CN115073435A - Near-infrared fluorescent probe for detecting hydrogen sulfide and preparation method thereof - Google Patents
Near-infrared fluorescent probe for detecting hydrogen sulfide and preparation method thereof Download PDFInfo
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- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 69
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
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- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
The invention discloses a near-infrared fluorescent probe for detecting hydrogen sulfide and a preparation method thereof, and the near-infrared fluorescent probe specifically comprises the following steps: mixing 6-hydroxy-1-tetralone with concentrated sulfuric acid, cooling, adding 4- (diethylamino) salicylaldehyde, heating, stirring, and performing column chromatography separation and purification to obtain a fluorophore FR-OH; dissolving 2-mercaptopyridine in chloroform, adding 2-mercaptosalicylic acid and thionyl chloride, refluxing, stirring and filtering to obtain 2- (2-pyridyldithio) benzoic acid PBA; mixing and stirring the anhydrous dichloromethane solution, the fluorophores FR-OH, PBA, EDU and DMAP, and performing column chromatography separation. The probe molecule has good water solubility, has specific response to hydrogen sulfide under the excitation of 580nm wavelength, has excellent selectivity and anti-interference performance, and realizes the visual detection of the endogenous hydrogen sulfide of cells.
Description
Technical Field
The invention belongs to the technical field of analysis and detection, and particularly relates to a near-infrared fluorescent probe for detecting hydrogen sulfide, and a preparation method of the near-infrared fluorescent probe.
Background
Hydrogen sulfide has been considered as a toxic gas having a smell of rotten eggs, but with the development of scientific technology, hydrogen sulfide is considered as a third gas signal molecule, and its concentration abnormality in the human body is related to various diseases. Endogenous hydrogen sulfide is mainly generated in a living body through an endogenous enzyme catalytic pathway, namely L-cysteine is used as a substrate, and hydrogen sulfide is generated under the catalysis of three enzymes, namely cystathionine-beta-synthetase CBS, cystathionine-gamma-lyase CSE and 3-mercaptoketonic acid mercaptotransferase 3-MST respectively. The three enzymes are distributed in brain, heart, lung, liver, kidney, blood vessel, pancreas and intestinal tract of human body. And the abnormal concentration of hydrogen sulfide can cause related diseases, such as: diabetes, heart disease, hypertension, liver cirrhosis, etc.
In recent years, scientific researchers have also constructed a number of fluorescent probes for detecting hydrogen sulfide. However, due to the poor specificity of the probe, especially the existence of thiol in complex biological environment, the recognition response of the probe to hydrogen sulfide is interfered. Therefore, it is of great significance to design a near-infrared fluorescent probe which can specifically identify hydrogen sulfide, has good water solubility and can perform cell imaging on endogenous hydrogen sulfide.
Disclosure of Invention
The invention aims to provide a near-infrared fluorescent probe for detecting hydrogen sulfide, and the fluorescent probe molecule has good selectivity and anti-interference capability on the detection of hydrogen sulfide.
The invention also aims to provide a preparation method of the near-infrared fluorescent probe for detecting hydrogen sulfide.
The invention adopts the technical scheme that a near-infrared fluorescent probe for detecting hydrogen sulfide has a structural formula shown as the following formula (I):
the invention adopts another technical scheme that a preparation method of a near-infrared fluorescent probe for detecting hydrogen sulfide is implemented according to the following steps:
step 1, mixing 6-hydroxy-1-tetralone with concentrated sulfuric acid, cooling to 0 ℃, adding 4- (diethylamino) salicylaldehyde, stirring uniformly, carrying out heating and stirring reaction under the protection of nitrogen, cooling, pouring into an ice water bath at-5-0 ℃, completely melting reactants, and carrying out column chromatography separation and purification to obtain a fluorophore FR-OH;
2, dissolving 2-mercaptopyridine in chloroform, adding 2-mercaptosalicylic acid and thionyl chloride, refluxing and stirring for 1.0h at room temperature, and performing suction filtration by using a Buchner funnel to obtain a light yellow solid, namely a product 2- (2-pyridyldithio) benzoic acid PBA;
step 3, mixing the anhydrous dichloromethane solution, the fluorophores FR-OH, PBA, EDU and DMAP, stirring at room temperature, and performing column chromatography separation to obtain a product, namely the near-infrared fluorescent probe FR-H for detecting hydrogen sulfide 2 S。
In the step 1, the mass ratio of the 6-hydroxy-1-tetralone to the concentrated sulfuric acid to the 4- (diethylamino) salicylaldehyde is 1:9.38: 1; the reaction temperature is 90 ℃ and the reaction time is 6 h.
