CN115141358B

CN115141358B - Organic polymer molecule or organic polymer nano particle with long afterglow luminescence property and application thereof

Info

Publication number: CN115141358B
Application number: CN202210656291.4A
Authority: CN
Inventors: 宋国胜; 廖师夷; 李哲
Original assignee: Hunan University
Current assignee: Hunan University
Priority date: 2022-06-10
Filing date: 2022-06-10
Publication date: 2023-04-18
Anticipated expiration: 2042-06-10
Also published as: CN115141358A

Abstract

The invention discloses an organic polymer molecule or organic polymer nano particle with long afterglow luminescence property and application thereof. According to the invention, through structural design, organic polymer molecules with thiophene structures are used as a luminous body, amphiphilic polymers are used as a surfactant, and the organic polymer nanoparticles (organic long afterglow luminous body) are obtained through ultrasonic treatment. The invention also provides the application of the organic long afterglow luminescent system in cell or in vivo imaging, the system takes organic polymer molecules containing thiophene structures as luminescent substances, can construct an afterglow system with near infrared region long afterglow emission, and can still generate strong long afterglow luminescence for a long time after the excitation light stops.

Description

Organic polymer molecule or organic polymer nano particle with long afterglow luminescence property and application thereof

Technical Field

The invention belongs to the field of long afterglow luminescent materials, and particularly relates to organic polymer molecules or organic polymer nanoparticles with long afterglow luminescent properties and application thereof.

Background

Long afterglow luminescence refers to a phenomenon in which a substance can continuously emit light even after irradiation with excitation light is stopped. The long afterglow material is one of the earliest studied and applied materials, and many natural ores have long afterglow luminescent characteristics, such as luminous pearls and the like. In recent decades, long afterglow materials have been used in the emerging fields of emergency lighting, traffic signs, interior decoration, displays, anti-counterfeiting, optical recording, biochemistry and the like due to their good characteristics that do not require real-time excitation light. The long-afterglow luminescent materials widely used at present comprise inorganic long-afterglow luminescent materials and organic long-afterglow luminescent materials. However, the inorganic afterglow materials all contain rare earth heavy metals such as Gd, yb and Eu, and the surface of the inorganic afterglow materials is difficult to modify. Therefore, there is a need to design an organic long-afterglow luminescent system which is easier in structural design and thus can regulate and control the luminescent performance.

Disclosure of Invention

The invention aims to provide organic polymer molecules or organic polymer nanoparticles with long afterglow luminescence properties and application thereof. The invention uses organic polymer molecules or organic polymer nano particles containing thiophene structures as luminescent substances, and can continuously emit long-afterglow luminescence after the excitation light stops.

The invention provides the following technical scheme:

the organic polymer molecule with long afterglow luminescence property contains thiophene structure and has the following general formula:

wherein R and R' represent any organic structure.

Preferably, the polymerization degree n of the organic polymer molecule is in the range of 2 to 1000.

Preferably, the organic polymer molecules include, but are not limited to, the following structural formulas:

the invention also provides a class of organic polymer nanoparticles with long afterglow luminescence properties, wherein the nanoparticles comprise organic polymer molecules and a surfactant.

Further, the surfactant is any one or combination of polyvinylpyrrolidone, long-chain fatty acid, fatty alcohol, polyoxyethylene-polyoxypropylene copolymer, distearoyl phosphatidyl ethanolamine-polyethylene glycol, polyether, poly (styrene-maleic anhydride) and sodium dodecyl benzene sulfonate.

Furthermore, the size range of the nano particles is 1-1000 nanometers.

The invention also provides a preparation method of the organic polymer nano particle, which specifically comprises the following steps:

mixing organic polymer molecules with a surfactant dispersion liquid, and adding water for ultrasonic treatment to prepare the organic polymer nanoparticles (organic long afterglow luminescent system).

The organic polymer molecule or organic polymer nano particle provided by the invention can continuously emit long-afterglow luminescence after the excitation light stops.

Specifically, the afterglow luminescence time is 1 second to 24 hours.

Specifically, the long afterglow luminous intensity is 10 ³ ～10 ⁹ p/sec/cm ² /sr。

Specifically, the wavelength range of the exciting light is 200-1500 nm, and the wavelength range of the afterglow emitting light is 200-1500 nm.

The invention also provides application of the organic long-afterglow luminescent system in cell or in-vivo imaging.

