CN116102485B - Half cyanine analog ratio type fluorescent probe for detecting sulfur dioxide derivative and preparation method and application thereof - Google Patents
Half cyanine analog ratio type fluorescent probe for detecting sulfur dioxide derivative and preparation method and application thereof Download PDFInfo
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- CN116102485B CN116102485B CN202211549570.7A CN202211549570A CN116102485B CN 116102485 B CN116102485 B CN 116102485B CN 202211549570 A CN202211549570 A CN 202211549570A CN 116102485 B CN116102485 B CN 116102485B
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical class O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 32
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical class [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title abstract description 9
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- 238000000034 method Methods 0.000 claims abstract description 17
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- 239000007864 aqueous solution Substances 0.000 claims description 8
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
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- NHJVRSWLHSJWIN-UHFFFAOYSA-N 2,4,6-trinitrobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O NHJVRSWLHSJWIN-UHFFFAOYSA-N 0.000 description 3
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- ZKHQWZAMYRWXGA-KQYNXXCUSA-J ATP(4-) Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O)[C@@H](O)[C@H]1O ZKHQWZAMYRWXGA-KQYNXXCUSA-J 0.000 description 2
- ZKHQWZAMYRWXGA-UHFFFAOYSA-N Adenosine triphosphate Natural products C1=NC=2C(N)=NC=NC=2N1C1OC(COP(O)(=O)OP(O)(=O)OP(O)(O)=O)C(O)C1O ZKHQWZAMYRWXGA-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
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- NOESYZHRGYRDHS-UHFFFAOYSA-N insulin Chemical compound N1C(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(NC(=O)CN)C(C)CC)CSSCC(C(NC(CO)C(=O)NC(CC(C)C)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CCC(N)=O)C(=O)NC(CC(C)C)C(=O)NC(CCC(O)=O)C(=O)NC(CC(N)=O)C(=O)NC(CC=2C=CC(O)=CC=2)C(=O)NC(CSSCC(NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2C=CC(O)=CC=2)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)C(CCC(O)=O)NC(=O)C(C(C)C)NC(=O)C(CC(C)C)NC(=O)C(CC=2NC=NC=2)NC(=O)C(CO)NC(=O)CNC2=O)C(=O)NCC(=O)NC(CCC(O)=O)C(=O)NC(CCCNC(N)=N)C(=O)NCC(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC=CC=3)C(=O)NC(CC=3C=CC(O)=CC=3)C(=O)NC(C(C)O)C(=O)N3C(CCC3)C(=O)NC(CCCCN)C(=O)NC(C)C(O)=O)C(=O)NC(CC(N)=O)C(O)=O)=O)NC(=O)C(C(C)CC)NC(=O)C(CO)NC(=O)C(C(C)O)NC(=O)C1CSSCC2NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C(CCC(N)=O)NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(N)CC=1C=CC=CC=1)C(C)C)CC1=CN=CN1 NOESYZHRGYRDHS-UHFFFAOYSA-N 0.000 description 2
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- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 2
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
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- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 102000004357 Transferases Human genes 0.000 description 1
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- 239000000809 air pollutant Substances 0.000 description 1
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- 238000010898 silica gel chromatography Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
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- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 230000024883 vasodilation Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
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- 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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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Abstract
The invention belongs to the field of organic micromolecule fluorescent probes, and provides a hemicyanine analog type fluorescent probe for detecting sulfur dioxide derivatives, and a preparation method and application thereof. The structure of the compound is shown as a formula (I).The probe provided by the invention has AIE property, can rapidly and highly selectively identify sulfur dioxide derivatives through colorimetry and fluorescence, and has strong anti-interference capability. The probe is successfully applied to detection of endogenous and exogenous sulfur dioxide derivatives in living cells. In addition, the probe is also successfully used for detecting sulfur dioxide derivatives in wheat root systems, and a novel and simple method is provided for better understanding the influence of the sulfur dioxide derivatives on crops.
