Porphyrins and their derivatives are abundant in nature and play an important role in plant photosynthesis. To mimic the photosynthetic reactions in plants, researchers have developed numerous porphyrin‐based nanomaterials to convert light into chemical energy. And the porous porphyrin‐based nanomaterials attract great interest in photocatalysis owing to their high surface areas, designable structure, and favorable photocatalytic behavior. In this review, we highlight the recent progress of porous porphyrin‐based nanomaterials for photocatalysis. We offer a structured description of the main classes of the porous porphyrin‐based nanomaterials which consist of metal‐organic frameworks (MOFs), covalent‐organic frameworks (COFs), amorphous porous organic polymers (APOPs), and hydrogen bonding‐organic frameworks (HOFs). Strategies to improve their photocatalytic behavior in respect of how to boost the photoexcited electron‐hole separation and increase the accessible active sites are mainly highlighted. At last, the prospects and challenges of porous porphyrin‐based nanomaterials for photocatalysis are also discussed.

Photothermal therapy (PTT) has attracted great attention due to its noninvasive and effective use against cancer. Various photothermal agents (PTAs) including organic and inorganic PTAs have been developed in the last decades. Organic PTAs based on small‐molecule dyes exhibit great potential for future clinical applications considering their good biocompatibility and easy chemical modification or functionalization. In this review, we discuss the recent progress of organic PTAs based on small‐molecule dyes for enhanced PTT. We summarize the strategies to improve the light penetration of PTAs, methods to enhance their photothermal conversion efficiency, how to optimize PTAs’ delivery into deep tumors, and how to resist photobleaching under repeated laser irradiation. We hope that this review can rouse the interest of researchers in the field of PTAs based on small‐molecule dyes and help them to fabricate next‐generation PTAs for noninvasive cancer therapy.

Reactive oxygen species (ROS)-induced cell apoptosis has emerged as an efficient strategy for cancer therapy. However, tumor hypoxia and insufficient amounts of endogenous hydrogen peroxide (H 2 O 2 ) in the tumor microenvironment are currently the main limitations of photodynamic therapy (PDT) and chemodynamic therapy (CDT). Moreover, the glutathione (GSH) scavenging effect on ROS further hinders the efficiency of ROS-mediated therapy. Here, a CaO 2 -based nanosystem (named as CF@CO@HC) with ROS self-amplification and GSH-depletion abilities was developed by a bottom-up approach. This hybrid nanoparticle consisted of a photosensitizer-doped calcium peroxide (CaO 2 ) core (CaO 2 -FM), a hybrid organosilica framework (Cu-ONS) incorporated with Fenton reagents (Cu 2+ ) and tetrasulfide groups, and a local hydrophobic cage (HC) shell. The photosensitizer was fluorescein derivative 4-FM with a thermally activated delayed fluorescence (TADF) property. The HC shell was built to protect the CaO 2 and the photosensitizer from being attacked by water. Upon being internalized into cancer cells, the nanosystem was decomposed through the reduction reactions of Cu 2+ and the tetrasulfide bond-doped silica shell by GSH, thus releasing Cu + for Cu + -mediated CDT. Meanwhile, the exposed CaO 2 -FM can react with H 2 O to liberate photosensitizer 4-FM and generate H 2 O 2 and O 2 to overcome barriers in CDT and PDT. Thus, our study provided an open-source and reduced-expenditure strategy via GSH depletion and ROS self-amplification behaviors for ROS generation and significantly achieved an improved synergistic PDT/CDT for cancers.

Recently, supramolecular coordination complexes (SCCs) based on photosensitizers as bridging ligands have attracted great attention in cancer therapy owing to their synergistic effect between photodynamic therapy (PDT) and chemotherapy. Herein, a highly emissive supramolecular platinum triangle BTZPy-Pt based on a novel type of photosensitizer BTZPy with thermally activated delayed fluorescence (TADF) was fabricated. The BTZPy and BTZPy-Pt exhibited strong luminescence emission in the visible range with high quantum yields (quantum yields (QYs) for BTZPy and BTZPy-Pt were about 78 and 62% in ethanol solutions, respectively). Additionally, BTZPy had been proved to be an excellent photosensitizer with superior 1 O 2 generation capability (the 1 O 2 generation quantum yield reached up to ca. 95%) for PDT. By the combination of the excellent phototoxicity of BTZPy and the antitumor activity of the Pt center, the platinum triangle BTZPy-Pt demonstrated a highly efficient anticancer performance toward HeLa cells (IC 50 : 0.5 μg mL −1 ). This study not only provides a blueprint to fabricate new types of photosensitizers but also paves a way to design novel SCCs for efficient PDT.

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