CN113024463B - Preparation and application of 1, 8-naphthalimide hydrogen sulfide fluorescent molecular probe - Google Patents
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Abstract
Hair brushThe invention discloses a preparation method of a 1, 8-naphthalimide hydrogen sulfide fluorescent molecular probe and application thereof in hydrogen sulfide identification and detection. The probe of the invention uses N- (p-benzyl) -4-hydroxy-1, 8-naphthalimide as a fluorescent parent and 2, 4-dinitrophenyl ether as a recognition group to obtain the fluorescent molecular probe with double recognition sites, and hydrogen sulfide hydrolyzes the 2, 4-dinitrophenyl ether to expose the hydroxy group of the fluorophore, thereby realizing the enhancement of the fluorescence intensity (more than 30 times). The fluorescent molecular probe has the advantages of stable photochemical property, high fluorescence quantum yield, low price and the like, can specifically identify hydrogen sulfide, and is free from Na+、Ca2+、NO2 ‑、H2O2、ClO‑、HSO4 ‑、CN2H4S、HSO3 ‑、S2O5 2‑、S2O8 2‑The interference of plasma and the linear detection range are increased to 0-40 mu mmol/L, so that the method can be used for quantitative detection of high-concentration hydrogen sulfide such as river water, rainwater, drinking water, drilling fluid, marsh liquid and the like, and has potential practical application value.
Description
Technical Field
The invention belongs to the technical field of chemical analysis and detection, and particularly relates to a preparation method of a novel 1, 8-naphthalimide hydrogen sulfide fluorescent molecular probe and application thereof in hydrogen sulfide identification and detection.
Background
Hydrogen sulfide (H) as one of the three major gas molecules2S) are closely related to human health, plant growth and environmental issues. For human health, intracellular H2S plays an important role in the regulation of the digestive, nervous, cardiovascular and urinary systems, H2An imbalance in S concentration can lead to diseases such as arterial and pulmonary hypertension, alzheimer' S disease, bone damage, liver cirrhosis, and the like. Exogenous H2S is also considered to be second only to cyanide, a highly toxic, low concentration of H2S can regulate the content of osmotic pressure regulating factors in plants and maintain the water balance of the plants. In addition, hydrogen sulfide can also corrode metal equipment and accelerate non-goldBelonging to the aging of materials. Therefore, it is of great significance to detect the concentration of hydrogen sulfide, and people have paid attention to the search for more sensitive detection methods.
In recent years, several methods for detecting hydrogen sulfide have been explored, such as iodometry, methylene blue, chromatography, fluorescent molecular probes, and electrochemical analysis. The fluorescent molecular probe has the advantages of good selectivity, high sensitivity, convenient operation and the like, and provides an effective method for detecting hydrogen sulfide. Currently, several fluorescent molecular probes for detecting hydrogen sulfide have been synthesized, most of which are based on well-known fluorophores such as coumarin, rhodamine, fluorescein, naphthalimide, borodipyrrolidine dye (BODIPY), and benzothiazole. As a typical D-. pi. -A fluorescent dye, 1, 8-naphthalimide compounds have been widely studied. They are considered ideal fluorophores due to their stable photochemical properties, intense fluorescence, high fluorescence quantum yields, long excitation and emission wavelengths. 1, 8-naphthalimide is used as a raw material to synthesize a plurality of fluorescent molecular probes. However, most of them have only one recognition site, fluorescence intensity and H2The narrow linear range of S concentration (between 0-20. mu. mmol/L) limits it to high concentrations of H2Application in S environment, so that novel fluorescent molecular probe is designed and H is widened2The linear detection range of S has important significance.
Disclosure of Invention
Aiming at the defects, the invention provides a preparation method and application of a 1, 8-naphthalimide hydrogen sulfide fluorescent molecular probe. By introducing more receptors, the fluorescent molecular probe with wider linear detection range is prepared, and can be used for quantitative detection of high-concentration hydrogen sulfide such as drilling fluid, marsh liquid and the like.
