CN113264898B

CN113264898B - Benzoxazole colorimetric fluorescent probe ZY15 for detecting mercury ions and preparation method and application thereof

Info

Publication number: CN113264898B
Application number: CN202110547722.9A
Authority: CN
Inventors: 张勇; 刘桂琴; 邵秀荣; 隋宁; 徐来; 左小华
Original assignee: Huangshi Famu Pharmaceutical Co ltd; Hubei Polytechnic University; Hubei Normal University
Current assignee: Huangshi Famu Pharmaceutical Co ltd; Hubei Polytechnic University; Hubei Normal University
Priority date: 2021-05-19
Filing date: 2021-05-19
Publication date: 2022-05-06
Anticipated expiration: 2041-05-19
Also published as: CN113264898A

Abstract

The invention provides a benzoxazole colorimetric fluorescent probe ZY15 for detecting mercury ions, and a preparation method and application thereof. It can be obtained by reacting 4-chloro-7-chlorosulfonyl-2, 1, 3-benzoxadiazole with ammonia water and di (2- (ethylthio) ethyl) amine in sequence according to a certain proportion. The fluorescent probe ZY15 has high selectivity and sensitivity to mercury ions, short response time and strong anti-interference capability, and has the lowest detection limit to mercury ions of 9.6nmol/L along with obvious changes of fluorescence intensity and fluorescence color. The probe ZY15 can detect the content of mercury ions in different water body samples, and has good application prospect in the aspect of environmental monitoring.

Description

Benzoxazole colorimetric fluorescent probe ZY15 for detecting mercury ions and preparation method and application thereof

[ technical field ] A method for producing a semiconductor device

The invention belongs to the field of organic micromolecule fluorescent probes and preparation and application thereof, and particularly relates to a benzoxazole colorimetric fluorescent probe ZY15 for detecting mercury ions, and a preparation method and application thereof.

[ background of the invention ]

Mercury ionSon (Hg)²⁺) Is a common heavy metal ion with extremely physiological toxicity, is easily absorbed and accumulated by organisms, can cause damage to the central nervous system, and can cause respiratory failure and even death in severe cases. Hg²⁺Once in the environment, it can directly cause great pollution to soil, air and water sources. Hg passive plant enrichment in the environment²⁺The organic mercury with higher toxicity can be generated through biotransformation, and various forms of mercury can finally enter human bodies through water bodies and food chains. The water guarantee disease is the public hazard caused by unreasonable discharge of industrial wastewater containing mercury. Therefore, Hg²⁺The mercury in drinking water is harmful to human bodies and environment, and the maximum allowable value of mercury in drinking water is 10nmol/L which is regulated by the Ministry of China and the United states environmental protection agency. Therefore, a method capable of detecting Hg in real time, in situ and rapidly is established²⁺The method has very important research significance.

At present, for detecting Hg²⁺The traditional analysis methods comprise atomic absorption spectrometry, an electrochemical method, chromatography, capillary electrophoresis and the like, but the application of the traditional analysis methods is limited to a certain extent due to the influence of factors such as complex sample pretreatment, time consumption, expensive instruments and the like. Compared with the traditional detection method, the organic small-molecule fluorescent probe detection technology becomes an important Hg because of the advantages of high detection sensitivity, good selectivity, rapid and convenient detection and the like²⁺And (3) a detection method. Hg is a mercury vapor²⁺The interaction with the fluorescent small molecular probe can cause the photophysical and photochemical property changes, thereby realizing the Hg-Hg interaction²⁺High selectivity identification.

For detecting Hg²⁺The fluorescent probes have been reported at present, but the probes really applied to practice are few, mainly because the fluorescent probes have limitations such as slow response time, poor interference resistance and the like. Therefore, high performance Hg was developed²⁺Fluorescent probes are a difficult problem to be solved by those skilled in the art.

[ summary of the invention ]

The invention aims to overcome the defects in the prior art and provides a benzoxadiazole analog color fluorescent probe ZY15 which is good in selectivity, high in sensitivity, convenient to use, strong in anti-interference capability and fast in response, and a preparation method and application thereof.

