CN113735872B - Fluorescent probe for rapidly detecting hydrazine compounds and synthesis and application thereof - Google Patents
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Abstract
The invention relates to the technical field of fluorescent probes, in particular to a fluorescent probe for rapidly detecting hydrazine compounds, which comprises A-1 and A-2, and discloses a synthetic method of the fluorescent probe for rapidly detecting the hydrazine compounds and application of the fluorescent probe for rapidly detecting the hydrazine compounds, including a detection method. The probe disclosed by the invention can realize quick response to hydrazine, hydrazine sulfate, hydrazine nitrate and unsymmetrical dimethylhydrazine, has remarkable fluorescence enhancement, lower detection limit and good anti-interference property and selectivity.
Description
Technical Field
The invention relates to the technical field of fluorescent probes, in particular to a fluorescent probe for rapidly detecting hydrazine compounds and synthesis and application thereof.
Background
Hydrazine (N)2H4) Also called hydrazine, is colorless oily liquid, has irritant odor similar to ammonia, has strong reducibility, high alkalinity and good water solubility, and can be applied to jet engines, rocket fuels and chemical production. Hydrazine, however, is highly toxic and hydrazine and water can be mixed in any volume ratio to form hydrazine hydrate, which is detrimental to human health. Industrial production sewage usually contains hydrazine compounds such as hydrazine nitrate, hydrazine sulfate and the like, and is discharged randomly to cause serious harm to the ecological environment.
The patent publication No. CN110452171A discloses a fluorescent probe for detecting hydrazine with a naphthalimide parent structure, 4-bromo-1, 8-dinaphthoic acid anhydride reacts with 4- (2-aminoethyl) morpholine to obtain an intermediate product, and the intermediate product reacts with 2, 4-dinitrobenzenesulfonyl chloride to obtain the probe.
The patent with publication number CN110452250A discloses a fluorescent probe for detecting hydrazine with a fluorescein parent structure, which is designed and synthesized based on dichlorofluorescein, and the molecular structure of the fluorescent probe is correspondingly characterized and analyzed, so that the fluorescent probe has the advantages of short response time, interference resistance, good selectivity and the like for hydrazine identification, but the detection limit of the hydrazine is 3.1ppb, which is still high, and the production cost is high.
The patent with publication number CN108982447B discloses a preparation method and application of a ratio-type fluorescent probe for detecting hydrazine, the molecular probe prepared by the patent can be applied to biological sample detection, and has the advantages of low biotoxicity, good selectivity, obvious phenomenon, easy observation, high accuracy and the like.
Disclosure of Invention
The invention aims to provide a fluorescent probe for rapidly detecting hydrazine compounds, so as to solve the problems in the background technology.
The invention is realized by the following technical scheme:
a fluorescent probe for rapidly detecting hydrazine compounds comprises A-1 and A-2, and the chemical structural formula of the fluorescent probe is as follows:
A-1：
A-2：
a synthetic method of a fluorescent probe for rapidly detecting hydrazine compounds comprises the following steps:
(1) preparation A-1: adding dichlorofluorescein into a round-bottom flask, adding dichloromethane under the protection of nitrogen, stirring for dissolving, then sequentially adding triethylamine and acryloyl chloride at 0 ℃ in an ice bath, mixing and stirring for 10min, reacting at room temperature for 12h, identifying and qualitatively analyzing a small amount of substances by TLC during the reaction, tracking the reaction process, removing the solvent in vacuum after the reaction is finished, and obtaining a probe A-1 after column chromatography;
(2) preparation A-2: adding fluorescein into a round-bottom flask, adding dichloromethane under the protection of nitrogen, stirring for dissolving, then sequentially adding triethylamine and acryloyl chloride at 0 ℃ in an ice bath, mixing and stirring for 10min, reacting at room temperature for 12h, identifying and qualitatively analyzing a small amount of substances by TLC during the reaction, tracking the reaction process, removing the solvent in vacuum after the reaction is finished, and obtaining the probe A-2 after column chromatography.
(3) Preparing a fluorescent probe: and (3) mixing the probe A-1 obtained in the step (1) and the probe A-2 obtained in the step (2) in proportion to obtain the fluorescent probe.
