solution is added with the other coexisting metal ions respectively, and then the change of the absorbance value at 558nm is realized. Indicating that the probe detects Al³⁺The absorbance of (b) is not affected by the coexistence of the above ions. The test was carried out after 1 hour of action. The maximum absorption wavelength tested was 558 nm. The ordinate is absorbance value and the abscissa is metal ion. See in particular fig. 14.

15. The probe at a concentration of 10. mu.M fluoresces very weakly in 1, 4-dioxane solution. In the 1, 4-dioxane/H₂Water content in O-mixed solventThe influence on the fluorescence intensity of the probe is small, and the fluorescence at 480nm and 585nm is only weakly enhanced along with the increase of the water content in the mixed solvent, which indicates that the single probe cannot detect the water content in the 1, 4-dioxane. The test was carried out after 1 hour of action. See in particular fig. 15.

16. Probe-Hg at a concentration of 10. mu.M ²⁺1, 4-dioxane/H of complex in different volume ratios₂Change in fluorescence spectrum in the O mixed solvent. Probe-Al³⁺The fluorescence intensity of the complex is greatly influenced by the volume percentage of water in the mixed solvent, when the water content is 1 percent, the fluorescence peak is changed from 530nm to 585nm, the wavelength is red-shifted by about 55nm, and the fluorescence intensity is obviously enhanced; when the water content is more than 1%, the fluorescence intensity at 585nm gradually decreases with increasing water content; when the water content reaches 30%, the probe-Hg²⁺The fluorescence intensity of (a) is almost quenched. Indicating that under these conditions the probe-Hg²⁺The complex can sensitively detect the water content in 1, 4-dioxane. After 1 hour of action, the excitation wavelength was measured to be 360 nm. See in particular fig. 16.

17. Probe-Hg at a concentration of 10. mu.M²⁺The complex is in 1, 4-dioxane solution with H₂The percentage of O volume increased and the fluorescence intensity at 585nm was measured after 1 hour of action. The ordinate is fluorescence intensity value, and the abscissa is H in 1, 4-dioxane₂Volume percent of O and excitation wavelength of 360 nm. See in particular fig. 17.

18. Probe-Hg at a concentration of 10. mu.M²⁺The fluorescence intensity of the complex at 585nm varies with the percentage by volume of water in 1, 4-dioxane from 1% to 10%. After 1 hour of action, the excitation wavelength was measured to be 360 nm. See in particular fig. 18.

19. Probe-Hg at a concentration of 10. mu.M²⁺The fluorescence intensity of the complex at 585nm varies with the volume percentage of water in 1, 4-dioxane ranging from 10% to 20%. After 1 hour of action, the excitation wavelength was measured to be 360 nm. See in particular fig. 19.

20. Probe-Al with a concentration of 10. mu.M ³⁺1, 4-dioxane/H of complex in different volume ratios₂Change in fluorescence spectrum in the O mixed solvent. Probe-Al³⁺Fluorescence intensity of the ComplexThe influence of the water content in the mixed solvent is great, when the water content is 1 percent, the fluorescence peak is changed from 530nm to 585nm, the wavelength red shift is about 55nm, and the fluorescence intensity is obviously enhanced; when the water content is more than 1%, the fluorescence intensity at 585nm gradually decreases with increasing water content; when the water content reaches 10%, the probe-Al³⁺The fluorescence intensity of (a) is almost quenched. Shows that the probe-Al is present under these conditions³⁺The complex can sensitively detect the water content in 1, 4-dioxane. After 1 hour of action, the excitation wavelength was measured to be 360 nm. See in particular fig. 20.

21. Probe-Al with a concentration of 10. mu.M³⁺The complex is in 1, 4-dioxane solution with H₂The percentage of O volume increased and the fluorescence intensity at 585nm was measured after 1 hour of action. The ordinate is fluorescence intensity value, and the abscissa is H in 1, 4-dioxane₂O volume percent and excitation wavelength of 360 nm. See in particular fig. 21.

22. Probe-Al with a concentration of 10. mu.M³⁺The fluorescence intensity of the complex at 588nm varied with the volume percent water in 1, 4-dioxane. After 1 hour of action, the excitation wavelength was measured to be 360 nm. See in particular fig. 22.

23. Probe-Zn at a concentration of 10. mu.M ²⁺1, 4-dioxane/H of complex in different volume ratios₂Change in fluorescence spectrum in the O mixed solvent. Probe-Zn²⁺The fluorescence intensity of the complex is greatly influenced by the water content in the mixed solvent, and Zn is contained in the 1, 4-dioxane pure solvent²⁺The probe can form strong fluorescence at 590nm, and the fluorescence is immediately quenched when the water content in the mixed solvent reaches 1%; probe-Zn with increasing water content²⁺When a new fluorescence peak appears at 548nm, the wavelength is blue-shifted by about 42nm, and the water content in the mixed solvent is less than 20 percent, the probe-Zn²⁺The fluorescence intensity of the probe is increased linearly, and when the water content is between 20 and 50 percent, the probe-Zn²⁺The fluorescence intensity of the probe tends to be flat, and when the water content is more than 50 percent, the probe-Zn²⁺The fluorescence intensity of (a) gradually decreases again. Indicating that the probe-Zn was present under these conditions²⁺The complex can sensitively detect the water content in 1, 4-dioxane. After 1 hour of action, the excitation wavelength was measured to be 360 nm. See in particular fig. 23.

