CN113004216B - Preparation method and application of benzoxazine hypochlorous acid fluorescent molecular probe - Google Patents

Preparation method and application of benzoxazine hypochlorous acid fluorescent molecular probe Download PDF

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CN113004216B
CN113004216B CN201911322539.8A CN201911322539A CN113004216B CN 113004216 B CN113004216 B CN 113004216B CN 201911322539 A CN201911322539 A CN 201911322539A CN 113004216 B CN113004216 B CN 113004216B
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
    • C07D265/38—[b, e]-condensed with two six-membered rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K49/00—Preparations for testing in vivo
    • A61K49/001—Preparation for luminescence or biological staining
    • A61K49/0013—Luminescence
    • A61K49/0017—Fluorescence in vivo
    • A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
    • A61K49/0021—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules the fluorescent group being a small organic molecule
    • A61K49/0028—Oxazine dyes
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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"
    • 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
    • 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
    • G01N21/645—Specially adapted constructive features of fluorimeters
    • G01N21/6456—Spatial resolved fluorescence measurements; Imaging
    • G01N21/6458—Fluorescence microscopy
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • C09K2211/1007—Non-condensed systems
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
    • C09K2211/1029—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

Abstract

The invention discloses a preparation method and application of a novel benzoxazine hypochlorous acid fluorescent molecular probe, and the chemical structural formula is as follows:

