CN108752371A - A kind of two-photon hydrogen peroxide fluorescence probe based on quinoline - Google Patents

A kind of two-photon hydrogen peroxide fluorescence probe based on quinoline Download PDF

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Publication number
CN108752371A
CN108752371A CN201810767815.0A CN201810767815A CN108752371A CN 108752371 A CN108752371 A CN 108752371A CN 201810767815 A CN201810767815 A CN 201810767815A CN 108752371 A CN108752371 A CN 108752371A
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hydrogen peroxide
probe
compound
detection
fluorescence
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CN108752371B (en
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范春华
路亚男
吕正亮
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University of Jinan
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University of Jinan
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • 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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    • 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
    • G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
    • 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
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • 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
    • 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
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • 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
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
    • 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"
    • G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks

Abstract

The invention discloses a kind of fluorescence probes of detection hydrogen peroxide, belong to technical field of analytical chemistry.The probe is by 6-（Benzo [d] thiazol-2-yl）Return stirring obtains in acetone for naphthalene -2- alcohol and 4- boron fat bromobenzyl.The fluorescence probe synthesis of the present invention is simple, easy to use, has the advantages that preferable selectivity, sensitivity, detection limit are low to hydrogen peroxide, can be applied to the detection of the hydrogen peroxide in cell.

Description

A kind of two-photon hydrogen peroxide fluorescence probe based on quinoline
Technical field
The present invention provides a kind of fluorescence probes of detection hydrogen peroxide, belong to fluorescent probe technique field.
Technical background
Active oxygen includes hydroperoxy radical（HO2·）, superoxide radical（O2·）, peroxy radical（RO2·）, Hydroxyl radical free radical（HO·）, hypochlorous acid（HOCl）, singlet oxygen（1O2）And hydrogen peroxide（H2O2）Deng.Hydrogen peroxide is as a kind of Important reactive oxygen species have of crucial importance in living organism activity and external environment.Research shows that hydrogen peroxide participates in Physiology and pathology adjustment process, it is closely bound up with the Proliferation, Differentiation and transition process of cell.In addition to this, internal appropriate level Hydrogen peroxide be beneficial to the normal physiology course of biology, such as inflammation, body defenses etc. also play important work With；But many diseases are also due to caused by excessive hydrogen peroxide, such as the diseases such as cancer, Alzheimer's disease.Therefore Hydrogen peroxide in the detection living organism and external environment of real-time quantitative has very important significance.
The detection technique of hydrogen peroxide includes electrochemical process, colorimetric method, gas detection method, fluorescence method etc. at present.Wherein Since fluorescence probe has easy to operate, radiationless, highly sensitive and high-resolution advantage, become having for detection hydrogen peroxide Effect means.In recent years, the fluorescence probe for detecting hydrogen peroxide has been reported very much, however most probes are all that single photon is sharp Hair, it is larger to the injury of cell, live body.It is well known that the excitation wavelength of two-photon organic molecule fluorescence probe is usually single Twice or so of photon excitation, therefore, excitation wavelength is normally near infrared region（700-1000nm）, the excitation of this wave band The light not only focusing with height and region stimulation effect, but will not damaging biological tissues, but also may be implemented in biological tissue Imaging deep, in addition, due to using two-photon excitation, the biological fluorescence of itself will not be excited, double compared to one-photon excitation Photon excitation can not only effectively avoid the interference of the bias light of organism Lipofusion, realize dark-field imaging, and can also Reduce photobleaching, phototoxicity.In the prior art, patent CN106749359 A provide a kind of hydrogen peroxide probe compound, But the probe compound completed the detection of hydrogen peroxide at 60 minutes；In addition, since hydrogen peroxide existence time is short, Yi Yuqi Its substance reaction generates new active oxygen species, and therefore, it is short to design a kind of response time, high sensitivity, the strong probe of selectivity It has a very important significance.
Invention content
In view of the above shortcomings of the prior art, the present invention provides a kind of Fluorescence Increasing type probe of detection hydrogen peroxide, and Study the application of its spectral quality and intraor extracellular.
A kind of fluorescence probe of detection hydrogen peroxide of the present invention, which is characterized in that the chemistry of the fluorescence probe Structural formulaIt is shown：
。
The fluorescence probe of above-mentioned detection hydrogen peroxide is prepared in the following manner：
The synthesis of compound I
Compound II, 4- boron fat bromobenzyl and potassium carbonate are dissolved in acetone, and return stirring is overnight, and vacuum concentration obtains crude product, are passed through Column chromatography obtains compound as white solid I.
, according to the invention it is preferred to, the molar ratio of the compound ii, 4- boron fat bromobenzyls and potassium carbonate is 1:1:1；
, according to the invention it is preferred to, the synthesis whole process of compound I carries out under nitrogen protection.
Fluorescence probe of the present invention can be used for the real-time detection of the hydrogen peroxide in aqueous solution.
It is further preferred that the fluorescence probe is used for the DMSO in pH 7.4 and the peroxide in PBS buffer solution mixed liquor Change the quick detection of hydrogen, detection is limited to 1.40 × 10-7 mol/L。
Fluorescence probe of the present invention is for having hydrogen peroxide with PBS buffer solution mixed liquor in the DMSO of pH 7.4 Specificly-response performance.The present invention by experimental verification, by hydrogen peroxide instill the fluorescence probe pH7.4 DMSO with After in PBS buffer solution, using the light source of 420nm wavelength as exciting light, solution sends out strong yellow fluorescence at 542nm.It should Probe is not responding to other active oxygens.Therefore, fluorescent probe compounds of the invention have very high selectivity to hydrogen peroxide.
Fluorescence probe of the present invention detects the application of hydrogen peroxide in cell.
Fluorescence probe of the present invention can be applied to the detection of intracellular hydrogen peroxide.Specifically detection method is：It will change It closes object I to be incubated 15 minutes jointly with Hela cells, hydrogen peroxide is then added, cell sends out strong yellow fluorescence.Test table Bright, compound I can identify intracellular hydrogen peroxide.
A kind of fluorescence probe of detection hydrogen peroxide according to the present invention, shows high selectivity, sensitivity is good, can be thin The advantages that intracellular is imaged.
Description of the drawings
Fig. 1 is compound I1H NMR spectras.
Fig. 2 is the selective light spectrogram of compound I.
Fig. 3 is that compound I changes fluorescence spectra with concentration of hydrogen peroxide.
Fig. 4 is the images of the compound I of two-photon excitation in the cell.
Specific implementation mode
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings, but not limited to this.It is each in embodiment Kind raw material is bought both from market.
The synthesis of 1 compound I of embodiment
By 0.25 g of compound II, 0.2 gram of 4- boron fat bromobenzyl and 0.26 gram of potassium carbonate are dissolved in acetone, and return stirring is overnight, very Sky is concentrated to give crude product, and compound as white solid I, yield 50% are obtained through column chromatography.
2 probe compound I of embodiment is selectively analyzed
The hydrogen peroxide of 100 equivalents is added dropwise in DMSO/PBS buffer solution containing 5 μM of compound I, testing result is as schemed 2, as a length of 420nm of excitation light wave, probe compound I sends out 542nm yellow fluorescences, and probe compound I is not by other Peroxide interferes, and illustrates that probe compound I is good to hydrogen peroxide selectivity.
3 probe compound I of embodiment is to hydrogen peroxide titrimetry
When the hydrogen peroxide of 0 to 40 equivalents is added dropwise in the buffer solution containing 5 μM of probe compound I, fluorescence response intensity with The increase of amount of hydrogen peroxide is added and increases sharply, as a result testing result such as Fig. 3 illustrates that probe compound I is dense to hydrogen peroxide The sensitivity of degree is higher.
The detection of 4 compound I on cell hydrogen peroxide of embodiment
After compound I is incubated together with Hela cells, hydrogen peroxide is added, cell is issued in the light excitation of 800nm wavelength Go out bright yellow fluorescence, imaging results such as Fig. 4.Experiment shows that probe compound I can identify the hydrogen peroxide in cell.