The invention has the following beneficial technical effects:

according to the invention, through structural design, organic polymer molecules with thiophene structures are used as a luminous body, amphiphilic polymers are used as a surfactant, and the organic polymer nanoparticles (organic long afterglow luminous body) are obtained through ultrasonic treatment.

The invention also provides the application of the organic long afterglow luminescent system in cell or in vivo imaging, the system takes organic polymer molecules containing thiophene structures as luminescent substances, can construct an afterglow system with near infrared region long afterglow emission, and can still generate strong long afterglow luminescence for a long time after the excitation light stops.

Drawings

FIG. 1 is a schematic diagram of the construction and application of an organic long afterglow luminescent system based on organic polymers.

FIG. 2 is an ultraviolet image of NIR-R prepared in example 1.

FIG. 3 is a fluorescence plot of NIR-R prepared in example 1.

FIG. 4 is an ultraviolet plot of NIR-R @ DSPE-mPEGNPs prepared in example 2.

FIG. 5 is a fluorescence plot of NIR-R @ DSPE-mPEGNPs prepared in example 2.

FIG. 6 is a graph of afterglow of NIR-R @ DSPE-mPEGNPs prepared in example 2.

FIG. 7 is a TEM image of NIR-3@ DSPE-mPEGNPs obtained in example 3.

FIG. 8 is a DLS plot of NIR-3@ DSPE-mPEGNPs obtained in example 3.

FIG. 9 is a graph of afterglow imaging intensities at different wavebands for NIR-3@ DSPE-mPEG NPs obtained in example 3.

FIG. 10 is a graph of afterglow emission intensity of NIR-3@ DSPE-mPEG NPs obtained in example 3 after irradiation with light for various periods of time.

FIG. 11 is a graph of the decay of the afterglow emission intensity over time after cessation of illumination with NIR-3@ DSPE-mPEG NPs obtained in example 3.

FIG. 12 is a graph of NIR afterglow imaging cell quantification in the NIR region of NIR-3@ DSPE-mPEG NPs obtained in example 4.

FIG. 13 is the NIR afterglow imaging subcutaneous tumor map (a) and the imaging intensity quantification map (b) of NIR-3@ DSPE-mPEG NPs obtained in example 5.

FIG. 14 is an afterglow plot of WXS-R @ DSPE-mPEGNPS prepared in example 6.

Detailed Description

The experimental procedures described in the following examples are conventional unless otherwise specified, and the reagents and materials described therein are commercially available without further specification.

The organic polymer (NIR-1, NIR-2, NIR-3) according to the invention is prepared in the following manner:

s1, adding a compound 1, tetrakis (triphenylphosphine) palladium and a tin compound (Sn-R-Sn) of R according to a set proportion under a protective atmosphere, heating the mixed solution to 100-120 ℃, stirring for 10-36 hours, and obtaining a mixture after the reaction is finished;

s2, filtering and purifying the mixture, and drying to obtain a target product, namely a compound NIR-R, wherein the reaction process is as follows:

the technical solution of the present invention is further illustrated by the following specific experimental means.

Example 1 Synthesis and Property verification based on NIR-R

The embodiment of the invention is based on NIR-R synthesis and property research, and the specific synthesis method comprises the following steps:

compound 1 (0.20g, 0.21mmol) and Compound 2 (0.19g, 0.21mmol) (or Compound 3 (0.20g, 0.21mmol), compound 4 (0.11g, 0.21mmol)) were dissolved in 10mL of toluene, and after repeating evacuation and argon-charging for 3 times, tetrakis (triphenylphosphine) palladium (19mg, 0.01mmol) was rapidly added, and then, the reaction was heated to 110 ℃ and stirred for 24 hours;

the reaction was cooled to room temperature and poured into 200mL of methanol solution to precipitate a solid, and the solid was collected with filter paper, extracted with methanol, hexane, acetone and chloroform, respectively, for 12 hours with a soxhlet extractor, the chloroform extracted solution was cooled to room temperature and concentrated by rotary evaporation, and finally, the solid was precipitated in methanol, filtered and dried to obtain the compounds NIR-1, NIR-2 and NIR-3.

The chemical reaction formula is as follows:

characterization of NIR-R: the resulting NIR-R solid was dissolved in tetrahydrofuran and the fluorescent uv spectrum of the molecule was then tested by fluorescence and uv instrumentation.

