Xiang Wang,Hengrui Li,Le Wang,Yihan Ma,Miao Qin,Ruonan Sun,Jing Hu
Tumor hypoxia is a major barrier to oxygen-dependent photodynamic therapy (PDT), markedly limiting its therapeutic efficacy in hepatocellular carcinoma (HCC). Herein, a self‑oxygenating and redox-amplifying metal-organic framework (MOF) nanoplatform is constructed by co-loading sorafenib (Sor) and plumbagin (PLB) into a surface galactose functionalized Mn-porphyrinic PCN-224(Mn) (PM) framework to afford SorPLB@Gal-PM for asialoglycoprotein receptor (ASGPR)-mediated HCC targeting. The Mn-porphyrin centers endow SorPLB@Gal-PM with catalase-like activity, enabling in situ decomposition of endogenous H 2 O 2 to generate O 2 and thereby sustaining 1 O 2 -based PDT under irradiation. Meanwhile, Sor/PLB co-delivery, together with PLB-mediated GPX4 suppression, promotes oxidative stress amplification. In hypoxic liver cancer stem cell-like C5WN1 cells, SorPLB@Gal-PM elicits markedly enhanced intracellular ROS upon irradiation, showing approximately 3.4-fold and 2.9-fold higher DCFH-DA signals than SorPLB@Gal-PCN-224 and PM, respectively, accompanied by downregulation of hypoxia-inducible factor-1α (HIF-1α) and glutathione peroxidase 4 (GPX4). In a C5WN1 tumor-bearing nude mouse model, SorPLB@Gal-PM combined with irradiation achieves the most potent tumor suppression with a tumor inhibition rate of 83.70% ± 4.12%. Collectively, SorPLB@Gal-PM provides a hypoxia-adaptive nanoplatform integrating Mn-assisted self‑oxygenation and redox-amplified chemo-PDT for effective HCC therapy.
Herein, a novel dual-mode probe for organophosphorus pesticides (OPs) colorimetric and photothermal detection was developed based on manganese modified porphyrin metal–organic framework (PCN-224-Mn). PCN-224-Mn had excellent oxidase-like activity and oxidized colorless 3,3,5,5-tetramethylbenzidine (TMB) to blue–green oxidation state TMB (oxTMB), which exhibited high temperature under near-infrared irradiation. l -ascorbate-2-phosphate was hydrolyzed by acid phosphatase to produce ascorbic acid, which weakened colorimetric and photothermal signals by impacting oxTMB generation. The presence of OPs blocked the production of ascorbic acid by irreversibly inhibiting the activity of acid phosphatase, causing the restoration of chromogenic reaction and the increase of temperature. Under the optimal conditions, the probe showed a good linear response to OPs in the concentration range of 5 ∼ 10000 ng/mL, using glyphosate as the analog. The detection limits of glyphosate in colorimetric mode and photothermal mode were 1.47 ng/mL and 2.00 ng/mL, respectively. The probe was successfully used for sensitive identification of OPs residues in tea, brown rice, and wheat flour. This work proposes a simple and reliable colorimetric/photothermal platform for OPs identification, which overcomes the problem that single-mode detection probes are susceptible to external factors, and has broad application potential in the field of food safety.
危险品化学品经营许可证（带存储）