New Insights into Gas-Solid Interactions of NO2/MoS2 Monolayers: a Comparative Study with MoSe2 and MoTe2 Monolayers.

Understanding the microscopic electronic structure determines the macroscopic properties of the materials. Sufficient sampling has the same foundational importance in understanding the interactions. The NO2/MoS2 interaction is well known, but there are still many inconsistencies in the basic data, and the source of the NO2 direct dissociation activity has not been revealed. Based on a large-scale sampling density functional theory (DFT) study, the optimal adsorption of the NO2/MoS2 monolayer system is determined. The impurity state on the top of the valence band of the S-vacancy monolayer (MoS2-VS) was determined by cross-analysis of the band structure and density of states, which has been neglected for a long time. This provides a reasonable explanation for the direct dissociation of NO2 on the MoX2 monolayers. Further atomic structure analysis reveals that the impurity state originates from the not-fully occupied valence orbitals. This also corroborates the fact that the Mo material has dissociation activity, while the W material does not. There is no impurity state on the top of the valence band of the X-vacancy WS2 and WSe2 monolayers. Interestingly, NO2 dissociation did not occur in the MoTe2-VTe monolayer. This may be related to the 6s inert electron pair effect of the Te atom. The double-oriented adsorption behavior of NO2is also revealed. In contrast to the MoSe2 and MoTe2 monolayers, NO2-oriented adsorption on the MoS2 perfect monolayer deviates obviously, which is speculated to be related to space limitation and larger electronegativity of the S atom. The oriented adsorption ability of the MoX2 monolayers followed the order MoTe2 (64.4%) > MoSe2 (44.8%) > MoS2 (42.7%), according to the directed proportion. Renewed insights into the adsorption basic data and the understanding of the electronic structure of NO2/MoX2 (X = S, Se, Te) monolayer systems provide a basic understanding of the gas-surface interactions and various future surface-related advanced applications.

Human Serum Albumin Mediated Controllable Synthesis of Defect-Rich Copper Hydroxide Nanowire for Cuproptosis-Based Anti-Tumor Therapy.

Cuproptosis, as a newly identified form of programmed cell death, shows great promise in cancer treatment. Efficient Cu+ delivery while avoiding systemic toxicity and elimination of the resistance from over-expressed intracellular copper chelator glutathione (GSH) are critical for cuproptosis. Herein, this work innovatively constructs a biocompatible and defect-rich copper hydroxide nanowire (HCu nanowire) through a human serum albumin (HSA) mediated biomineralization method. This work finds that the morphology and size of HCu nanowires can be controlled adjusted by the feed ratio of HSA and Cu2+. Remarkably, except for outstanding biocompatibility, HSA coordination endows HCu nanowires abundant oxygen vacancies (OVs), and the defect-rich HCu nanowire possesses excellent GSH consumption efficiency. Density functional theory studies indicate that OVs change GSH absorption energy on defective HCu nanowires. In cancer cells, HCu nanowires deplete GSH and simultaneously produce sufficient free Cu+ for enhanced cuproptosis. Meanwhile, Cu+ can catalyze endogenous H2O2 into hydroxyl radicals (·OH) via a Fenton-like reaction. Thus, synergetic cuproptosis and ROS mediated apoptosis against tumor are achieved. The experimental results show that HCu nanowires have a better performance in both antitumor efficiency and safety compared with chemotherapeutic drug Dox at the same dose, demonstrating its great potential in clinical applications.