Claims (1)

1. a kind of fluorescence probe of detection biological thiol, which is characterized in that the chemical structural formula of the fluorescence probe is as shown in I
。
CN201810767815.0A 2018-07-13 2018-07-13 Two-photon hydrogen peroxide fluorescent probe based on quinoline Expired - Fee Related CN108752371B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113004310A (en) * 2019-12-20 2021-06-22 湖南超亟化学科技有限公司 Preparation method and application of hydrogen peroxide ratio type fluorescent molecular probe based on DCPO parent nucleus

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106632441A (en) * 2016-12-16 2017-05-10 济南大学 Ratio type fluorescent probe for identifying hydrogen peroxide
CN108129500A (en) * 2018-01-11 2018-06-08 中南大学 A kind of synthesis and application of the ratio type fluorescence probe for identifying hydrogen peroxide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106632441A (en) * 2016-12-16 2017-05-10 济南大学 Ratio type fluorescent probe for identifying hydrogen peroxide
CN108129500A (en) * 2018-01-11 2018-06-08 中南大学 A kind of synthesis and application of the ratio type fluorescence probe for identifying hydrogen peroxide

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LINGYU ZENG等: "Two-Photon Fluorescent Probe for Detection of Exogenous and Endogenous Hydrogen Persulfide and Polysulfide in Living Organisms", 《ANAL. CHEM.》 *
YANAN LU等: "A fast-response two-photonfluorescent probe for imaging endogenous H2O2in living cells and tissues", 《SPECTROCHIMICA ACTA PART A: MOLECULAR AND BIOMOLECULAR SPECTROSCOPY》 *
YUZHI CHEN等: "A Fluorescent Probe for Hydrogen Peroxide in Vivo Based on the Modulation of Intramolecular Charge Transfer", 《ANAL. CHEM.》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113004310A (en) * 2019-12-20 2021-06-22 湖南超亟化学科技有限公司 Preparation method and application of hydrogen peroxide ratio type fluorescent molecular probe based on DCPO parent nucleus
CN113004310B (en) * 2019-12-20 2022-07-08 湖南超亟检测技术有限责任公司 Preparation method and application of hydrogen peroxide ratio type fluorescent molecular probe based on DCPO parent nucleus

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