24. Probe-Zn at a concentration of 10. mu.M²⁺The complex is in 1, 4-dioxane solution with H₂The percentage of O volume increased and the intensity of fluorescence at 548nm was measured after 1 hour of action. The ordinate is fluorescence intensity value, and the abscissa is H in 1, 4-dioxane₂O volume percent and excitation wavelength of 360 nm. See in particular fig. 24.

25. Probe-Zn at a concentration of 10. mu.M²⁺The fluorescence intensity of the complex at 548nm varies with the volume percent of water in the 1, 4-dioxane. After 1 hour of action, the excitation wavelength was measured to be 360 nm. See in particular fig. 25.

26. Probe-Zn at a concentration of 10. mu.M²⁺The fluorescence intensity of the complex at 548nm varies with the volume percent of water in the 1, 4-dioxane. After 1 hour of action, the excitation wavelength was measured to be 360 nm. See in particular fig. 26.

27. probe-Hg at a concentration of 10. mu.M in the cuvette²⁺Adding H with the volume ratio of 0%, 1% and 30% into 1, 4-dioxane solvent of the complex respectively₂O, standing for 1 hour, and probing with a probe-Hg under a 365nm ultraviolet lamp²⁺The fluorescence color of the solution is green, red, fluorescence quenching respectively, and is along with H in 1, 4-dioxane solvent₂The change in volume percentage of O, the fluorescence color change was sharp. See in particular fig. 27.

28. 10 μ M Probe-Al in the cuvette³⁺Adding H with the volume ratio of 0%, 1% and 10% into 1, 4-dioxane solvent of the complex respectively₂O, standing for 1 hour, and then, under a 365nm ultraviolet lamp, and using a probe-Al³⁺The fluorescence color of the solution is green, red, fluorescence quenching respectively, and is along with H in 1, 4-dioxane solvent₂The change in volume percentage of O, the fluorescence color change was sharp. See in particular fig. 28.

29. 10 μ M Probe-Al in the cuvette³⁺Adding H with the volume ratio of 0%, 1% and 10% into 1, 4-dioxane solvent of the complex respectively₂O, standing for 1 hour, and then, under a 365nm ultraviolet lamp, and using a probe-Al³⁺The fluorescence color of the solution is green, red, fluorescence quenching respectively, and is along with H in 1, 4-dioxane solvent₂Change in volume percent of OThe fluorescence color changes sharply.

Compared with the prior art, the invention has the following beneficial effects:

1) the detection performance is superior. The probe has the function of single-probe multi-target detection, and is 1, 4-dioxane/H₂In O mixed solvent, the trace metal ion Hg is realized by adopting fluorescence and ultraviolet-visible absorption spectrum²⁺、Al³⁺Detecting;

2) Probe-Hg in 1, 4-dioxane solvent²⁺The complex is green fluorescence and is in a 1, 4-dioxane solvent when H is₂The O content is 1-30%, and the probe-Hg²⁺The complex shows red fluorescence with H₂The content of O is increased, the red fluorescence is gradually reduced, so that the content of trace and constant water in the 1, 4-dioxane solvent can be quantitatively detected by using a fluorescence spectrum, and the content of water in the 1, 4-dioxane solvent can be qualitatively and semi-quantitatively detected by using a visual colorimetry;

3) probe-Al in 1, 4-dioxane solvent³⁺The complex is green fluorescence and is in a 1, 4-dioxane solvent when H is₂O content is 1-10%, probe-Al³⁺The complex shows red fluorescence with H₂The content of O is increased, the red fluorescence is gradually reduced, so that the content of trace and constant water in the 1, 4-dioxane solvent can be quantitatively detected by using a fluorescence spectrum, and the content of water in the 1, 4-dioxane solvent can be qualitatively and semi-quantitatively detected by using a visual colorimetry;

4) in 1, 4-dioxane solvent, probe-Zn²⁺The complex is red fluorescence; in 1, 4-dioxane solvent H₂No fluorescence when the O content is 1%; at more than 1% to 50%, probe-Zn²⁺Exhibits yellow fluorescence with H₂The yellow fluorescence is gradually enhanced when the content of O is increased, and when the content of H is increased₂When the O content is 50-70%, the yellow fluorescence is gradually reduced, so that the content of trace and constant water in the 1, 4-dioxane solvent can be quantitatively detected by using a fluorescence spectrum, and the content of water in the 1, 4-dioxane solvent can be qualitatively and semi-quantitatively detected by using a visual colorimetry;

the probe can be used for quantitatively detecting Hg by fluorescence and absorption spectrum²⁺、Al³⁺. Meanwhile, the method can also be used for quantitatively, qualitatively and semi-quantitatively detecting H in the 1, 4-dioxane organic solvent by using a spectrum and visual colorimetry₂The method has the advantages of simple and rapid method, sharp and visual color change, strong applicability, visibility and multiple functions. The single-probe multi-target identification technology is mainly embodied in the aspects of ingenious probe design, simple structure, low preparation cost, various identification modes, excellent detection performance, easy control of operation conditions, good application prospect and the like.