Description
Technical Field
The invention belongs to the field of organic micromolecule fluorescent probes, and particularly relates to a hemicyanine analog ratio type fluorescent probe for detecting sulfur dioxide derivatives, and a preparation method and application thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Sulfur dioxide is both an air pollutant and an important biological signal molecule involved in vasodilation, regulating blood insulin levels, and maintaining redox balance. Sulfur dioxide is very easily converted to sulfite/bisulfite in aqueous solutions. Endogenous sulfur dioxide is mainly derived from sulfur-containing amino acids and participates in various physiological processes in the form of its derivatives sulfite/bisulfite. Sulfur dioxide derivatives are important bleaching agents, preservatives and antioxidants, and are widely used in the fields of foods, medicines, agricultural products and the like. Studies have shown that excessive sulfite/bisulfite intake can lead to respiratory diseases, cardiovascular diseases, lung cancer and various neurological diseases. In addition, sulfur dioxide also produces harm to plants, and leaves are withered and yellow, so that the yield of crops is reduced. After the excessive sulfite/bisulfite is absorbed by plants, the generation of Adenosine Triphosphate (ATP) during photosynthesis and respiration can be inhibited, and oxidation damage can be caused to some biomacromolecules. Therefore, the development of reliable and effective methods for detecting sulfur dioxide derivatives in foods and organisms is of great importance.
Current methods for detecting sulfur dioxide derivatives include fluorescent probe methods, electrochemical methods, capillary electrophoresis analysis, redox titration methods, and the like. Among these methods, fluorescent probes, particularly probes having dual responses of colorimetry and fluorescence, are considered as powerful tools for analyte detection due to the advantages of convenient observation, simple sample pretreatment, suitability for real-time monitoring and bioimaging analysis, etc. Most small organic molecule fluorescent probes have aggregation-induced quenching effect (ACQ) in aqueous solution, so that the practical application value of the small organic molecule fluorescent probes is limited. The aggregation-induced emission (AIE) probe can emit fluorescence in aqueous solution and solid state, can effectively solve the problem of ACQ, and has wide application prospect. However, few AIE-type fluorescent probes are currently used for detecting sulfur dioxide derivatives, and few fluorescent probes are used for detecting sulfur dioxide derivatives in plants.
Disclosure of Invention
Aiming at the problems that most of fluorescent probes for detecting sulfur dioxide derivatives in the prior art are ACQ probes, few probes can be used for detecting sulfur dioxide derivatives in plants, and the like, the invention provides a half-cyanine analogy ratio type fluorescent probe, a preparation method and application thereof. In addition, the probe can be used for detection and fluorescence imaging of sulfur dioxide derivatives in solutions, living cells and plants.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
in a first aspect of the invention, a half cyanine analog fluorescent probe for detecting sulfur dioxide derivatives is provided, and the structure of the half cyanine analog fluorescent probe is shown as a formula (I):
the invention develops a ratio type fluorescent probe which has AIE effect and can be used for detecting sulfur dioxide derivatives in cells and plants, and has important significance for detecting sulfur dioxide derivatives.
In a second aspect of the present invention, there is provided a method for preparing a fluorescent probe for detecting a sulfur dioxide derivative, comprising:
dissolving compound 1 and compound 2 in solvent, adding K 2 CO 3 The aqueous solution is added with Pd (PPh) under the protection of inert atmosphere 3 ) 4 Heating and refluxing for reaction, cooling, concentrating, separating and purifying after the reaction is completed to obtain a compound 3;
dissolving the compound 3 and methyl iodide in a solvent, and reacting for 15-16 h at 60-70 ℃; cooling the reaction liquid, carrying out suction filtration, leaching a filter cake by using ethyl acetate, and drying to obtain a compound 4;
dissolving a compound 4 and 4-morpholinobenzaldehyde in a solvent, reacting for 1.5-2 hours at 80-85 ℃, cooling, concentrating the reaction liquid, and separating and purifying to obtain a probe TPE-Hcy;
wherein, compound 1, compound 2, K 2 CO 3 And Pd (PPh) 3 ) 4 The molar ratio of (2) is 1-1.2:1-1.2:2-2.4:0.05-0.06;
the mol ratio of the compound 3 to the methyl iodide is 1-1.2:5-6;
the molar ratio of the compound 4 to the 4-morpholinobenzaldehyde is 1-1.5:1.2-1.8.
In a third aspect, the invention provides an application of the half-cyanine analog fluorescent probe in detecting sulfur dioxide derivatives, wherein the detected object is endogenous or exogenous sulfur dioxide derivatives in solution, cells and plant roots.
