CN115215839B - Indolyl benzimidazole near-infrared fluorescent dye and preparation method and application thereof - Google Patents

Indolyl benzimidazole near-infrared fluorescent dye and preparation method and application thereof Download PDF

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CN115215839B
CN115215839B CN202211002474.0A CN202211002474A CN115215839B CN 115215839 B CN115215839 B CN 115215839B CN 202211002474 A CN202211002474 A CN 202211002474A CN 115215839 B CN115215839 B CN 115215839B
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benzimidazole
indolyl
fluorescent dye
infrared fluorescent
near infrared
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CN115215839A (en
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徐海军
柴智勇
赵越
顾婷婷
孙磊
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Nanjing Forestry University
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Nanjing Forestry University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/14—Styryl dyes
    • C09B23/145—Styryl dyes the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5
    • 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
    • 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
    • G01N21/645—Specially adapted constructive features of fluorimeters
    • G01N21/6456—Spatial resolved fluorescence measurements; Imaging
    • 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
    • C09K2211/1029—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
    • 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
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms

Abstract

The invention discloses an indolyl benzimidazole near-infrared fluorescent dye, a preparation method and application thereof, wherein 4-benzimidazole-vinyl benzaldehyde derivative (II) and iodized 2, 3-trimethyl-1-propyl-3H-indole salt (III) undergo Knoevenagel condensation reaction to obtain the indolyl benzimidazole derivative shown as formula (I). The compound has the advantages of simple preparation method, mild reaction condition and high yield, the indolyl benzimidazole near-infrared fluorescent dye has obvious solvent effect, the maximum emission wavelength of the indolyl benzimidazole near-infrared fluorescent dye in a dimethyl sulfoxide solvent is about 680nm, and the indolyl benzimidazole near-infrared fluorescent dye has large Stokes shift (more than 200 nm). In addition, the indolyl benzimidazole near-infrared fluorescent dye also has excellent cell permeability and biocompatibility, and has good application prospects in various fields such as biological tissue staining, biological probes, fluorescent imaging and the like.