In order to solve the technical problem, the invention provides a 1, 8-naphthalimide hydrogen sulfide fluorescent molecular probe, which is N- ((2, 4-dinitrophenoxy) phenyl) -4- (2, 4-dinitrophenoxy) -1, 8-naphthalimide, is marked as a probe NTE-1, and has the following structural formula:
the preparation method of the probe comprises the following steps:
(1) synthesis of intermediate compound 1 a:
under the protection of nitrogen, 4-bromo-1, 8-naphthalic anhydride and 4-aminophenol are used as raw materials, absolute ethyl alcohol is used as a solvent, and the reaction is carried out for 8 hours at the reflux temperature; stopping heating after the raw materials are completely converted, and cooling; carrying out suction filtration, washing and full drying to obtain N- (4-hydroxyphenyl) -4-bromo-1, 8-naphthalimide which is a compound 1 a;
wherein the molar mass ratio of the 4-bromo-1, 8-naphthalic anhydride to the 4-aminophenol is 1: (1-1.5); the weight volume ratio of the 4-bromo-1, 8-naphthalic anhydride to the absolute ethyl alcohol is (5-6) g: 100 mL.
(2) Synthesis of intermediate compound 1 a:
under the protection of nitrogen, taking the compound 1a, anhydrous potassium carbonate and potassium iodide as raw materials, taking anhydrous methanol as a solvent, and reacting for 8 hours at 75 ℃; after the reaction is finished, cooling, rotary steaming, washing and drying to obtain N- (4-hydroxyphenyl) -4-methoxy-1, 8-naphthalimide which is a compound 1 b;
wherein the molar mass ratio of the compound 1a to the anhydrous potassium carbonate to the potassium iodide is 1: (4-6): (0.02-0.03); the weight volume ratio of the compound 1a to the absolute methanol is (4-5) g: 120 mL.
(3) Synthesis of intermediate compound 1 c:
under the protection of nitrogen, taking the intermediate product 1b and hydroiodic acid as raw materials, and reacting for 36 hours at 130 ℃; after the reaction is finished, cooling, adjusting the pH value to 7, separating out solids in the process, performing suction filtration to obtain a crude product, and performing column chromatography separation and purification to obtain N- (4-hydroxyphenyl) -4-hydroxy-1, 8-naphthalimide which is a compound 1 c;
wherein the mass-volume ratio of the compound 1b to the hydroiodic acid is (2-3): 30 mL; hydriodic acid is preferably 57% hydriodic acid.
(4) Synthesis of Probe NTE-1:
under the protection of nitrogen, taking a compound 1c, anhydrous potassium carbonate, potassium iodide and 2, 4-dinitrobromobenzene as raw materials, taking anhydrous N, N-dimethylformamide as a solvent, adding a phase transfer catalyst, and reacting for 5 hours at 100 ℃; stopping heating, cooling, and filtering; extracting, drying, filtering, removing the solvent to obtain a crude product, and performing column chromatography separation to obtain a target product N- ((2, 4-dinitrophenoxy) phenyl) -4- (2, 4-dinitrophenoxy) -1, 8-naphthalimide, namely the probe NTE-1.
Wherein, cetyl trimethyl ammonium bromide is used as a phase transfer catalyst.
The molar mass ratio of the compound 1c, anhydrous potassium carbonate, potassium iodide, hexadecyl trimethyl ammonium bromide and 2, 4-dinitrobromobenzene is 1: (4-6): (0.02-0.04): (0.02-0.04): (2-3).
Dissolving 2, 4-dinitrobromobenzene in anhydrous N, N-dimethylformamide, and slowly dripping into the reaction solution for about 8-15 min.
And (4) separating and purifying the crude products obtained in the step (3) and the step (4) by using a silica gel column, wherein the eluent is petroleum ether: ethyl acetate ═ (2-4): 1.
it is another object of the present invention to use the above-synthesized probe for identification and detection of high concentration hydrogen sulfide in river water, rainwater, drinking water, drilling fluid, marsh liquid, etc. containing hydrogen sulfide.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention synthesizes a novel double recognition site H by taking N- (p-benzyl) -4-hydroxy-1, 8-naphthalimide as a fluorophore2S fluorescent probe, H2S enables the fluorophore to expose hydroxyl through the sulfhydrolysis of the 2, 4-dinitrophenyl ether, thereby realizing the enhancement of fluorescence intensity, and having the advantages of longer excitation and emission wavelength, stable photochemical property, high fluorescence quantum yield, low price and economy and the like.