Description

Preparation method and application of benzoxazine hypochlorous acid fluorescent molecular probe
Technical Field
The invention belongs to the technical field of analytical chemistry, and relates to a preparation method and application of a novel benzoxazine hypochlorous acid fluorescent molecular probe.
Background
Hypochlorous acid (Hypochlorous acid, HOCl) is produced by the catalysis of hydrogen peroxide and chloride ions by Myeloperoxidase (MPO), an important member of the active oxygen family in vivo, playing an important role in physiological and pathological processes. HOCl is strongly oxidative and kills pathogens, thus contributing to host defense, and endogenous HClO can also serve as a signal to activate caspases and mediate apoptosis. However, excessive HClO in the body causes oxidative damage to biomolecules such as nucleic acids, proteins and lipids, which may lead to various diseases such as cardiovascular diseases, atherosclerosis, osteoarthritis, rheumatoid arthritis and lung injury. Thus, monitoring the concentration level of HClO in cells is of great importance for further understanding of its biological role and early diagnosis of related diseases.
In recent years, electrochemical, colorimetric, chemiluminescent, fluorescent imaging and other methods have been applied to the detection of HClO. The fluorescence imaging method has the advantages of high sensitivity, strong specificity, short response time, real-time monitoring and the like, and is widely applied to detection and imaging of HClO. CN 110357869A reports that a fluorescent molecular probe based on naphthalimide parent nucleus and used for HClO specific detection has good chemical and light stability. However, the probe gradually reduces fluorescence at 510 and nm after being in response to HClO, and shows a "Turn-OFF" type fluorescence response, is easily affected by environment, and has a large detection error. CN 109400563A reports a fluorescent probe CoPh-ClO, which allows for rapid detection of HClO specificity, as a specific indicator of HClO presence in aqueous solutions and within biological cells. However, the probe has the problem of short emission wavelength (510-nm) and is easily interfered by background fluorescence during intracellular imaging. CN 109942504A reports that a probe molecule with HClO response is constructed by using near infrared fluorophore alkali blue as a fluorescent molecular skeleton, and uses the transition between a reduced state and an oxidized state to realize fluorescence opening, and when HClO is added, the probe exhibits fluorescence enhancement at 670 nm, so that detection of HClO can be realized. However, the poor water solubility of this probe results in poor biocompatibility, limiting its further use for in vivo detection of HClO. Therefore, the development of the red light-emitting fluorescent molecular probe with high sensitivity, high specificity and good water solubility has very important significance for realizing the detection of the HClO in the environment and organisms.
Disclosure of Invention
Aiming at the defects of the existing HClO fluorescent molecular probe, the invention aims to provide the HClO fluorescent molecular probe which has good water solubility, high specificity and red light emission.
The second object of the present invention is to provide a method for efficiently preparing the fluorescent molecular probe.
The third object of the present invention is to provide the application of the fluorescent molecular probe in detecting HClO in water solution and organism.
In order to achieve the above object, the present invention provides a fluorescent molecular probe having the structure of formula I:
i is a kind of
The preparation method of the fluorescent probe preferably comprises the following steps:
dissolving benzoxazine in anhydrous DMF solution, 0 o Adding 60% NaH solution and bromobenzyl bromide in portions under the condition of C, stirring at room temperature to finish the reaction, and cooling to 0 o C, dropwise adding water to quench the reaction, and respectively using water and saturated NaHCO 3 The solution and saturated saline are extracted, the organic layers are combined, dried and concentrated, and the white product can be obtained after column chromatography purification. Dissolving the purified product in CHCl 3 The solution was added with NBS in portions and the reaction was stirred at room temperature to completion. Taking down the reaction, adding water dropwise to quench the reaction, and respectively using water and saturated NaHCO 3 The solution and saturated brine are extracted, the organic layers are combined, dried and concentrated, and ethyl acetate is recrystallized to obtain white solid. The purified product, 4-nitrophenol, potassium acetate and Pd (dppf) Cl 2 DCM was dissolved in anhydrous DMF solution and heated to reflux under argon until the reaction was complete. Taking down the reaction, cooling to room temperature, and respectively using water and saturationAnd NaHCO 3 Extracting the solution and saturated saline, combining the organic layers, drying, concentrating, and purifying by column chromatography to obtain a white product. The purified product and SnCl 2 ·2H 2 O is added to CH 3 OH, concentrated HCl and H 2 In the mixed solution of O, stirring at room temperature until the reaction is complete, using saturated Na 2 CO 3 The pH of the solution is adjusted to be alkaline, and water and saturated NaHCO are respectively used 3 Extracting the solution and saturated saline, combining organic layers, drying, concentrating, and purifying by column chromatography to obtain the target molecular probe.
The synthesis of the invention is as follows:
the invention provides an application of the fluorescent probe, which can be applied to detection of HClO. The detection mechanism of the probe is as follows:
compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the fluorescent molecular probe for detecting HClO has the following advantages:
(1) The fluorescent probe has the advantages of stable and high chemical property and high optical stability, and has no autoxidation and no bleaching phenomenon;
(2) The fluorescent probe has the advantages of good water solubility, quick response and high specificity, can avoid the interference of other objects to be detected, is beneficial to the quick detection of HClO in the environment, and has stronger practical application value in the field of environmental science;
(3) The probe has stronger red light emission, can effectively avoid the interference of biological autofluorescence, has good cell membrane permeability and small cytotoxicity, can be used for the biological imaging of HClO, and has stronger practical application value in the field of life science.
Drawings
FIG. 1 is a graph showing the emission spectrum of fluorescence intensity of a fluorescent probe according to HClO concentration in the practice of the present invention;
FIG. 2 is a graph showing the selectivity of fluorescent probes for HClO in the practice of the present invention;