In the step 2, the mass ratio of the 2-mercaptopyridine to the chloroform to the 2-mercaptosalicylic acid to the thionyl chloride is 2:67:1: 1.
In step 3, the mass ratio of the anhydrous dichloromethane solution, the fluorophores FR-OH, PBA, EDU and DMAP is 3900:10:10:10: 1.
The probe molecule designed by the invention has good water solubility, has specific response to hydrogen sulfide under the excitation of 580nm wavelength, has excellent selectivity and anti-interference performance, and realizes the visual detection of the endogenous hydrogen sulfide of cells.
Drawings
FIG. 1 is a schematic diagram of a method of preparing a near-infrared fluorescent probe according to the present invention;
FIG. 2 shows the fluorescent probe FR-H under different organic solvent to water volume ratios of 1:1 2 Fluorescence emission spectrum of S (5. mu. mol/L);
FIG. 3 shows the fluorescent probe FR-H under different organic solvent to water volume ratios of 1:1 2 (S) (5 mu mol/L) and hydrogen sulfide response fluorescence emission spectrogram;
FIG. 4 is a graph of the change in fluorescence of probe molecules (5. mu. mol/L) in solution with 1% DMSO at various pHs in response to hydrogen sulfide;
FIG. 5 is the FR-H probe in a solution containing 1% DMSO 2 Spectrograms of fluorescence intensity of S molecules (5 mu mol/L) along with time;
FIG. 6 is the FR-H probe in a solution containing 1% DMSO 2 Trend graph of fluorescence intensity of S molecule (5 μmol/L) with time;
FIG. 7 is the FR-H probe in a solution containing 1% DMSO 2 Ultraviolet absorption spectrogram responding to S molecules (5 mu mol/L) and hydrogen sulfide with different concentrations;
FIG. 8 shows the FR-H probe in a solution containing 1% DMSO 2 Responding a fluorescence emission spectrogram by an S molecule (5 mu mol/L) and hydrogen sulfide with different concentrations;
FIG. 9 shows the FR-H probe in a solution containing 1% DMSO 2 A linear fitting graph of fluorescence intensity and hydrogen sulfide concentration before and after S molecule (5 mu mol/L) response;
FIG. 10 shows the FR-H probe in a solution containing 1% DMSO 2 Fluorescence emission spectra of S molecules (5. mu. mol/L) in selective response to polysulfides and other small amino acids;
FIG. 11 shows the FR-H probes in a solution containing 1% DMSO 2 Histogram of fluorescence intensity of competitive responses of S molecules (5. mu. mol/L) with hydrogen sulfide and other various amino acids;
FIG. 12 shows probe FR-H 2 Experimental picture of S molecule to cytotoxicity;
FIG. 13 shows probe FR-H 2 And (3) imaging the hydrogen sulfide detection cell by the S molecule in the A549 cell.
Detailed Description
The present invention will be described in detail with reference to the following detailed description and accompanying drawings.