Description

Indolyl benzimidazole near-infrared fluorescent dye and preparation method and application thereof
Technical Field
The invention belongs to the fields of fine organic synthesis and near infrared fluorescent dyes, and relates to a preparation method and application of indolyl benzimidazole near infrared fluorescent dyes.
Background
Benzoxazole compounds are a common class of benzoheterocyclic compounds. The special structure of the modified cellulose has excellent biological activity and reactivity, so that the modified cellulose is widely applied in various fields. The benzimidazole compound has a conjugated system rich in electrons and has good luminous performance, and meanwhile, the nitrogen-containing heterocyclic compound causes the benzimidazole compound to have good biological activity; so that the fluorescent probe can be used as chromophore of fluorescent probe and is often applied to the aspects of optics, medicine, biological research and the like. Benzimidazole can also be used as electron pair donor to coordinate with metal to form complex and applied to CO 2 Chemical immobilization, ion detection, biological imaging, fluorescent probes, and the like. In addition, in the case of the optical fiber,1, 2-disubstituted benzimidazoles are often selected for use as electron transport units in OLED materials. Benzimidazole compounds containing various substituents have been shown to have significant antiviral, antitumor, antihypertensive, antidiabetic, anti-HIV and excellent antifungal and antibacterial effects. However, most benzimidazole fluorescent dyes applied to the current market are positioned in an ultraviolet-visible light region, and most of the most suitable excitation wavelength is below 600nm, if the excitation wavelength can be increased to above 600nm, the problem of self background interference of biological tissues can be eliminated to a certain extent, the sensitivity of a biological detection technology can be better improved, and therefore the application of fluorescent dye molecules in the biological field is further promoted.
Indole is also called azaindene or benzopyrrole, and is formed by fusing benzene and pyrrole together with two carbon atoms. The C-2 and C-3 electron cloud density is higher, the strong nucleophilicity is shown, the indole compound takes a place in the medicines in a plurality of treatment fields such as anti-tumor, antihypertensive, antiproliferative, antiviral, analgesic, anti-inflammatory and antibacterial by being taken as a typical structural skeleton of a micromolecule chemical medicine, and the number of the medicine molecules on the market at present is more than hundred. At present, derivatization of indole compounds is to perform functional modification and dearomatization reaction around an indole skeleton under the condition of not changing a parent nucleus, and to manufacture a new molecule by changing an indole skeleton structure through bond breaking and recombination. However, currently available indole near infrared fluorescent dyes are still very limited, and many of them fail to reach the near infrared region and have problems of poor photo-thermal stability.
The invention designs and synthesizes the indolyl benzimidazole near-infrared fluorescent dye by taking indole salt and 4-benzimidazole vinyl benzaldehyde derivative as raw materials. The benzimidazole and the indole group form conjugation, a molecular conjugation system is increased, meanwhile, the delocalization of electron cloud of the molecular system is promoted, and the HOMO-LUMO energy level of the molecule is reduced, so that the overall optical performance of the molecule is improved. The fluorescent dye has excellent biocompatibility, good cell membrane permeability, good stability in organisms, good fluorescence performance and good application prospect in various fields such as biological tissue staining, biological probes, fluorescence imaging and the like.
Disclosure of Invention
The invention aims to: the invention aims to provide a preparation method and application of an indolyl benzimidazole near-infrared fluorescent dye.
The technical scheme is as follows: in order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention relates to an indolyl benzimidazole near-infrared fluorescent dye which has the following structure:
the invention relates to a synthetic route of an indolyl benzimidazole near-infrared fluorescent dye, which comprises the following steps:
the preparation process of the indolyl benzimidazole near infrared fluorescent dye comprises the following steps:
dissolving the 4-benzimidazole vinyl benzaldehyde derivative (II) and iodized 2, 3-trimethyl-1-propyl-3H-indole salt (III) in absolute ethyl alcohol, dropwise adding piperidine into the solution, and carrying out reflux reaction for 12H at 80 ℃ under the protection of argon. After the reaction is finished, cooling to room temperature, filtering to remove filtrate to obtain dark red solid, and separating and purifying the obtained indolyl benzimidazole near infrared fluorescent dye (I) through silica gel column chromatography.
In the above reaction step, the mass ratio of the 4-benzimidazole vinylbenzaldehyde derivative (II) to the iodinated 2, 3-trimethyl-1-propyl-3H-indole salt (III) was 1:1.
The invention has the beneficial effects that:
compared with the prior art, the indolyl benzimidazole near-infrared fluorescent dye and the preparation method thereof have the advantages that: (1) The indolyl benzimidazole near-infrared fluorescent dye has remarkable solvent effect, the maximum fluorescence emission wavelength in a dimethyl sulfoxide solvent is about 680nm, and the indolyl benzimidazole near-infrared fluorescent dye has large Stokes shift (> 200 nm); (2) The fluorescent dye has better cell permeability and biocompatibility, and can be used for fluorescence imaging of HeLa cells; (3) The synthesis method is simple, the reaction condition is mild, the reaction selectivity is good, the separation method is simple, the universality is realized, and the method can be popularized and applied to the synthesis of near infrared fluorescent dye.
Drawings
FIG. 1 is a graph showing the UV-visible absorption spectra of the indolyl benzimidazole near infrared fluorescent dye (I) of the present invention in various solvents;
FIG. 2 is a graph showing fluorescence emission spectra of the indolyl benzimidazole near infrared fluorescent dye (I) of the present invention in various solvents;
FIG. 3 is a laser confocal fluorescence imaging of the indolyl benzimidazole near infrared fluorescent dye (I) of the present invention after co-incubating with HeLa cells.
Detailed Description
The invention will be further explained with reference to specific examples, which are not intended to limit the invention in any way.
The structure of the compounds was characterized by high resolution mass spectrometry, uv-vis spectroscopy, fluorescence spectroscopy and the photophysical properties of the compounds were studied. The detection instrument comprises: U.S. Thermo ELECTRON CORPORATION high resolution mass spectrometry workstation, shimadzu UV-3100 ultraviolet-visible spectrophotometer (scanning range 300-900 nm, light path slit 2 nm), fluorescence spectrum was tested with U.S. Amico Bowman Series 2 Luminescence Spectrometer. The fluorescence copolymerization microscope for cell imaging was Olympus FV3000 of Japan.
Example 1
4-benzimidazole vinyl benzaldehyde derivative (II) (248 mg,1 mmol) and iodinated 2, 3-trimethyl-1-propyl-3H-indole salt (III) (330 mg,1 mmol) were dissolved in 15mL of absolute ethanol, and one drop of piperidine was added dropwise thereto, and heated to 80℃under argon atmosphere, and reflux reaction was carried out with stirring for 12 hours. After the reaction is stopped, the solvent is dried by spin-drying under reduced pressure, and silica gel column chromatography is carried out by using methylene dichloride-methanol (v: v=20:1) as eluent, and then the indolyl benzene is obtained by normal hexane/methylene dichloride recrystallizationThe yield of the imidazole near infrared fluorescent dye (I) is 70%. 1 H-NMR(600MHz，DMSO-d 6 ，ppm)：δ＝8.51(d，J＝16.2Hz，1H)，8.32(d，J＝8.4Hz，2H)，8.00-7.99(m，1H)，7.94-7.91(m，3H)，7.79(d，J＝4.8Hz，1H)，7.76(d，J＝5.4Hz，1H)，7.67-7.64(m，2H)，7.59(s，2H)，7.50(d，J＝16.2Hz，1H)，1.22(q，J＝3.0Hz，2H)，4.73(t，J＝7.8Hz，2H)，1.95-1.89(m，2H)，1.85(s，6H)，1.03(t，J＝7.2Hz，3H)；Esi-MS：calculated for C 30 H 30 N 3 + ：432.2434，found：432.2421[M-I - ] + 。
Example 2 UV-visible absorption Spectrum of Indolylbenzimidazole near infrared fluorescent dye (I) in different solvents
The indolyl benzimidazole near infrared fluorescent dye (I) is respectively dissolved in dichloromethane, methanol, tetrahydrofuran and dimethyl sulfoxide to prepare the dye with the concentration of 1 multiplied by 10 -5 The ultraviolet-visible absorption spectrum of the solution with mol/L is measured; FIG. 1 shows the UV-visible absorption spectra of the fluorochromes (I) prepared in example 1 according to the invention in different solvents, showing a remarkable solvent effect.
Example 3 fluorescence emission spectra of Indolylbenzimidazole near infrared fluorescent dye (I) in different solvents
The indolyl benzimidazole near infrared fluorescent dye (I) is respectively dissolved in dichloromethane, methanol, tetrahydrofuran and dimethyl sulfoxide to prepare the dye with the concentration of 1 multiplied by 10 -5 The fluorescence emission spectrum of the solution of mol/L was measured. FIG. 2 is a graph showing fluorescence spectra of solutions of the fluorochromes (I) prepared in example 1 according to the present invention in different solvents.
Example 4 Indolylbenzimidazole near infrared fluorescent dye (I) for tumor cell fluorescence imaging
And (3) incubating the indolyl benzimidazole near infrared fluorescent dye (I) with HeLa cells, and observing an imaging photograph of the HeLa cells under a confocal fluorescent microscope. FIG. 3 is a photograph of laser confocal fluorescence imaging of HeLa cells incubated with fluorescent dye (I). Hoechst 33342 dye excitation wavelength is 347nm; the mHoney Dew excitation wavelength is 509nm; mered is the superimposed state. After the fluorescent dye (I) is added into HeLa cells for co-hatching, the fluorescent dye enters the HeLa cells for clear imaging, and the near infrared fluorescent dye (I) of indolyl benzimidazole has better biocompatibility and cell permeability and can be used for biological cell imaging.

