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CN-118638125-B - Two-photon two-state luminous porphyrin fluorescent dye and preparation method thereof

CN118638125BCN 118638125 BCN118638125 BCN 118638125BCN-118638125-B

Abstract

The application relates to the technical field of preparation of functionalized porphyrin derivatives, and discloses a two-photon two-state luminescent porphyrin fluorescent dye and a preparation method thereof. The preparation method comprises the steps of dissolving salicylaldehyde porphyrin in a solvent to obtain a solution A, dissolving aromatic amine in the solvent to obtain a solution B, mixing the solution A and the solution B, stirring, heating to 110-120 ℃ for reflux, distilling the reaction solution under reduced pressure, recrystallizing, and drying to obtain the two-photon two-state luminescent porphyrin fluorescent dye. The porphyrin fluorescent dye can be excited by near infrared light of 780nm and emit red fluorescence of about 650nm, can emit fluorescence in both solution and solid state, and has dual performances of two-photon and two-state luminescence. The method can effectively reduce photodamage, reduce interference of background fluorescence and improve penetration depth while maintaining continuity of fluorescent signals, and has good application prospect. The preparation method has simple synthesis process, easy purification of the product and suitability for industrial production.

Inventors

  • ZENG RONGJIN
  • HE CHUN
  • ZHANG PEISHENG
  • CHENG FENMIN
  • Ai Yihui
  • WANG YANING
  • CHEN SHU
  • HAO YUANQIANG

Assignees

  • 湖南科技大学

Dates

Publication Date
20260512
Application Date
20240527

Claims (7)

  1. 1. A two-photon two-state luminescent porphyrin fluorescent dye, which is characterized by having a chemical structure shown in a formula (1): (1) wherein R is: 、 Or (b) 。
  2. 2. The method for preparing the two-photon bi-state luminescent porphyrin fluorescent dye according to claim 1, comprising the steps of: Dissolving salicylaldehyde porphyrin in a solvent to obtain a solution A, dissolving aromatic amine in the solvent to obtain a solution B, mixing the solution A and the solution B, stirring, and heating to 110-120 ℃ for reflux; distilling the reaction liquid under reduced pressure, recrystallizing, and drying to obtain the two-photon two-state luminescent porphyrin fluorescent dye; the salicylaldehyde porphyrin is 5- (4-hydroxy-3-formylphenyl) -10,15, 20-triphenyl porphyrin, and has a chemical structure shown in a formula (2): (2)。
  3. 3. the method of claim 2, wherein the 5- (4-hydroxy-3-formylphenyl) -10,15, 20-triphenylporphyrin is prepared by: s1, preparing hydroxy porphyrin by using p-hydroxy benzaldehyde, benzaldehyde and pyrrole; s2, dissolving hydroxyporphyrin and urotropine in trifluoroacetic acid, and refluxing at 70 ℃ for 24-36 h, wherein the molar ratio of hydroxyporphyrin to urotropine is 1:2; s3, adding hydrochloric acid into the reaction liquid, and then adding alkali liquor to adjust the pH to 7-8; s4, extracting the reaction liquid with dichloromethane to collect an organic phase, drying, filtering and distilling the organic phase under reduced pressure to obtain a crude product; S5, purifying the crude product by chromatography to obtain purple solid, namely salicylaldehyde porphyrin; the chromatography adopts a silica gel column, and the eluting agent is a mixture of petroleum ether and ethyl acetate in a volume ratio of 3:1.
  4. 4. A process according to claim 3, wherein the hydroxy porphyrin is prepared from p-hydroxybenzaldehyde, benzaldehyde and pyrrole, in particular: adding p-hydroxybenzaldehyde and benzaldehyde into propionic acid, heating to reflux, slowly dripping pyrrole into propionic acid solution, refluxing at 130-150deg.C for 1-2 hr, distilling the reaction solution under reduced pressure to remove propionic acid, adding absolute ethanol, stirring, standing at-20deg.C, suction filtering, washing the filter cake, and drying to obtain crude product; purifying the crude product by silica gel column chromatography to obtain purple solid, namely hydroxy porphyrin.
  5. 5. The preparation method according to claim 2, wherein the solvent is a mixed solution of toluene and n-butanol, and the volume ratio of toluene to n-butanol is 1 (1-2).
  6. 6. The method of claim 2, wherein the molar ratio of salicylaldehyde porphyrin to aromatic amine is 1 (2-3).
  7. 7. The method according to claim 2, wherein the solvent used for the recrystallization is methanol, ethanol, n-propanol or n-butanol.