Therefore, the probe can realize single-probe multi-target detection, namely can be simultaneously used for detecting Hg²⁺、Al³⁺And H₂And O, the detection cost is low, and the detection efficiency is high. And facilitates the analysis of complex microscopic systems.

Description of the drawings:

FIG. 1 shows the detection of Hg by probe²⁺、Al³⁺A fluorescence spectrum of (a);

FIG. 2 shows Hg concentration in different ranges²⁺A fluorescence spectrum titration chart with the probe;

FIG. 3 is a probe for detecting Hg²⁺The fluorescence intensity calibration curve of (1);

FIG. 4 shows the detection of Hg by a probe in which metal ions coexist²⁺A fluorescence intensity influence map of (a);

FIG. 5 shows different concentrations of Al³⁺A fluorescence spectrum titration chart with the probe;

FIG. 6 is probe detection of Al³⁺The fluorescence intensity correction curve of (1);

FIG. 7 shows the detection of Al by the coexisting metal ion pair probe³⁺A fluorescence intensity influence map of (a);

FIG. 8 is probe detection of Hg²⁺、Al³⁺Ultraviolet-visible absorption spectrum of (a);

FIG. 9 shows Hg concentration at various concentrations²⁺Ultraviolet-visible absorption spectrum titration chart with probe;

FIG. 10 is probe detection of Hg²⁺The absorbance calibration graph of (a);

FIG. 11 shows the detection of Hg by a probe with coexisting metal ions²⁺The absorbance influence graph of (a);

FIG. 12 shows different concentrations of Al³⁺Purple with probeExo-visible absorption spectrum titrimetric chart;

FIG. 13 is probe detection of Al³⁺The absorbance calibration graph of (a);

FIG. 14 shows the detection of Hg by a probe in which metal ions coexist²⁺The absorbance influence graph of (a);

FIG. 15 is a fluorescence spectrum of water detected by the probe;

FIG. 16 is probe-Hg²⁺Detecting a fluorescence spectrogram of water by using the complex;

FIG. 17 is probe-Hg²⁺Detecting the fluorescence intensity change curve of water by the compound;

FIG. 18 is probe-Hg²⁺The calibration curve graph of the complex for detecting trace water;

FIG. 19 is probe-Hg²⁺A calibration curve graph of the complex detection constant water;

FIG. 20 shows a probe-Al³⁺Detecting a fluorescence spectrogram of water by using the complex;

FIG. 21 shows probe-Al³⁺Detecting a fluorescence intensity change curve chart of water;

FIG. 22 shows probe-Al³⁺A correction curve chart of the water content of the complex detection;

FIG. 23 shows probe-Zn²⁺Detecting a fluorescence spectrogram of water by using the complex;

FIG. 24 shows probe-Zn²⁺Detecting a fluorescence intensity change curve chart of water by the compound;

FIG. 25 shows probe-Zn²⁺The calibration curve chart of the trace water content of the complex detection;

FIG. 26 shows probe-Zn²⁺A calibration curve graph of the complex detection constant water content;

FIG. 27 is probe-Hg²⁺The color change photo of the trace water is detected by the visual colorimetry of the complex;

FIG. 28 shows probe-Al³⁺The color change photo of the trace water is detected by the visual colorimetry of the complex;

FIG. 29 shows probe-Zn²⁺The color change photo of the trace water is detected by visual colorimetry of the complex.

Detailed Description

Example 1:

1. a probe having a chemical formula:

the synthetic route of the probe is as follows:

the specific preparation method of the probe comprises the following steps:

weighing tris (2-aminoethyl) amine (4.00g, 27.36mmol) in a 100mL three-neck flask under the protection of nitrogen, weighing 20mL of absolute ethanol, stirring, heating, refluxing, weighing rhodamine B (1.64g, 3.42mmol) to dissolve in 40mL of absolute ethanol, adding into a constant pressure funnel, slowly dropping into the three-neck flask, refluxing for 36h after dropping, distilling off the ethanol under reduced pressure, extracting with dichloromethane (3 × 100mL), drying an organic phase with anhydrous sodium sulfate overnight, distilling off a solvent to obtain a red viscous substance, and performing silica gel column chromatography separation, wherein the eluent is methanol/trichloromethane/triethylamine (9/1/1 (v/v/v)), so that 1.63g of colorless viscous intermediate a is obtained, and the yield is 83.1%. The structural characterization data are:¹H NMR(500MHz,CDCl₃,ppm)δ:7.887(s,1H,ArH)，7.452(s,2H,ArH),7.097(bs,1H,ArH)，6.396(d,J＝12.5Hz,4H,ArH)，6.282(d,J＝9.0Hz,2H,ArH)，3.365～3.337(m,8H,-CH₂CH₃)，3.154(t,J＝7.8Hz,2H,O＝CNCH₂-)，2.557(t,J＝6.0Hz,4H,-CH₂NH₂)，2.357(t,J＝6.0Hz,4H,NCH₂CH₂)，2.237(t,J＝7.5Hz,2H,NCH₂CH₂),1.251(m,6H,-CH₂CH₃)，1.169(t,J＝7.0Hz,12H,-CH₃)。

