The rational integration of chemotherapy and hydroxyl radical (·OH)‐mediated chemodynamic therapy (CDT) holds great potential for cancer treatment. Herein, a smart biocompatible nanocatalyst based on porous core–shell cuprous oxide nanocrystals (Cu2O‐PEG (polyethylene glycol) NCs) is reported for acid‐triggered chemo/chemodynamic synergistic therapy. The in situ formed high density of hydrophilic PEG outside greatly improves the stability and compatibility of NCs. The porosity of Cu2O‐PEG NCs shows the admirable capacity of doxorubicin (DOX) loading (DOX@Cu2O‐PEG NCs) and delivery. Excitingly, Cu (Cu+/2+) and DOX can be controllably released from DOX@Cu2O‐PEG NCs in a pH‐responsive approach. The released Cu+ exerts Fenton‐like catalytic activity to generate toxic ·OH from intracellular overexpressed hydrogen peroxide (H2O2) for CDT via reactive oxygen species (ROS)‐involved oxidative damage. Exactly, DOX can not only induce cell death for chemotherapy but also enhance CDT by self‐supplying endogenous H2O2. After the intravenous injection, Cu2O‐PEG NCs can effectively accumulate in tumor region via passive targeting improved by external high‐density PEG shell. Additionally, the effect of boosted CDT combined with chemotherapy presents excellent in vivo antitumor ability without causing distinct systemic toxicity. It is believed that this smart nanocatalyst responding to the acidity provides a novel paradigm for site‐specific cancer synergetic therapy.

Photodynamic therapy (PDT) as a noninvasive therapy mode has attracted considerable attention in the field of oncotherapy. However, the PDT efficacy is restricted either by the tumor hypoxia environment or the inherent properties of photosensitizers (PSs) including bad water solution, photobleaching, and easy aggregation. Herein, we designed and synthesized a new two-dimensional (2D) metal−organic framework, Sm-tetrakis(4-carboxyphenyl)porphyrin (TCPP) nanosheets, by assembling transition metal ions (Sm 3+ ) and PSs (TCPP), on which the catalase (CAT)-mimicking platinum nanozymes were then in situ grown for sufficient oxygen supply during PDT. The prepared Sm-TCPP with nanoplate morphology (∼100 nm in diameter) and ultrathin thickness (<10 nm) showed significantly enhanced 1 O 2 generation capacity due to the improved physicochemical properties and the enhanced intersystem crossing from heavy Sm nodes. More importantly, the CAT-mimicking Pt nanozyme on the Sm-TCPP nanosheets could effectively convert over-expressed H 2 O 2 in the tumor microenvironment into O 2 to relieve tumor hypoxia. Further, the triphenylphosphine (TPP) molecule was introduced to Sm-TCPP-Pt to develop a mitochondrion-targeting and O 2 self-supply PDT system. The in vitro and in vivo experimental results based on the MCF-7 breast cancer model revealed that Sm-TCPP-Pt/TPP could relieve tumor hypoxia and the generated reactive oxygen species nearby intracellular mitochondria significantly induced cell apoptosis. This study offers an engineering strategy to integrate 2D PS-based metal−organic frameworks and nanozymes into a nanoplatform to surmount the pitfalls of traditional PDT.

Herein, a biocompatible 2D metal-organic frameworks (Cu-TCPP(Fe)) based on TCPP(M) (TCPP = tetrakis (4-carboxyphenyl) porphyrin, M = Fe) and copper ion were synthesized as a novel drug carrier. Sequentially, the cisplatin was loaded on the merge of carboxyl-rich Cu-TCPP(Fe) through forming favorable carboxyl-drug interactions. The prepared Pt/Cu-TCPP(Fe) showed highly enhanced cytotoxicity than that of free cisplatin in human pulmonary carcinoma A549 cells, whereas inverse inhibitory effects were observed in human normal BEAS-2B cells. Further, the mechanism of action about the desirable results was also elaborated. Our study highlighted the potential synergies between the nanocarrier and the anticancer drugs.

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Owing to the critical roles it plays for both structure and functionality, hydrogen bonding has high hopes for the orientated applications in hydrogen-bonded organic frameworks (HOFs). Here in this work, a hydrogenbonding strategy is performed for adjusting the structure and functionality of a heme-like ligand meso-tetra(carboxy-phenyl)-porphyrin (TCPP) with co-former 1,3-di(4-pyridyl) propane (1,3-DPP). A 3D dynamic HOF TCPP-1,3-DPP, with permanent porosity is obtained. For this HOF, the two components form novel robust 1D porous stripes, with the 1,3-DPP molecules acting as the lining for the pores that are confined within the region between adjacent carboxyphenyl moieties of TCPP. This confinement has tuned the affinities of TCPP from hydrophobic into hydrophilic. Interestingly, the 1D stripes are further stacked by weak π…π interactions into a 3D framework, the latter is highly dynamic with 1D stripes sliding back and forth, upon pressurized and water adsorption in the solid-state under ambient conditions, respectively. The activated TCPP-1,3-DPP has a Brunauer-Emmett-Teller surface area of 258 m 2 g −1 , and shows a maximum adsorption capacity about 9.8% for water during the adsorption-desorption cycles, demonstrating a promising candidate for the real-world application in effective dehydration of industrial gases under ambient conditions.