A diketopyrrolopyrrole-based small molecule with an extended conjugated skeleton and J-aggregation behavior for 808 nm laser triggered phototheranostics.

The development of phototheranostic agents, specifically those based on organic small molecules (OSMs) with long wavelength excitation/emission, is an attractive but challenging project. In this contribution, we designed and synthesized a novel conjugate small molecule with a linear structure, named DPP-OPIC. Water-soluble nanoparticle DPP-OPIC NPs were fabricated. They exhibited strong absorption in the region of 600-1000 nm, which was due to the extended conjugate length of the molecular skeleton and J-aggregation behavior. Under 808 nm laser excitation, DPP-OPIC NPs were capable of producing outstanding near-infrared-II (NIR-II, 900-1700 nm) fluorescence. The photoluminescence quantum yield was determined as 0.58%, which enabled high-resolution in vivo tumor imaging. Additionally, a notable photothermal effect with a high photothermal conversion efficiency (41.5%) was achieved by the irradiation of DPP-OPIC NPs. Hence, DPP-OPIC NPs can be used as superior phototheranostic agents, providing valuable contributions to NIR-II fluorescence imaging and photothermal therapy.

High-Performance Hybrid Phototheranostics for NIR-IIb Fluorescence Imaging and NIR-II-Excitable Photothermal Therapy.

Photothermal therapy operated in the second near-infrared (NIR-II, 1000-1700 nm) window and fluorescence imaging in the NIR-IIb (1500-1700 nm) region have become the most promising techniques in phototheranostics. Their combination enables simultaneous high-resolution optical imaging and deep-penetrating phototherapy, which is essential for high-performance phototheranostics. Herein, carboxyl-functionalized small organic photothermal molecules (Se-TC) and multi-layered NIR-IIb emissive rare-earth-doped nanoparticles (NaYF4:Yb,Er,Ce@NaYF4:Yb,Nd@NaYF4, RENP) were rationally designed and successfully synthesized. Then, high-performance hybrid phototheranostic nanoagents (Se-TC@RENP@F) were easily constructed through the coordination between Se-TC and RENP and followed by subsequent F127 encapsulation. The carboxyl groups of Se-TC can offer strong binding affinity towards rare-earth-doped nanoparticles, which help improving the stability of Se-TC@RENP@F. The multilayered structure of RENP largely enhance the NIR-IIb emission under 808 nm excitation. The obtained Se-TC@RENP@F exhibited high 1064 nm absorption (extinction coefficient: 24.7 L g-1 cm-1), large photothermal conversion efficiency (PCE, 36.9%), good NIR-IIb emission (peak: 1545 nm), as well as great photostability. Upon 1064 nm laser irradiation, high hyperthermia can be achieved to kill tumor cells efficiently. In addition, based on the excellent NIR-IIb emission of Se-TC@RENP@F, in vivo angiography and tumor detection can be realized. This work provides a distinguished paradigm for NIR-IIb-imaging-guided NIR-II photothermal therapy and establishes an artful strategy for high-performance phototheranostics.

Photoactive oligomer with D-D'-A-D'-D''-D'-A-D'-D scaffold for high-efficiency NIR-II phototheranostics.

A D-D'-A-D'-D''-D'-A-D'-D type photoactive oligomer (O-BT) based nanoparticles (NPs) were prepared for biomedical application. The O-BT NPs possessed a high extinction coefficient, excellent hyperthermia generation ability, satisfactory NIR-II fluorescence emission, and good batch-to-batch reproducibility, and could be used as high-efficiency phototheranostics for photothermal therapy and NIR-II fluorescence imaging.

pH-responsive supramolecular vesicles based on water-soluble pillar[6]arene and ferrocene derivative for drug delivery.

The drug delivery system based on supramolecular vesicles that were self-assembled by a novel host-guest inclusion complex between a water-soluble pillar[6]arene (WP6) and hydrophobic ferrocene derivative in water has been developed. The inclusion complexation between WP6 and ferrocene derivative in water was studied by (1)H NMR, UV-vis, and fluorescence spectroscopy, which showed a high binding constant of (1.27 ± 0.42) × 10(5) M(-1) with 1:1 binding stoichiometry. This resulting inclusion complex could self-assemble into supramolecular vesicles that displayed a significant pH-responsive behavior in aqueous solution, which were investigated by fluorescent probe technique, dynamic laser scattering, and transmission electron microscopy. Furthermore, the drug loading and in vitro drug release studies demonstrated that these supramolecular vesicles were able to encapsulate mitoxantrone (MTZ) to achieve MTZ-loaded vesicles, which particularly showed rapid MTZ release at low-pH environment. More importantly, the cellular uptake of these pH-responsive MTZ-loaded vesicles by cancer cells was observed by living cell imaging techniques, and their cytotoxicity assay indicated that unloaded vesicles had low toxicity to normal cells, which could dramatically reduce the toxicity of MTZ upon loading of MTZ. Meanwhile, MTZ-loaded vesicles exhibited comparable anticancer activity in vitro as free MTZ to cancer cells under examined conditions. This study suggests that such supramolecular vesicles have great potential as controlled drug delivery systems.

Formation of polypseudorotaxane networks by cross-linking the quadruple hydrogen bonded linear supramolecular polymers via bisparaquat molecules.

The creation of novel crown ether-paraquat polypseudorotaxane networks, constructed by bisparaquat monomers threading into the cavity of the crown ether units of linear supramolecular polymers that are formed based on the quadruple hydrogen bonded unit ureidopyrimidinone (Upy) in the concentrated solution, is described.

New linear supramolecular polymers that are driven by the combination of quadruple hydrogen bonding and crown ether-paraquat recognition.

Novel linear supramolecular polymers, based on the combination of two classical binding interactions: the quadruple hydrogen bonding ureidopyrimidinone units and crown ether-paraquat host-guest recognition motifs, have been constructed from two heteroditopic monomers.