weighing the intermediate a (500mg,0.87mmol) and benzothiazole aldehyde (350mg,1.31mmol) in a 100mL three-necked flask, dissolving in 60mL dry ethanol, refluxing for 4h under the protection of nitrogen, evaporating the solvent under reduced pressure to obtain a yellow-green solid, and separating by silica gel column chromatography, wherein the eluent is dichloromethane/n-hexane/diethylamine-60/40/2 (v/v/v), so as to obtain 362mg of the yellow-green solid, and the yield is 50.3%. (ii) aThe structural characterization data are: IR (KBr, v cm)^-1):3428(O-H),2962(-CH₃),1690(C＝N),1640(C＝O),1596(C＝C),1472(C＝C),1349(N-CH₃),803(Ar-H)，745(Ar-H).¹H NMR(500MHz,CDCl₃,ppm)δ:11.717(s,1H,-OH),8.117(s,2H,-CH＝N×2),7.970(s,1H,ArH),7.861(d,J＝8.5Hz,2H,ArH×2),7.726(d,J＝8.5Hz,1H,ArH),7.534(d,J＝8.5Hz,2H,ArH×2),7.410(m,2H,ArH),7.198(d,J＝8.0Hz,1H,ArH),7.138(bs,1H,ArH),6.890(d,J＝9.5Hz,1H,ArH),6.524(m,J＝9.5Hz,4H,ArH),6.388(d,J＝5.5Hz,2H,ArH),3.479(m,J＝5.5Hz,4H,-CH₂-),3.376～3.289(m,8H,-CH₂CH₃),2.753(t,J＝5.5Hz,4H,-CH₂NH₂),2.444(t,J＝8.0Hz,2H,NCH₂CH₂),1.444(t,J＝7.0Hz,2H,CH₂NH₂),1.214(t,J＝7.0Hz,12H,-CH₃).¹³C NMR(500M,CDCl₃,ppm)δ:168.50,165.09,160.30,153.52,153.19,152.62,151.66,149.88,148.92,132.94,132.42,131.80,129.19,126.46,125.52,123.90,122.68,122.18,121.37,119.20,118.69,114.64,108.21,105.67,97.70,77.28,77.03,76.77,57.09,54.72,54.17,4.13.MS(MALDI-TOF)Calcd for[C₄₆H₅₀N₁₂O₈]:m/z 1076.417,Found:m/z 1077.269[M+H]⁺。

Example 2 reagent preparation

(1) Preparing a probe solution: 10.76mg of the probe prepared in example 1 was weighed, dissolved in 1.4 dioxane, and prepared into 10mL of a 1mM probe stock solution;

(2)Hg²⁺preparing a stock solution: weighing 226.8mg of mercuric perchlorate, dissolving the mercuric perchlorate by ultrapure water, and preparing 50mL of 20mM aqueous solution; mercury perchlorate is weighed and dissolved by acetonitrile to prepare an anhydrous solution with the concentration of 1 mM.

(3)Al³⁺Preparing a stock solution: weighing 343.3mg of aluminum perchlorate nonahydrate, dissolving with ultrapure water, and preparing into 50mL of 20mM aqueous solution; weighing aluminum perchlorate, dissolving the aluminum perchlorate with acetonitrile, and preparing into an anhydrous solution with the concentration of 1 mM;

(4) other metal ions (Li)⁺，Na⁺，K⁺，Mg²⁺，Ca²⁺，Ba²⁺，Sr²⁺，Fe³⁺，Sr²⁺，Zn²⁺，Co²⁺，Ni²⁺，Cd²⁺，Pb²⁺，Cr³⁺，Ag⁺，Cu²⁺，Mn²⁺) Preparing a stock solution: respectively taking perchlorates of corresponding metal ions, dissolving the perchlorates in ultrapure water, and preparing into 20mM metal ion stock solution.

Example 3 detection of Hg by fluorescence Spectroscopy²⁺、Al³⁺

1. Detection of Hg²⁺

A10 mL volumetric flask was charged with probe solution (1mM, 100. mu.L) and diluted with 1, 4-dioxane/water so that the probe solution had a composition of 1, 4-dioxane/water in a volume ratio of 97/3, and shaken. 3ml of the solution was added to a 1cm cuvette, and fluorescence spectrometry was carried out with 360nm as a fluorescence excitation wavelength.

There was substantially no fluorescence emission in a solution with a 1, 4-dioxane/water volume ratio of 97/3 and a probe concentration of 10. mu.M. Separately, 100. mu.M of metal ions were added: hg is a mercury vapor²⁺，Al³⁺，Li⁺，Na⁺，K⁺，Zn²⁺，Mg²⁺，Ca²⁺，Ba²⁺，Sr²⁺，Cr³⁺，Fe³⁺，Co²⁺，Ni²⁺，Cu²⁺，Pb²⁺，Cd²⁺，Ag⁺，Mn²⁺Left for 1 hour, only Al³⁺、Hg²⁺The addition of (2) significantly enhanced the fluorescence peak of the probe at 585nm (see FIG. 1).

