CN115260120A - ESIPT fluorescent compound for hydrazine specificity detection and preparation method and application thereof - Google Patents
ESIPT fluorescent compound for hydrazine specificity detection and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an ESIPT fluorescent compound for specifically detecting hydrazine, a preparation method and application thereof, wherein the fluorescent compound is 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate), and can specifically detect hydrazine in cells and organisms; the fluorescent material has good cell membrane permeability and low cytotoxicity, can enter living cells and rapidly generate Michael addition cyclization reaction with intracellular and extracellular endogenous hydrazine to generate strong fluorescence which can be distinguished by naked eyes; the fluorescent compound is analyzed by a fluorescence spectrophotometry method, has excellent selectivity on hydrazine under various interferents, and has strong anti-interference capability on common biomolecules; the fluorescent compound also has the potential of quantitatively detecting hydrazine in different environmental water samples; not only can selectively identify endogenous and exogenous hydrazine in cells, but also can detect the hydrazine with high sensitivity in various living cell growth environments, and is applied to the imaging of living cells and zebra fish.
Description
Technical Field
The invention relates to the technical field of organic small molecule fluorescent probes, in particular to an ESIPT fluorescent compound for hydrazine specificity detection and a preparation method and application thereof.
Background
The inorganic pollutants in the environment are wide in source and complex in variety, most of the pollutants can enter the human body, and can pose a threat to the environment and the human health when the content of the pollutants exceeds a safety threshold, hydrazine (N2H 4) is an important inorganic compound with certain reducibility, and has been widely applied to the fields of pesticide production, aerospace, chemical industry and the like, however, the hydrazine (N2H 4) is a highly toxic water-soluble biochemical reagent with carcinogenic, teratogenic and mutagenic effects, N2H4 can cause damage to the liver, respiratory system and nervous system through mouth-nose breathing and skin infiltration, no clear evidence currently indicates whether the human body contains endogenous N2H4, but part of the medicines entering the human body can generate N2H4, for example, the isonicotinamide is a medicine for treating recessive and active tuberculosis, can be metabolized into hydrazine, the liver is damaged, the United States Environmental Protection Agency (USEPA) and the World Health Organization (WHO) have determined that the N2H4 is a potential carcinogen, the approved threshold (mu g/L) is 10 mu M), the special-effect method is needed for developing a high-effect and high-sensitivity test method for visualizing the environmental toxicity of the N2H4 in the human body, and can be provided by a reliable method for carrying out a visual test and a high-based method for evaluating the environmental-based on the N2H4 and the environmental-based on the environmental-related method;
the detection of N2H4 usually uses chromatography-mass spectrometry, surface enhanced Raman spectroscopy, electrochemistry and chemiluminescence detection, and the methods have the defects of high cost, complex sample pretreatment and operation procedures, long analysis time, expensive instruments and the like, and compared with the fluorescence detection, the method has the advantages of simple operation, high sensitivity and low cost, in particular, the method can carry out noninvasive analysis on the biological sample and is suitable for imaging analysis of living cells and even whole organisms, and the fluorescent probe is the first choice method for detecting certain environmental pollutants and endogenous biomolecules until now;
to date, many chemical sensors for detecting N2H4 have been reported, and due to the nucleophilicity of N2H4, several mechanisms such as Gabriel reaction, hydrazone formation, addition reaction with aldehyde and ester hydrolysis reaction are used in the process of detecting N2H4, wherein the application of the hydrazinolysis reaction can improve the response rate of detection, since the first bromo ester-based fluorescent probe developed by Sarkar group in 2013, the rapid development of fluorescent probes based on the hydrazinolysis reaction was promoted, and as a typical hydrazinolysis reaction, a hydroxyl group on the fluorescent structure may be an effective hydrazinolysis site, and more encouraging that the introduction of a hydroxyl group into the structure of the fluorescent probe is easily achieved;
in conclusion, 2- (benzo [ d ] thiazole-2-yl) benzene-1,4-diphenol is selected as a fluorescent parent structure, hydroxyl on the 2- (benzo [ d ] thiazole-2-yl) benzene-1,4-diphenol is modified by utilizing 4-bromobutyryl ester, the fluorescence of the fluorescent parent structure is quenched, the sensitivity of the fluorescent parent structure is improved, and a novel fluorescent compound which can specifically identify hydrazine and can be applied to cell and living tissue imaging is expected to be developed;
therefore, it is necessary to provide an ESIPT fluorescent compound for hydrazine-specific detection, and a preparation method and application thereof to solve the above technical problems.
