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CN-122011371-A - Bifuran polyamide with high quantum yield and yellowish green wavelength light, and preparation method and application thereof

CN122011371ACN 122011371 ACN122011371 ACN 122011371ACN-122011371-A

Abstract

The invention belongs to the technical field of fluorescent high polymer materials, and particularly discloses a furan-linked polyamide with high quantum yield and yellowish green wavelength light, and a preparation method and application thereof. The method comprises the steps of dissolving a difuranyl chloride monomer in an organic solvent to obtain an organic phase, adding an alkaline aqueous solution into the organic phase to form a phase interface, adding a diamine monomer, stirring to perform interfacial polymerization reaction, filtering, precipitating, washing and drying after the reaction is finished to obtain the difuran polyamide. According to the invention, the polymer main chain structure and the chain rigidity and flexibility are regulated and controlled by diamine monomers with specific molecular structures to prepare the bifuran polyamide, under 480 nm excitation light, the emission wavelength of the amorphous bifuran polyamide can reach 540-552 nm, and after crystallization, the amorphous bifuran polyamide is red-shifted to 565-568 nm, so that long-wavelength yellow-green luminescence, high quantum yield luminescence and good biocompatibility are realized, and the application of the bio-based polyamide in the field of biological imaging is expanded.

Inventors

  • XIONG BIJIN
  • Long Chijin
  • ZHU JINTAO
  • LIAO YONGGUI
  • YIN GUOCHUAN

Assignees

  • 华中科技大学

Dates

Publication Date
20260512
Application Date
20260316

Claims (10)

  1. 1. A preparation method of a furan polyamide with high quantum yield and yellowish green wavelength light is characterized by comprising the steps of dissolving furan acyl chloride monomer in an organic solvent to obtain an organic phase, adding an alkaline aqueous solution into the organic phase to form a phase interface, adding diamine monomer, stirring to perform interfacial polymerization reaction, filtering, precipitating, washing and drying after the reaction is finished to obtain the furan polyamide, wherein the diamine monomer is aliphatic diamine monomer or alicyclic diamine monomer.
  2. 2. The method for producing a furan polyamide with high quantum yield and yellowish green wavelength light according to claim 1, wherein said aliphatic diamine monomer is 1, 6-hexamethylenediamine, 1, 8-octanediamine or 1, 10-decanediamine, and said alicyclic diamine is piperazine or 4,4' -bipiperidine.
  3. 3. The method for producing a furan polyamide with high quantum yield and yellowish green wavelength according to claim 1, wherein said aqueous alkaline solution is aqueous KOH solution, and said aqueous alkaline solution is 0.5-2 mol/L.
  4. 4. The method for producing a high quantum yield and yellowish green wavelength light furan polyamide as claimed in claim 1, wherein said molar ratio of said furan acid chloride monomer to said diamine monomer is 1:1.
  5. 5. The method for producing a furan polyamide with high quantum yield and yellowish green wavelength according to claim 1, wherein the interfacial polymerization reaction is carried out for 20 to 30 hours with stirring.
  6. 6. The method for preparing the furan polyamide with high quantum yield and yellowish green wavelength light, according to claim 1, wherein the furan acid chloride monomer is prepared by carrying out reflux reaction on furan dicarboxylic acid and excessive thionyl chloride under the action of a catalyst, and obtaining the furan acid chloride monomer through post-treatment.
  7. 7. The method for preparing a furan polyamide with high quantum yield and yellowish green wavelength according to claim 6, wherein the catalyst is N, N-dimethylformamide, the addition amount of the N, N-dimethylformamide is 0.5-0.8% of the weight of the furan dicarboxylic acid, and the reflux reaction time is 3-8 hours.
  8. 8. The furan polyamide produced by the production method according to any one of claims 1 to 7, wherein when the diamine monomer is an aliphatic diamine monomer, the produced furan polyamide is an amorphous polymer, the maximum emission wavelength is within the range of 540 to 568 nm under 480 nm excitation light, and when the diamine monomer is an alicyclic diamine monomer, the produced furan polyamide is a crystalline polymer, and the maximum emission wavelength is within the range of 565 to 568 nm under 480 nm excitation light.
  9. 9. The bisfuran polyamide produced by the production process according to claim 8, wherein the bisfuran polyamide produced when the diamine monomer is 1, 10-decamethylene diamine has a fluorescence quenching response to Fe 3+ .
  10. 10. Use of a bifuran polyamide obtainable by the process of any of claims 1-7 for the preparation of a bioimaging fluorescent probe.