FIG. 3 is a fluorescence confocal image of fluorescent probes in HeLa cells in the practice of the present invention.
Detailed Description
The following embodiments are intended to further illustrate the invention and are not limiting thereof.
Example 1
Synthesis of Compound 1:
benzoxazine (1830 mg,10 mmol) was dissolved in 25 mL anhydrous DMF at 0 o 60% NaH solution (4727 mg,12 mmol) was added in portions at C, and after stirring continued for 10 minutes p-bromobenzyl bromide (3000 mg,12 mmol) was added in portions and the reaction stirred at room temperature to completion. Cooling to 0deg.C, adding dropwise water to quench the reaction, respectively adding water and saturated NaHCO 3 The solution and saturated brine were extracted, and the organic layers were combined, dried over anhydrous magnesium sulfate, concentrated, and purified by column chromatography to give the white product 2899 mg in 82.3% yield.
Synthesis of Compound 2:
compound 1 (2817.6 mg,8 mmol) was dissolved in 25 mL HCl 3 To the solution, NBS (2854.6 mg,9.08mmol) was added in portions, and the reaction was stirred at room temperature until the end. Taking down the reaction, adding water dropwise to quench the reaction, and respectively using water and saturated NaHCO 3 The solution and saturated brine were extracted, and the organic layers were combined, dried over anhydrous magnesium sulfate, concentrated and dried to give a crude product, which was recrystallized from ethyl acetate to give 2044.1 mg as a white solid in 50.1% yield.
Synthesis of Compound 3:
compound 2 (2040 mg,4 mmol), 4-nitrophenol (2225.6 mg,16 mmol), potassium acetate (2348.7 mg,24 mmol) and Pd (dppf) Cl 2 DCM (2817.7 mg,0.4 mmol) was dissolved in 7 mL anhydrous DMF and heated to reflux under argon until the reaction was complete. Taking down the reaction, cooling to room temperature, and respectively using water and saturated NaHCO 3 Extracting the solution with saturated saline, mixing organic layers, drying with anhydrous magnesium sulfate, concentrating, drying, purifying by column chromatography to obtain white product 1128.2 mg,the yield was 41.2%. 1 H NMR (300 MHz, CDCl3)δ8.82 (d, 6H,J=7.8 Hz), 7.43 (d, 2H,J=8.3 Hz), 7.28 (d, 2H,J=8.3 Hz), 7.21 (d, 6H,J=7.8 Hz), 6.66 (s, 2 H), 6.52-6.51(m, 4H), 4.32 (s, 2H)。
Synthesis of target molecular probes:
to compound 3 (684.6 mg,1 mmol) and SnCl 2 ·2H 2 O (3371.4 mg,15 mmol) was added to 16 mLCH 3 OH: concentrated HCl: h 2 The mixed solution of o=3:2:3 was stirred at room temperature until the reaction was complete. After the reaction, saturated Na was used 2 CO 3 The pH of the solution is adjusted to be alkaline, and water and saturated NaHCO are respectively used 3 The solution and saturated brine were extracted, and the organic layers were combined, dried over anhydrous magnesium sulfate, and concentrated to dryness. After purification by column chromatography, the target molecular probe 319.3. 319.3 mg was obtained in 53.7% yield. 1 H NMR (300 MHz, CDCl3)δ7.35 (d, 2H,J=8.4 Hz), 7.30 (d, 2H,J=8.4 Hz), 7.21 (d, 6H,J=7.8 Hz), 6.76-6.73 (m, 12H), 6.65 (s, 2H), 6.53-6.50 (m, 4H), 6.27 (s, 6H), 4.30 (s, 2 H)。HRMS (ESI):calculated [M+H] + : 595.22670, found [M+H] + : 595.21371。
Example 2
Preparation of fluorescent Probe stock solution
Accurately weighing the product with purity of above 99%, transferring into 50 mL volumetric flask, and adding CH at room temperature 3 CN solution is completely dissolved, and the volume is fixed to the scale mark, so that probe mother liquor with the concentration of 1 mM is obtained. During the test, 20. Mu.L of the above solution was measured with a microsyringe each time and dissolved in the test system so that the total volume of each test was 2 mL, at which time the concentration of the fluorescent probe was 10. Mu.M.
Example 3
Preparation of HClO mother liquor
HClO was prepared as a stock solution with 5 mL different concentration gradients (0.1 mM, 0.3 mM, 0.6 mM, 1.0 mM, 1.5 mM, 2.0 mM, 3.0 mM, 4.0 mM) with PBS buffer. The rest substances to be tested are prepared into mother solution with concentration of 3 mM by using PBS buffer solution.
Example 4
Relationship between fluorescence intensity of fluorescent probe and HClO concentration
Measuring 4.900 mL of PBS buffer solution, dissolving 50 mu L of probe mother solution with the concentration of 1 mM, and then transferring 50 mu L of HClO mother solution with different concentrations into the solution so that the final concentration of the probe of the whole detection system is 10 mu M and Hg 2+ The concentration of (C) is 1. Mu.M, 3. Mu.M, 6. Mu.M, 10. Mu.M, 15. Mu.M, 20. Mu.M, 30. Mu.M, 40. Mu.M, respectively. After incubation at room temperature for 20 min, the fluorescence spectra of the different systems were measured in cuvettes of 10 mm, respectively (fig. 1). The results showed that as the HClO concentration was increased, the fluorescence emission intensity of the system was increased at 590 nm.
Example 5
Selectivity of fluorescent probe for HClO detection
50. Mu.L of probe stock solution with a concentration of 1 mM was dissolved in 4.900 mL of PBS buffer solution, and 50. Mu.L of O with a concentration of 3 mM was removed 2 -、NO、H 2 O 2 T-butyl peroxy alcohol, NO 3 -, L-cysteine, L-glutathione, fe 3+ The mother solutions were added to the system and incubated at room temperature for 20 min, and their fluorescence spectra were measured, respectively, and the fluorescence intensity values of 590 nm (FIG. 2) were recorded. As shown in the figure, the results show that the fluorescence of the fluorescent probe is significantly enhanced when only HClO is added, and that no or only weak fluorescence changes are observed when other test metal ions or molecules are added. The fluorescent probe has good selectivity.
Example 6
Response of fluorescent probes to HClO in cells
Adding 10 μm fluorescent probe solution into HeLa culture medium, and standing at 37 o C, 5% CO 2 After incubation in an incubator for 30 minutes, the probe molecules that did not enter the cells were removed by washing three times with 0.1M PBS buffer (10 mm, ph=7.4), then the medium was changed, and further incubated with HClO buffer (25 μm) for 30 minutes, washed three times with 0.1M PBS buffer (10 mm, ph=7.4), and the fluorescence change was observed under a fluorescence microscope, and the results are shown in fig. 3. Experiments show that the probe enters the cell bodyThe needle molecule reacts with HClO to emit intense red fluorescence, so that the fluorescent probe has good imaging effect on HClO in cells and can be used for detecting HClO in organisms.
While the specific embodiments of the invention have been described above with reference to the drawings, it is not intended to limit the scope of the invention, and various modifications or variations which would be apparent to those skilled in the art from the disclosure herein without the benefit of the teachings of this invention are within the scope of the invention.

