CN115073435B - 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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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 65
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 21
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 16
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004440 column chromatography Methods 0.000 claims abstract description 10
- XFVZSRRZZNLWBW-UHFFFAOYSA-N 4-(Diethylamino)salicylaldehyde Chemical compound CCN(CC)C1=CC=C(C=O)C(O)=C1 XFVZSRRZZNLWBW-UHFFFAOYSA-N 0.000 claims abstract description 9
- FNSQPQKPPGALFA-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-2h-naphthalen-1-one Chemical compound O=C1CCCC2=CC(O)=CC=C21 FNSQPQKPPGALFA-UHFFFAOYSA-N 0.000 claims abstract description 9
- IZMCGGDHSRRCEI-UHFFFAOYSA-N 6-hydroxy-6-sulfanylcyclohexa-2,4-diene-1-carboxylic acid Chemical compound SC1(C(C(=O)O)C=CC=C1)O IZMCGGDHSRRCEI-UHFFFAOYSA-N 0.000 claims abstract description 9
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- RUIJLVVKEFHVGK-UHFFFAOYSA-N 2-(pyridin-2-yldisulfanyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1SSC1=CC=CC=N1 RUIJLVVKEFHVGK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
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- 238000000034 method Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 34
- 239000000243 solution Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
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- 238000002474 experimental method Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 4
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
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- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- 102100034976 Cystathionine beta-synthase Human genes 0.000 description 1
- 108010073644 Cystathionine beta-synthase Proteins 0.000 description 1
- 102100035429 Cystathionine gamma-lyase Human genes 0.000 description 1
- 108010045283 Cystathionine gamma-lyase Proteins 0.000 description 1
- 101000937647 Drosophila melanogaster Probable malonyl-CoA-acyl carrier protein transacylase, mitochondrial Proteins 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
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- 235000013878 L-cysteine Nutrition 0.000 description 1
- 231100000002 MTT assay Toxicity 0.000 description 1
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
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- 102000004357 Transferases Human genes 0.000 description 1
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- 206010012601 diabetes mellitus Diseases 0.000 description 1
- XEYBHCRIKKKOSS-UHFFFAOYSA-N disodium;azanylidyneoxidanium;iron(2+);pentacyanide Chemical compound [Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].[O+]#N XEYBHCRIKKKOSS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- 230000001568 sexual effect Effects 0.000 description 1
- -1 small molecule amino acids Chemical class 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229940083618 sodium nitroprusside Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—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
- 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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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6447—Fluorescence; Phosphorescence by visual observation
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- C09K2211/1018—Heterocyclic compounds
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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Abstract
The invention discloses a near infrared fluorescent probe for detecting hydrogen sulfide and a preparation method thereof, which specifically comprises the following steps: mixing and cooling 6-hydroxy-1-tetralone with concentrated sulfuric acid, adding 4- (diethylamino) salicylaldehyde, heating and stirring, and separating and purifying by column chromatography to obtain a fluorophore FR-OH; dissolving 2-mercaptopyridine in chloroform, adding 2-mercaptosalicylic acid and thionyl chloride, refluxing, stirring, and suction filtering to obtain 2- (2-pyridyldithio) benzoic acid PBA; mixing and stirring the anhydrous dichloromethane solution, the fluorophore FR-OH, PBA, EDU and the DMAP, and separating by column chromatography. The probe molecule provided by the invention has good water solubility, has specific response to hydrogen sulfide under excitation of 580nm wavelength, and is excellent in selectivity and anti-interference performance, so that visual detection of endogenous hydrogen sulfide of cells is realized.
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 with a bad egg smell, but with the development of science and technology, hydrogen sulfide is considered as a third gas signal molecule, and its concentration abnormality in the human body is associated with various diseases. Endogenous hydrogen sulfide is mainly produced in a living body through an endogenous enzyme catalysis way, namely L-cysteine is taken as a substrate, and hydrogen sulfide is produced under the catalysis of three enzymes, namely cystathionine-beta-synthase CBS, cystathionine-gamma-lyase CSE and 3-mercapto-keto acid sulfhydryl transferase 3-MST. The three enzymes are distributed in the brain, heart, lung, liver, kidney, vascular pancreas and intestinal tract of human body. The concentration of hydrogen sulfide is abnormal to cause related diseases, such as: diabetes, heart disease, hypertension, liver cirrhosis, etc.