Preferably, the eluent of the column chromatography is petroleum ether-ethyl acetate, wherein the volume ratio of petroleum ether to ethyl acetate is 6: and 1, carrying out column chromatography, and eluting with a gradient of 25% -65%/60 min at a flow rate of 6 mL/min.
Preferably, the mixing ratio of the probe A-1 to the probe A-2 is 1: 3-1: 5.
based on the fluorescent probe, the invention also provides an application of the fluorescent probe for rapidly detecting the hydrazine compounds, which comprises a detection method and comprises the following specific steps:
adding the hydrazine compound into a buffer solution containing the probes A-1 and A-2 for full reaction for 1h, realizing naked eye identification of the hydrazine compound through the change of the color of a solution system after the reaction, and realizing fluorescence identification of the hydrazine compound through detecting the fluorescence intensity of the reaction solution at 523 nm.
Preferably, the buffer solution is a PBS solution and a DMSO solution, the concentration of the buffer solution is 10 μ M, the pH is 7.4, and the volume ratio of PBS to DMSO is 9: 1.
compared with the prior art, the invention has the beneficial effects that:
1. the invention innovates the synthesis method, does not use thionyl chloride and N, N-dimethylformamide with high toxicity in the raw materials, and has the advantages of low price of the raw materials and environmental protection, thereby having low synthesis cost and high synthesis yield.
2. The invention takes fluorescein and dichlorofluorescein as fluorescent parent bodies and acryloyl chloride as identification groups to synthesize 'turn-on' type fluorescent probes A-1 and A-2 capable of detecting hydrazine compounds.
3. According to the invention, the A-1 and the A-2 are mixed, compared with the single probe A-1, the production cost is low, the rapid and efficient detection of the hydrazine compound can be realized, and the detection of the hydrazine compound has a lower detection limit.
4. In the invention, under the coexistence environment of interfering substances, the probes A-1 and A-2 can realize quick response to hydrazine compounds, the fluorescence enhancement is obvious, and the invention has better selectivity and anti-interference capability.
5. The pH adaptability of the invention is good, and the fluorescence response of the object to be measured is obvious and stable in the range of pH 7-10.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of the synthetic route of A-1 of the present invention;
FIG. 2 is a schematic diagram of the synthetic route of A-2 of the present invention;
FIGS. 3-6 are graphs showing the linear relationship between the response of A-1 to the concentrations of hydrazine, hydrazine sulfate, hydrazine nitrate and unsymmetrical dimethylhydrazine, respectively;
FIGS. 7-10 are graphs showing the linear relationship between the response of A-2 to the concentrations of hydrazine, hydrazine sulfate, hydrazine nitrate and unsymmetrical dimethylhydrazine, respectively, in accordance with the present invention;
FIGS. 11-14 are schematic diagrams of the response times of A-1 to hydrazine, hydrazine sulfate, hydrazine nitrate and unsymmetrical dimethylhydrazine, respectively, in accordance with the present invention;
FIGS. 15-18 are schematic diagrams of the response times of A-2 of the present invention to hydrazine, hydrazine sulfate, hydrazine nitrate and unsymmetrical dimethylhydrazine, respectively;
FIGS. 19-21 are schematic diagrams of the selective response of A-1 of the present invention to interferents;
FIGS. 22-24 are schematic illustrations of the selective response of the invention A-2 to interferents;
FIG. 25 is a graph showing the degree of response of the present invention A-1 to a target at various pHs;
FIG. 26 is a graph showing the degree of response of the present invention A-2 to a target substance at various pH values.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the embodiment provides a synthesis method of a fluorescent probe for rapidly detecting a hydrazine compound, which comprises the following steps of A-1 and A-2:
the method for preparing 0.3g of probe A-1 included the following steps: accurately weighing 0.60g (1.5mmol) of dichlorofluorescein, adding the dichlorofluorescein into a 100mL round-bottom flask, adding 20mL of dichloromethane under the protection of nitrogen, stirring for dissolving, then sequentially adding 0.20mL of triethylamine (1.8mmol) and 0.25mL of acryloyl chloride (3mmol) under the ice bath at 0 ℃, mixing and stirring for 10min, reacting at room temperature for 12h, identifying and qualitatively analyzing a small amount of substances by TLC during the reaction, tracking the reaction process, removing the solvent in vacuum after the reaction is finished, and adding the dichlorofluorescein into the 100mL round-bottom flask in a volume ratio of 6: the petroleum ether-ethyl acetate eluent of the probe A1 is eluted in a gradient of 25% -65%/60 min, the flow rate during elution is 6mL/min, the probe A-1 is obtained after column chromatography, and the synthetic route of the probe A-1 is shown in figure 1.