(2) H synthesized by the invention2S fluorescent probe NTE-1 can selectively detect H2S, in the presence of small molecular thiol L-Cys and GSH, the probe has no obvious enhancement of fluorescence intensity, better specificity and sensitivityHigher.
(3) H synthesized by the invention2S fluorescent probes NTE-1 to H2The absorption spectrum of S shows larger red shift (more than 100nm), the fluorescence enhancement is more than 30 times, the linear detection range is increased to 0-40 mu mmol/L, and the method can be used for quantitative detection of high-concentration hydrogen sulfide such as river water, rainwater, drinking water, drilling fluid, marsh liquid and the like.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a fluorescent molecular probe NTE-1 of hydrogen sulfide synthesized by the present invention;
FIG. 2 is the nuclear magnetic resonance carbon spectrum of the synthesized hydrogen sulfide fluorescent molecular probe NTE-1;
FIG. 3 shows H synthesized by the present invention2Fluorescence spectrum of the S fluorescent molecular probe NTE-1(10 mu mmol/L) added with 1mmol/L sodium sulfide solution;
FIG. 4 shows H synthesized by the present invention2Linear concentration curve of the S fluorescent molecular probe NTE-1;
FIG. 5 shows H synthesized by the present invention2An interfering ion experiment and a competitive ion experiment of an S fluorescent molecular probe NTE-1; the ions added from left to right are: (1) free, (2) Na+,(3)Ca2+,(4)NO2 -,(5)H2O2,(6)ClO-,(7)HSO4 -,(8)CN2H4S,(9)HSO3 -,(10)S2O5 2-,(11)S2O8 2-(12) L-Cys, (13) GSH; the left bar chart in FIG. 5 is probe + interfering ions, and the right bar chart in FIG. 5 is probe + sodium sulfide + interfering ions.
Detailed Description
The invention provides a naphthalimide H2The probe is N- ((2, 4-dinitrophenoxy) phenyl) -4- (2, 4-dinitrophenoxy) -1, 8-naphthalimide (NTE-1), and the structural formula of the probe is as follows:
the 1, 8-naphthoyleneAmines H2The fluorescent molecular probe with double recognition sites is formed by adopting N- (p-benzyl) -4-hydroxy-1, 8-naphthalimide as a fluorescent parent and 2, 4-dinitrophenyl ether as a recognition group; 4-bromo-1, 8-naphthalic anhydride is used as a raw material, and a new fluorescent molecular probe is synthesized through a series of reactions such as substitution, etherification and the like.
The synthetic route of the probe is shown as follows:
to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention will be described in detail below with reference to the accompanying drawings, and it is obvious that the described embodiments are some, but not all embodiments of the present invention, and all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the protection scope of the present invention.
Example 1: 1, 8-naphthalimides H2Synthesis of S fluorescent molecular probe
1. Synthesis of N- (4-hydroxyphenyl) -4-bromo-1, 8-naphthalimide (intermediate compound 1 a):
under the protection of nitrogen, 2.77g (10.00mmol) of 4-bromo-1, 8-naphthalic anhydride was dissolved in 50mL of anhydrous ethanol, and after stirring thoroughly at room temperature, 1.31g (12.00mmol) of 4-aminophenol was added, the reaction mixture was further stirred, the temperature was raised to 80 ℃ and the reaction was refluxed for 8 hours. After TLC monitoring raw material complete conversion (the developing solvent is petroleum ether: ethyl acetate 2: 1, V/V), stopping heating, cooling reaction liquid, and gradually separating out solid in the cooling process. The mixture was filtered, washed and dried to give a brown solid (3.34 g) in 90.76% yield.
2. Synthesis of N- (4-hydroxyphenyl) -4-methoxy-1, 8-naphthalimide (intermediate compound 1 b):
under nitrogen, 2.15g (5.85mmol) of 3a was dissolved in 60mL of anhydrous methanol and stirred at room temperature for 20 minutes. To the reaction mixture were added anhydrous potassium carbonate 4.04g (29.25mmol) and potassium iodide 0.02g (0.12mmol), and the reaction system was heated to 75 ℃ with stirring and refluxed for 8 hours. After the completion of the reaction was monitored by TLC (the developing solvent was petroleum ether: ethyl acetate 1: 1, V/V), it was cooled, rotary evaporated, and the obtained solid was washed three times with distilled water and dried to obtain 1.42g of a yellow solid product with a yield of 76.08%.