In recent years, many fluorescent probes for detecting hydrogen sulfide have been constructed by scientific researchers. However, the probe has an interfering nature with respect to the recognition response of hydrogen sulfide due to the poor specificity of the probe, especially due to the presence of thiols in complex biological environments. Therefore, it is of great importance to design a near infrared fluorescent probe which can specifically recognize 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 for detecting hydrogen sulfide.
Another object of the present invention is to provide a method for preparing the near infrared fluorescent probe for detecting hydrogen sulfide.
The technical scheme adopted by the invention is that the near infrared fluorescent probe for detecting hydrogen sulfide has a structural formula shown in the following formula (I):
the invention adopts another technical scheme that the preparation method of the 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, heating and stirring for reaction under the protection of nitrogen, pouring into an ice water bath at the temperature of-5 ℃ to 0 ℃ after cooling, completely melting reactants, and separating and purifying by column chromatography to obtain a fluorophore FR-OH;
step 2, dissolving 2-mercaptopyridine in chloroform, adding 2-mercaptosalicylic acid and thionyl chloride, refluxing and stirring for 1.0h at room temperature, and carrying out suction filtration by using a Buchner funnel to obtain a pale yellow solid, namely the product 2- (2-pyridyldithio) benzoic acid PBA;
step 3, mixing the anhydrous dichloromethane solution, the fluorophore FR-OH, PBA, EDU and DMAP, stirring at room temperature, and separating by column chromatography 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, the concentrated sulfuric acid and the 4- (diethylamino) salicylaldehyde is 1:9.38:1; the reaction temperature was 90℃and the reaction time was 6 hours.
In the step 2, the mass ratio of the 2-mercaptopyridine, the chloroform, the 2-mercaptosalicylic acid and the thionyl chloride is 2:67:1:1.
In step 3, the mass ratio of the anhydrous methylene chloride solution, the fluorophore FR-OH, PBA, EDU and the DMAP was 3900:10:10:10:1.
The invention has the beneficial effects that the probe molecule designed by the invention has good water solubility, has specific response to hydrogen sulfide under the excitation of 580nm wavelength, and has excellent selectivity and anti-interference performance, thereby realizing the visual detection of 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 is a graph of fluorescence probe FR-H under different organic solvent to water volume ratios of 1:1 2 S (5 mu mol/L) fluorescence emission spectrum;
FIG. 3 is a graph of fluorescence 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 spectrum;
FIG. 4 is a graph showing fluorescence change of probe molecules (5. Mu. Mol/L) in a solution containing 1% DMSO in response to hydrogen sulfide at different pH values;
FIG. 5 is a probe FR-H in solution containing 1% DMSO 2 A spectrum of the fluorescence intensity of the S molecule (5 mu mol/L) with time;
FIG. 6 is a graph containing 1% DMSOProbe FR-H in solution 2 Trend graph of S molecule (5 mu mol/L) fluorescence intensity with time;
FIG. 7 is a probe FR-H in solution containing 1% DMSO 2 S molecules (5 mu mol/L) and hydrogen sulfide with different concentrations are subjected to ultraviolet absorption spectrogram;
FIG. 8 is a probe FR-H in solution containing 1% DMSO 2 S molecules (5 mu mol/L) and hydrogen sulfide with different concentrations are subjected to a fluorescence emission spectrum;
FIG. 9 is a probe FR-H in solution containing 1% DMSO 2 Linear fitting of S molecules (5 mu mol/L) response front and back fluorescence intensity to hydrogen sulfide concentration;
FIG. 10 is a probe FR-H in solution containing 1% DMSO 2 Fluorescence emission spectrum of S molecule (5. Mu. Mol/L) selective response to polysulfide and other small molecule amino acids;
FIG. 11 is a probe FR-H in solution containing 1% DMSO 2 Fluorescence intensity histogram of competing response of S molecules (5. Mu. Mol/L) with hydrogen sulfide and other different amino acids;
FIG. 12 is a probe FR-H 2 S molecule versus cytotoxicity experimental diagram;
FIG. 13 is a probe FR-H 2 S molecule images hydrogen sulfide detecting cells in a549 cells.
