4T1-Luc cells (1 × 106) were injected subcutaneously into the left flank of female mice to evaluate the efficacy of PTT in combination with αPD-L1 on primary tumors. When the tumor volume reached about 100 mm3, the tumor-bearing mice were randomly divided into five groups (n = 6 per group): PBS as the control group; αPD-L1, BPQDs with NIR irradiation; BBPQDs with NIR irradiation; and BBPQDs with NIR irradiation and αPD-L1. Then, 100 μL of therapeutic agents at a dose of 10 mg/kg were injected into the mice via the tail vein on day 0. At 24 h after injection, the tumor region was irradiated by the NIR laser (808 nm, 1.0 W/cm2) four times every three days for 5 min. The αPD-L1 was intraperitoneally injected into mice at a dose of 10 mg/kg four times every three days for αPD-L1 monotherapy or combination therapy. The tumor volume (0.5 × length × width2) and weight of mice were recorded every two days during the treatment period. Bioluminescence imaging was acquired through intraperitoneal injection of D-luciferin (150 mg/kg body weight, PerkinElmer). The survival time of mice was recorded from the day of tumor inoculation. The survival curve was plotted by Kaplan–Meier survival analysis. After treatment, tumor tissues and major organs of mice were taken, dehydrated, embedded, and sectioned for 3 μm. The sections were then stained with hematoxylin and eosin (H&E) and Ki-67 for histological analysis. The apoptosis of tumor cells was detected by TUNEL assays. The whole blood was harvested and then analyzed by a blood biochemistry analyzer (MNCHIP, China) and auto hematology analyzer (MC-6200VET) through the end of the experiments.

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