To probe solutions with a concentration of 10. mu.M and a volume ratio of 1, 4-dioxane/water of 97/3, Hg was added at different concentrations²⁺Ion, left for 1 hour, and subjected to fluorescence spectroscopic titration (see FIG. 2). Measurement of Hg²⁺Fluorescence intensity of the probe at 585nm with varying concentration, a fluorescence calibration curve was obtained (see FIG. 3). Measuring and calculating the standard deviation of the 11 blank values according to the slope of the calibration curve to obtain the Hg detected by the probe fluorescence method²⁺The linear range of concentration and the detection limit of (B) are shown in Table 1.

At a 1, 4-dioxane/water volume ratio of 97/3 concentration of 10 μM probe solution, 100. mu.M Hg was added²⁺Then, probe-Hg was added again²⁺Adding other metal ions such as Li into the system in equal amount⁺，Na⁺，K⁺，Mg²⁺，Ca²⁺，Ba²⁺，Zn²⁺，Sr² ⁺，Ni²⁺，Cd²⁺，Pb²⁺，Co²⁺，Al³⁺，Cr³⁺，Fe³⁺，Ag⁺，Cu²⁺，Mn²⁺After standing for 1 hour, the change in fluorescence intensity was measured. Fe³⁺Ion pair probe detection of Hg²⁺Has weak influence; probe-Hg of other metal ion pairs²⁺The system had no effect. (see FIG. 4)

2. Detection of Al³⁺

There was substantially no fluorescence emission in a probe solution with a 1, 4-dioxane/water volume ratio of 97/3 and a concentration of 10. mu.M. Separately, 100. mu.M of metal ions were added: hg is a mercury vapor²⁺，Al³⁺，Li⁺，Na⁺，K⁺，Zn²⁺，Mg²⁺，Ca²⁺，Ba²⁺，Sr²⁺，Cr³⁺，Fe³⁺，Co²⁺，Ni²⁺，Cu²⁺，Pb²⁺，Cd²⁺，Ag⁺，Mn²⁺Left for 1 hour, only Al³⁺、Hg²⁺The addition of (2) significantly enhanced the fluorescence peak of the probe at 585nm (see FIG. 1).

To probe solutions with a concentration of 10. mu.M and a volume ratio of 1, 4-dioxane/water of 97/3, Al was added in different concentrations³⁺Ion, left for 1 hour, and subjected to fluorescence spectroscopic titration (see FIG. 5). Determination of Al³⁺Fluorescence intensity of the probe at 585nm with varying concentration, a fluorescence calibration curve was obtained (see FIG. 6). The slope of the calibration curve and the standard deviation of the measured 11 blank values are measured and calculatedDetection of Al by probe fluorescence method³⁺The linear range of concentration and the detection limit of (B) are shown in Table 1.

To a probe solution having a concentration of 10. mu.M and a volume ratio of 1, 4-dioxane/water of 97/3, 100. mu.M of Al was added³⁺Then, probe-Al is again introduced³⁺Adding other metal ions such as Li into the system in equal amount⁺，Na⁺，K⁺，Mg²⁺，Ca²⁺，Ba²⁺，Zn²⁺，Sr² ⁺，Ni²⁺，Cd²⁺，Pb²⁺，Co²⁺，Hg²⁺，Cr³⁺，Fe³⁺，Ag⁺，Cu²⁺，Mn²⁺After standing for 1 hour, the change in fluorescence intensity was measured. Fe³⁺Detection of Al by ion-pair probe³⁺Has weak influence; other metal ion Pair Probe-Al³⁺The system had no effect. (see FIG. 7)

Example 4 detection of Hg by UV-Vis absorption Spectroscopy²⁺、Al³⁺。

1. Detection of Hg²⁺

A10 mL volumetric flask was charged with probe solution (1mM, 100. mu.L) and diluted with 1, 4-dioxane/water so that the probe solution had a composition of 1, 4-dioxane/water in a volume ratio of 97/3, and shaken. 3ml of the solution was put into a 1cm cuvette and subjected to ultraviolet-visible absorption spectroscopy. .

To a probe solution having a concentration of 10. mu.M and a volume ratio of 1, 4-dioxane/water of 97/3, 100. mu.M of metal ions: hg is a mercury vapor²⁺，Al³⁺，Li⁺，Na⁺，K⁺，Zn²⁺，Mg²⁺，Ca²⁺，Ba²⁺，Sr²⁺，Cr³⁺，Fe³⁺，Co²⁺，Ni²⁺，Cu²⁺，Pb²⁺，Cd²⁺，Ag⁺，Mn²⁺Left for 1 hour, only Al³⁺、Hg²⁺The addition of (2) significantly enhanced the absorbance of the probe at 558nm (see FIG. 8).

To probe solutions with a concentration of 10. mu.M and a volume ratio of 1, 4-dioxane/water of 97/3, Hg was added at different concentrations²⁺Ion, left for 1 hour, and subjected to absorption spectrum titration (see FIG. 9). Measurement of Hg²⁺Absorbance calibration curves were obtained for the probe at 558nm with varying concentrations (see figure 10). From the slope of the calibration curve and the standard deviation of the measured 11 blank values, the Hg detection by probe absorption spectrometry is determined and calculated²⁺The linear range of concentration and the detection limit of (B) are shown in Table 1.