The method for preparing 0.2g of probe A-2 included the following steps: accurately weighing 0.40g of fluorescein (1.2mmol) and adding the fluorescein into a 50mL round-bottom flask, adding 20mL of dichloromethane under the protection of nitrogen and stirring for dissolution, then sequentially adding 0.17mL of triethylamine (1.2mmol) and 0.25mL of acryloyl chloride (3mmol) under the ice bath at 0 ℃, mixing and stirring for 10min, reacting at room temperature for 12h, identifying and qualitatively analyzing a small amount of substances by TLC during the reaction, tracking the reaction process, removing the solvent in vacuum after the reaction is finished, and adding the fluorescein into the flask in a volume ratio of 6: the petroleum ether-ethyl acetate eluent of the step 1 is eluted at a gradient of 25% -65%/60 min, the flow rate during elution is 6mL/min, the probe A-2 is obtained after column chromatography, and the synthetic route of the probe A-2 is shown in figure 2.
The probe A-1 and the probe A-2 were mixed in a ratio of 1: 3-1: 5 to obtain the target fluorescent probe.
Example 2:
the embodiment provides application of a fluorescent probe for rapidly detecting hydrazine compounds, and illustrates that the fluorescent probe synthesized in the embodiment 1 can realize naked eye detection of the hydrazine compounds.
mu.L of hydrazine compound (500. mu.M, 50eq) was added to the buffer solution containing the fluorescent probe in a volume ratio of 9: 1, the concentration of the PBS and the DMSO solution is 10 mu M, the pH value is 7.4, after the full reaction for 1 hour, compared with a blank solution, a solution system is obviously changed into yellow green after the reaction of the fluorescent probe and a substance to be detected under natural light; under an ultraviolet lamp of 325nm, the hydrazine compound is found to be obvious yellow green fluorescence, and the result shows that the fluorescent probe synthesized in the example 1 can realize the detection of the hydrazine compound by naked eyes.
Example 3:
referring to FIGS. 2-10, this example provides an application of a fluorescent probe for rapid detection of hydrazine compounds, which illustrates that the fluorescence intensity of the fluorescent probe synthesized in example 1 increases with the concentration of hydrazine compounds.
A-1: hydrazine, hydrazine sulfate, hydrazine nitrate, and unsymmetrical dimethylhydrazine were added to the buffer solution of the probe A-1 at concentrations of 0, 50, 100, 150, 200, 250, 300, 350, 400, 450, and 500. mu.M, respectively, to detect changes in fluorescence intensity at 523nm, respectively. The results are shown in fig. 3-6, the fluorescence intensity of the probe A-1 is obviously enhanced along with the increase of the concentration of the substance to be detected, and the detection limits of the probe A-1 on hydrazine, hydrazine sulfate, hydrazine nitrate and unsymmetrical dimethylhydrazine are calculated as follows: 0.21. mu.M (6.7ppb), 0.24. mu.M (31.2ppb), 0.21. mu.M (19.9ppb) and 0.64. mu.M (38.5 ppb).
A-2: hydrazine, hydrazine sulfate, hydrazine nitrate, and unsymmetrical dimethylhydrazine were added to the buffer solution of the probe A-2 at concentrations of 0, 50, 100, 150, 200, 250, 300, 350, 400, 450, and 500. mu.M, respectively, to detect changes in fluorescence intensity at 523nm, respectively. The results are shown in FIGS. 7-10, the fluorescence intensity of the probe A-2 is enhanced with the increase of the concentration of the substance to be detected, and the detection limits of the probe A-2 on hydrazine, hydrazine sulfate, hydrazine nitrate and unsymmetrical dimethylhydrazine are calculated as follows: 2.4. mu.M (76.8ppb), 5.2. mu.M (676.0ppb), 2.9. mu.M (275.5ppb) and 5.8. mu.M (348 ppb).
Example 4:
as shown in fig. 11 to 18, this example provides an application of a fluorescent probe for rapid detection of a hydrazine compound, which illustrates that the response time of the fluorescent probe synthesized in example 1 to the hydrazine compound is different.
