Suffering from the laborious synthesis and undesirable tumor microenvironment response,t he exploitation of novel NIR-II absorbing organic photothermal agents is of importance to promote phototherapeutic efficacy.Herein, two kinds of charge-transfer complex nanoparticles (TMB-F4TCNQ and TMB-TCNQ) are prepared by supramolecular assembly.Because of the larger energy gap between donor and acceptor,T MB-F4TCNQ presents higher charge-transfer degree (72 %) than that of TMB-TCNQ (48 %) in nanoaggregates.T herefore,T MB-F4TCNQ exhibits stronger NIR-II absorption ability with am ass extinction coefficient of 15.4 Lg À1 cm À1 at 1300 nm and excellent photothermal effect. Impressively,the specific cysteine response can make the TMB-F4TCNQ effectively inhibit the intracellular biosynthesis of GSH, leading to redoxd syhomeostasis and ROS-mediated ferroptosis.T MB-F4TCNQ can serve as ac ontrast agent for NIR-II photoacoustic imaging to guide precise and efficient photothermal therapyinv ivo.

A mitochondria-targeting nanosystem, BP@PDA–Ce6&TPP NSs, has been constructed, and exhibit excellent performance in imaging-guided synergistic photothermal and photodynamic cancer therapy.

Scheme 1. Schematic representation of the supramolecular self-encapsulation strategy for wide-bandgap LCPs. A) Typical molecular model of our supramolecular self-encapsulated LCPs (SMART: Synergistically Molecular Attractor-Repulsor Theory). B) Chemical structures of the model polymer, PHDPF-Cz, together with the controlled polyfluorenes. C) Computer-generated model of PHDPF-Cz: i) axial and ii) lateral views. Schematic diagram illustrating the ideal molecular packing model for a PHDPF-Cz self-assembled superstructure, where the pendent Cz groups self-assemble into a sheath and act as an encapsulated layer to isolate the chain and inhibit the interchain interaction between π-π backbones, similar to previous studies. [47,52,53] The blue rings signify the backbone chain. The red loops indicate the Cz-threaded layers. The yellow arrow represents the 2D charge transport channel. The orange-yellow arrow denotes the penetration path for various gases, which is disrupted by the Cz-threaded layer.

Insufficient oxygen supply (hypoxia), short half-life (<40 ns) of singlet oxygen, and up-regulation of the heat shock protein expression in solid tumors impede the photodynamic and photothermal therapeutic efficacy. Herein, a near-infrared carrier-free nanoconjugate directacting antiviral (DAA) with synergistic antivascular activity and pH-responsive photodynamic/photothermal behavior was designed and synthesized to improve cancer treatment efficacy. Obtained by the self-assembly approach, the biocompatible DAA nanoparticles (NPs) displayed amplifying pH-responsive photodynamic/photothermal performance in an acidic tumor microenvironment due to the protonation of diethylaminophenyl units. Most important, the antivascular agent 5,6-dimethylxanthenone-4-acetic acid, targeting the vascular endothelial growth factor, can be smartly released from the pro-drug DAA via ester bond hydrolysis at the subacid endocytosis organelles in the endothelial cells, which can effectively destroy the vascular region to prevent tumor proliferation and metastasis. Hence, DAA NPs can specifically target vascular endothelial cells and tumorous lysosomes with desired cellular damage properties in vitro. Therefore, the tumors can be ablated completely with no recurrence and side effects in vivo, which implies that DAA NPs provide a promising approach for cancer treatment via synergistic antivascular activity and photodynamic/photothermal therapy.