The beneficial effects of the invention are that
(1) The fluorescent probe designed and synthesized by the invention combines the characteristics of the tetraphenyl ethylene and the hemicyanine dye, has a certain AIE effect, has the advantages of good selectivity, strong anti-interference capability, quick response and the like, and can realize dual response of colorimetric and fluorescence ratio on sulfur dioxide derivatives. The probe can be used for detecting the sulfur dioxide derivative in the aqueous solution, can be successfully applied to fluorescent imaging of the sulfur dioxide derivative in living cells and plant roots, and has potential application value for detecting the sulfur dioxide derivative in the environment and a biological system.
(2) The preparation method is simple, has strong practicability and is easy to popularize.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 shows the change in fluorescence intensity of probe TPE-Hcy at 628nm in solvents with different water contents.
FIG. 2 is an ultraviolet-visible absorption spectrum of a solution of probe TPE-Hcy (10. Mu.M) after addition of various analytes.
FIG. 3 shows the fluorescence emission spectra of a solution of the probe TPE-Hcy (10. Mu.M) after addition of different analytes.
FIG. 4 is a sample SO in a solution of probe TPE-Hcy (10. Mu.M) 3 2- Co-existence of different interferents I 525 /I 628 A histogram of changes.
FIG. 5 (a) is the SO of probe TPE-Hcy (10. Mu.M) 3 2- Fluorescence titration graphs; (b) Is I 525 /I 628 SO-dependent 3 2- Curve of concentration change.
FIG. 6 shows the exogenous two probes TPE-Hcy to HeLa cellsFluorescence imaging of sulfur oxide derivatives. (a) fluorescence image of cells after 30min incubation with 10. Mu.M probe; (b) Cells were first treated with 20. Mu.M SO 3 2- Culturing for 30min, and culturing for 30min by using a 10 mu M probe to obtain a fluorescence image; (c) Cells were first treated with 50. Mu.M SO 3 2- Culturing for 30min, and culturing for 30min by using a 10 mu M probe to obtain a fluorescence image; (d) The cells were first treated with 100. Mu.M SO 3 2- Culturing for 30min, and culturing for 30min by using a 10 mu M probe. Lambda (lambda) ex =405 nm, green fluorescent channel λ em =480-560 nm, red fluorescence channel λ em ＝600-700nm。
FIG. 7 is a fluorescent image of endogenous sulfur dioxide derivative in HeLa cells with probe TPE-Hcy. (a) fluorescence image of cells after 30min incubation with 10. Mu.M probe; (b) Culturing the cells with 500 mu M GSH for 30min, and culturing with 10 mu M probe for 30 min; (c) Cells were first treated with 500. Mu.M GSH and 250. Mu.M Na 2 S 2 O 3 Culturing for 30min, and culturing for 30min by using a 10 mu M probe to obtain a fluorescence image; (d) Cells were first incubated with 20mM TNBS for 30min, followed by 500. Mu.M GSH and 250. Mu.M Na 2 S 2 O 3 Culturing for 30min, and culturing for 30min by using a 10 mu M probe. Lambda (lambda) ex =405 nm, green fluorescent channel λ em =480-560 nm, red fluorescence channel λ em ＝600-700nm。
FIG. 8 is a fluorescent image of the probe TPE-Hcy versus sulfur dioxide derivative in the wheat root system. SO with different concentrations for wheat root system 3 2- Culturing for 1h, and culturing for 1h by using a 10 mu M probe. (a) a control group; (b) 10. Mu.M probe; (c) 20 mu M SO 3 2- +10. Mu.M probe; (d) 50 mu M SO 3 2- +10. Mu.M probe; (e) 100 mu M SO 3 2- +10. Mu.M probe. Lambda (lambda) ex =405 nm, green fluorescent channel λ em =480-560 nm, red fluorescence channel λ em ＝600-700nm。
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
A half cyanine analogy ratio type fluorescent probe is abbreviated as TPE-HCy, and has a structure of combining tetraphenyl ethylene and half cyanine, and the structure is shown as a formula (I):
the invention claims a synthesis method of the fluorescent probe, which comprises the following synthesis routes:
in some embodiments, the method for synthesizing the probe comprises the following specific steps:
(1) Preparation of compound 3: after dissolving compound 1 and compound 2 in THF, K was added 2 CO 3 The aqueous solution was added with Pd (PPh) under nitrogen protection 3 ) 4 Heated to reflux for 16 hours.