Detailed Description
The present invention will be described in detail with reference to the following detailed description and the accompanying drawings.
The invention discloses a near infrared fluorescent probe for detecting hydrogen sulfide, which has a structural formula shown in the following formula (I):
the invention discloses 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, heating and stirring under the protection of nitrogen, cooling, pouring into an ice-water bath at-5-0 ℃ to completely melt reactants, and separating and purifying by column chromatography to obtain a fluorophore FR-OH, wherein the structural formula is shown as a formula (II);
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 hours;
step 2, dissolving 2-mercaptopyridine in chloroform, adding 2-mercaptosalicylic acid and thionyl chloride, refluxing and stirring for 1.0h at room temperature, and carrying out suction filtration by using a Buchner funnel to obtain a pale yellow solid, namely a product 2- (2-pyridyldithio) benzoic acid PBA, wherein the structural formula of the product is shown as a formula (III);
the mass ratio of the 2-mercaptopyridine, the chloroform, the 2-mercaptosalicylic acid and the thionyl chloride is 2:67:1:1;
step 3, mixing an anhydrous dichloromethane solution, fluorophores FR-OH, PBA, 4-dimethylaminopyridine EDU and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride DMAP, stirring at room temperature, and separating by column chromatography 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, the fluorophore FR-OH, PBA, EDU and the DMAP is 3900:10:10:10:1;
the design principle of the fluorescent probe prepared by the method is shown in figure 1, and the probe FR-H is shown in the specification 2 The identification process of S to hydrogen sulfide is roughly divided into three steps as shown in the figure: (1) Hydrogen sulfide and probe FR-H 2 S generates nucleophilic substitution reaction to attack disulfide bond; (2) Probe FR-H 2 S, disulfide bond in the 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 fluorescent signal is generated. Mercaptan fraction compared to hydrogen sulfideThe probes FR-H are because the probes, for example Cys, hcy, GSH, can undergo a similar nucleophilic reaction but cannot undergo further intramolecular cyclization reactions 2 S can only specifically respond to hydrogen sulfide recognition.
Examples
The invention discloses 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, 6-hydroxy-1-tetralone and 4- (diethylamino) salicylaldehyde are used as raw materials to react to generate a fluorophore FR-OH shown in the following formula (II);
the method comprises the following steps: in a 5mL round bottom flask, 0.3g of 6-hydroxy-1-tetralone was placed with 1.0mL of concentrated sulfuric acid, and cooled to 0 ℃. Then adding 0.392g of 4- (diethylamino) salicylaldehyde, fully stirring, stirring the obtained mixture for 6 hours under the heating condition of 90 ℃ under the protection of nitrogen, cooling, pouring into ice water, and separating and purifying by column chromatography after the mixture is completely melted to obtain a product FR-OH;
wherein, the product characterization data is 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 (2.31 g,15.0 mmol) to form 2- (2-pyridyldithio) benzoic acid PBA;
the method comprises the following steps: 2-mercaptopyridine (3.33 g,30.0 mmol) was dissolved in chloroform (80.0 mL), added to a 250mL round bottom flask, and then added with 2-mercaptosalicylic acid (2.31 g,15.0 mmol) and thionyl chloride (1.10 mL,15.0 mmol), stirred at room temperature under reflux for 1.0 hour, and suction filtered with a Buchner funnel to give a pale yellow solid as the product PBA without further isolation and purification;
wherein, the product characterization data is 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, bridging the fluorophore FR-OH and PBA to synthesize the near infrared fluorescent probe FR-H 2 S；
The method comprises the following steps: adding FR-OH (0.32 g), PBA (0.263 g), EDU (0.192 g), DMAP (0.0122 g) into a 100mL round bottom flask, stirring at room temperature, and separating by column chromatography to obtain the final product 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 performance test in different organic solvents:
excitation wavelength was 570nm, and fluorescence probe FR-H was tested 2 S (5. Mu. Mol/L) fluorescence emission in different organic solvents for investigation of the probes FR-H before and after addition of Hydrogen sulfide 2 S fluorescence intensity values in different solvents, a more proper solvent environment is selected, and seven common solvents are selected, wherein the method comprises the following steps: methanol (MeOH), acetonitrile (MeCN), ethanol (EtOH), dimethylsulfoxide (DMSO), N-Dimethylformamide (DMF), acetone (actone), and Tetrahydrofuran (THF). Fluorescence intensities were 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 conditions of organic solvent to aqueous phase=1:1. As shown in fig. 2 and 3, the pure probe has the weakest fluorescence intensity in DMSO, and the emission wavelength is 630nm; in the presence of the probe and the recognition agent sodium hydrosulfide, the probe emission wavelength was still 630nm in DMSO, and the fluorescence intensity was increased approximately 5 times compared to that of the pure probe, so DMSO was chosen as the test solvent.
