Supramolecular prodrug-like nanotheranostics with dynamic and activatable nature for synergistic photothermal immunotherapy of metastatic cancer.

Synergistic photothermal immunotherapy has attracted widespread attention due to the mutually reinforcing therapeutic effects on primary and metastatic tumors. However, the lack of clinical approval nanomedicines for spatial, temporal, and dosage control of drug co-administration underscores the challenges facing this field. Here, a photothermal agent (Cy7-TCF) and an immune checkpoint blocker (NLG919) are conjugated via disulfide bond to construct a tumor-specific small molecule prodrug (Cy7-TCF-SS-NLG), which self-assembles into prodrug-like nano-assemblies (PNAs) that are self-delivering and self-formulating. In tumor cells, over-produced GSH cleaves disulfide bonds to release Cy7-TCF-OH, which re-assembles into nanoparticles to enhance photothermal conversion while generate reactive oxygen species (ROSs) upon laser irradiation, and then binds to endogenous albumin to activate near-infrared fluorescence, enabling multimodal imaging-guided phototherapy for primary tumor ablation and subsequent release of tumor-associated antigens (TAAs). These TAAs, in combination with the co-released NLG919, effectively activated effector T cells and suppressed Tregs, thereby boosting antitumor immunity to prevent tumor metastasis. This work provides a simple yet effective strategy that integrates the supramolecular dynamics and reversibility with stimuli-responsive covalent bonding to design a simple small molecule with synergistic multimodal imaging-guided phototherapy and immunotherapy cascades for cancer treatment with high clinical value.

Hierarchical Co2 P/CoS2 @C@MoS2 Composites with Hollow Cavity and Multiple Phases Toward Wideband Electromagnetic Wave Absorption.

The synergistic effect of hollow cavities and multiple hetero-interfaces displays huge advantages in achieving lightweight and high-efficient electromagnetic wave absorption, but still confronts huge challenges. Herein, hierarchical Co2 P/CoS2 @C@MoS2 composites via the self-sacrificed strategy and a subsequent hydrothermal method have been successfully synthesized. Specifically, ZIF-67 cores first act as the structural template to form core-shell ZIF-67@poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol) (ZIF-67@PZS) composites, which are converted into hollow Co2 P@C shells with micro-mesoporous characteristics because of the gradient structural stabilities and preferred coordination ability. The deposition of hierarchical MoS2 results in phase transition (Co2 P→Co2 P/CoS2 ), yielding the formation of hierarchical Co2 P/CoS2 @C@MoS2 composites with hollow cavities and multiple hetero-interfaces. Benefiting from the cooperative advantages of hollow structure, extra N,P,S-doped sources, lattice defects/vacancies, diverse incoherent interfaces, and hierarchical configurations, the composites deliver superior electromagnetic wave capability (-56.6 dB) and wideband absorption bandwidth (8.96 GHz) with 20 wt.% filler loading. This study provides a reliable and facile strategy for the precise construction of superior electromagnetic wave absorbents with efficient absorption attenuation.