Description

Bifuran polyamide with high quantum yield and yellowish green wavelength light, and preparation method and application thereof Technical Field The invention belongs to the technical field of fluorescent high polymer materials, and particularly relates to a furan-linked polyamide with high quantum yield and yellowish green wavelength light, and a preparation method and application thereof. Background The fluorescent material has wide application prospect in the fields of chemical sensing, biological imaging, photoelectric devices and the like. The traditional fluorescent material is mostly based on a conjugated system or heavy metal complex, and has the problems of complex synthesis, poor biocompatibility, high potential toxicity and the like. In recent years, unconjugated clustered light emitting (Clusterization-TRIGGERED EMISSION, CTE) materials have received attention because of their unique light emitting mechanism and good biocompatibility. The material mainly forms a luminescent cluster through space conjugation by the lone pair electrons of hetero atoms (such as N, O, P and the like) so as to realize fluorescence emission. As an important engineering plastic, the polyamide has good mechanical property and thermal stability. However, the fluorescence emission of conventional aromatic polyamides (such as PA 6T) mainly results from the aggregation effect of benzene rings and amide groups, which have a short emission wavelength (about 509 nm), and limited quantum yield. How to realize long wavelength emission (especially yellow-green light wave band) and high quantum yield of polyamide materials through molecular structure design, and expand the application of the polyamide materials in the biomedical field is one of the hot spots of current research. Furanedicarboxylic acid (FDCA) and derivatives thereof are taken as renewable bio-based platform compounds, and provide a new idea for designing novel polyamide materials. And compared with benzene rings, furan rings have weaker aromatic stabilization energy and electron donating effect, and are expected to regulate and control the fluorescence performance of the material. However, research on the clustered luminescence properties of bisfuran polyamides and their use in cell imaging is currently left blank. Disclosure of Invention Aiming at the defects or improvement demands of the prior art, the invention provides a furan-linked polyamide with high quantum yield and yellowish green wavelength light, a preparation method and application thereof, and the furan-linked polyamide is prepared by interfacial polymerization of furan acyl chloride monomer and diamine monomer with a specific structure, wherein the HOMO-LUMO energy gap is reduced by utilizing weak aromatic stabilization energy of furan ring, electron donating effect of oxygen atom and a conjugated system of furan extension, long wavelength yellowish green light emission and high quantum yield light emission are realized, and the defects of short light emission wavelength, low quantum yield and insufficient biocompatibility application research of the existing polyamide fluorescent material are overcome. In order to achieve the above object, in one aspect of the present invention, there is provided a method for preparing a furan polyamide with high quantum yield and yellowish green wavelength light, comprising dissolving a furan acyl chloride monomer in an organic solvent to obtain an organic phase, adding an alkaline aqueous solution into the organic phase to form a phase interface, adding a diamine monomer, stirring to perform an interfacial polymerization reaction, filtering to precipitate after the reaction is completed, washing, and drying to obtain a furan polyamide, wherein the diamine monomer is an aliphatic diamine monomer or an alicyclic diamine monomer. Preferably, the aliphatic diamine monomer is 1, 6-hexamethylenediamine, 1, 8-octanediamine or 1, 10-decanediamine, and the alicyclic diamine is piperazine or 4,4' -bipiperidine. Preferably, the alkaline aqueous solution is KOH aqueous solution, and the alkaline aqueous solution is 0.5-2 mol/L. Preferably, the molar ratio of the bisfuran acid chloride monomer to the diamine monomer is 1:1. Preferably, the interfacial polymerization reaction is carried out with stirring for 20 to 30 hours. Preferably, the difuranyl chloride monomer is prepared by carrying out reflux reaction on difuran dicarboxylic acid and excessive thionyl chloride under the action of a catalyst, and obtaining the difuranyl chloride monomer through post-treatment. Preferably, the catalyst is N, N-dimethylformamide, the addition amount of the N, N-dimethylformamide is 0.5-0.8% of the mass of the difuran dicarboxylic acid, and the reflux reaction time is 3-8 hours. In another aspect of the present invention, there is provided a furan-linked polyamide prepared by the preparation method according to any one of the above-mentioned aspects, wherein when the diamine monomer is an al