100. mu.M Hg was added to a probe solution having a concentration of 10. mu.M and a volume ratio of 1, 4-dioxane/water of 97/3²⁺Then, probe-Hg was added again²⁺Adding other metal ions such as Li into the system in equal amount⁺，Na⁺，K⁺，Mg²⁺，Ca²⁺，Ba²⁺，Zn²⁺，Sr² ⁺，Ni²⁺，Cd²⁺，Pb²⁺，Co²⁺，Al³⁺，Cr³⁺，Fe³⁺，Ag⁺，Cu²⁺，Mn²⁺After standing for 1 hour, the absorbance change was measured. probe-Hg of other metal ion pairs²⁺The system had no effect. (see FIG. 11).

2. Detection of Al³⁺

A10 mL volumetric flask was charged with probe solution (1mM, 100. mu.L) and diluted with 1, 4-dioxane/water so that the probe solution had a composition of 1, 4-dioxane/water in a volume ratio of 97/3, and shaken. 3ml of the solution was put into a 1cm cuvette and subjected to ultraviolet-visible absorption spectroscopy.

At a 1, 4-dioxane/water volume ratio of 97/3, concentratedAdding Al with different concentrations into probe solution with the concentration of 10 μ M³⁺Ion, left for 1 hour, and subjected to absorption spectrum titration (see FIG. 12). Determination of Al³⁺Absorbance calibration curves were obtained for the probe at 558nm as the concentration was varied (see figure 13). Measuring and calculating the standard deviation of the 11 blank values from the slope of the calibration curve to obtain the Al detected by the probe absorption spectrometry³⁺The linear range of concentration and the detection limit of (B) are shown in Table 1.

100. mu.M Al was added to a probe solution having a concentration of 10. mu.M and a volume ratio of 1, 4-dioxane/water of 97/3³⁺Then, probe-Al is again introduced³⁺Adding other metal ions such as Li into the system in equal amount⁺，Na⁺，K⁺，Mg²⁺，Ca²⁺，Ba²⁺，Zn²⁺，Sr² ⁺，Ni²⁺，Cd²⁺，Pb²⁺，Co²⁺，Hg²⁺，Cr³⁺，Fe³⁺，Ag⁺，Cu²⁺，Mn²⁺After standing for 1 hour, the absorbance change was measured. Other metal ion Pair Probe-Al³⁺The system had no effect. (see FIG. 14)

TABLE 1 Probe detection of Hg²⁺,Al³⁺Analysis parameter of

Example 5 Probe-Hg²⁺probe-Al³⁺probe-Zn²⁺Complex detection for H in 1, 4-dioxane₂O

1. Fluorescence spectroscopy detection

1) Probe-Hg²⁺Complex detection

A10 mL volumetric flask was charged with 100. mu.L of 1, 4-dioxane stock solution containing 1mM probe and 1mM Hg²⁺Acetonitrile stock solution of (5) in 100. mu.L, with H₂Diluting with mixed solvent of O/1, 4-dioxane, and shaking. 3ml of the solution was added to a 1cm cuvette and subjected to fluorescence spectrometry.

At a concentration of 10. mu.M probe-Hg²⁺In the solution of 1, 4-dioxane, the mixed solvent H is changed₂The volume ratio of O/1, 4-dioxane was left for 1 hour, and fluorescence spectrometry was performed at 360nm as the fluorescence excitation wavelength (see FIG. 16). Determination of H in 1, 4-dioxane₂probe-Hg at varying volume ratio of O²⁺The fluorescence intensity of the complex reagent at 585nm is used for obtaining a probe-Hg²⁺Detecting the change curve of the fluorescence intensity of water (see figure 17), and respectively obtaining H in 1, 4-dioxane₂Two fluorescence calibration curves (see fig. 18 and 19) with the volume percentage of O in the range of 1-10% and 10-20%, so that the calibration curves can quantitatively detect the water content in the mixed solvent.

2) Probe-Al³⁺Complex detection

A10 mL volumetric flask was charged with 100. mu.L of 1, 4-dioxane stock solution containing 1mM probe and 1mM Al³⁺Acetonitrile stock solution of (5) in 100. mu.L, with H₂Diluting with mixed solvent of O/1, 4-dioxane, and shaking. 3ml of the solution was added to a 1cm cuvette and subjected to fluorescence spectrometry. .

Probe-Al at a concentration of 10. mu.M³⁺Changing mixed solvent H in 1, 4-dioxane solution of complex reagent₂The volume ratio of O/1, 4-dioxane was left for 1 hour, and fluorescence spectrometry was performed at 360nm as the fluorescence excitation wavelength (see FIG. 20). Determination of H in 1, 4-dioxane₂probe-Al at varying O volume ratio³⁺The fluorescence intensity of the complex reagent at 585nm is used for obtaining the probe-Al³The change curve of fluorescence intensity of water was detected (see FIG. 21), and H in 1, 4-dioxane was obtained₂A fluorescence calibration curve (see FIG. 22) in which the percentage by volume of O is in the range of 1% to 9%, whereby the calibration curve allows quantitative determination of the water content in the mixed solvent.