After cooling, the reaction solution was evaporated to dryness by a rotary evaporator, and then purified by a silica gel column chromatography to obtain compound 3.
(2) Preparation of Compound 4: compound 3 and methyl iodide were dissolved in Ethyl Acetate (EA), and heated to 60 ℃ to react for 16 hours. After the reaction solution was cooled, the precipitated solid was filtered, and the cake was washed with EA and dried to obtain compound 4.
(3) Preparation of fluorescent probe TPE-HCy: compound 4 and 4-morpholinobenzaldehyde were dissolved in EtOH, a catalytic amount of piperidine was added and heated to reflux for 6 hours. And cooling the reaction liquid, evaporating the reaction liquid by a rotary evaporator, and purifying the reaction liquid by a chromatographic silica gel column to obtain the probe TPE-HCy.
In some embodiments, compound 1, compound 2, pd (PPh) in step (1) 3 ) 4 And K 2 CO 3 Is 1:1:0.05:2, THF and H 2 The volume ratio of O is 4:1, and the reaction temperature is 80 ℃.
In some embodiments, the molar ratio of compound 3 to methyl iodide in step (2) is 1:5 and the reaction temperature is 60 ℃.
In some embodiments, the molar ratio of compound 4 to 4-morpholinobenzaldehyde in step (3) is 1:1.2 and the reaction temperature is 80 ℃.
In addition, the invention also claims the application of the fluorescent probe in detecting sulfur dioxide derivatives,
comprising sulfur dioxide derivatives for detecting aqueous solutions, living cells and wheat root systems.
The specific detection method for the application comprises the following steps:
(1) Dissolving the probe in ethanol and the object to be detected in pure water to prepare mother solution of the probe and the object to be detected;
(2) Mixing a certain volume of probe and mother solution of an object to be detected, and diluting with a buffer solution of EtOH: PBS=3:7 (volume ratio, pH=7.4);
(3) Testing the ultraviolet-visible absorption spectrum of the liquid to be tested and observing the color change of the liquid; testing the fluorescence spectrum of the liquid to be tested, and observing the change of fluorescence peak values at 628nm and 525 nm; fluorescence was collected at 480nm to 560nm and 600nm to 700nm using a confocal laser fluorescence microscope excited with a 405nm light source.
The invention will now be described in further detail with reference to the following specific examples, which should be construed as illustrative rather than limiting.
Example 1:
a method for synthesizing a probe comprises the following specific steps:
(1) Synthesis of Compound 3:
compound 1 (synthesized according to the methods of documents Journal of Materials Chemistry C: materials for Optical and Electronic Devices,6 (26), 6940-6948;2018, 79mg, 2.77 mmol) and Compound 2 (available from Shanghai Teng quasi-Biotech Co., ltd., brand Macklin, CAS 1607-57-4, 928mg,2.77 mmol) were weighed and placed in a reverse reactionIn a flask, 20mL THF was added for dissolution, followed by K 2 CO 3 (764 mg,5.54 mmol) in water (4 mL). Pd (PPh) was added under nitrogen blanket 3 ) 4 (127 mg,0.11 mmol) was heated to 80℃and reacted at reflux for 16h. After cooling, the reaction solution was concentrated with petroleum ether: ethyl acetate=4:1 as eluent, and purification by silica gel column (200-300 mesh) gave 995mg of yellow solid in 87% yield. The characterization of compound 3 is as follows:
nuclear magnetic resonance hydrogen spectrum: 1 H NMR(400MHz,CDCl 3 )δ7.30(d,J＝8.0Hz,1H),712-6.98(m,15H),6.93(dd,J＝8.0,4.0,1H),2.23(s,3H),1.03(s,6H)。
