Porphyrins and their derivatives have excellent photophysical and electrochemical properties, which have attracted great interest in the fields of catalysis, biosensing, gas storage, solar cells, biomedicine, etc. However, the inherent limitations, such as self-quenching, weak absorption at biological spectral windows and poor photochemical stability, severely hinder their applications in biomedicine, especially in the field of photodynamic therapy (PDT). In recent years, metal–organic frameworks (MOFs) have received increasing attention as a class of hybrid porous coordination polymers assembled from metal ions/secondary building units (SBUs) and organic linkers. By introducing porphyrins into MOFs via the encapsulation in the pores as well as grafting on the surface to form porphyrin@MOFs or using porphyrins as organic linkers to construct porphyrin-MOFs, not only the unique properties of porphyrins and MOFs are combined, but also the limitations of porphyrins are overcome and their applications are facilitated in the biomedicine field. This article reviews important synthetic strategies of forming porphyrin-based MOFs (including porphyrin@MOFs and porphyrin-MOFs), which focuses on the recent research achievements and progress in PDT and tumor therapy fields. Furthermore, by carefully designing the composition of MOFs (such as the modification of organic linkers), MOFs could respond to the tumor microenvironment for on-demand treatment. In addition, some other strategies, including chemotherapy, photothermal therapy (PTT) and the latest cancer immunotherapy, are also combined in the review. Finally, the challenges and prospects in biomedical applications of this class of emerging materials are discussed.

An in situ coupling strategy to prepare Co₉S₈/S and N dual-doped graphene composite (Co₉S₈/NSG) has been proposed. The key point of this strategy is the function-oriented design of organic compounds. Herein, cobalt porphyrin derivatives with sulfo groups are employed as not only the coupling agents to form and anchor Co₉S₈ on the graphene in situ, but also the heteroatom-doped agent to generate S and N dual-doped graphene. The tight coupling of multiple active sites endows the composite materials with fast electrochemical kinetics and excellent stability for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The obtained electrocatalyst exhibits better activity parameter (ΔE = 0.82 V) and smaller Tafel slope (47.7 mV dec⁻¹ for ORR and 69.2 mV dec⁻¹ for OER) than commercially available Pt/C and RuO₂. Most importantly, as electrocatalyst for rechargeable Zn–air battery, Co₉S₈/NSG displays low charge–discharge voltage gap and outstanding long-term cycle stability over 138 h compared to Pt/C–RuO₂. To further broaden its application scope, a homemade all-solid-state Zn–air battery is also prepared, which displays good charge–discharge performance and cycle performance. The function-oriented design of N₄-metallomacrocycle derivatives might open new avenues to strategic construction of high-performance and long-life multifunctional electrocatalysts for wider electrochemical energy applications.

Thermo-, pH- and glucose-responsive polymeric nanoparticles are of great interest in developing a self-regulated drug delivery system. The novel core-shell nanoparticles were synthesized by self-assembly of a phenylboronic acid-based block copolymer poly-(N-isopropylacrylamide)-block-poly(3-acrylamidophenylboronic acid) (PNIPAM₁₃₆-b-PAPBA₁₆) and a fluorescent complex glucosamine-poly(N-isopropylacrylamide)/Eu(III) (GA-PNIPAM)/Eu(III) based on the cross-linking between PBA- and GA-containing blocks in this work. The nanoparticles can be tuned via thermo-induced collapse or glucose-induced swelling at appropriate pH and temperatures; they had an average kinetic radius was about 80nm, and which showed excellent fluorescence. MTT assays revealed the nanocarriers had no significant cytotoxic response of the micelle when it was observed in the cell line over the concentration range from 0.1 to 1000 μg/ml at any exposure times. GRAPHICAL ABSTRACT