In order to achieve the purpose, the invention provides a benzoxadiazole analog color fluorescent probe ZY15 for detecting mercury ions, which is characterized in that the molecular formula is C₁₄H₂₂N₄O₃S₃The structural formula is as follows:

the invention also provides a preparation method of the probe ZY15, which is characterized by comprising the following steps:

(1) dissolving 4-chloro-7-chlorosulfonyl-2, 1, 3-benzoxadiazole in tetrahydrofuran, adding ammonia water, evaporating the solvent after reaction to obtain a crude product I, adding water into the crude product I, extracting with dichloromethane for three times, combining organic phases, drying with anhydrous magnesium sulfate, and evaporating the solvent to obtain an intermediate, namely 4-chloro-7-sulfonamido-2, 1, 3-benzoxadiazole;

(2) and (2) dissolving the intermediate obtained in the step (1) in tetrahydrofuran, adding bis (2- (ethylthio) ethyl) amine and triethylamine, reacting, evaporating a solvent to obtain a crude product II, and separating the crude product II by column chromatography to obtain a product probe ZY 15.

Preferably, in the step (1), the molar ratio of the 4-chloro-7-chlorosulfonyl-2, 1, 3-benzoxadiazole to the ammonia water is 1: 1-1: 3, the reaction temperature is 0-50 ℃, and the reaction time is 5-30 minutes.

Preferably, the molar ratio of the intermediate, bis (2- (ethylthio) ethyl) amine and triethylamine in step (2) is 1:1: 1-1: 3:1, the reaction temperature is 10-60 ℃, the reaction time is 1-4 hours, and the volume ratio of ethyl acetate and petroleum ether used as eluents for column chromatography purification is 3: 1-6: 1.

The synthetic route of the probe ZY15 is as follows:

。

the invention also provides the probe ZY15 in Hg²⁺Use in detection.

Preferably, the use is in the detection of Hg in a body of water²⁺The content of (a).

Preferably, the method of detection is fluorescence intensity detection.

The invention has the beneficial effects that:

1. the recognition unit of the probe ZY15 provided by the invention contains electron-donating nitrogen atoms and sulfur atoms, Hg²⁺The combination of the fluorescent probe and the probe weakens the electron pushing and supplying capability of the probe, the intramolecular charge transfer process of the probe is blocked, the fluorescence of a reaction system is quenched, and the fluorescence color of the probe is changed from yellow green to colorless, so that Hg can be realized²⁺Specific recognition of (3). In addition, probe ZY15 was used for Hg²⁺High response speed, high anti-interference ability, high selectivity and sensitivity, and high sensitivity to Hg²⁺The minimum detection limit is 9.6nmol/L, and can meet Hg requirements of the national ministry of health and the United states environmental protection agency²⁺The detection limit requirement of (2).

2. Probe ZY15 for Hg²⁺The detection process is quick and convenient, a large-scale detection instrument is not needed, and Hg can be realized²⁺The method can be applied to the detection of Hg in the actual water body²⁺The content of (b) has important application value in the field of water environment monitoring.

3. The probe ZY15 has good stability and can be stored for a long time.

[ description of the drawings ]

FIG. 1 is a graph showing fluorescence spectra of examples 4 in which various metal ions were added to a probe ZY15, respectively;

FIG. 2 shows fluorescence intensity and Hg of probe ZY15 in example 4²⁺A linear plot of concentration;

FIG. 3 identification of Hg by different Metal ion interference Probe ZY15 in example 5²⁺A fluorescence data plot of (a);

FIG. 4 shows probes ZY15 and Hg in example 5²⁺Graph of fluorescence versus time after action;

FIG. 5 shows probe ZY15 in example 5 with Hg added²⁺Fluorescence color change plot before (left) and after (right) 4 min (365nm UV lamp)Illumination).