3. Synthesis of N- (4-hydroxyphenyl) -4-hydroxy-1, 8-naphthalimide (intermediate Compound 1 c):
2.62g (7.30mmol) of 3b was dissolved in 30mL of 57% hydroiodic acid under nitrogen, and the mixture was stirred at room temperature for 10 minutes, then the temperature was raised to 130 ℃ and the reaction was refluxed for 36 hours. After the reaction is finished, cooling, adjusting the pH to 7 by using 20% sodium hydroxide under an ice bath condition, separating out a large amount of solids in the process, and performing suction filtration to obtain a crude product. The crude product was further purified by column chromatography (eluent petroleum ether: ethyl acetate 4: 1, V/V) to give 1.60g of a yellow solid product in 72.07% yield.
4. Synthesis of N- ((2, 4-dinitrophenoxy) phenyl) -4- (2, 4-dinitrophenoxy) -1, 8-naphthalimide (probe NTE-1):
under nitrogen, 0.92g (3.00mmol) of 3c was dissolved in 30mL of anhydrous DMF, and 2.08g (15.00mmol) of anhydrous potassium carbonate, 0.01g (0.06mmol) of potassium iodide and 0.02g (0.06mmol) of CTMAB were added in this order, followed by stirring at room temperature for 20 minutes. 5mL of anhydrous DMF containing 1.85g (7.50mmol) of 2, 4-dinitrobromobenzene was slowly added dropwise over a period of about 10 minutes. After the dropwise addition, the reaction solution was heated to 100 ℃ and the reaction was continued for 5 hours with heat preservation. Stopping heating, cooling, and filtering. To the filtrate, 50mL of distilled water was added, extracted 3 times with dichloromethane, and the three obtained extract phases were combined and dried over anhydrous magnesium sulfate for several hours. After drying, filtering, and rotatably removing the solvent from the filtrate to obtain a crude product. Column chromatography separation to obtain the target product NTE-1 (the eluent is petroleum ether and ethyl acetate is 4: 1, V/V), and finally 0.59g of milky white solid product is obtained, and the yield is 30.89%.
The structural characterization data of the probe NTE-1 prepared in example 1 are shown below:
melting point m.p. >200 ℃;
hydrogen spectrum of nuclear magnetic resonance1H NMR (400MHz, DMSO-d6) δ:9.04(d, J ═ 2.8Hz,1H),8.95(d, J ═ 2.8Hz,1H),8.69 to 8.50(m,5H),8.02(t, J ═ 7.9Hz,1H),7.63 to 7.53(m,4H),7.50 to 7.42(d, J ═ 7.9Hz,2H),7.36 to 7.30(d, J ═ 8.1Hz, 1H); FIG. 1 shows the NMR spectrum of the synthesized fluorescent molecular probe NTE-1.
Nuclear magnetic resonance carbon spectrum13C NMR (101MHz, DMSO-d6) delta: 164.01,163.39,156.03,154.96,153.99,153.44,143.69,142.21,140.84,140.20,133.95,132.59,132.26,132.00,130.63,130.29,130.00,128.59,128.38,124.16,123.53,122.83,122.71,122.42,120.89,120.26,120.12,115.17, respectively; FIG. 2 shows the nuclear magnetic resonance carbon spectrum of the synthesized hydrogen sulfide fluorescent molecular probe NTE-1.
High resolution mass spectrum HRMS [ M + Na ]]+calculated for C30H15N5O12 660.0609 found 660.0592。
Example 2: 1, 8-naphthalimides H2Application of S fluorescent molecular probe
Due to H2S is more than HS in neutral environment－The form exists, similar to the ion distribution of sodium sulfide under neutral conditions, therefore, sodium sulfide solution is used in this example instead of H2And S, testing.