The invention relates to a near-infrared fluorescent probe for detecting hydrogen sulfide, which has a structural formula shown as the following formula (I):
the invention relates to a near-infrared fluorescent probe for detecting hydrogen sulfide, which is implemented by the following steps:
step 1, mixing 6-hydroxy-1-tetralone with concentrated sulfuric acid, cooling to 0 ℃, adding 4- (diethylamino) salicylaldehyde, stirring uniformly, carrying out heating and stirring reaction under the protection of nitrogen, cooling, pouring into an ice water bath at the temperature of-5-0 ℃ to completely melt reactants, and carrying out column chromatography separation and purification to obtain a fluorophore FR-OH, wherein the structural formula of the fluorophore FR-OH is shown as a formula (II);
the mass ratio of the 6-hydroxy-1-tetralone to the concentrated sulfuric acid to the 4- (diethylamino) salicylaldehyde is 1:9.38: 1;
the reaction temperature is 90 ℃, and the reaction time is 6 h;
step 2, dissolving 2-mercaptopyridine in chloroform, adding 2-mercaptosalicylic acid and thionyl chloride, refluxing and stirring for 1.0h at room temperature, and performing suction filtration by using a Buchner funnel to obtain a light yellow solid, namely a product 2- (2-pyridyldithio) benzoic acid PBA, wherein the structural formula of the light yellow solid is shown as a formula (III);
the mass ratio of the 2-mercaptopyridine to the chloroform to the 2-mercaptosalicylic acid to the thionyl chloride is 2:67:1: 1;
step 3, mixing the anhydrous dichloromethane solution, the fluorophore FR-OH, PBA, 4-dimethylaminopyridine EDU and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride DMAP, stirring at room temperature, and performing column chromatography separation to obtain a product, namely the near-infrared fluorescent probe FR-H for detecting hydrogen sulfide 2 S；
The mass ratio of the anhydrous dichloromethane solution to the fluorophores FR-OH, PBA, EDU and DMAP is 3900:10:10:10: 1;
the design principle of the fluorescent probe prepared by the method of the invention is shown in figure 1, and the probe FR-H 2 The identification process of S on hydrogen sulfide is as shown in the figureThe method comprises the following three steps: (1) hydrogen sulfide and Probe FR-H 2 S carries out nucleophilic substitution reaction to attack disulfide bond; (2) probe FR-H 2 The disulfide bond in the S structure is broken to generate an intermediate containing sulfhydryl; (3) the intermediate undergoes intramolecular cyclization reaction to release the fluorophore FR-OH, and a red fluorescence signal is generated. Thiol molecules such as Cys, Hcy, GSH all react with similar nucleophilicity to the probe but do not undergo further intramolecular cyclization as compared to hydrogen sulfide, so probe FR-H 2 S can only specifically recognize and respond to hydrogen sulfide.
Examples
The invention relates to a preparation method of a near-infrared fluorescent probe for detecting hydrogen sulfide, which is implemented according to the following steps:
the reaction formula is as follows:
step 1, taking 6-hydroxy-1-tetralone and 4- (diethylamino) salicylaldehyde as raw materials to react to generate a fluorophore FR-OH shown in a following formula (II);
the method specifically comprises the following steps: in a 5mL round-bottom flask, 0.3g of 6-hydroxy-1-tetralone and 1.0mL of concentrated sulfuric acid were placed therein and cooled to 0 ℃. Then adding 0.392g of 4- (diethylamino) salicylaldehyde, fully stirring, stirring the obtained mixture for 6 hours under the condition of nitrogen protection at the heating temperature of 90 ℃, cooling, pouring into ice water, and after completely melting, performing column chromatography separation and purification to obtain a product FR-OH;
wherein, the product characterization data are as follows:
1 H NMR(400MHz,DMSO-d 6 )δ11.12(s,1H),8.63(s,1H),8.16(d,J＝8.6Hz,1H),7.91(d,J＝9.4Hz,1H),7.41(d,J＝9.4Hz,1H),7.27(s,1H),6.94(d,J＝8.7Hz,1H),6.87(s,1H),3.69–3.64(m,5H),3.01(s,5H),1.24(t,J＝7.0Hz,8H). 13 C NMR(100MHz,DMSO-d 6 )δ164.8,164.3,158.3,155.3,148.4,146.2,132.1,129.5,120.7,118.0,117.7,116.2,96.2,45.8,27.0,25.2,12.9。
HRMS:Calcd.for C 21 H 22 NO 2 [M] + :320.1645；Found:320.1608.
step 2, reacting 2-mercaptopyridine with 2-mercaptosalicylic acid (2.31g, 15.0mmol) to generate 2- (2-pyridyldithio) benzoic acid PBA;
the method specifically comprises the following steps: dissolving 2-mercaptopyridine (3.33g, 30.0mmol) in chloroform (80.0mL), adding the solution into a 250mL round-bottom flask, adding 2-mercaptosalicylic acid (2.31g, 15.0mmol) and thionyl chloride (1.10mL, 15.0mol), refluxing and stirring for 1.0 hour at room temperature, and performing suction filtration by using a Buchner funnel to obtain a light yellow solid, namely the PBA product without further separation and purification;
wherein, the product characterization data are as follows:
1 H NMR(400MHz,DMSO-d 6 )δ13.55(s,1H),8.48(s,2H),8.03(d,J＝7.5Hz,2H),7.78(dd,J＝17.5,7.9Hz,3H),7.60(dd,J＝17.4,8.8Hz,3H),7.50(d,J＝8.0Hz,1H),7.35(dd,J＝15.6,7.8Hz,2H),7.30–7.23(m,2H). 13 C NMR(100MHz,DMSO-d 6 )δ168.48,158.24,150.54,139.77,138.83,134.11,132.27,128.52,126.91,125.73,122.55,120.25.HRMS:Calcd.for C 12 H 9 NO 2 S 2 [M+H] + :264.0147；Found:264.0124.