Disclosure of Invention
The invention aims to solve the first technical problem of developing a fluorescent compound capable of selectively detecting hydrazine, wherein the fluorescent compound has the characteristics of strong specificity and anti-interference performance and the like.
The second technical problem to be solved by the invention is to provide a preparation method of a fluorescent compound capable of selectively detecting hydrazine.
The third technical problem to be solved by the invention is to research a novel method capable of visualizing the migration and distribution rules of the endogenous and exogenous hydrazine in the cells and the living body.
In order to achieve the purpose, the invention provides the following technical scheme: an ESIPT fluorescent compound for specific hydrazine detection, comprising 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) having the chemical structure shown in formula I:
the invention also provides a preparation method of the ESIPT fluorescent compound for specifically detecting hydrazine, which comprises the following operation steps:
(1) 2- (benzo [ d ] thiazole-2-yl) benzene-1,4-diphenol is prepared by reacting 2-aminothiophenol, 2,5-dihydroxybenzaldehyde and sodium thiosulfate;
(2) And (2) modifying the 2- (benzo [ d ] thiazole-2-yl) benzene-1,4-diphenol obtained in the step (1) by 4-bromobutyrate ester to obtain 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate).
Specifically, in step (1), 500mg (3.99 mmol) of 2-aminothiophenol and 580mg (4.2 mmol) of 2,5-dihydroxybenzaldehyde were dissolved in 20mL of N, N-dimethylformamide, and 0.70g (4.20 mmol) of sodium thiosulfate was added with continuous stirring; the reaction mixture was refluxed for 2 hours and monitored by TLC, after completion of the reaction, cooled to room temperature, added 50mL of water, collected a solid precipitate on a suction filter funnel and recrystallized from methanol to yield 702mg (72%) of 2- (benzo [ d ] thiazol-2-yl) benzene-1,4-diol as a white solid.
Specifically, in step (2), 730mg (3 mmol) of 2- (benzo [ d ] thiazol-2-yl) benzene-1,4-diol and 455mg (4.5 mmol) of triethylamine were dissolved in 60mL of dichloromethane under ice bath conditions; 668mg (3.6 mmol) of 4-bromobutyryl chloride was slowly added to the mixture using an isopiestic dropping funnel and the reaction was then carried out at room temperature, the progress of the reaction was monitored by thin layer chromatography silica gel plate (TLC), when the reaction was complete, the solvent was evaporated to dryness and the product was isolated by eluting silica gel column using an eluent consisting of petroleum ether and ethyl acetate in a volume ratio of 3:1, and preparing the composition.
The invention also provides application of the ESIPT fluorescent compound for specifically detecting the hydrazine, and the fluorescent compound is used as a fluorescent chemical sensor for detecting the hydrazine.
Further, the ESIPT fluorescent compound for hydrazine specificity detection is used for detecting hydrazine in a solution system, and the operation steps are as follows:
(a) Preparing the fluorescent compound into a fluorescent compound solution with the concentration of 10 mu M by using 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES) and dimethyl sulfoxide (DMSO) buffer solution, wherein the volume ratio of the HEPES to the DMSO in the buffer solution is 1:9, the pH value of the buffer solution is 7.4;
(b) Adding 100 mu M of aqueous solutions of tryptophan (Try), cysteine (Cys), threonine (Thr), tyrosine (Tyr), histidine (His), glutamic acid (Glu) and aspartic acid (Asp), potassium chloride (KCl), calcium chloride (CaCl 2), sodium chloride (NaCl), magnesium chloride (MgCl 2), copper chloride (CuCl 2), barium chloride (BaCl 2), ferric chloride (FeCl 3), silver chloride (AgCl) and nickel chloride (NiCl 2) sodium hydrosulfide (NaHS) into the 10 mu M fluorescent compound solution prepared in the step (a), and measuring the fluorescence intensity after the reaction is completed;
(c) Through the research of the relation between the fluorescence intensity and the reaction time, the fluorescent compound only generates fluorescence enhancement on the hydrazine, namely the fluorescent compound can specifically recognize the hydrazine.
The ESIPT fluorescent compound for specifically detecting the hydrazine is used for quantitatively detecting the hydrazine in an environmental water sample, and the operation steps are as follows:
(a) Preparing the fluorescent compound into a fluorescent compound solution with the concentration of 10 mu M by using 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES) and dimethyl sulfoxide (DMSO) buffer solution, wherein the volume ratio of the HEPES to the DMSO in the buffer solution is 1:9, the pH value of the buffer solution is 7.4;
(b) Selecting different types of environmental water samples, adding hydrazine with the concentration of 0.10,0.50 and 1.0mg/L into the different environmental water samples, utilizing the specificity detection of the prepared fluorescent compound on the hydrazine in the step (a) to perform an experiment of adding and recovering the hydrazine by the fluorescent compound, and comparing the added concentration with the obtained result to obtain the recovery rate of 72-111%, so that the fluorescent compound can quantitatively detect the hydrazine in the different environmental water samples.