A-1: hydrazine with the concentration of 1000 mu M (100eq), hydrazine sulfate, hydrazine nitrate and unsymmetrical dimethylhydrazine solution to be tested are respectively added into a buffer solution containing 10 mu M of the probe A-1, so as to obtain a relation graph of the change of the fluorescence intensity along with the time. As shown in FIGS. 11-14, probe A-1 responded most rapidly to hydrazine, the reaction was almost equilibrated at 10min, the response time to hydrazine nitrate was 25min, hydrazine sulfate was 35min, compared to unsymmetrical dimethylhydrazine over 40 min.
A-2: to a buffer solution containing 10. mu.M of the probe A-2, hydrazine sulfate, hydrazine nitrate and unsym-dimethylhydrazine solutions to be tested were added at a concentration of 1000. mu.M (100eq) respectively to obtain a graph showing the change of fluorescence intensity with time. The result is shown in fig. 15-18, the probe A-2 continuously responds to the hydrazine compound within 10min, the fluorescence response degree can achieve the effect of naked eye detection, and the fluorescence intensity of the reaction of the probe A-2 and hydrazine is higher under the same reaction time, which indicates that the probe A-2 has the fastest response to hydrazine, hydrazine nitrate is second, and hydrazine sulfate and unsym-dimethylhydrazine are similar.
Example 5:
as shown in fig. 19 to 24, this example provides an application of a fluorescent probe for rapidly detecting a hydrazine compound, which indicates that the fluorescent probe synthesized in example 1 has good selectivity and strong anti-interference capability when detecting the hydrazine compound.
A-1: adding common anions and cations and nitrogen-containing small molecules including Zn into the solution containing the probe A-12+、Mn2+、Cu2+、Cd2+、Fe3+、Ba2+、Mg2+、NO2-、NO3-、HSO3-、SO3-、SH-、Et3N、DMF、NH3·H2O，Et3N、DMF、NH3·H2The fluorescence intensity of the probe is not changed by adding the three amine molecules O, and the test result shows that the probe A-1 has almost no response to the interfering substances. The hydrazine compounds are added into a test system to carry out an anti-interference experiment, the result is shown in figures 19-21, the probe A-1 still has good response to the hydrazine compounds in the environment of coexistence of interference substances, and the probe A-1 is proved to have good selectivity and strong anti-interference capability.
A-2: adding common anions and cations and nitrogen-containing small molecules including Zn into the solution containing probe A-22+、Mn2+、Cu2+、Cd2+、Fe3+、Ba2+、Mg2+、NO2-、NO3-、HSO3-、SO3-、SH-、Et3N、DMF、NH3·H2O，Et3N、DMF、NH3·H2The fluorescence intensity of the probe is not changed by adding the three amine molecules O, and the test result shows that the fluorescence intensity of the probe except HSO is not changed3-In addition, probe A-2 had little response to other interfering substances, HSO3-The change in fluorescence intensity is small compared to that after the hydrazine compound is added, which indicates that the fluorescence intensity is small in HSO3-Under the interference, the probe A-2 can still generate stronger fluorescence response with hydrazine compounds. The results of the anti-interference experiments performed by adding hydrazine compounds to the test system are shown in FIGS. 22 to 24, in which Et is a coexisting nitrogen-containing molecule3N and NH3·H2O pair probeA-2 produces a relatively obvious fluorescent response, but DMF does not substantially interfere with A-2, indicating that the probe A-2 has good selectivity on partial nitrogen-containing molecules.
Example 6:
as shown in fig. 25, this example provides an application of a fluorescent probe for rapidly detecting a hydrazine compound, which illustrates that the fluorescent probe synthesized in example 1 has different response degrees to a target substance at different phs, and the fluorescent probe has high stability in a system with a pH of 7 to 10.
A-1: as shown in FIG. 19, in a system with pH less than or equal to 5, the probe A-1 has reduced nucleophilic ability due to protonation of nitrogen atoms in hydrazine compounds under acidic conditions, reduced reactivity and insignificant fluorescence response; in a system with the pH value of more than or equal to 6, the probe A-1 is hydrolyzed along with the enhancement of alkalinity, the fluorescence response gradually appears, the H & lt + & gt in the system is gradually reduced along with the increase of the pH value, and the reactivity of the probe A-1 and a hydrazine compound is gradually improved; in a system with pH of 7-10, the fluorescence response of the hydrazine compound is obvious and stable, which indicates that the probe A-1 has good pH adaptability.
