A NIR‐II Photoactivatable “ROS Bomb” with High‐Density Cu2O‐Supported MoS2 Nanoflowers for Anticancer Therapy

Abstract The fast conversion of hydrogen peroxide (H2O2) into reactive oxygen species (ROS) at tumor sites is a promising anticancer strategy by manipulating nanomedicines with near‐infrared light in the second region (NIR‐II). However, this strategy is greatly compromised by the powerful antioxidant capacity of tumors and the limited ROS generation rate of nanomedicines. This dilemma mainly stems from the lack of an effective synthesis method to support high‐density copper‐based nanocatalysts on the surface of photothermal nanomaterials. Herein, a multifunctional nanoplatform (MCPQZ) with high–density cuprous (Cu2O) supported molybdenum disulfide (MoS2) nanoflowers (MC NFs) is developed for the efficient killing of tumors via a potent ROS storm by an innovative method. Under NIR‐II light irradiation, the ROS intensity and maximum reaction velocity (V max) produced by MC NFs are 21.6 and 33.8 times that of the non–irradiation group in vitro, which is much higher than most current nanomedicines. Moreover, the strong ROS storm in cancer cells is efficiently formed by MCPQZ (increased by 27.8 times compared to the control), thanks to the fact that MCPQZ effectively pre–weakens the multiple antioxidant systems of cancer cells. This work provides a novel insight to solve the bottleneck of ROS‐based cancer therapy.


Figure S3 .
Figure S3.(A) The content ratio of Cu and Mo elements of MC NFs prepared at different feed ratios.Data are presented as mean±S.D. (n = 3).

Figure S4 .
Figure S4.(A) XPS spectrum of MC NFs and the high-resolution of S 2p (B) and O1s (C) XPS

Figure S7 .
Figure S7.(A) 1 H NMR spectra of GSH.(B) 1 H NMR spectra of and commercial GSSG and the reduction product.

Figure S8 .
Figure S8.Heating and cooling curves (red and blue line) and the time constant (τs) for the heat transfer from the system were determined by applying the linear time data from the cooling period (black line) of (A) MoS2, MC NFs prepared under feed ratio at (B) 10:1, (C) 10:2, (D) 10:3, (E) 10:4, and (F) 10:5.

Figure S9 .
Figure S9.PTC efficiency of MC NFs prepared by different feed ratios.

Figure S10 .
Figure S10.(A)•OH generation of MC NFs prepared with different feed ratios under 1064 nm laser irradiation or not.(B) The ratios of fluorescence intensity at 430 nm of MC NFs prepared with different feed ratios after and before 1064 nm laser irradiation (F+ NIR-Ⅱ/F-NIR-Ⅱ).

Figure S11 .
Figure S11.(A) UV-Vis absorption of MC NFs with different concentrations.(B) Standard absorption curves of MC NFs with different concentrations at 1064 nm.

Figure S12 .
Figure S12.Infrared thermal imaging of MC NFs irradiated with 1064 nm laser (1 W/cm 2 ) for different times.

Figure S13 .
Figure S13.(A) The generation of •OH and (B) corresponding quantitative analysis of PBS, MoS2,

Figure
Figure S15.(A) TEM image and (B) size distribution of MCPQZ.(C) Zeta potential of MC NFs, MCP and MCPQZ.Data are presented as mean±S.D. (n=3).

Figure S18 .
Figure S18.Release of QE and Znpp IX form MCPQZ. (A) QE release curves under different pH.(B) Standard concentration working curve of QE solutions.(C) Znpp IX release curves under different pH.(D) Standard concentration working curve of Znpp IX solutions.

Figure S24 .
Figure S24.The biodistribution of MCPQZ in 4T1 tumor-bearing mice at different time points.The data are presented as mean ± S.D. (n=3).

Figure S26 .
Figure S26.Experimental procedure and H&E staining of tumor and its surface skin tissue of 4T1-tumor bearing mice intravenous injected with PBS or MCPQZ (equivalent to 10 mg MoS2 or 8.596 mg QE or 0.269 mg Znpp IX kg -1 mice) irradiated with 1064 nm laser (1 W cm -2 , 5 min).