Fluorescent probe FR-H 2 S pH stability test:
stability of fluorescent probes in 1% DMSO solvent system at different pH (1-12) ranges was tested and as shown in fig. 4, the study found: the fluorescence intensity of the pure probe was very weak in the ph=1 to 12 range. When hydrogen sulfide is added, the probe has stable fluorescence intensity within the pH=6-9 range; under the condition of polar acid and polar base, the probe FR-H 2 The fluorescence of S is quenched, indicating that the probe can be used for the detection of hydrogen sulfide under physiological conditions.
Test probe FR-H under the addition of 600. Mu. Mol/L hydrogen sulfide 2 S (5. Mu. Mol/L) change in fluorescence intensity over time at 630nm, the solvent system was aqueous (1% DMSO, pH=7.4). As can be seen from FIGS. 5 and 6, after hydrogen sulfide addition, the probe FR-H was detected within the first 30min 2 The fluorescence intensity of S increases rapidly. Within 30-120min period, probe FR-H 2 The fluorescence intensity of S increases more gradually. At about 2 hours, the fluorescence intensity of the probe tends to stabilize.
Probe FR-H 2 S fluorescence titration experiment:
probe FR-H was tested in an aqueous (1% dmso, ph=7.4) solvent system 2 And S is respectively changed along with the ultraviolet absorbance value and the fluorescence intensity value when the concentration of the hydrogen sulfide is increased. As shown in FIGS. 7 and 8, the pure probe FR-H 2 The absorption peak at 580nm and the emission peak at 630nm of S are both low. As the concentration of hydrogen sulfide increases, the probe FR-H 2 Both the ultraviolet absorbance value and the fluorescence intensity value of S increase. When the concentration of hydrogen sulfide reached 600. Mu. Mol/L, the fluorescence intensity increased by about 5-fold to the 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 value of S increases linearly, and the probe FR-H 2 The regression equation for S is y=304.73+2.60 x (R 2 = 0.9936). The probe FR-H is calculated according to the calculation formula 3 delta/k of the detection limit 2 The limit of detection of S for hydrogen sulfide was 8.66. Mu.M. Because the probe has better solubility, the probe can be used for detecting the concentration of hydrogen sulfide in cells.
Probe FR-H 2 S selectivity experimental performance test:
under the detection condition of aqueous solution (1% DMSO, pH=7.4), the probe concentration is 5 mu mol/L, the concentration of the object 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, naI as an analyte, whether or not the probe has a recognition response thereto was tested. As shown in FIG. 10, at an emission wavelength of 630nm, only the addition of hydrogen sulfide resulted in the probe FR-H 2 The fluorescence signal of S is obviously increased, the addition of other substances to be detected does not cause obvious change of the fluorescence signal of the probe, and the result shows that the probe FR-H 2 S has special purpose for hydrogen sulfideA sexual identification response.