As can be seen from FIGS. 2 and 3, the ultraviolet range of the molecule is 600-650 nm, the fluorescence spectrum is in the range of 750-800 nm, and NIR-3 has the strongest fluorescence emission intensity.

Example 2 Synthesis and Property verification of NIR-R @ DSPE-mPEGNPs

The embodiment of the invention is based on the synthesis and property research of NIR-R @ DSPE-mPEGNPs, and the specific synthesis method comprises the following steps:

(1) Preparation of organic small molecule (NIR-R @ DSPE-mPEGNPs) nanoparticles:

organic small molecule nanoparticles based on NIR-R @ DSPE-mPEG NPs are directly synthesized by a nano coprecipitation method, firstly 1mL of THF mother liquor containing NIR-R (200 mu g) and distearoyl phosphatidyl ethanolamine-polyethylene glycol 2000 (DSPE-mPEG 2 k) (5 mg) is prepared, and 9mL of THF mother liquor is taken ₂ Placing O in a round-bottom flask, quickly injecting the prepared tetrahydrofuran solution, and performing ultrasonic treatment for 8min; after removing THF by rotary evaporation, centrifugation (4500 rpm,5 min), washing with deionized water, and final concentration, calibration concentration with NIR-R (NIR-R concentration 1 mg/mL), and keeping away from light;

(2) Property Studies of NIR-R @ DSPE-mPEGNPs: the obtained NIR-R @ DSPE-mPEG NPs are diluted to a certain degree, and then the ultraviolet spectrum of the molecules is tested by a fluorescence and ultraviolet instrument.

The construction and the action principle of the organic long-afterglow luminescent system are shown in figure 1.

As can be seen from FIGS. 4 and 5, the UV of the three molecules is 600-700 nm and the fluorescence emission is 750-850 nm.

(3) Afterglow luminescence intensity studies of NIR-R @ DSPE-mPEGNPs: we used a small animal imager to acquire the afterglow signal of NIR-R @ DSPE-mPEGNPs.

As can be seen from FIG. 6, the near infrared afterglow imaging capability of NIR-3@ DSPE-mPEG NPs is the strongest at the same mass concentration.

Example 3 Synthesis and Property verification of NIR-3@ DSPE-mPEGNPs

The embodiment of the invention is based on the property research of NIR-3@ DSPE-mPEGNPs, and the specific synthetic steps are as in the step (1) of the embodiment 2.

FIG. 7 is a TEM image of NIR-3@ DSPE-mPEG NPs obtained in example 3, and it can be seen from FIG. 7 that the synthesized particles have a particle size of about 30nm.

FIG. 8 is a DLS graph of NIR-3@ DSPE-mPEGNPs obtained in example 3, and it can be seen from FIG. 8 that the synthesized particles have a particle size of about 43nm, which is slightly larger than the particle size measured by TEM because of the hydrated particle size measured by DLS.

(1) Study on afterglow luminescence wavelength band of NIR-3@ DSPE-mPEGNPs: the obtained NIR-3@ DSPE-mPEGNPs are illuminated for different time, and then afterglow imaging images are collected by a small animal imager in different wave bands (510-570 nanometers, 570-650 nanometers, 690-700 nanometers and 800-820 nanometers).

As can be seen from figure 9, the afterglow luminescence of NIR-3@ DSPE-mPEG NPs is mainly concentrated at 800-820 nanometers, and the afterglow luminescence has near-infrared afterglow emission capability.

(2) Afterglow luminescence property study of NIR-3@ DSPE-mPEGNPs: and (3) irradiating the obtained NIR-3@ DSPE-mPEGNPs for different times, and then respectively testing afterglow imaging graphs of the molecules irradiated for different times by a small animal imager.

From FIG. 10, it can be seen that the afterglow luminescence intensity of NIR-3@ DSPE-mPEG NPs increases with the increase of illumination time.

(3) Afterglow luminescence time study of NIR-3@ DSPE-mPEGNPs: and (3) after the obtained NIR-3@ DSPE-mPEGNPs are illuminated for 15 seconds, collecting afterglow luminescence images through a small animal imager at different time points after illumination is stopped.

As can be seen from FIG. 11, after the excitation light was stopped for 10 minutes, the afterglow luminescence in the near infrared region of NIR-3@ DSPE-mPEGNPs could still be collected.