Weighing 1mmol of probe NTE-1(0.0064g) and dissolving in 10mL of anhydrous dimethyl sulfoxide (DMSO) to prepare 1mmol/L of probe mother solution; then 100 μ L of the probe stock was removed and placed in a 10mL volumetric flask followed by mixing with PBS: ethanol ═ 1: 2(V/V) solvent was added to make a volume of 10mL to prepare a 1X 10-5mol/L test solution. 1mL of the test solution was placed in a four-side transparent quartz cuvette, and 1mmol/L sodium sulfide solution was added to measure the fluorescence spectrum, and the result is shown in FIG. 3, in which the probe NTE-1 itself had no fluorescence, and after 1mmol/L sodium sulfide was added, the fluorescence intensity at 549nm increased to 30 times that without sodium sulfide after 2 hours. The linear concentration curve of probe NTE-1 is shown in FIG. 4, in sulfurWhen the sodium concentration is between 0 and 40 mu mmol/L, the fluorescence emission intensity of the probe NTE-1 at 549nm is in a linear function relationship with the sodium sulfide concentration, and the method is suitable for high-concentration H2And (4) quantitatively detecting S. In addition, the molecular probe NTE-1 is not influenced by Na+、Ca2+、NO2 -、H2O2、ClO-、HSO4 -、CN2H4S、HSO3 -、S2O5 2-、S2O8 2-Interference of plasma, as shown in FIG. 5, the probe NTE-1 is directed to H even in the presence of interfering ions2S still has good response and good specificity, so that the fluorescent molecular probe can be used for H in the analytical detection fields of biochemistry, environmental protection science and the like2And the detection of S has potential practical application value.
In conclusion, the invention uses N- (p-benzyl) -4-hydroxy-1, 8-naphthalimide as a fluorescent parent and 2, 4-dinitrophenyl ether as a recognition group to obtain the fluorescent molecular probe with double recognition sites, and hydrogen sulfide hydrolyzes the 2, 4-dinitrophenyl ether to expose the hydroxy group of the fluorophore, thereby realizing the enhancement of the fluorescence intensity (more than 30 times). The fluorescent molecular probe has the advantages of stable photochemical property, high fluorescence quantum yield, low price and the like, can specifically identify hydrogen sulfide, and is free from Na+、Ca2 +、NO2 -、H2O2、ClO-、HSO4 -、CN2H4S、HSO3 -、S2O5 2-、S2O8 2-The interference of plasma and the linear detection range are increased to 0-40 mu mmol/L, so that the method can be used for quantitative detection of high-concentration hydrogen sulfide such as river water, rainwater, drinking water, drilling fluid, marsh liquid and the like, and has potential practical application value.
Although the present invention has been described in connection with the accompanying drawings, the present invention is not limited to the above-described embodiments, which are intended to be illustrative rather than restrictive, and many modifications may be made by those skilled in the art without departing from the spirit of the present invention as disclosed in the appended claims.
Claims (10)
1. The 1, 8-naphthalimide hydrogen sulfide fluorescent molecular probe is characterized in that the probe is N- ((2, 4-dinitrophenoxy) phenyl) -4- (2, 4-dinitrophenoxy) -1, 8-naphthalimide, is marked as a probe NTE-1, and has the following structural formula:
2. the method for preparing the 1, 8-naphthalimide hydrogen sulfide fluorescent molecular probe according to claim 1, which is characterized by comprising the following steps:
(1) synthesis of intermediate compound 1 a:
under the protection of nitrogen, 4-bromo-1, 8-naphthalic anhydride and 4-aminophenol are used as raw materials, absolute ethyl alcohol is used as a solvent, and the reaction is carried out for 8 hours at the reflux temperature; stopping heating after the raw materials are completely converted, and cooling; carrying out suction filtration, washing and full drying to obtain N- (4-hydroxyphenyl) -4-bromo-1, 8-naphthalimide which is a compound 1 a;
(2) synthesis of intermediate compound 1 b:
under the protection of nitrogen, taking the compound 1a, anhydrous potassium carbonate and potassium iodide as raw materials, taking anhydrous methanol as a solvent, and reacting for 8 hours at 75 ℃; after the reaction is finished, cooling, rotary steaming, washing and drying to obtain N- (4-hydroxyphenyl) -4-methoxy-1, 8-naphthalimide which is a compound 1 b;
(3) synthesis of intermediate compound 1 c:
under the protection of nitrogen, taking the intermediate product 1b and hydroiodic acid as raw materials, and reacting for 36 hours at 130 ℃; after the reaction is finished, cooling, adjusting the pH value to 7, separating out solids in the process, performing suction filtration to obtain a crude product, and performing column chromatography separation and purification to obtain N- (4-hydroxyphenyl) -4-hydroxy-1, 8-naphthalimide which is a compound 1 c;
(4) synthesis of Probe NTE-1:
under the protection of nitrogen, taking a compound 1c, anhydrous potassium carbonate, potassium iodide and 2, 4-dinitrobromobenzene as raw materials, taking anhydrous N, N-dimethylformamide as a solvent, adding a phase transfer catalyst, and reacting for 5 hours at 100 ℃; stopping heating, cooling, and filtering; extracting, drying, filtering, removing the solvent to obtain a crude product, and performing column chromatography separation to obtain a target product N- ((2, 4-dinitrophenoxy) phenyl) -4- (2, 4-dinitrophenoxy) -1, 8-naphthalimide, namely the probe NTE-1.