Claims (5)

1. The indolyl benzimidazole near infrared fluorescent dye is characterized by having a chemical structure shown in (I):
2. a process for the preparation of an indolyl benzimidazole near infrared fluorescent dye of formula (I) according to claim 1, wherein the process comprises: 4-benzimidazole vinyl benzaldehyde (II) is used as a raw material to undergo Knoevenagel condensation reaction with iodized 2, 3-trimethyl-1-propyl-3H-indole salt (III) to obtain indolyl benzimidazole near infrared fluorescent dye shown in a formula (I);
3. the preparation method according to claim 2, characterized in that the preparation method comprises the steps of:
dissolving 4-benzimidazole vinyl benzaldehyde (II) and iodized 2, 3-trimethyl-1-propyl-3H-indole salt (III) in absolute ethyl alcohol, dropwise adding a certain amount of piperidine into the solution, carrying out reflux reaction for 12 hours at 80 ℃ under argon atmosphere, cooling to room temperature after the reaction is finished, filtering to remove filtrate to obtain dark red solid, and separating by silica gel column chromatography to obtain the indolyl benzimidazole near infrared fluorescent dye (I).
4. The process according to claim 3, wherein the mass ratio of 4-benzimidazole vinylbenzaldehyde (II) to iodinated 2, 3-trimethyl-1-propyl-3H-indole salt (III) is 1:1.
5. Use of the indolyl benzimidazole near infrared fluorescent dye of claim 1 in near infrared fluorescence imaging.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6761952B1 (en) * 2003-05-14 2004-07-13 Industrial Technology Research Institute Bis-styryl dye and method for manufacturing the same and its use for a high density optical recording medium
CN113527257A (en) * 2021-07-06 2021-10-22 南京林业大学 Indolyl conjugated 8-hydroxyquinoline near-infrared fluorescent dye and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10808128B2 (en) * 2018-06-11 2020-10-20 Institute For Stem Cell Biology And Regenerative Medicine (Instem) Compounds as fluorescent probes, synthesis and applications thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6761952B1 (en) * 2003-05-14 2004-07-13 Industrial Technology Research Institute Bis-styryl dye and method for manufacturing the same and its use for a high density optical recording medium
CN113527257A (en) * 2021-07-06 2021-10-22 南京林业大学 Indolyl conjugated 8-hydroxyquinoline near-infrared fluorescent dye and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Aggregation Control of Hemicyanine Fluorescent Dye by Using of Cucurbit[7]uril and Pillar[6]arene;Meijiao Cao等;Chin. J. Chem.;第33卷;351-355 *
取代吲哚菁染料的合成及荧光性质;赵春;葛裕华;韩沛;;化工时刊;24(05);4-8 *
新型对苯二乙烯二菁荧光染料的合成;李德鹏, 王桂兰, 袁景利;化学研究与应用;16(05);635-638 *

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