Example 4 cellular near-Infrared afterglow imaging based on NIR-3@ DSPE-mPEGNPs

Culturing cancer cells (CT 26) in a 96-well plate, adding materials with different concentrations after the cells adhere to the wall, incubating for 4h, respectively illuminating the cells added with the materials with different concentrations for 15s, and then carrying out afterglow imaging on the cells by using a small animal imager.

FIG. 12 is an image of the afterglow of cells obtained in example 4 after adding materials at different concentrations.

Example 5 near-infrared region afterglow imaging of tumors based on NIR-3@ DSPE-mPEGNPs nanoparticle system

For subcutaneous tumors, different concentrations of NIR-3@ DSPE-mPEG NPs,660 nanometer laser (0.8W/cm) ² ) After the subcutaneous tumor area is illuminated for 25s, the small animal imager is used for carrying out afterglow imaging on the subcutaneous tumor area.

FIG. 13 is an image (a) and an image (b) of the afterglow of subcutaneous tumors obtained by intratumoral injection of different concentrations of the materials (0 mg/mL, 0.25mg/mL, 0.5mg/mL, 1 mg/mL) in example 5.

Example 6 Synthesis and Property verification of WXS-R @ F127 NPs

The embodiment of the invention is based on the synthesis and property research of WXS-R @ F127 NPs, and the specific synthesis method is as follows:

(1) The synthesis reaction formula of the semiconductor polymer WXS-R is as follows:

(2) Preparation of organic small molecule (WXS-R @ F127 NPs) nanoparticles:

organic small molecule nano-particles based on WXS-R @ F127 NPs directly adopt nano-particlesAnd (3) synthesis by a coprecipitation method: first, 1mL of THF stock solution containing WXS-R (50. Mu.g) and polyether (Pluronic F-127) (2.5 mg) was prepared, and 9mL of THF stock solution was taken ₂ Placing O in a round-bottom flask, quickly injecting the prepared tetrahydrofuran solution, and performing ultrasonic treatment for 8min; removing THF by rotary evaporation, centrifuging (4500 rpm,5 min), washing with deionized water, concentrating, calibrating with WXS-R (the concentration of WXS-R is 50 μ g/mL), and storing in dark;

(3) Study of afterglow luminescence intensity of WXS-R @ F127 NPs: we used a small animal imager to acquire the afterglow signal of WXS-R @ F127 NPs.

As can be seen from FIG. 14, the afterglow imaging ability of WXS-13@ F127 NPs is strongest at the same mass concentration.

The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims

1. An organic polymer molecule containing thiophene structure with long afterglow luminescence property, which is characterized in that: the structural formula of the organic polymer molecule is as follows:

the polymerization degree n of the organic polymer molecule is in the range of 2 to 1000.

2. An organic polymer nanoparticle having long afterglow luminescent properties, characterized in that: the nanoparticle comprises a surfactant and the organic polymer molecule containing the thiophene structure and having the long afterglow luminescence property of claim 1.

3. The organic polymeric nanoparticle having long afterglow luminescent properties of claim 2, wherein: the surfactant is one or more of polyvinylpyrrolidone, long-chain fatty acid, fatty alcohol, polyoxyethylene-polyoxypropylene copolymer, distearoyl phosphatidyl ethanolamine-polyethylene glycol, polyether, poly (styrene-maleic anhydride) and sodium dodecyl benzene sulfonate.

4. The organic polymer nanoparticles with long afterglow luminescent properties of claim 2, wherein: the size range of the nano particles is 1-1000 nanometers.

5. The organic polymer nanoparticles having long afterglow luminescent properties according to any one of claims 2 to 4, wherein: after the excitation light stops, the long afterglow luminescence can continue to be emitted.

6. The organic polymeric nanoparticle having long afterglow luminescent properties of claim 5, wherein: the afterglow luminescence time is 1 second to 24 hours.

7. The organic polymer nanoparticles with long afterglow luminescent properties of claim 5, wherein: the long afterglow luminous intensity is 10 ³ ～10 ⁹ p/sec/cm ² /sr。

8. The organic polymeric nanoparticle having long afterglow luminescent properties of claim 5, wherein: the wavelength range of the exciting light is 200-1500 nm, and the wavelength range of the afterglow emitting light is 200-1500 nm.