nuclear magnetic resonance carbon spectrum: 13 C NMR(101MHz,CDCl 3 )δ187.78,144.18,144.14,143.58,143.21,143.16,140.72,140.41,140.32,130.92,130.83,130.81,130.27,125.97,125.85,125.74,124.50,118.37,83.24,52.64,24.37,22.51,22.30,14.78。
high resolution mass spectrometry (ESI): [ M+H ]] + calcd for[C 31 H 28 N] + ：414.2216，found 414.2205。
(2) Synthesis of Compound 4:
compound 3 (500 mg,1.21 mmol) and methyl iodide (1 g,7.04 mmol) were dissolved in 5mL ethyl acetate and reacted at 60℃for 16h. The reaction solution was cooled and a large amount of solids precipitated. Suction filtration, leaching the filter cake with ethyl acetate 3 times, and drying gave 550mg of white solid in 97% yield. The characterization of compound 4 is as follows:
nuclear magnetic resonance hydrogen spectrum: 1 H NMR(400MHz,DMSO-d 6 )δ7.71(d,J＝8.0Hz,1H),7.32(s,1H),7.22-7.10(m,10H),7.03-6.96(m,6H),3.88(s,3H),2.68(s,3H),1.26(s,6H)。
nuclear magnetic resonance carbon spectrum: 13 C NMR(101MHz,DMSO-d 6 )δ195.81,144.61,142.77,142.48,142.30,142.28,141.00,140.23,139.37,130.91,130.58,130.41,127.98,127.86,126.92,126.82,126.69,125.66,114.61,53.42,34.62,24.68,21.55,14.03。
high resolution mass spectrometry (ESI): [ M+H ]] + calcd for[C 32 H 30 IN-I] + ：428.2373，found 428.2366。
(3) Synthesis of probe TPE-HCy
Compound 4 (275 mg,0.50 mmol) and 4-morpholinobenzaldehyde (115 mg,0.60 mmol) are dissolved in 10mL absolute ethanol and reacted at 80℃for 2 hours. After cooling, the reaction solution was concentrated and taken up in methylene chloride: methanol=20:1 as eluent, and purification by silica gel column (200-300 mesh) gave 240mg of yellow solid in 66% yield. The characterization of TPE-HCy is as follows:
nuclear magnetic resonance hydrogen spectrum: 1 H NMR(400MHz,DMSO-d 6 )δ8.21(d,J＝16.0Hz,1H),8.07(d,J＝8.0Hz,2H),7.73(d,J＝8.0Hz,1H),7.56(d,J＝8.0Hz,1H),7.33-7.24(m,2H),7.19-7.14(m,7H),7.11-7.06(m,4H),7.04-6.99(m,6H),3.93(s,3H),3.49(t,J＝8.0Hz,4H),3.34(t,J＝8.0Hz,4H),1.47(s,6H)。
nuclear magnetic resonance carbon spectrum: 13 C NMR(101MHz,DMSO-d 6 )δ190.36,179.93,154.89,154.43,153.37,143.22,142.99,142.70,142.53,142.09,141.88,140.27,139.64,133.61,131.37,131.02,130.70,130.67,130.51,127.98,127.94,127.87,126.90,126.78,126.69,126.65,125.20,123.96,113.49,113.38,113.17,106.96,73.47,65.77,65.75,50.52,46.55,46.32,33.40,25.84,24.92。
high resolution mass spectrometry: [ M+H ]] + calcd for[C 43 H 41 IN 2 O-I] + ：601.3213，found 601.3207。
Example 2
AIE Property test of probe TPE-HCy prepared in example 1:
the final concentration of the probe was set to 10. Mu.M, and the fluorescence intensity of the probe at 628nm was measured at different ratios of ethanol and water and plotted with the water content on the abscissa and the fluorescence intensity at 628nm on the ordinate. As shown in fig. 1, the fluorescence intensity reached the maximum at a water content of 70%, so EtOH was selected: pbs=3:7 (ph=7.4) as solvent.
Example 3
Test of selectivity of the probe TPE-HCy prepared in example 1 for sulfur dioxide derivative:
the probe TPE-HCy was dissolved in ethanol to prepare a stock solution at a concentration of 1 mM. Various test substances (HSO) 3 - ,SO 3 2- ,F - ,Cl - ,Br - ,I - ,CH 3 COO - ,CO 3 2- ,HCO 3 - ,SO 4 2- ,NO 3 - ,NO 2 - ,HS - ,S 2- ,SCN - ,CN - ,OCl - ,H 2 O 2 Cys, GSH, hcy) was dissolved in pure water to prepare a mother liquor having a concentration of 10 mM. In the test system, the solvent was EtOH: pbs=3:7 (ph=7.4), final probe concentration of 10 μm, analyte concentration of 100 μm, and uv-vis absorption spectrum and fluorescence spectrum were measured.