3) Probe-Zn²⁺Complex detection

A10 mL volumetric flask was charged with 100. mu.L of 1, 4-dioxane stock solution containing 1mM probe and 1mM Zn²⁺Acetonitrile stock solution of (5) in 100. mu.L, with H₂Diluting with mixed solvent of O/1, 4-dioxane, and shaking. 3ml of the solution was added to a 1cm cuvette and subjected to fluorescence spectrometry. .

At a concentration of10 μ M Probe-Zn²⁺Changing mixed solvent H in 1, 4-dioxane solution of complex reagent₂The volume ratio of O/1, 4-dioxane was left for 1 hour, and fluorescence spectrometry was performed at a fluorescence excitation wavelength of 360nm (see FIG. 23). Determination of H in 1, 4-dioxane₂probe-Zn at varying O volume ratio²⁺The fluorescence intensity of the complex reagent at 548nm is used for obtaining the probe-Zn²Detecting the change curve of the fluorescence intensity of water (see figure 24), and respectively obtaining H in 1, 4-dioxane₂Two fluorescence calibration curves (see fig. 25 and 26) with the volume ratio of O in the range of 1-20% and 50-70%, so that the calibration curves can quantitatively detect the water content in the mixed solvent.

2. Visual colorimetric detection

1) Probe-Hg²⁺Complex detection

1, 4-dioxane stock solution with 1mM probe and 1mM Hg in a series of cuvettes²⁺The acetonitrile stock solution is prepared into probe-Hg with the concentration of 50 mu M²⁺The complex reagent solution is respectively diluted by mixed solvent with the volume ratio of 0 percent to 1 percent to 30 percent of water in 1, 4-dioxane, placed for 1 hour, and subjected to probe-Hg under a 365nm ultraviolet lamp²⁺The color of the fluorescence emitted by the complex reagent solution changes from green to orange as the volume percent of water in the 1, 4-dioxane increases and then quenches. Through visual colorimetry, the content of water in the mixed solvent with the volume percentage of 1% of water in the 1, 4-dioxane can be detected at the lowest, and the content of water in the mixed solvent with the volume percentage of 30% of water in the 1, 4-dioxane can be detected at the highest. The color change was sharp and clear (see fig. 27).

2) Probe-Al³⁺Complex detection

1, 4-Dioxane stock solution with a 1mM concentration of probe and 1mM concentration of Al in a series of cuvettes³⁺The acetonitrile stock solution is prepared into probe-Al with the concentration of 50 mu M³⁺The complex reagent solution is respectively diluted by mixed solvent with the volume ratio of 0 percent to 1 percent to 10 percent of water in 1, 4-dioxane, placed for 1 hour, and subjected to probe-Al under a 365nm ultraviolet lamp³⁺The color of the fluorescent emitted by the complex reagent solution is changed with the 1, 4-dioxygenThe increase in the volume percent of water in the six rings changed from green to orange and then quenched. Through visual colorimetry, the content of water in the mixed solvent with the volume percentage of 1% in 1, 4-dioxane can be detected at the lowest, and the content of water in the mixed solvent with the volume percentage of 10% in 1, 4-dioxane can be detected at the highest. The color change is sharp and clear (see fig. 28).

3) Probe-Zn²⁺Complex detection

1, 4-dioxane stock solution with 1mM probe and Znl with 1mM probe in a series of cuvettes²⁺The acetonitrile stock solution is prepared into probe-Zn with the concentration of 10 mu M²⁺The complex reagent solution is respectively diluted by mixed solvent with the volume ratio of 0 percent to 1 percent to 40 percent of water in 1, 4-dioxane, placed for 1 hour, and the probe-Znl is placed under a 365nm ultraviolet lamp²⁺The color of the fluorescence emitted by the complex reagent solution changed from orange to yellow as the percentage of water in the 1, 4-dioxane increased by volume and then quenched. Through visual colorimetry, the content of water in the mixed solvent with the volume percentage of 1% in 1, 4-dioxane can be detected at the lowest, and the content of water in the mixed solvent with the volume percentage of 10% in 1, 4-dioxane can be detected at the highest. The color change is sharp and clear (see fig. 29).

Claims

1. A probe, characterized by: the chemical name of the probe is: tris [2, 2' -bis [ (4-benzothiazol-2-yl) -2, 5-dihydroxybenzaldehyde ] aminefhyl-2- "-rhodamine carboxamidoethyl ] amine; the chemical structural formula of the probe is as follows:

2. the method for preparing the probe according to claim 1, wherein: is synthesized according to the following route:

3. the method for preparing the probe according to claim 2, wherein: the method comprises the following steps:

(2) weighing 0.87mmol of intermediate a and 1.31mmol of 2, 5-dihydroxy-4-benzothiazolylbenzaldehyde in a 100mL three-necked flask, dissolving in 60mL dry ethanol, refluxing for 4h under the protection of nitrogen, evaporating the solvent under reduced pressure to obtain a yellow-green solid, and separating by silica gel column chromatography, wherein the eluent is dichloromethane, n-hexane and diethylamine in a volume ratio of 60: 40: 2 to obtain 362mg of yellow-green solid, namely the probe.

