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Herein, we designed a metal-coordinated carrier-free nanodrug (USFe3+LA NPs) with near sphere shape by co-assembling of UA, SRF, Fe3+, low molecular weight protamine (LMWP), and epithelial cell adhesion molecule (EpCAM) aptamer via a facile self-assembly method to improve the efficacy of chemotherapy monotherapy and achieve synergistic therapy. USFe3+LA NPs could inhibit tumor metastasis by inhibiting the intercellular adhesion molecule-1 (ICAM-1) and vascular endothelial growth factor (VEGF) expression. In addition, USFe3+LA NPs could enhance immune response and sensitize tumors to immune checkpoint inhibitors PD-L1 antibody. It was demonstrated that USFe3+LA NPs significantly inhibited tumor growth and metastasis, showing that this nano-delivery system synergistically enhanced its anti-tumor effect. These nanodrugs will provide a new strategy for combined chemotherapy, CDT, ferroptosis, and immunotherapy. [Display omitted] The heterogeneity of hepatocellular carcinoma (HCC) and the complexity of the tumor microenvironment (TME) pose challenges to efficient drug delivery and the antitumor efficacy of combined or synergistic therapies. Herein, a metal-coordinated carrier-free nanodrug (named as USFe3+ LA NPs) was developed for ferroptosis-mediated multimodal synergistic anti-HCC. Natural product ursolic acid (UA) was incorporated to enhance the sensitivity of tumor cells to sorafenib (SRF). Surface decoration of cell penetration peptide and epithelial cell adhesion molecule aptamer facilitated the uptake of USFe3+ LA NPs by HepG2 cells. Meanwhile, Fe3+ ions could react with intracellular hydrogen peroxide, generating toxic hydroxyl radical (·OH) for chemodynamical therapy (CDT) and amplified ferroptosis by cystine/glutamate antiporter system (System X c −), which promoted the consumption of glutathione (GSH) and inhibited the expression of glutathione peroxidase 4 (GPX4). Notably, these all-in-one nanodrugs could inhibit tumor metastasis and induced immunogenic cell death (ICD). Last but not least, the nanodrugs demonstrated favorable biocompatibility, augmenting the immune response against the programmed death-ligand 1 (PD-L1) by increasing cytotoxic T cell infiltration. In vivo studies revealed significant suppression of tumor growth and distant metastasis. Overall, our work introduced a novel strategy for applications of metal-coordinated co-assembled carrier-free nano-delivery system in HCC combination therapy, especially in the realms of cancer metastasis prevention and immunotherapy. [ABSTRACT FROM AUTHOR]

The introduced Cr 3 C 2 phase into FeNi alloys suppress the thermal coarsening of alloy nanoparticles and induce the charge rearrangement around interface, thereby increasing the number of active sites and intrinsic activity of per sites, respectively. [Display omitted] Exploring high active electrocatalysts for oxygen evolution reaction (OER) is of great significance for a sustainable hydrogen economy. The development of non-precious transition metals, with sufficient active sites and ample intrinsic activity, remains a challenge. Herein, a new type of FeNi–Cr 3 C 2 heterostructure anchored on carbon sheets (FeNi–Cr 3 C 2 @C) was reported, which can effectively catalyze OER with swift kinetics and outstanding intrinsic activity. The introduced Cr 3 C 2 phase not only serves as a support material but also effectively suppresses the thermal coarsening of FeNi alloy nanoparticle. The FeNi–Cr 3 C 2 @C displays a robust OER activity with a low overpotential of 283 mV at the current density of 10 mA cm−2, a high turnover frequency value of 1.69 s−1 at the overpotential of 300 mV (10 times higher than that of FeNi@C) and good stability in alkaline media. Density functional theory calculations (DFT) calculations show that Cr 3 C 2 can facilitate the generation of electron-rich region at the Ni site in FeNi alloys as an active site, exhibiting an optimized adsorption behavior toward oxygen intermediate species with regard to decreased thermodynamic energy barriers. Our work opens up a promising path to modulate the electrocatalytic active sites using inexpensive and durable Cr 3 C 2 for electrochemical catalytic reactions. [ABSTRACT FROM AUTHOR]

[Display omitted] • The structure of MnOx@aTiOy showed the increasing capacity being activated to maintain for a long-term cycling (829.5 mAh g−1 at 1 A g−1 after 2000 cycles). • The oxygen defects in the coating layer of modified TiO 2 boosted the pseudocapacitance effect for electrochemical performance. • The DFT calculations reveals the oxygen defects, the transformation of α-MnO 2 into Bixbyite-O Mn 2 O 3 , would decrease the kinetics of Li+ on lithium migrating paths and energy barriers. In this work, we developed Manganese and Titanium based oxide composites with oxygen defects (MnO x @aTiO y) via plasma processing as anodes of lithium ion batteries. By appropriately adjusting the defect concentration, the ion transport kinetics and electrical conductivity of the electrodes are significantly improved, showing stable capacity retention. Furthermore, the incremental capacity is further activated and long-term stable cycling performance is achieved, with a specific capacity of 829.5 mAh/g at 1 A/g after 2000 cycles. To scrutinize the lithium migration paths and energy barriers in MnO 2 and Mn 2 O 3 , the density functional theory (DFT) calculations is performed to explore the lithium migration paths and energy barriers. Although the transformation of MnO 2 into Mn 2 O 3 through oxygen defects was initially surmised to inhibit Li ions along their standard routes, our results indicate quite the contrary. In fact, the composite's lithium diffusion rate saw a substantial increase. This can be accredited to the pronounced enhancement of conductivity and ion transport efficiency in the amorphous and porous TiO y. [ABSTRACT FROM AUTHOR]