3. The method for preparing the 1, 8-naphthalimide hydrogen sulfide fluorescent molecular probe according to claim 2, wherein in the step (1), the molar mass ratio of the 4-bromo-1, 8-naphthalic anhydride to the 4-aminophenol is 1: 1 to 1.5; the weight-volume ratio of the 4-bromo-1, 8-naphthalic anhydride to the absolute ethyl alcohol is (5-6) g: 100 mL.
4. The preparation method of the 1, 8-naphthalimide hydrogen sulfide fluorescent molecular probe according to claim 2, wherein in the step (2), the molar mass ratio of the compound 1a to the anhydrous potassium carbonate to the potassium iodide is 1 to (4-6) to (0.02-0.03); the weight-volume ratio of the compound 1a to the absolute methanol is (4-5) g: 120 mL.
5. The method for preparing the 1, 8-naphthalimide hydrogen sulfide fluorescent molecular probe according to claim 2, wherein in the step (3), the mass-to-volume ratio of the compound 1b to the hydroiodic acid is (2-3) to 30 mL; hydriodic acid with a hydriodic acid concentration of 57%.
6. The method for preparing a 1, 8-naphthalimide hydrogen sulfide fluorescent molecular probe according to claim 2, wherein in the step (4), cetyl trimethyl ammonium bromide is used as a phase transfer catalyst.
7. The preparation method of the 1, 8-naphthalimide hydrogen sulfide fluorescent molecular probe according to claim 6, wherein in the step (4), the molar mass ratio of the compound 1c, anhydrous potassium carbonate, potassium iodide, hexadecyl trimethyl ammonium bromide and 2, 4-dinitrobromobenzene is 1: 4-6: 0.02-0.04: 2-3.
8. The method for preparing the 1, 8-naphthalimide hydrogen sulfide fluorescent molecular probe according to claim 2, wherein in the step (4), the 2, 4-dinitrobromobenzene is dissolved in anhydrous N, N-dimethylformamide and then slowly dripped into the reaction solution for 8-15 min.
9. The method for preparing 1, 8-naphthalimide hydrogen sulfide fluorescent molecular probe according to claim 2, wherein the crude products obtained in step (3) and step (4) are separated and purified by silica gel column, and the eluent is petroleum ether: and ethyl acetate is (2-4) to 1.
10. The probe of claim 1 for use in the identification and detection of hydrogen sulfide in a liquid containing hydrogen sulfide.
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| CN114874142B (en) * | 2022-06-27 | 2023-10-10 | 河南省人民医院 | Fluorescent probe based on 1, 8-naphthalimide derivative, and preparation method and application thereof |
| CN116444432B (en) * | 2023-03-20 | 2024-04-05 | 湖北南博生物工程有限公司 | H based on 1, 8-naphthalimide 2 S fluorescent probe and preparation method and application thereof |
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| CN107298654A (en) * | 2017-05-19 | 2017-10-27 | 济南大学 | The fluorescence probe of hydrogen sulfide in a kind of detection endoplasmic reticulum |
| CN113979998B (en) * | 2021-11-19 | 2022-08-26 | 江苏科技大学 | Aluminum ion detection fluorescent probe based on 1, 8-naphthalimide as matrix and preparation method and application thereof |
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