step 3, the fluorophore FR-OH and the PBA are bridged to synthesize the near-infrared fluorescent probe FR-H 2 S；
The method specifically comprises the following steps: adding 25mL of anhydrous dichloromethane solution into a 100mL round-bottom flask, adding FR-OH (0.32g), PBA (0.263g), EDU (0.192g) and DMAP (0.0122g), stirring at room temperature, and performing column chromatography separation to obtain a product, namely the probe FR-H 2 S。
Wherein the product is characterized as follows:
1 H NMR(400MHz,DMSO-d 6 )δ8.76(s,1H),8.54(s,1H),8.49(ddd,J＝8.0,4.0,3.2Hz,1H),8.36(t,J＝7.4Hz,1H),8.00(d,J＝9.5Hz,1H),7.91(d,J＝8.2Hz,1H),7.85–7.79(m,1H),7.79–7.74(m,1H),7.66–7.57(m,1H),7.57–7.53(m,1H),7.51(d,J＝7.4Hz,1H),7.39(s,1H),7.30(ddd,J＝7.5,4.9,0.8Hz,1H),3.76(dd,J＝24.7,18.3Hz,1H),3.22–3.03(m,1H),1.26(t,J＝7.0Hz,1H). 13 C NMR(100MHz,DMSO-d 6 )δ164.1,161.4,158.8,157.2,156.1,154.7,150.2,149.1,144.0,140.6,138.5,135.0,132.6,132.4,127.6,126.9,125.9,125.7,124.7,122.9,122.2,121.9,121.4,120.1,119.7,119.0,95.9,45.9,39.8,26.5,24.6.
HRMS:Calcd.for C 33 H 29 N 2 O 3 S 2 [M+H] + :565.1614；Found:565.1703.
the fluorescence emission performance of the fluorescent probe prepared in this example was tested as follows:
fluorescence properties in different organic solvents:
an excitation wavelength of 570nm, and a fluorescent probe FR-H is tested 2 Fluorescence emission of S (5. mu. mol/L) in different organic solvents, in order to investigate the FR-H probe before and after addition of hydrogen sulfide 2 Selecting a more suitable solvent environment and selecting seven common solvents according to the fluorescence intensity values of S in different solvents, wherein the selection comprises the following steps: methanol (MeOH), acetonitrile (MeCN), ethanol (EtOH), dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), Acetone (Acetone), and Tetrahydrofuran (THF). The fluorescence intensity was measured in the presence of only the probe (5. mu. mol/L) and in the presence of both the probe (5. mu. mol/L) and sodium hydrosulfide (50. mu. mol/L), respectively, under the condition that the ratio of the organic solvent to the aqueous phase was 1: 1. As shown in FIGS. 2 and 3, the pure probe was found to have the weakest fluorescence intensity in DMSO and an emission wavelength of 630 nm; in the presence of both the probe and the identifier sodium hydrosulfide, the emission wavelength of the probe in DMSO is still 630nm, and the fluorescence intensity is increased by nearly 5 times compared with that of the pure probe, so that DMSO is selected as a test solvent.
Fluorescent probe FR-H 2 pH stability test of S:
in a 1% DMSO solvent system, the stability of the fluorescent probe in different pH (1-12) ranges is tested, and as shown in FIG. 4, the study finds that: the fluorescence intensity of the pure probe is weak in the range of pH 1-12. After hydrogen sulfide is added, the fluorescence intensity of the probe is stable in the pH range of 6-9; under the condition of polar acid and polar base, probe FR-H 2 The fluorescence of S is quenched, indicating that the probe can be used for detecting hydrogen sulfide under physiological conditions.