Probe FR-H 2 S, interference immunity experimental performance test:
under the detection conditions of aqueous solution (1% dmso, ph=7.4), the probe concentration was 5 μmol/L and the hydrogen sulfide concentration was 600 μmol/L, while 1000 μmol/L of analyte was added as an interference condition, and the fluorescence intensity of the probe at an emission wavelength of 630nm was tested. As shown in FIG. 11, when only hydrogen sulfide was added, the probe FR-H was obtained 2 The fluorescence intensity of S is obviously increased. Probe FR-H under interference conditions in the presence of other analytes 2 S has no obvious reduction of the hydrogen sulfide detection capability, and the existence of most interferents has no effect on the FR-H of the probe 2 The fluorescence intensity of S is affected. The results indicate that the probe FR-H 2 S has specific recognition on 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:
cytotoxicity was detected by MTT assay, and probes FR-H were prepared at concentrations of 2.5. Mu. Mol/L, 5. Mu. Mol/L, 10. Mu. Mol/L, 20. Mu. Mol/L, 50. Mu. Mol/L, 100. Mu. Mol/L in this order 2 S, A549 cells were selected and cell viability at different concentrations was recorded. 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 more than 90%, which indicates that the probe FR-H 2 S has little toxicity to cells and can be used in the subsequent cell imaging experimental research process.
Probe FR-H 2 Fluorescence imaging experiment of S:
in a cell fluorescence imaging experiment, A549 cells are selected, the cells are respectively pretreated by sodium nitroprusside SNP and N-ethylmaleimide NEM, the SNP can stimulate the cells to generate more hydrogen sulfide, the NEM can inhibit the generation of hydrogen sulfide and thiol substances in the cells, and four groups of experiments including an experiment group, an inhibition group, an induction group and a blank group are designed. As shown in FIG. 13, only probe FR-H was added to A549 cells 2 At S, there is almost no fluorescent signal; bright red fluorescence was observed under confocal microscopy after exogenous incubation with sodium hydrosulfide; when (when)After incubation with NEM, the probe FR-H was added 2 At S, almost no fluorescence signal was observed; when the probes FR-H are added after incubation with SNP 2 At S, a bright red fluorescence signal is again presented under the confocal microscope. The results indicate that the probe FR-H 2 S can be used for recognition detection of endogenous hydrogen sulfide of cells.
According to the invention, coumarin-like is taken as a fluorophore framework, PBA is taken as a recognition group, and one nucleophilic reaction activated near infrared fluorescent probe with the emission wavelength of 630nm is designed and synthesized. The probe FR-H was shown by a series of optical tests 2 S only has recognition response to hydrogen sulfide, is not interfered by thiol 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 is increased along with the increase of the concentration of hydrogen sulfide 2 The fluorescence intensity value of S increases linearly. The probe has little toxicity to cells, and can be used for fluorescent imaging experiments of exogenous and endogenous hydrogen sulfide of cells.
Claims (3)
1. The near infrared fluorescent probe for detecting hydrogen sulfide is characterized by having a structural formula shown in the following formula (I):
2. the method for preparing the near infrared fluorescent probe for detecting hydrogen sulfide according to claim 1, which is characterized by comprising the following steps:
step 1, mixing 6-hydroxy-1-tetralone with concentrated sulfuric acid, cooling to 0 ℃, adding 4- (diethylamino) salicylaldehyde, stirring uniformly, heating and stirring for reaction under the protection of nitrogen, pouring into an ice water bath at the temperature of-5 ℃ to 0 ℃ after cooling, completely melting reactants, and separating and purifying by column chromatography to obtain a fluorophore FR-OH;
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 hours;
step 2, dissolving 2-mercaptopyridine in chloroform, adding 2-mercaptosalicylic acid and thionyl chloride, refluxing and stirring for 1.0h at room temperature, and carrying out suction filtration by using a Buchner funnel to obtain a pale yellow solid, namely the product 2- (2-pyridyldithio) benzoic acid PBA;
the mass ratio of the 2-mercaptopyridine, the chloroform, the 2-mercaptosalicylic acid and the thionyl chloride is 2:67:1:1;
step 3, mixing the anhydrous dichloromethane solution, the fluorophore FR-OH, PBA, EDU and DMAP, stirring at room temperature, and separating by column chromatography to obtain a product, namely the near infrared fluorescent probe FR-H for detecting hydrogen sulfide 2 S。
3. The method for preparing a near infrared fluorescent probe for detecting hydrogen sulfide according to claim 2, wherein in the step 3, the mass ratio of the anhydrous dichloromethane solution, the fluorophore FR-OH, PBA, EDU and the DMAP is 3900:10:10:10:1.
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