WO2023093399A1 - Sonde fluorescente à base de benzothiazole-parent pour la détection d'ions palladium, procédé de préparation associé et utilisation correspondante - Google Patents

Sonde fluorescente à base de benzothiazole-parent pour la détection d'ions palladium, procédé de préparation associé et utilisation correspondante Download PDF

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WO2023093399A1
WO2023093399A1 PCT/CN2022/126624 CN2022126624W WO2023093399A1 WO 2023093399 A1 WO2023093399 A1 WO 2023093399A1 CN 2022126624 W CN2022126624 W CN 2022126624W WO 2023093399 A1 WO2023093399 A1 WO 2023093399A1
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fluorescent probe
formula
benzothiazole
palladium
parent
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PCT/CN2022/126624
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English (en)
Chinese (zh)
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蒋春辉
陆鸿飞
邵琦
郑绍军
陈梁
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江苏科技大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • G01N21/6428—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
    • 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
    • C09K2211/104—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with other heteroatoms
    • 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

Definitions

  • the invention belongs to the technical field of fluorescent probes, and in particular relates to a palladium ion detection fluorescent probe based on a benzothiazole parent and its preparation method and application.
  • Palladium is a very important transition metal element, which belongs to the platinum group metal elements. It is widely used in jewelry industry, electronics and electrical industry, industrial catalysis industry and fuel cell industry, etc. Palladium is one of the most important catalysts in catalytic converters of automobile exhaust emission devices. During the normal driving of automobiles, the emission speed of palladium ions is 0.1-0.8 ⁇ g ⁇ km -1 ⁇ car -1 , so on both sides of the expressway The content of palladium ions on the facilities and plant leaves is very high. In addition, palladium is a very important catalyst in the chemical and pharmaceutical fields. It can catalyze coupling reactions such as Suzuki reaction, Heck reaction and Sonogashira reaction.
  • palladium ions are the second largest metal sensitizer besides nickel ions, especially palladium chloride, which can strongly irritate the skin and eyes of humans and animals after contact.
  • palladium ions after palladium ions enter the human body, due to their very strong coordination properties, they can coordinate with important biological macromolecules in the human body, such as sulfur-containing amino acids, DNA, RNA, protein and vitamin B6, thereby inhibiting many of the cells. Normal function, which leads to diseases such as asthma, allergies, conjunctivitis and so on.
  • the European Medicines Supervision Center stipulates that the content of palladium in medicines should be lower than 0.005 ⁇ 0.01 ⁇ . Therefore, it is very necessary to detect palladium ions quickly and efficiently.
  • the fluorescence analysis method uses fluorescence as the output signal. Compared with the above methods, it has the characteristics of high sensitivity, good selectivity, easy operation, and low price. It can not only be detected in the solution, but also can be observed on the interface. Therefore, the design It is of great practical significance to develop highly sensitive and highly selective Pd 2+ probes.
  • the present invention provides a palladium ion detection fluorescent probe based on a benzothiazole parent and its preparation method and application.
  • the fluorescent probe compound is a benzothiazole-based parent and can rapidly detect Pd + Schiff base-type fluorescent probe, which has the advantages of specific recognition, short response time and high sensitivity for palladium ions.
  • a kind of palladium ion detection fluorescent probe based on benzothiazole parent, its structural formula is as follows:
  • the preparation method of the above-mentioned palladium ion detection fluorescent probe based on the benzothiazole parent comprises the following steps:
  • step S1 2-aminothiophenol and 2-aminobenzaldehyde are added in acetic acid successively, heated, after the reaction is complete, sodium bicarbonate aqueous solution is added, and dichloromethane is used for extraction, and finally Anhydrous sodium sulfate was added to remove water, and after suction filtration, the filtrate was distilled off under reduced pressure to remove the organic solvent, and the crude product was purified by recrystallization to obtain the intermediate of formula (II).
  • step S2 is: add 3-methyl-1-phenyl-2-pyrazolin-5-one into DMF, first slowly add POCl 3 dropwise under ice-water bath conditions, and wait until the dropwise addition is completed Afterwards, high-temperature reflux reaction, and then after cooling to room temperature, adding water, reaction at room temperature, and suction filtration to obtain the intermediate of formula (III).
  • step S3 are as follows: dissolve the intermediate of formula (II) and intermediate of formula (III) in an organic solvent, and then reflux and stir. After the reaction is completed, filter with suction and wash the solid with ice ethanol to obtain fluorescent probe.
  • the present invention has a palladium ion detection fluorescent probe based on benzothiazole parent and its preparation method and application.
  • the specific advantages are as follows:
  • the present invention uses benzothiazole derivatives and 3-methyl-1-phenyl-2-pyrazolin-5-one-4-formaldehyde as fluorescent groups and amino as connecting groups to synthesize a
  • the palladium ion fluorescent probe of the benzothiazole parent has easy-to-obtain raw materials and a simple method, and the obtained product is a solid powder, which is easy to store and has good stability;
  • the benzothiazole derivatives are selected as the flat steel plane, which has the advantages of low biological toxicity and strong binding ability between nitrogen atoms and metals;
  • the fluorescent probe has specific recognition for palladium ions, short response time, high sensitivity, high sensitivity and high selectivity to trace Pd 2+ in solution, and it has the characteristics of stable structure.
  • Fig. 6 is the probe test paper and the palladium ion of different concentrations prepared by the fluorescent probe prepared in embodiment 1;
  • Fig. 7 is the response time figure when the fluorescent probe that makes in embodiment 1 detects palladium ion
  • Fig. 8 is the mass spectrum MS spectrogram of the fluorescent probe prepared in embodiment 1;
  • Fig. 9 is the nuclear magnetic resonance 1 H-NMR spectrogram of the fluorescent probe prepared in embodiment 1;
  • FIG. 10 is the nuclear magnetic resonance 13 C-NMR spectrum of the fluorescent probe prepared in Example 1.
  • the experimental methods used in the present invention are conventional methods unless otherwise specified.
  • the materials and reagents used in the experiment can be obtained from commercial sources unless otherwise specified. All the following reagents used in the examples are commercially available analytically pure or chemically pure.
  • various metal ion solutions in the embodiments are prepared by adding deionized water to chloride salt chemical reagents such as anhydrous zinc chloride and anhydrous ferric chloride with a purity of more than 99%.
  • Embodiment 1 prepares the palladium ion fluorescent probe compound of benzothiazole parent
  • Embodiment 2 Performance test of palladium ion fluorescent probe
  • the test shows that the maximum excitation wavelength of the fluorescent probe is 372nm, and the maximum emission The wavelength is 444nm;
  • Interference test of different metal ions for palladium ion detection fluorescent probe add 30 ⁇ L of probe stock solution and 50 ⁇ L of any other metal ion ( Co 2+ , Ni 2+ , Al 3+ , Mn 2+ , Mg 2+ , Ba 2+ , Pb 2+ , Fe 2+ , Cd 2+ , K + , Ca 2+ , Cs 2+ , Na + , Ag + and Cu 2+ ) stock solution, and finally 50 ⁇ L of Pd 2+ stock solution was added to the blank solution to test its fluorescence intensity.
  • the presence of other metal ions has no obvious interference on the recognition of aluminum ions by the aluminum ion fluorescent probe compound of the present invention, as shown in FIG. 4 .
  • the test strips were respectively soaked in 0mM, 0.3mM, 1mM palladium ion concentration solutions, soaked for a few minutes, and dried, and a band of rapid discoloration was observed under a 365nm ultraviolet lamp, indicating that the probe of the present invention can be detected in a solid state Palladium ion, see Figure 6.
  • the present invention uses benzothiazole derivatives and 3-methyl-1-phenyl-2-pyrazolin-5-one-4-carbaldehyde as fluorescent groups and amino as linking groups to synthesize a benzothiazole-based
  • the palladium ion fluorescent probe of the thiazole parent the preparation method is easy to get raw materials, the method is simple, the obtained product is a solid powder, easy to store, has specific recognition for palladium ions, short response time, high sensitivity, and is sensitive to trace amounts of Pd in the solution. 2+ exhibits high sensitivity and high selectivity, and at the same time it has the characteristics of stable structure.