Test the addition of 600. mu. molProbe FR-H under hydrogen sulfide condition of/L 2 S (5 μmol/L) change in fluorescence intensity at 630nm over time, and the solvent system was an aqueous solution (1% DMSO, pH 7.4). As can be seen from FIGS. 5 and 6, the FR-H probe was detected within the first 30min after the addition of hydrogen sulfide 2 The fluorescence intensity of S increases very rapidly. Within a time period of 30-120min, probe FR-H 2 The increase in fluorescence intensity of S is gradual. At about 2h, the fluorescence intensity of the probe tends to stabilize.
Probe FR-H 2 Fluorescence titration experiment of S:
the probe FR-H was tested in an aqueous (1% DMSO, pH 7.4) solvent system 2 And the change conditions of the ultraviolet absorbance value and the fluorescence intensity value when the S is respectively increased along with the concentration of the hydrogen sulfide. As shown in FIGS. 7 and 8, the pure probe FR-H 2 The absorption peak of S at 580nm and the emission peak at 630nm are both low. Probe FR-H when the concentration of hydrogen sulfide increases 2 The UV absorbance and fluorescence intensity values of S are increased. When the hydrogen sulfide concentration reached 600. mu. mol/L, the fluorescence intensity increased by about 5 times to a maximum. As shown in FIG. 9, when the concentration of hydrogen sulfide is 0 to 500. mu. mol/L, FR-H increases with the increase of the concentration of hydrogen sulfide 2 The fluorescence intensity of S is increased linearly, probe FR-H 2 The regression equation for S is 304.73+2.60x (R) 2 0.9936). Calculating the FR-H of the probe according to the calculation formula 3 delta/k of the detection limit 2 The detection limit of S on hydrogen sulfide is 8.66 mu M. The probe has good solubility, so that the probe can be used for detecting the concentration of hydrogen sulfide in cells.
Probe FR-H 2 Selective experimental performance testing of S:
under the detection condition of aqueous solution (1% DMSO, pH 7.4), the probe concentration is 5 mu mol/L, the concentration of the substance to be detected is 1000 mu mol/L, and Arg, Val, Thr, Lys, Hcy, GSH, Cys and Na are selected 2 S 2 O 3 ，Na 2 S 2 O 4 ，Na 2 SO 4 ，Na 2 SO 3 ，NaHSO 3 ，NaNO 2 ，NaNO 3 ，Na 2 CO 3 ，NaHCO 3 ，KSCN，H 2 O 2 NaClO, NaF, NaBr and NaI are taken as objects to be detected,it is tested whether the probe has an identifying response to it. As shown in FIG. 10, at the emission wavelength of 630nm, only the addition of hydrogen sulfide resulted in the probe FR-H 2 The fluorescent signal of S is obviously increased, and the fluorescent signal of the probe is not obviously changed by adding other substances to be detected, so that the result shows that the probe FR-H 2 S has specific recognition response to hydrogen sulfide.
Probe FR-H 2 And (3) testing the anti-interference experimental performance of S:
the fluorescence intensity of the probe at the emission wavelength of 630nm was tested under detection conditions of aqueous solution (1% DMSO, pH 7.4), probe concentration of 5 μmol/L, hydrogen sulfide concentration of 600 μmol/L, and simultaneously with addition of 1000 μmol/L of analyte as an interference condition. As shown in FIG. 11, when only hydrogen sulfide was added, the probe FR-H 2 The fluorescence intensity of S is obviously increased. Probe FR-H under interfering conditions in the presence of other analytes 2 The detection capability of S on hydrogen sulfide is not obviously reduced, and most of interferents do not exist on the probe FR-H 2 The fluorescence intensity of S has an influence. The results showed that the probe FR-H 2 S has specific recognition to hydrogen sulfide in a complex environment, is not interfered by other analytes in the environment and has good anti-interference capability.
Probe FR-H 2 Cytotoxicity of S:
the cytotoxicity is detected by MTT experiment, and the probes FR-H with the concentrations of 2.5 mu mol/L, 5 mu mol/L, 10 mu mol/L, 20 mu mol/L, 50 mu mol/L and 100 mu mol/L are prepared 2 S, selecting A549 cells and recording the cell survival rate under different concentrations. As shown in FIG. 12, when the probe FR-H 2 When the concentration of S is 100 mu mol/L, the survival rate of the cells is still over 90 percent, which indicates that the probe FR-H 2 S has little toxicity to cells and can be used for the subsequent cell imaging experiment research process.