[ detailed description ] embodiments

The technical solution of the present invention will now be described in detail with reference to the accompanying drawings and examples. It should be understood that the following examples are only illustrative of the present invention and are not intended to limit the scope of the present invention. It is intended that all modifications or alterations to the steps or conditions of the present invention be made without departing from the spirit or essential characteristics thereof.

Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.

EXAMPLE 1 Synthesis of Probe ZY15

(1) 4-chloro-7-chlorosulfonyl-2, 1, 3-benzoxadiazole (1.01g,4mmol) was dissolved in 20mL of tetrahydrofuran, and aqueous ammonia (0.28g,8mmol) was added dropwise with stirring at room temperature. After the dropwise addition, the reaction is carried out for 10min at room temperature, and then the solvent is distilled off to obtain a crude product I. Adding 10mL of water into the crude product I, extracting with 30mL of dichloromethane for three times in sequence, combining organic phases, drying with anhydrous magnesium sulfate, and evaporating solvent dichloromethane to obtain an intermediate, namely 4-chloro-7-sulfonylamino-2, 1, 3-benzoxadiazole;

0.69 g. The yield is 74%; ESI-MS 253.02[ M + H ]]⁺；¹HNMR(400MHz,CDCl₃,ppm):δ7.96(d,1H,J＝7.2Hz),7.52(d,1H,J＝7.8Hz)；¹³CNMR(100MHz,CDCl₃,ppm):δ145.87,144.66,128.19,127.44,123.67,122.18。

(2) The intermediate (0.47g,2mmol) was dissolved in 20mL of tetrahydrofuran, and bis (2- (ethylthio) ethyl) amine (0.58g,3mmol) and triethylamine (0.20g,2mmol) were added thereto, followed by reaction at room temperature for 2h and evaporation of the solvent tetrahydrofuran to give crude product II. And separating the crude product II by column chromatography by using ethyl acetate and petroleum ether at a ratio of 4:1(V/V) as an eluent to obtain a probe ZY150.59g. The yield is 76%; the melting point is 99-101 ℃; ESI-MS: M/z 390.14 (M)⁺)；¹HNMR(400MHz,CDCl₃,ppm):δ1.21(t,J＝7.6Hz,6H),2.52(q,J＝7.2Hz,4H),2.69(t,J＝6.8Hz,4H),3.67(t,J＝7.6Hz,4H),6.74(d,J＝7.6Hz,1H),7.22(s,2H),7.72(d,J＝8.4Hz,1H)；¹³C NMR(100MHz,CDCl₃):δ143.1,141.2,131.2,125.1,112.3,99.8,59.6,29.9,25.8,15.1。

EXAMPLE 2 Synthesis of Probe ZY15

(1) 4-chloro-7-chlorosulfonyl-2, 1, 3-benzoxadiazole (1.01g,4mmol) was dissolved in 20mL of tetrahydrofuran, and aqueous ammonia (0.14g,4mmol) was added dropwise with stirring at room temperature. After the dropwise addition, the reaction is carried out for 5min at 50 ℃, and then the solvent is evaporated to obtain a crude product I. Adding 10mL of water into the crude product I, extracting with 30mL of dichloromethane for three times in sequence, combining organic phases, drying with anhydrous magnesium sulfate, and evaporating solvent dichloromethane to obtain an intermediate, namely 4-chloro-7-sulfonylamino-2, 1, 3-benzoxadiazole;

0.51 g. The yield is 55%; ESI-MS 253.02[ M + H ]]⁺；¹HNMR(400MHz,CDCl₃,ppm):δ7.96(d,1H,J＝7.2Hz),7.52(d,1H,J＝7.8Hz)；¹³CNMR(100MHz,CDCl₃,ppm):δ145.87,144.66,128.19,127.44,123.67,122.18。