4. Use of the probe of claim 1 for non-diagnostic, non-therapeutic purposes, wherein: for detecting Hg²⁺、Al³⁺And/or H₂O。

5. Use of the probe of claim 4 for non-diagnostic, non-therapeutic purposes, wherein: the method is used for detecting Hg²⁺、Al³⁺And/or H₂O comprises:

(3) using a probe-Hg²⁺probe-Al³⁺Or a probe-Zn²⁺Fluorescence spectrometry for H with complex as reagent₂Detecting O;

6. Use of the probe of claim 5 for non-diagnostic, non-therapeutic purposes, wherein: the probe is used as a reagent to carry out fluorescence spectrometry on trace Hg²⁺、Al³⁺The detection of (1) is:

trace Hg is detected by fluorescence spectrometry with probe as reagent²⁺The detection of (a) is; in a volume ratio of 97/3 of 1, 4-dioxane/H₂In the O solution, metal ions are added into the probe solution and are placed for 1 hour, 360nm is used as an excitation wavelength, and the fluorescence intensity of the probe at 585nm and Hg are detected²⁺The concentration is in a linear relation; hg detection by calibration curve method²⁺The other coexisting metal ion is Al³⁺，Li⁺，Na⁺，K⁺，Mg²⁺，Ba²⁺，Ca²⁺，Sr²⁺，Zn²⁺，Cd²⁺，Ni²⁺，Co²⁺，Pb²⁺，Cr³⁺，Ag⁺，Cu²⁺，Mn²⁺One, concentration and Hg²⁺At the same time, other above metal ion pairs Hg²⁺The measurement is not interfered;

7. Use of the probe of claim 5 for non-diagnostic, non-therapeutic purposes, wherein: the probe is used as a reagent to treat trace Hg by ultraviolet-visible absorption spectrometry²⁺、Al³⁺The detection of (1) is:

micro Hg is treated by ultraviolet-visible absorption spectrometry with a probe as a reagent²⁺The detection of (a) is; in a volume ratio of 97/3 of 1, 4-dioxane/H₂In the O solution, after the metal ions are added into the probe solution and placed for 1 hour, the absorbance of the probe at 558nm and Hg²⁺The concentration is in a linear relation, and other metal ions do not interfere with detection; hg detection by calibration curve method²⁺(ii) a Other coexisting metal ions: al (Al)³⁺，Li⁺，Na⁺，K⁺，Mg²⁺，Ba²⁺，Ca²⁺，Sr²⁺，Zn²⁺，Cd²⁺，Ni²⁺，Co²⁺，Pb²⁺，Cr³⁺，Fe³⁺，Ag⁺，Cu²⁺，Mn²⁺One, concentration and Hg²⁺For the same Hg²⁺The measurement is not interfered;

8. Use of the probe of claim 5 for non-diagnostic, non-therapeutic purposes, wherein: the probe-Hg is used² ⁺probe-Al³⁺Or probe-Zn²⁺Fluorescence spectrometry for H with complex as reagent₂The detection of O is:

(1) using a probe-Hg²⁺The complex is used as a reagent for detecting water in 1, 4-dioxane by a fluorescence spectrum method: is to detect H₂When O is required, H with different volume ratios is respectively added into the 1, 4-dioxane₂O, standing for 1 hour, and exciting by a wavelength of 360nm to obtain a probe-Hg²⁺The fluorescence peak at 530nm is red-shifted to 585nm along with the change of the volume percentage of water in 1, 4-dioxane, the fluorescence intensity at 585nm is gradually reduced along with the increase of the volume percentage of water, the fluorescence intensity and the water content are in a linear relation when the water content is in the range of 1-10% and 10-20%, and H is detected by a correction curve method₂O；

(3) With probe-Zn²⁺The complex is used as a reagent for detecting water in 1, 4-dioxane by a fluorescence spectrum method: is to detect H₂When O is required, H with different volume ratios is respectively added into the 1, 4-dioxane₂O, standing for 1 hour, and exciting by a wavelength of 360nm to obtain probe-Zn²⁺The fluorescence peak at 590nm is blue-shifted to 548nm along with the change of the volume percentage of water in 1, 4-dioxane, and when the water content is 1-20 percent, the fluorescence intensity at 548nm is linearly increased; the water content is 20When the percentage is 50 percent, the fluorescence intensity tends to be stable; when the water content is 50-70%, the fluorescence intensity is linearly reduced, and H is detected by using a calibration curve method₂O。

9. Use of the probe of claim 5 for non-diagnostic, non-therapeutic purposes, wherein: the probe-Hg is used² ⁺probe-Al³⁺Or probe-Zn²⁺The complex is a reagent, and the detection of H2O by a visual colorimetry is as follows:

(2) probe-Al under 365nm UV lamp³⁺Adding H with the volume ratio of 0%, 1% and 10% into 1, 4-dioxane solvent of the complex respectively₂O, standing for 1 hour, probe-Al³⁺The fluorescence color of the solution is green, red and fluorescence quenching respectively; with H in 1, 4-dioxane solvent₂The change of volume percentage of O, the change of fluorescence color is sharp; detection of H₂The lower limit of detection of the volume percent of O is 1%;