A-2: as shown in FIG. 26, in a system with pH less than or equal to 5, the probe A-2 has reduced nucleophilic ability due to protonation of nitrogen atoms in hydrazine compounds under acidic conditions, reduced reactivity and insignificant fluorescence response; in a system with pH being more than or equal to 6, along with the enhancement of alkalinity, the probe A-2 is hydrolyzed, and the fluorescence response gradually appears; in a system with the pH value of 7-10, the fluorescence response of the hydrazine compound is obvious and stable, which indicates that the probe A-2 has a wide pH adaptation range, and the stability of the hydrazine compound detected in the system with the pH value of 7-10 is high.
In summary, the fluorescent probe obtained in example 1 can achieve fast response to hydrazine, hydrazine sulfate, hydrazine nitrate and unsymmetrical dimethylhydrazine, and has significant fluorescence enhancement, a low detection limit, and good anti-interference and selectivity. After the fluorescent probe reacts with a hydrazine compound, a solution system is changed from colorless to green, naked eye identification can be realized, the response time of A-1 to hydrazine is faster than that of A-2, the detection limit of A-1 is lower than that of A-2, the selectivity and the anti-interference capability of A-1 are stronger than that of A-2, the pH adaptability of A-1 is better than that of A-2, but the production cost of A-2 is lower than that of A-1, the occupation ratio of the probe A-1 in the probes A-1 and A-2 is lower than that of A-2, stable response time can be realized by mixing the A-1 and the A-2 in proportion, and quick detection can be realized in an interference environment.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (4)
1. The fluorescent probe for rapidly detecting the hydrazine compounds is characterized by comprising A-1 and A-2, wherein the mixing ratio of the probe A-1 to the probe A-2 is 1: 3-1: 5, the chemical structural formula is as follows:
A-1：
A-2：
2. the method for synthesizing the fluorescent probe for rapidly detecting the hydrazine compound based on the claim 1 is characterized by comprising the following steps of:
(1) preparation A-1: adding dichlorofluorescein into a round-bottom flask, adding dichloromethane under the protection of nitrogen, stirring for dissolving, then sequentially adding triethylamine and acryloyl chloride at 0 ℃ in an ice bath, mixing and stirring for 10min, reacting at room temperature for 12h, identifying and qualitatively analyzing a small amount of substances by TLC during the reaction, tracking the reaction process, removing the solvent in vacuum after the reaction is finished, and obtaining a probe A-1 after column chromatography;
(2) Preparation A-2: adding fluorescein into a round-bottom flask, adding dichloromethane under the protection of nitrogen, stirring for dissolving, then sequentially adding triethylamine and acryloyl chloride at 0 ℃ in an ice bath, mixing and stirring for 10min, reacting at room temperature for 12h, identifying and qualitatively analyzing a small amount of substances by TLC during the reaction, tracking the reaction process, removing the solvent in vacuum after the reaction is finished, and obtaining a probe A-2 after column chromatography;
(3) preparing a fluorescent probe: mixing the probe A-1 obtained in the step (1) and the probe A-2 obtained in the step (2) in proportion to obtain the fluorescent probe;
the eluent of the column chromatography is petroleum ether-ethyl acetate, wherein the volume ratio of the petroleum ether to the ethyl acetate is 6: 1;
the mixing ratio of the probe A-1 to the probe A-2 is 1: 3-1: 5.
3. the application of a fluorescent probe for rapidly detecting hydrazine compounds is characterized in that: the detection method of the fluorescent probe comprises the following steps: adding the hydrazine compound into the buffer solution of the probes A-1 and A-2 for full reaction for 1h, realizing naked eye identification of the hydrazine compound through the change of the color of the solution system after the reaction, and realizing fluorescence identification of the hydrazine compound through detecting the fluorescence intensity of the reaction solution at 523 nm.
4. The use of the fluorescent probe for rapidly detecting hydrazine compounds as claimed in claim 3, wherein: the buffer solution is PBS and DMSO solution, the concentration of the buffer solution is 10 μ M, the pH is 7.4, and the volume ratio of PBS to DMSO is 9: 1.
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