(2) The intermediate (0.47g,2mmol) was dissolved in 20mL of tetrahydrofuran, and bis (2- (ethylthio) ethyl) amine (0.39g,2mmol) and triethylamine (0.20g,2mmol) were added thereto, followed by reaction at 60 ℃ for 1 hour and evaporation of the solvent tetrahydrofuran to give crude product II. The crude product II is separated by column chromatography with ethyl acetate and petroleum ether in a ratio of 3:1(V/V) as eluent to obtain probe ZY150.45g. The yield is 58%; the melting point is 99-101 ℃; ESI-MS M/z 390.14 (M)⁺)；¹HNMR(400MHz,CDCl₃,ppm):δ1.21(t,J＝7.6Hz,6H),2.52(q,J＝7.2Hz,4H),2.69(t,J＝6.8Hz,4H),3.67(t,J＝7.6Hz,4H),6.74(d,J＝7.6Hz,1H),7.22(s,2H),7.72(d,J＝8.4Hz,1H)；¹³C NMR(100MHz,CDCl₃):δ143.1,141.2,131.2,125.1,112.3,99.8,59.6,29.9,25.8,15.1。

EXAMPLE 3 Synthesis of Probe ZY15

(1) 4-chloro-7-chlorosulfonyl-2, 1, 3-benzoxadiazole (1.01g,4mmol) was dissolved in 20mL of tetrahydrofuran, and aqueous ammonia (0.42g,12mmol) was added dropwise with stirring at room temperature. After the dropwise addition, the reaction is carried out for 30min at room temperature of 0 ℃, and then the solvent is evaporated to obtain a crude product I. Adding 10mL of water into the crude product I, sequentially extracting with 30mL of dichloromethane for three times, combining organic phases, drying by using anhydrous magnesium sulfate, and evaporating solvent dichloromethane to obtain an intermediate, namely 4-chloro-7-sulfonylamino-2, 1, 3-benzoxadiazole;

0.62 g. The yield is 66%; ESI-MS 253.02[ M + H ]]⁺；¹HNMR(400MHz,CDCl₃,ppm):δ7.96(d,1H,J＝7.2Hz),7.52(d,1H,J＝7.8Hz)；¹³CNMR(100MHz,CDCl₃,ppm):δ145.87,144.66,128.19,127.44,123.67,122.18。

(2) The intermediate (0.47g,2mmol) was dissolved in 20mL of tetrahydrofuran, bis (2- (ethylthio) ethyl) amine (1.16g,6mmol) and triethylamine (0.20g,2mmol) were added thereto, reacted at 10 ℃ for 4h, and the solvent tetrahydrofuran was distilled off to obtain crude product II. And separating the crude product II by column chromatography by using ethyl acetate and petroleum ether at a ratio of 6:1(V/V) as an eluent to obtain a probe ZY150.56g. The yield is 72%; the melting point is 99-101 ℃; ESI-MS: M/z 390.14 (M)⁺)；¹HNMR(400MHz,CDCl₃,ppm):δ1.21(t,J＝7.6Hz,6H),2.52(q,J＝7.2Hz,4H),2.69(t,J＝6.8Hz,4H),3.67(t,J＝7.6Hz,4H),6.74(d,J＝7.6Hz,1H),7.22(s,2H),7.72(d,J＝8.4Hz,1H)；¹³C NMR(100MHz,CDCl₃):δ143.1,141.2,131.2,125.1,112.3,99.8,59.6,29.9,25.8,15.1。

Example 4 Probe ZY15 vs Hg²⁺Fluorescence detection of

Dissolving the probe ZY15 prepared in example 1 in ethanol to prepare a probe stock solution with the concentration of 1 mmol/L; various metal ions (K)⁺,Ca²⁺,Na⁺,Mg²⁺,Cr³⁺,Mn²⁺,Fe³⁺,Fe²⁺,Co²⁺,Ni²⁺,Cu²⁺,Zn²⁺,Pb²⁺,Ag⁺,Cd²⁺，Hg²⁺) Stock solutions were prepared with distilled water at 1 mmol/L. Mixing the probe and metal ion at a ratio of 1:2, and diluting with ethanol and distilled water (V)_EtOH:V_H2O1:1) and mixed well and tested for their fluorescence spectra using a fluorescence spectrometer. From FIG. 1, it can be seen that probe ZY15 is directed to Hg²⁺Showing better selectivity. To probe ZY15 (10. mu. mol/L) were gradually added dropwise different equivalents of Hg²⁺The fluorescence emission intensity of the solution at 505nm was found to be vs. Hg²⁺The concentration (0.1 to 6.5. mu. mol-L) exhibit a good linear relationship (linear equation y-530.65-156.51 x, R)²0.9888), a highly sensitive quantitative detection of mercury ions in this concentration range can be achieved (fig. 2). Hg is a mercury vapor²⁺The minimum detection limit of the mercury is 9.6nmol/L calculated according to 3 sigma/k, and the detection limit can meet the requirement of the United states environmental protection agency on Hg²⁺The detection limit requirement of (2).