The ESIPT fluorescent compound for specifically detecting the hydrazine is used for detecting exogenous hydrazine in cervical carcinoma cells (HeLa), and the operation steps are as follows:
(a) Preparing the fluorescent compound into a fluorescent compound solution with the concentration of 20 mu M by using 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES) and dimethyl sulfoxide (DMSO) buffer solution, wherein the volume ratio of the HEPES to the DMSO in the buffer solution is 1:9, the pH value of the buffer solution is 7.4;
(b) Five experimental groups of A, B, C, D and E are set:
group a blank: heLa cells without any treatment;
group B hydrazine treatment control: heLa cells were incubated with 50. Mu.M hydrazine solution for 30 min;
group C probe treatment control: heLa cells were incubated with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) (20. Mu.M) for 30 min;
group D experiment group 1: heLa cells were incubated with 50 μ M hydrazine for 30 minutes followed by 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) (20 μ M) for 30 minutes;
group E experimental group 2: heLa cells were incubated with 100 μ M hydrazine for 30 minutes and then with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) (20 μ M) for 30 minutes;
(a) The A, B, C, D, E fluorescence imaging result shows that 2- (benzo [ d ] thiazole-2-yl) -1, 4-phenylene bis (4-bromobutyrate) can enter the cell and react with exogenous hydrazine in the cell, and the cell imaging can obviously show the distribution of the exogenous hydrazine in the cell.
The ESIPT fluorescent compound for specifically detecting the hydrazine is used for detecting the exogenous hydrazine in the zebra fish, and the operation steps are as follows:
(a) Preparing the fluorescent compound into a fluorescent compound solution with the concentration of 20 mu M by using 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES) and dimethyl sulfoxide (DMSO) buffer solution, wherein the volume ratio of the HEPES to the DMSO in the buffer solution is 1:9, the pH value of the buffer solution is 7.4;
(b) Four experimental groups of A, B, C and D are set:
group a blank: untreated 3-day-old zebrafish;
group B probe treatment control: 3-day-old zebrafish treated with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) (30 μ M);
group C hydrazine treatment control: 3 days old zebrafish treated with hydrazine (50 μ M);
group D experimental groups: 3 days old zebrafish were treated with hydrazine for 30 minutes and incubated with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) (30 μ M) for 30 minutes;
(c) The results show that zebrafish treated simultaneously with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) and exogenous hydrazine at 28 ℃ showed significant fluorescence, whereas untreated zebrafish or zebrafish not treated simultaneously with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) and exogenous hydrazine were not found to be fluorescent; fluorescence imaging results show that 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate) can enter into the zebra fish body and react with exogenous hydrazine to generate strong fluorescence, so that the detection effect is achieved;
(d) The reaction mechanism of the fluorescent compound is that one N atom of hydrazine firstly generates nucleophilic substitution reaction with a carbon atom connected with a bromine atom on 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate), and a Br atom is substituted; then, another N atom of hydrazine attacks a carbonyl C atom on 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate) to generate a stable six-membered ring compound through addition cyclization, and another 4-bromobutyryl on 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate) also reacts through the mechanism, so that the fluorescent group 2- (benzo [ d ] thiazole-2-yl) benzene-1,4-diphenol is completely released to cause fluorescence enhancement, and the purpose of detecting hydrazine is achieved.