(1) As shown in FIG. 2, the probe TPE-Hcy has three absorption peaks of 288nm, 328nm and 543 nm. Adding sulfur dioxide derivatives (SO) 3 2- /HSO 3 - ) After this, the absorption peak at 543nm disappeared, two enhanced absorption peaks appear at 300nm and 345nm, while the solution changes from red to colorless. The absorption spectrum and the solution color of the probe are hardly affected by other objects to be detected, which indicates that the probe TPE-Hcy can be used as a colorimetric probe to perform naked eye identification on sulfur dioxide derivatives.
(2) As shown in FIG. 3, the fluorescence emission peak of the probe TPE-Hcy is at 628nm, SO is added 3 2- /HSO 3 - After that, the peak at 628nm disappeared, a new emission peak appeared at 525nm, and the fluorescence spectrum of the probe TPE-Hcy was hardly changed in the presence of other test substances. The probe has good fluorescence selectivity to sulfur dioxide derivatives.
Example 4
Test of anti-interference ability of probe TPE-HCy prepared in example 1:
to a solution of probe TPE-HCy (10. Mu.M) was added 10 equivalents of SO 3 2- And then10 equivalents of the other test substance were added and their fluorescence spectra were measured. As shown in FIG. 4, the co-existence of interferents hardly affects the SO of the probe pair 3 2- Is a fluorescent response of (a).
Example 5
Titration experiments for detecting sulfur dioxide derivatives with the probe TPE-HCy prepared in example 1:
adding SO with different concentrations into a solution with a probe concentration of 10 mu M 3 2- Its fluorescence spectrum was tested. As can be seen from FIG. 5, with SO 3 2- The increase in concentration gradually decreases the fluorescence at 628nm and increases the fluorescence at 525 nm. 5 equivalents of SO are added 3 2- The post-fluorescence intensity substantially reaches saturation.
Example 6
Fluorescence imaging test of intracellular sulfur dioxide derivatives by probe TPE-HCy prepared in example 1:
HeLa cells were treated with different concentrations of SO 3 2- Culturing for 30min, and further culturing for 30min by using 10 mu M probe TPE-HCy. The culture broth was removed, washed 3 times with PBS and then fluorescence imaged using a laser confocal microscope. The excitation wavelength was 405nm and fluorescence in the range of 480-570nm and 600-700nm was collected. As shown in fig. 6, after incubation with probe TPE-HCy, cells exhibited fluorescence in the red fluorescent channel, while the green fluorescent channel did not; adding probes and SO 3 2- After co-cultivation, the fluorescence of the red fluorescence channel is lost, and the fluorescence of the green fluorescence channel is generated. The probe TPE-HCy was shown to be able to enter cells and perform fluorescence imaging of exogenous sulfur dioxide derivatives within the cells.
As shown in FIG. 7, heLa cells were incubated with GSH (500. Mu.M) for 30min, and then fluorescence imaging was performed after incubation with probe TPE-HCy (10. Mu.M) for 30min, with no fluorescence in the green channel and fluorescence in the red channel; with GSH (500. Mu.M) and Na 2 S 2 O 3 (250 mu M) co-culturing for 30min, and then culturing for 30min by using a probe TPE-HCy (10 mu M), wherein fluorescence appears in a green channel and fluorescence disappears in a red channel; culturing with thiosulfate transferase (TST) inhibitor 2,4, 6-trinitrobenzenesulfonic acid (TNBS, 10 mM) for 30min, followed by GSH (500 μM) and Na 2 S 2 O 3 (250. Mu.M) for 30min and finally with the probe TPE-HCy (10. Mu.M) for 30min, the cells were not fluorescent in the green channel and were fluorescent in the red channel. The results show that the probe TPE-HCy can perform fluorescence imaging on sulfur dioxide derivatives endogenous to cells.