Description

Two-photon two-state luminous porphyrin fluorescent dye and preparation method thereof Technical Field The application relates to the technical field of preparation of functionalized porphyrin derivatives, in particular to a two-photon two-state luminescent porphyrin fluorescent dye and a preparation method thereof. Background Porphyrin is a red light dye, has the properties of good photo-thermal stability, large Stokes shift, red light emission and the like, and has wide application in the aspects of photodynamic therapy, photoelectric devices, fluorescence analysis, photoelectrocatalysis, supermolecular chemistry and the like. Thus, synthesis of porphyrins and their derivatives has received extensive attention from researchers. However, in practical applications, most porphyrins currently have two main problems, which greatly limit the application of porphyrins. First, porphyrins, while having longer red emissions, have very short excitation wavelengths, on the order of 420nm, even shorter than the excitation wavelengths of conventional green-emitting fluorescent dyes. In biomedical applications, short wavelength excitation not only produces large photodamage, large background fluorescence interference, but also has limited penetration depth. Second, there is an aggregation-induced quenching (ACQ) problem. The fluorescence emission of porphyrins is limited to dilute solutions, and when the porphyrin concentration is high or becomes solid, fluorescence is greatly reduced or quenched due to strong pi-pi interactions between molecules. In applications that rely on fluorescence for analytical diagnostics (e.g., fluorescence sensing, photodynamic therapy, etc.), the change in fluorescence signal can produce large deviations that affect its accuracy. At present, related personnel successively discover and design and develop various two-photon and two-state luminescent fluorescent dyes, wherein the two-photon fluorescent (TPF) dye is a dye which adopts long wave excitation to generate short wave emission, also called anti-Stokes fluorescent dye, has the advantages of low light damage, low background fluorescence interference, stronger tissue penetrating power and the like in the near infrared region, and the two-state luminescent (DSE) dye has no or few ACQ effect, can emit fluorescence in a solution and solid state, has no limitation on the fluorescence emission, and can better maintain the continuity and stability of fluorescent signals. Based on the two-photon and two-state luminescence properties, the application develops a novel porphyrin dye to improve the application performance of porphyrin. Disclosure of Invention The application provides a two-photon two-state luminescent porphyrin fluorescent dye and a preparation method thereof, and aims to solve the problems of large photodamage, large background fluorescence interference, limited penetration depth, poor continuity of fluorescent signals and low accuracy caused by aggregation-induced quenching in the prior art. In order to achieve the above purpose, the present application is realized by the following technical scheme. In a first aspect of the present application, there is provided a two-photon two-state luminescent porphyrin fluorescent dye having a chemical structure represented by formula (1): wherein R comprises at least one benzene ring. In some embodiments, R is: In a second aspect of the present application, a preparation method of the two-photon two-state luminescent porphyrin fluorescent dye is provided, including: Dissolving salicylaldehyde porphyrin in a solvent to obtain a solution A, dissolving aromatic amine in the solvent to obtain a solution B, mixing the solution A and the solution B, stirring, and heating to 110-120 ℃ for reflux; and (3) distilling the reaction liquid under reduced pressure, recrystallizing, and drying to obtain the two-photon two-state luminescent porphyrin fluorescent dye. In some embodiments, the salicylaldehyde porphyrin is 5- (4-hydroxy-3-formylphenyl) -10,15, 20-triphenylporphyrin having a chemical structure represented by formula (2): in some embodiments, the 5- (4-hydroxy-3-formylphenyl) -10,15, 20-triphenylporphyrin is prepared by the following method: s1, preparing hydroxy porphyrin by using p-hydroxy benzaldehyde, benzaldehyde and pyrrole; S2, dissolving hydroxyporphyrin and urotropine in trifluoroacetic acid, and refluxing for 24-36 hours at 70 ℃, wherein the molar ratio of hydroxyporphyrin to urotropine is 1:2; s3, adding hydrochloric acid into the reaction liquid, and then adding alkali liquor to adjust the pH to 7-8; s4, extracting the reaction liquid with dichloromethane to collect an organic phase, drying, filtering and distilling the organic phase under reduced pressure to obtain a crude product; S5, purifying the crude product by chromatography to obtain purple solid, namely salicylaldehyde porphyrin; the chromatography adopts a silica gel column, and the eluting agent is a mixture of petroleum e