The beneficial technical effects of the invention are embodied in the following aspects:
1. the fluorescent compound only needs two steps to complete the synthesis of the fluorescent compound, and has mild reaction conditions and easy synthesis;
2. the fluorescent compound has strong anti-interference capability on common analytes in organisms, and can effectively detect hydrazine in various living cell growth environments, the fluorescent compound only reacts with the hydrazine, and the specificity of a hydrazine decomposition mechanism can effectively remove the interference of other common analytes;
3. the fluorescent compound has excellent selectivity on hydrazine under various interferents;
4. the detection limit of the fluorescent compound on Cys is as low as 0.1 mu M;
5. the fluorescent compound has better cell membrane permeability and lower cytotoxicity. The water partitioning coefficient of the fluorescent compound logP =5.91, indicating that the fluorescent compound is a lipophilic compound, i.e., can easily enter cells. As shown in fig. 5, cytotoxicity assays at different concentrations indicated that IPPA had lower cytotoxicity;
6. the hydrazine concentration in the actual water sample can be effectively detected. As shown in Table 6, hydrazine (0.10,0.50 and 1.0 mg/L) with different concentrations is added into different environmental water samples, and the recovery rate of the hydrazine is measured to be between 72 and 111 percent by using the fluorescent compound, so that the fluorescent compound can effectively and quantitatively detect the hydrazine in the environmental water samples;
7. the fluorescent compound has the biological application potential of detecting intracellular and extracellular endogenous hydrazine, as shown in figure 7, the fluorescent compound which is not treated with 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate) and exogenous hydrazine simultaneously shows strong green fluorescence after being respectively incubated for 30 minutes, and the cell imaging result shows that the fluorescent compound has the biological application potential of detecting intracellular and extracellular endogenous hydrazine, when the zebra fish is treated with the exogenous hydrazine for 30 minutes, the fluorescent compound (30 mu M) is used again, the fluorescent compound is obviously and strongly visible in zebra fish egg yolk distribution under the condition that the zebra fish is not only subjected to the excitation of the exogenous hydrazine and the fluorescence distribution of the zebra fish is not observed in the stomach, and the fluorescent compound is not only visualized in the stomach after the exogenous hydrazine is not only by the fluorescent compound which is not treated with 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate) and exogenous hydrazine is not treated with 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate) and exogenous hydrazine after being respectively incubated for 30 minutes.
Drawings
FIG. 1 is a NMR chart of 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) before and after reaction with hydrazine;
FIG. 2 is a high resolution mass spectrum of the reaction product of 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) and hydrazine;
FIG. 3 shows fluorescence emission spectra of 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) in working solution with different amino acids and compounds such as common ions of human body;
FIG. 4 is a theoretical calculation of the density of the reaction product of 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) with hydrazine;
FIG. 5 is a bar graph of the effect of different concentrations of 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) on cell survival;
FIG. 6 is a photograph of a fluorescent image of 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) in HeLa cells for exogenous hydrazine;
FIG. 7 is a graphic representation of the fluorescence of 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) in 3-day-old zebrafish;
Detailed Description
The invention discloses a fluorescent compound capable of specifically detecting hydrazine and a preparation method and application thereof, and the fluorescent compound is characterized by comprising two parts, wherein 4-bromobutyryl is taken as an identification group, 2- (benzo [ d ] thiazole-2-yl) benzene-1,4-diphenol is taken as an information report group, and the 4-bromobutyryl on the reported fluorescent compound can specifically react with hydrazine in a system to change the fluorescence of the fluorescent compound, so that the specific detection of the hydrazine is realized.
The invention will now be further described with reference to the following examples
Example 1 preparation of fluorescent Compounds for hydrazine detection
The fluorescent compound is 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate), and the specific preparation process is as follows:
500mg (3.99 mmol) of 2-aminothiophenol and 580mg (4.2 mmol) of 2,5-dihydroxybenzaldehyde are dissolved in 20mL of N, N-dimethylformamide and 0.70g (4.20 mmol) of sodium thiosulfate is added with continuous stirring; the reaction mixture was refluxed for 2 hours and the reaction was monitored by TLC. After the reaction was completed, it was cooled to room temperature and 50mL of water was added. The solid precipitate was collected on a suction filter funnel and recrystallized from methanol to yield 702mg (72%) of 2- (benzo [ d ] thiazol-2-yl) benzene-1,4-diol as a white solid. Hydrogen nuclear magnetic resonance spectroscopy: 1H NMR (600mhz, dmso-d 6): δ 10.84 (t, J =3.0 hz, 1h), 9.17 (t, J =3.1hz, 1h), 8.12 (dt, J =7.1,2.6hz, 1h), 8.00 (dd, J =7.6,3.1hz, 1h), 7.65-7.47 (m, 2H), 7.41 (dt, J =9.0,5.6hz, 1h), 6.91-6.88 (m, 1H), 6.83 (dq, J =8.7,3.4,2.9hz, 1h) high resolution mass spectrometry: HRMS (ESI, m/z) calculated for [ C13H9NO2S + H ] +:244.0432, found 244.0427.
