Design of donor-acceptor conjugated polymers based on diketopyrrolopyrrole for NIR-II multifunctional imaging.

Diketopyrrolopyrrole (DPP) is an excellent photosensitizer and photothermal agent with the advantages of good planarity, strong electron affinity, high electron mobility, easy purification, easy structural modification and high molar absorption coefficient. It is regarded as one of the ideal choices for the design and synthesis of efficient organic photovoltaic materials. Therefore, two kinds of donor-acceptor (D-A) conjugated polymers were designed and synthesized with DPP as the acceptor, and their optical properties and applications in the near-infrared region were studied. The quantum yield (QY) of PBDT-DPP is 0.46%, and the highest temperature reached within 10 minutes after irradiation with a 660 nm laser is 60 °C. Another polymer, EDOT-DPP, has a QY of 0.48%, and its semiconductor polymer nanoparticle aqueous solution can reach 60 °C within 12 minutes under laser irradiation, achieving photothermal treatment of nude mice tumors. Both polymer NPs have good biocompatibility and promising applications in bioimaging and photothermal therapy.

Donor-acceptor-donor small molecules for fluorescence/photoacoustic imaging and integrated photothermal therapy.

Here, a D-A-D type fluorescent conjugated molecule with a high molar absorption coefficient and emission at 1120 nm in the near-infrared region was synthesized. Conjugated molecules and two polyethylene glycol polymers with different lipophilic ends are assembled into water-soluble nanoparticles to improve their biocompatibility. Then, their physical and chemical properties were studied and compared. Compared with phospholipid-based PEG, styrene-based PEG can reduce the π-π stacking between molecules and the quenching caused by molecular aggregation. It has more advantages in particle size and fluorescence performance and can be better used in biological imaging. In addition, the Nano-particles have good photo-thermal conversion efficiency; the temperature rises to 62.8°C after 980 nm irradiation for 6 min, which can be used as a potential near-infrared II photothermal therapeutic agent. In vivo imaging experiments confirmed that nanomaterials have fluorescence, photoacoustic dual-modal imaging and good biological safety. STATEMENT OF SIGNIFICANCE: In this work, we constructed D-A-D type dual donor fluorescent molecules using BBTD, CPDT and EDOT, and used amphiphilic polymers to improve their biocompatibility. Compared with DSPE NPs, PS-NPs can reduce intermolecular π-π stacking and increase quantum yield (QY = 0.98 %). Deep penetration and low biological toxicity make it have biomedical value and realize the integration of multi-functional collaborative imaging. This work can still be further improved and supplemented, and the molecular structure can be optimized to improve its application in biomedical imaging.

Conjugated-Polymer-Based Nanoparticles with Efficient NIR-II Fluorescent, Photoacoustic and Photothermal Performance.

Fluorescence imaging (FI) and photoacoustic imaging (PA) play important roles in the real-time assessment of cell-based therapies. However, the limitations of conventional organic fluorescence contrast agents and the narrow range of the emission wavelength in the first near-infrared (NIR-I) window (750-900 nm) hamper applications of fluorescence imaging in living subjects. Herein, we report the design and synthesis of a short-wave infrared FI contrast agent and PA contrast agent based on a conjugated polymer-poly{2,5-bis[(5-thiophen-2-yl)methylene]-3,6-bis(2-octyldodecyl)-2,5-dihydropyrazine}-and its use to construct multifunctional nanoparticles to simplify photothermal therapy.