Claims (2)

1. The benzoxazine hypochlorous acid fluorescent molecular probe is characterized by having a structure shown in a formula I:
2. the method for preparing the benzoxazine hypochlorous acid fluorescent molecular probe according to claim 1, which is characterized in that: dissolving benzoxazine in anhydrous DMF solution, adding 60% NaH solution and benzyl bromide 4-BnBr in batches at 0 ℃, stirring at room temperature for reaction to finish, cooling to 0 ℃, adding water dropwise for quenching the reaction, and using water and saturated NaHCO respectively 3 Extracting the solution and saturated saline, mixing the organic layers, drying, concentrating, and purifying by column chromatography to obtain white product;
dissolving the purified white product in CHCl 3 Adding NBS into the solution in batches, and stirring at room temperature to finish the reaction;
after the reaction, water is added dropwise to quench the reaction, and water and saturated NaHCO are respectively used 3 Extracting the solution and saturated saline water, combining organic layers, drying, concentrating, and recrystallizing with ethyl acetate to obtain white solid;
white solid, 4-nitrophenol, potassium acetate and Pd (dppf) Cl 2 DCM was dissolved in anhydrous DMF and heated under argon to reflux until reaction was complete;
taking down the reaction, cooling to room temperature, and respectively using water and saturated NaHCO 3 Extracting the solution and saturated saline, mixing the organic layers, drying, concentrating, and purifying by column chromatography to obtain a white product;
the purified product and SnCl 2 ·2H 2 O is added to CH 3 OH, concentrated HCl and H 2 In the mixed solution of O, stirring at room temperature until the reaction is complete, using saturated Na 2 CO 3 The pH of the solution is adjusted to be alkaline, and water and saturated NaHCO are respectively used 3 Extracting the solution and saturated saline, combining the organic layers, drying, concentrating, and purifying by column chromatography to obtain the target fluorescent molecular probe.
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