(2) Dissolve 730mg (3 mmol) of 2- (benzo [ d ] thiazol-2-yl) benzene-1,4-diol and 455mg (4.5 mmol) triethylamine in 60mL dichloromethane under ice bath conditions; 668mg (3.6 mmol) of 4-bromobutyryl chloride was slowly added to the mixture using an isopiestic dropping funnel and the reaction was then carried out at room temperature, the progress of the reaction was monitored by thin layer chromatography silica gel plate (TLC), when the reaction was complete, the solvent was evaporated to dryness and the product was isolated by elution on a silica gel column to yield 740mg (76%) of 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) as a white solid, the eluent consisting of petroleum ether and ethyl acetate in a volume ratio of 3:1, and (2) preparing. Hydrogen nuclear magnetic resonance spectroscopy: 1H NMR (600mhz, dmso-d 6) δ 8.17-8.13 (m, 1H), 8.13-8.00 (m, 2H), 7.57 (ddd, J =8.3,7.2,1.3hz, 1h), 7.51-7.45 (m, 2H), 7.41 (dt, J =8.7,2.3hz, 1h), 3.75 (td, J =6.5, 1.4hz, 1h), 3.64 (t, J =6.6hz, 3h), 2.97 (td, J =7.2,2.7hz, 2h), 2.79 (t, J = 7.hz, 2h), 2.24-2.12 (m, 4H). Nuclear magnetic resonance carbon spectrum: 13C NMR (151 MHz, DMSO-d 6) delta 171.39,171.33,161.36,152.56,148.63,145.76, 135.27,127.29,126.70,126.38,123.50,122.84,122.64,44.93,44.81, 34.34,34.24,33.05,32.61,27.93,27.82 high resolution Mass Spectrometry: HRMS (ESI, m/z) calcd for [ C21H19Br2NO4S + H ] +:539.9474, found 539.9465.
The detection principle of the fluorescent compound 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate) is as follows:
the mechanism of specifically detecting hydrazine by the fluorescent compound 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate) is as follows: after hydrazine is added, a proton signal on 4-bromobutyryl in 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylene bis (4-bromobutyrate) disappears from a shift of 3.3ppm to 3.8ppm, and a new proton signal appears near a shift of 8.0ppm, corresponding to hydrogen atoms on two phenolic hydroxyl groups on the fluorophore 2- (benzo [ d ] thiazol-2-yl) benzene-1,4-diphenol (figure 1), wherein N atom contains lone pair electrons, so that hydrazine has strong nucleophilicity, and when hydrazine reacts with a fluorescent compound, one N atom of hydrazine first performs nucleophilic substitution reaction with bromine atom on 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylene bis (4-bromobutyrate), and bromine atom is substituted; then, another N atom of hydrazine attacks the carbonyl C atom on 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) to produce a stable six-membered ring compound by addition cyclization, and a compound with a molecular weight of 101.0789 found in the high resolution mass spectrum (FIG. 2) verifies the hypothesis that another 4-bromobutyryl group on 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) also reacts by this mechanism such that the fluorophore 2- (benzo [ d ] thiazol-2-yl) benzene-1,4-diphenol is completely released leading to fluorescence enhancement for the purpose of specific detection of hydrazine, and the appearance of a compound with a molecular weight of 244.0426 in high resolution mass spectrum predicts the establishment of this mechanism.
To further validate the reaction mechanism of the fluorescent compound 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) with hydrazine, the spatial distribution and orbital energy of 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) and 2- (benzo [ d ] thiazol-2-yl) benzene-1,4-diol were optimized in a gaussian 09 model in combination with the density-generalised function calculations. As shown in FIG. 3, HOMO is uniformly distributed at the site of the fluorophore, while LUMO is distributed in the vicinity of 4-bromobutyryl. 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) reacts with hydrazine resulting in complete transfer of the HOMO orbital to the fluorophore group resulting in complete release of 2- (benzo [ d ] thiazol-2-yl) benzene-1,4-diol. Furthermore, the energy level difference (Δ E = EHOMO-ELUMO) for 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) and 2- (benzo [ d ] thiazol-2-yl) benzene-1,4-diol was 3.66eV and 2.45eV, respectively. 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) is more susceptible to electronic transitions than 2- (benzo [ d ] thiazol-2-yl) benzene-1,4-diol. The calculation result of the density pan-function theory is consistent with the conclusion.