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  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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  • Engineering & Computer Science (AREA)
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  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)

Abstract

La présente invention concerne une sonde fluorescente à base de benzothiazole-parent pour la détection d'ions palladium, un procédé de préparation associé et une utilisation correspondante. La formule structurale de la sonde fluorescente est telle que présentée dans la formule (I) ci-dessous. Avec un dérivé de benzothiazole en tant que fluorophore et un amino en tant que groupe de liaison, la sonde fluorescente préparée présente une sensibilité et une sélectivité élevées pour le Pd2+ en solution, et a également la caractéristique d'une structure stable. Le procédé de préparation de la sonde fluorescente présente des étapes simples et utilise des matières premières facilement disponibles, et le produit obtenu est une poudre solide, est facile à stocker, a de larges perspectives d'application, et peut être produit et appliqué à grande échelle.
PCT/CN2022/126624 2021-11-25 2022-10-21 Sonde fluorescente à base de benzothiazole-parent pour la détection d'ions palladium, procédé de préparation associé et utilisation correspondante WO2023093399A1 (fr)

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CN202111409924.3 2021-11-25
CN202111409924.3A CN113912596B (zh) 2021-11-25 2021-11-25 一种基于苯并噻唑母体的钯离子检测荧光探针及其制备方法与应用

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CN113912596B (zh) * 2021-11-25 2022-12-02 江苏科技大学 一种基于苯并噻唑母体的钯离子检测荧光探针及其制备方法与应用
CN115353498B (zh) * 2022-09-01 2023-08-08 坛墨质检科技股份有限公司 一种苯并噻唑类锌离子荧光探针及其制备方法

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