Probe FR-H 2 Fluorescence imaging experiment of S:
in a cell fluorescence imaging experiment, A549 cells are selected and pretreated by sodium nitroprusside SNP and N-ethylmaleimide NEM respectively, the SNP can stimulate the cells to generate more hydrogen sulfide, and the NEM can inhibit cellsAnd (3) generating intracellular hydrogen sulfide and mercaptan substances, and designing four experiments of an experimental group, a restraining group, an inducing group and a blank group. As shown in FIG. 13, only the probe FR-H was added to A549 cells 2 S, almost no fluorescence signal is generated; after exogenous incubation with sodium hydrosulfide, bright red fluorescence can be observed under a confocal microscope; addition of Probe FR-H after incubation with NEM 2 S, almost no fluorescence signal is observed; when the probe FR-H was added after the SNP incubation 2 S, the fluorescence signal appears bright red again under the confocal microscope. The results showed that the probe FR-H 2 S can be used for identifying and detecting endogenous hydrogen sulfide of cells.
The invention designs and synthesizes a nucleophilic reaction activated near-infrared fluorescent probe with the emission wavelength of 630nm by using coumarin as a fluorophore skeleton and PBA as a recognition group. Through a series of optical tests, the FR-H probe 2 S only responds to hydrogen sulfide recognition, cannot be interfered by mercaptan molecules, and has good water solubility, high sensitivity and strong selectivity. In a solvent system containing 1% DMSO, the concentration of hydrogen sulfide is in the range of 0-500 mu mol/L, and the probe FR-H increases with the increase of the concentration of hydrogen sulfide 2 The fluorescence intensity value of S is linearly enhanced. The probe has little toxicity to cells, and can be used for fluorescence imaging experiments of hydrogen sulfide exogenous and endogenous to cells.
Claims (5)
1. A near-infrared fluorescent probe for detecting hydrogen sulfide is characterized in that the fluorescent probe has a structural formula shown as the following formula (I):
2. the preparation method of the near-infrared fluorescent probe for detecting hydrogen sulfide as claimed in claim 1, which is implemented by the following steps:
step 1, mixing 6-hydroxy-1-tetralone with concentrated sulfuric acid, cooling to 0 ℃, adding 4- (diethylamino) salicylaldehyde, stirring uniformly, carrying out heating and stirring reaction under the protection of nitrogen, cooling, pouring into an ice water bath at-5-0 ℃, completely melting reactants, and carrying out column chromatography separation and purification to obtain a fluorophore FR-OH;
2, dissolving 2-mercaptopyridine in chloroform, adding 2-mercaptosalicylic acid and thionyl chloride, refluxing and stirring for 1.0h at room temperature, and performing suction filtration by using a Buchner funnel to obtain a light yellow solid, namely the product 2- (2-pyridyldithio) benzoic acid PBA;
step 3, mixing the anhydrous dichloromethane solution, the fluorophores FR-OH, PBA, EDU and DMAP, stirring at room temperature, and performing column chromatography separation to obtain a product, namely the near-infrared fluorescent probe FR-H for detecting hydrogen sulfide 2 S。
3. The method for preparing the near-infrared fluorescent probe for detecting the hydrogen sulfide as claimed in claim 2, wherein in the step 1, the mass ratio of the 6-hydroxy-1-tetralone, the concentrated sulfuric acid and the 4- (diethylamino) salicylaldehyde is 1:9.38: 1; the reaction temperature is 90 ℃ and the reaction time is 6 h.
4. The method for preparing the near-infrared fluorescent probe for detecting hydrogen sulfide as claimed in claim 2, wherein in the step 2, the mass ratio of the 2-mercaptopyridine to the chloroform to the 2-mercaptosalicylic acid to the thionyl chloride is 2:67:1: 1.
5. The method for preparing a near-infrared fluorescent probe for detecting hydrogen sulfide of claim 2, wherein in the step 3, the mass ratio of the anhydrous dichloromethane solution to the fluorophores FR-OH, PBA, EDU and DMAP is 3900:10:10:10: 1.
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