Example 2 Selective detection of hydrazine in solution System
4-hydroxyethyl piperazine ethanesulfonic acid (HEPES)/dimethyl sulfoxide (DMSO) buffer solution and the fluorescent compound prepared in example 1 are prepared into a fluorescent compound detection solution with the concentration of 10 mu M, and hydrazine in the solution is selectively detected; the specific operation process is as follows:
after 10 equivalents of tryptophan (Try), cysteine (Cys), threonine (Thr), tyrosine (Tyr), histidine (His), glutamic acid (Glu) and aspartic acid (Asp), potassium chloride (KCl), calcium chloride (CaCl 2), sodium chloride (NaCl), magnesium chloride (MgCl 2), copper chloride (CuCl 2), barium chloride (BaCl 2), ferric chloride (FeCl 3), silver chloride (AgCl), sodium hydrosulfide (NaHS) are added to a prepared 10 μ M solution of a fluorescent compound, and the reaction is completed, fluorescence intensity measurement is performed, and the result of fig. 4 shows that 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) has a good selectivity for hydrazine, whereas 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) has a strong recognition specificity for hydrazine, i.e., the fluorescent compound has strong anti-interference characteristics.
Example 3 application to specific detection of hydrazine in environmental Water samples
When the fluorescent compound is used for quantitatively detecting hydrazine in an environmental water sample, a working solution with the concentration of 10 mu M is prepared by using a 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES)/dimethyl sulfoxide (DMSO) buffer solution and the fluorescent compound;
the specific operation process is as follows: collecting environmental water samples in different water areas, and filtering the water samples for later use; hydrazine with different concentrations (0.1, 0.5 and 1 mg/L) is respectively added into collected water samples to carry out an addition recovery test, the prepared fluorescent compound (10 mu M) reacts with the hydrazine in different water samples for 20 minutes, and then the change of the fluorescence intensity is measured by a fluorescence spectrophotometer, and the results shown in Table 1 show that the addition recovery rate is in the range of 72-111 percent, namely, the 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate) can carry out quantitative detection on the hydrazine in water samples in different environments;
TABLE 1. N in different environmental water samples2H4Addition recovery test of
aThe water samples are collected at a plurality of points, and the number of sampling points is not less than 5. Data are mean ± SE (bar) (n = 3).
Example 4 cytotoxicity
When the fluorescent compound is used for verifying the HeLa cytotoxicity of cervical cancer tissues, a working solution with the concentration of 10 mu M is prepared by using a 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES)/dimethyl sulfoxide (DMSO) buffer solution and the fluorescent compound;
the specific operation process is as follows: heLa cells were cultured in DMEM and supplemented with 37 ℃ 10% calf serum in 5% carbon dioxide, then HeLa cells (5X 104 per well) were supplemented with different concentrations of 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) (0-40. Mu.M) and after 24h of incubation the cell viability was examined by MTT method, the lowest viability of HeLa cells decreased progressively with increasing concentration of 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate), and the average viability after 24h exceeded 75% when the concentration of 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) reached 40. Mu.M (FIG. 5), indicating that 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) suitable for imaging of cells with lower cytotoxicity.
Example 5 HeLa intracellular fluorescence imaging
When the fluorescent compound is used for hydrazine detection in a HeLa cell of a cervical cancer tissue, a working solution with the concentration of 20 mu M is prepared by using a 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES)/dimethyl sulfoxide (DMSO) buffer solution and the fluorescent compound;
the specific operation process is as follows: five experimental groups of A, B, C, D and E were performed:
group a blank: heLa cells without any treatment;
group B hydrazine treatment control: heLa cells were incubated with 50. Mu.M hydrazine solution for 30 min;
group C probe treatment control: incubation of HeLa cells with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) (20. Mu.M) for 30 min;
group D experiment group 1: heLa cells were incubated with 50 μ M hydrazine for 30 minutes followed by 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) (20 μ M) for 30 minutes;
group E experimental group 2: heLa cells were incubated with 100 μ M hydrazine for 30 minutes followed by incubation with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) (20 μ M) for 30 minutes; the results of A, B, C, D, E group fluorescence imaging show that 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate) can enter cells and react with exogenous hydrazine in the cells, and the distribution of the exogenous hydrazine in the cells can be obviously seen by cell imaging.