EXAMPLE 5 anti-interference ability of Probe ZY15 and for Hg²⁺Time response of

Adding 10 times of Hg²⁺Amount of substance (20. mu. mol/L) of interfering ions (K)⁺,Ca²⁺,Na⁺,Mg²⁺,Cr³⁺,Mn²⁺,Fe³⁺,Fe²⁺,Co²⁺,Ni²⁺,Cu²⁺,Zn²⁺,Pb²⁺,Ag⁺,Cd²⁺) To probe ZY15 (10. mu. mol/L) and Hg²⁺In the reaction system (A), none of them was found to significantly affect ZY15 on Hg²⁺The detection proves that the probe ZY15 has stronger anti-interference capability (figure 3). In addition, 2 times the amount of Hg was added to the ZY15 solution²⁺After that, the fluorescence intensity had stabilized after 4 minutes (FIG. 4). The color of the solution changed from yellow-green to colorless when irradiated under a 365nm ultraviolet lamp (FIG. 5), and this rapid change in the color of the solution indicated that ZY15 was available for Hg²⁺Real-time visual detection of.

Example 6 Probe ZY15 for Hg in Water²⁺Detection of (2)

Three water samples, namely tap water commonly used in laboratories, mineral water sold under a certain brand and magnetic lake in North Hu Huangshi, are selected to replace distilled water used in fluorescence tests and are not treated. For Hg in water sample²⁺When the standard recovery experiment is carried out, Hg is not added²⁺Water samples of (a) were used as blanks. As can be seen from Table 1, none of ZY15 detected low concentration Hg in three waters²⁺And adding external Hg into the three water bodies²⁺The Relative Standard Deviation (RSD) of the test results is between 2.51% and 4.83%, Hg²⁺The recovery rate ranged between 95.0% and 104.2%, indicating that ZY15 can be applied to Hg in these actual water samples²⁺The quantitative determination of (4).

TABLE 1 Probe ZY15 for detecting Hg in water body samples²⁺Recovery test of

Claims

1. A benzoxadiazole analog color fluorescent probe ZY15 for detecting mercury ions is characterized in that the molecular formula is C₁₄H₂₂N₄O₃S₃The structural formula is as follows:

2. the method for preparing the benzoxadiazole analog color fluorescent probe ZY15 for detecting mercury ions according to claim 1, which comprises the following steps:

3. The method of claim 2, wherein: in the step (1), the molar ratio of the 4-chloro-7-chlorosulfonyl-2, 1, 3-benzoxadiazole to the ammonia water is 1: 1-1: 3, the reaction temperature is 0-50 ℃, and the reaction time is 5-30 minutes.

4. The production method according to claim 2 or 3, characterized in that: the molar ratio of the intermediate, bis (2- (ethylthio) ethyl) amine and triethylamine in the step (2) is 1:1: 1-1: 3:1, the reaction temperature is 10-60 ℃, the reaction time is 1-4 hours, and the volume ratio of ethyl acetate and petroleum ether used as eluents for column chromatography purification is 3: 1-6: 1.

5. The benzoxazole colorimetric fluorescent probe ZY15 for Hg in non-disease diagnosis and treatment according to claim 1² ⁺Use in detection.

6. Use according to claim 5, characterized in that: the application is to detect Hg in water body²⁺The content of (a).

7. Use according to claim 6, characterized in that: the detection method is fluorescence intensity detection.