Example 7
Fluorescence imaging test of the probe TPE-HCy prepared in example 1 on sulfur dioxide derivative in wheat root: wheat seeds were sterilized with 5% sodium hypochlorite solution and washed 3 times with deionized water. The seeds were covered with moist absorbent cotton and left at 25℃for 48h. Immersing wheat root in SO with different concentration 3 2- After incubation in solution for 1h and 3 washes with PBS, incubation was continued for 1h with 10. Mu.M probe solution. The root system was washed 3 times with PBS and sectioned, and fluorescence imaging was performed using a laser confocal microscope. As shown in fig. 8, the root systems of the control group were not fluorescent in both green and red channels; the root system cultured by using the probe TPE-HCy shows fluorescence in a red channel, and the green channel does not show fluorescence, so that the probe successfully enters the root system cells and emits red fluorescence; use of probes TPE-HCy and SO 3 2- The co-cultured root system fluoresces in the green channel and follows SO 3 2- The concentration is increased, the fluorescence of the green channel is gradually enhanced, and the fluorescence of the red channel is gradually disappeared, so that the probe TPE-HCy can carry out fluorescence imaging on sulfur dioxide derivatives in plant roots.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A half cyanine analog fluorescent probe for detecting sulfur dioxide derivatives is characterized in that the structure is shown as a formula (I):
2. the method for preparing a fluorescent probe for detecting sulfur dioxide derivatives, which is half cyanine analog ratio, according to claim 1, and is characterized by comprising the following steps:
dissolving compound 1 and compound 2 in solvent, adding K 2 CO 3 The aqueous solution is added with Pd (PPh) under the protection of inert atmosphere 3 ) 4 Heating and refluxing for reaction, cooling, concentrating, separating and purifying after the reaction is completed to obtain a compound 3;
dissolving the compound 3 and methyl iodide in a solvent, and reacting for 15-16 h at 60-70 ℃; cooling the reaction liquid, carrying out suction filtration, leaching a filter cake by using ethyl acetate, and drying to obtain a compound 4;
dissolving a compound 4 and 4-morpholinobenzaldehyde in a solvent, reacting for 1.5-2 hours at 80-85 ℃, cooling, concentrating the reaction liquid, and separating and purifying to obtain a probe TPE-Hcy;
wherein, compound 1, compound 2, K 2 CO 3 And Pd (PPh) 3 ) 4 The molar ratio of (2) is 1-1.2:1-1.2:2-2.4:0.05-0.06;
the mol ratio of the compound 3 to the methyl iodide is 1-1.2:5-6;
the mol ratio of the compound 4 to the 4-morpholinobenzaldehyde is 1-1.5:1.2-1.8;
the compound 1 is
The compound 2 is
The compound 3 is
The compound 4 is
3. The method for preparing a fluorescent probe for detecting sulfur dioxide derivatives according to claim 2, wherein the temperature of the heating reflux reaction is 80-85 ℃ for 15-16 h.
4. The method for preparing a half cyanine analog fluorescence probe for detecting sulfur dioxide derivatives according to claim 2, wherein the volume ratio of the compound 1 to the compound 2 in THF is 4-6:1-1.5.
5. The method for preparing a fluorescent probe for detecting sulfur dioxide derivatives of half cyanine analog ratio according to claim 2, wherein after cooling, the reaction solution is concentrated with petroleum ether: ethyl acetate in the volume ratio of=4:1 is used as an eluent, and the compound 3 is obtained through separation and purification by a silica gel column.
6. The method for preparing a fluorescent probe for detecting sulfur dioxide derivatives of half cyanine analog ratio according to claim 2, wherein the compound 3 and methyl iodide are dissolved in ethyl acetate.
7. The method for preparing a fluorescent probe for detecting sulfur dioxide derivatives of half cyanine analog ratio according to claim 2, wherein the compounds 4 and 4-morpholinobenzaldehyde are dissolved in absolute ethanol.
8. The method for preparing a fluorescent probe for detecting sulfur dioxide derivatives of half cyanine analog ratio according to claim 2, wherein the reaction solution is concentrated after cooling, and dichloromethane is used for: methanol with the volume ratio of = 20:1 is used as an eluent, and the eluent is separated and purified by a silica gel column to obtain the probe TPE-Hcy.
9. Use of the half cyanine analog fluorescent probe according to claim 1 for preparing a product related to detection of sulfur dioxide derivatives.
10. The use according to claim 9, wherein the object to be detected is an endogenous or exogenous sulfur dioxide derivative in solution, cells and plant roots.
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