Example 6 fluorescence imaging of Zebra fish
When the fluorescent compound is used for in-vivo ammonia detection of zebra fish, a working solution with the concentration of 20 mu M is prepared by using 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES)/dimethyl sulfoxide (DMSO) buffer solution and the fluorescent compound;
the specific operation process is as follows: four test groups A, B, C, D were performed:
group a blank: untreated 3-day-old zebrafish;
group B probe treatment control: 3-day-old zebrafish treated with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) (30 μ M);
group C hydrazine treatment control: 3 days old zebrafish treated with hydrazine (50 μ M);
group D experimental groups: 3 days old zebrafish were treated with hydrazine for 30 minutes and incubated with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) (30 μ M) for 30 minutes;
the results show that zebrafish treated simultaneously with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) and exogenous hydrazine at 28 ℃ showed significant fluorescence, whereas untreated zebrafish or zebrafish not treated simultaneously with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) and exogenous hydrazine were not found to be fluorescent; fluorescence imaging results show that 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate) can enter zebra fish bodies and react with exogenous hydrazine to generate strong fluorescence, so that the detection effect is achieved. Moreover, fluorescence is distributed in the yolk, stomach and digestive tract of zebrafish. Obviously, the fluorescent compound can be used for visualizing the exogenous hydrazine in the zebra fish and can accurately position the distribution of the exogenous hydrazine in the zebra fish.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (9)
1. An ESIPT fluorescent compound for use in the specific detection of hydrazine, wherein: comprises 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate), the chemical structural formula of which is shown as І:
formula I.
2. The method for preparing an ESIPT fluorescent compound for hydrazine specific detection as recited in claim 1, wherein the steps of operation are as follows:
(1) 2- (benzo [ d ] thiazole-2-yl) benzene-1,4-diphenol is prepared by reacting 2-aminothiophenol, 2,5-dihydroxy benzaldehyde and sodium thiosulfate;
(2) And (2) modifying the 2- (benzo [ d ] thiazole-2-yl) benzene-1,4-diphenol obtained in the step (1) by 4-bromobutyrate ester to obtain 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate).
3. The method of preparing an ESIPT fluorescent compound for hydrazine specific detection as claimed in claim 2, wherein: in step (1), 500mg (3.99 mmol) of 2-aminothiophenol and 580mg (4.2 mmol) of 2,5-dihydroxybenzaldehyde were dissolved in 20mL of N, N-dimethylformamide and 0.70g (4.20 mmol) of sodium thiosulfate was added with continuous stirring; the reaction mixture was refluxed for 2 hours and monitored by TLC, after completion of the reaction, cooled to room temperature, added 50mL of water, collected a solid precipitate on a suction filter funnel and recrystallized from methanol to obtain 2- (benzo [ d ] thiazol-2-yl) benzene-1,4-diol as a white solid.
4. The method of preparing an ESIPT fluorescent compound for hydrazine specific detection as claimed in claim 2, wherein: in step (2), 730mg (3 mmol) of 2- (benzo [ d ] thiazol-2-yl) benzene-1,4-diol and 455mg (4.5 mmol) of triethylamine were dissolved in 60mL of dichloromethane under ice bath conditions; 668mg (3.6 mmol) of 4-bromobutyryl chloride was slowly added to the mixture using an isopiestic dropping funnel and the reaction was then carried out at room temperature, the progress of the reaction was monitored by thin layer chromatography silica gel plate (TLC), when the reaction was complete, the solvent was evaporated to dryness, and the product was isolated by eluting silica gel column using an eluent consisting of petroleum ether and ethyl acetate in a volume ratio of 3:1, and preparing the composition.
5. The use of an ESIPT fluorescent compound for hydrazine specific detection as claimed in claim 1 wherein: the fluorescent compound is used as a fluorescent chemical sensor for detecting hydrazine.
6. Use of an ESIPT fluorescent compound for the specific detection of hydrazine according to claim 5, for the detection of hydrazine in solution systems, in the following operating steps:
(a) Preparing a fluorescent compound solution with the concentration of 10 μ M from the fluorescent compound of claim 1 by using 4-hydroxyethyl piperazine ethane sulfonic acid (HEPES) and dimethyl sulfoxide (DMSO) buffer solution, wherein the volume ratio of HEPES to DMSO in the buffer solution is 1:9, the pH value of the buffer solution is 7.4;
(b) Respectively adding 100 mu M of aqueous solution of tryptophan (Try), cysteine (Cys), threonine (Thr), tyrosine (Tyr), histidine (His), glutamic acid (Glu) and aspartic acid (Asp), potassium chloride (KCl), calcium chloride (CaCl 2), sodium chloride (NaCl), magnesium chloride (MgCl 2), copper chloride (CuCl 2), barium chloride (BaCl 2), ferric chloride (FeCl 3), silver chloride (AgCl) and nickel chloride (NiCl 2) sodium hydrosulfide (NaHS) into the 10 mu M fluorescent compound solution prepared in the step (a), and measuring the fluorescence intensity after the reaction is completed;
(c) Through the research of the relation between the fluorescence intensity and the reaction time, the fluorescent compound only generates fluorescence enhancement on the hydrazine, namely the fluorescent compound can specifically recognize the hydrazine.
7. Use of an ESIPT fluorescent compound for the specific detection of hydrazine according to claim 5, for the quantitative detection of hydrazine in an ambient water sample, by the following operating steps:
preparing a fluorescent compound solution with the concentration of 10 μ M from the fluorescent compound of claim 1 by using 4-hydroxyethyl piperazine ethane sulfonic acid (HEPES) and dimethyl sulfoxide (DMSO) buffer solution, wherein the volume ratio of HEPES to DMSO in the buffer solution is 1:9, the pH value of the buffer solution is 7.4;
selecting different types of environment water samples, and adding hydrazine with the concentration of 0.10,0.50 and 1.0mg/L into the different environment water samples; and (b) specifically detecting hydrazine by using the fluorescent compound prepared in the step (a), carrying out an experiment of adding and recovering hydrazine by using the fluorescent compound, and comparing the concentration with the added concentration to obtain recovery rates of 72-111%, so that the fluorescent compound can be used for quantitatively detecting hydrazine in water samples in different environments.
8. Use of an ESIPT fluorescent compound for hydrazine specific detection according to claim 5, for exogenous hydrazine detection in cervical cancer cells (HeLa), operating steps of:
(a) Preparing a fluorescent compound solution with the concentration of 20 μ M from the fluorescent compound of claim 1 through 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES) and dimethyl sulfoxide (DMSO) buffer solution, wherein the volume ratio of HEPES to DMSO in the buffer solution is 1:9, the pH value of the buffer solution is 7.4;
(b) Five experimental groups A, B, C, D and E are set:
group a blank: heLa cells without any treatment;
group B hydrazine treatment control: heLa cells were incubated with 50. Mu.M hydrazine solution for 30 min;
group C probe treatment control: incubation of HeLa cells with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) (20. Mu.M) for 30 min;
group D experimental group 1: heLa cells were incubated with 50 μ M hydrazine for 30 minutes followed by 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) (20 μ M) for 30 minutes;
group E experimental group 2: heLa cells were incubated with 100 μ M hydrazine for 30 minutes followed by incubation with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) (20 μ M) for 30 minutes;
(c) The results of A, B, C, D, E group fluorescence imaging show that 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate) can enter cells and react with exogenous hydrazine in the cells, and the distribution of the exogenous hydrazine in the cells can be obviously seen by cell imaging.
9. The use of an ESIPT fluorescent compound for the specific detection of hydrazine according to claim 5, for the detection of exogenous hydrazine in zebrafish, the operating steps of which are as follows:
(a) Preparing a fluorescent compound solution with the concentration of 20 μ M from the fluorescent compound of claim 1 through 4-hydroxyethyl piperazine ethanesulfonic acid (HEPES) and dimethyl sulfoxide (DMSO) buffer solution, wherein the volume ratio of HEPES to DMSO in the buffer solution is 1:9, the pH value of the buffer solution is 7.4;
(b) Four experimental groups of A, B, C and D are set:
group a blank: untreated 3-day-old zebrafish;
group B probe treatment control: 3-day-old zebrafish treated with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) (30 μ M);
group C hydrazine treatment control: 3 days old zebrafish treated with hydrazine (50 μ M);
group D experimental groups: 3 days old zebra fish were treated with hydrazine for 30 minutes and incubated with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) (30 μ M) for 30 minutes;
(c) The results show that zebra fish treated simultaneously with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) and exogenous hydrazine at 28 ℃ showed significant fluorescence, while untreated zebra fish or zebra fish not treated simultaneously with 2- (benzo [ d ] thiazol-2-yl) -1,4-phenylenebis (4-bromobutyrate) and exogenous hydrazine were not found to be fluorescent; fluorescence imaging results show that 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate) can enter into the zebra fish body and react with exogenous hydrazine to generate strong fluorescence, so that the detection effect is achieved;
(d) The reaction mechanism of the fluorescent compound is that one N atom of hydrazine firstly generates nucleophilic substitution reaction with a carbon atom connected with a bromine atom on 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate), and Br atom is substituted; then, another N atom of hydrazine attacks a carbonyl C atom on 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate) to generate a stable six-membered ring compound through addition cyclization, and another 4-bromobutyryl on 2- (benzo [ d ] thiazole-2-yl) -1,4-phenylene bis (4-bromobutyrate) also reacts through the mechanism, so that the fluorescent group 2- (benzo [ d ] thiazole-2-yl) benzene-1,4-diphenol is completely released to cause fluorescence enhancement, and the purpose of detecting hydrazine is achieved.
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