Palladium-based catalysts are among the most efficient for H2 production via HCOOH (FA) dehydrogenation at near-ambient pressure and temperature. Herein, we show that [PdO/Pd0/TiO2] nanocatalysts bearing a tetragonal PdO nanophase can be optimized for enhanced FA dehydrogenation via engineering of the [PdO:Pd0] ratio on the TiO2 support. We have developed a sequential-deposition flame spray pyrolysis (SD-FSP) technique for deposition of Pd on TiO2 at a high [PdO:Pd0] ratio up to 75%. In addition, we have synthesized low-[PdO:Pd0]-ratio catalysts using an oxygen-lean FSP protocol. The SD-FSP-made [PdO/Pd0/TiO2] nanocatalysts with a high [PdO:Pd0] ratio >70% can achieve a high H2 gas production rate of 534 mmol/g of Pd/min that supersedes by >300% the efficiency of [Pd0/TiO2] nanocatalysts with low PdO content. The thermodynamic basis of the role of [PdO:Pd0] was investigated by an Arrhenius study, which reveals that the activation energy barrier E a is decreasing significantly, i.e., up to 50%, upon an increase of the [PdO:Pd0] ratio. A reduction of surficial PdO toward Pd0, by in situ generated H2, exerts a strong inhibitory effect on the catalyst. Overall, the present data indicate that both [i] maximization of the [PdO:Pd0] ratio and [ii] minimization of PdO reduction during H2 production are key prerequisites for enhanced FA dehydrogenation by TiO2-supported/Pd catalysts.

In the present study, the nanoindentation creep behaviour of untreated and ultraviolet (UV) treated polydimethylsiloxane (PDMS) samples was investigated, accompanied with adhesion analysis and Fourier transform infrared spectroscopy (FTIR) characterisation. Different hold times, in the range of 5-2000 s (at 10 mN of applied load), were incorporated into each nanoindentation measurement. The increase in hold time results in an increase in change in depth of the indenter in both samples. The error in hardness/modulus due to creep can be neglected for hold times of y400 s or more for untreated PDMS and y200 s or more for UV treated PDMS. The FTIR obtained data revealed surface deterioration, while the bulk nanomechanical properties were almost identical. A decrease in adhesive energy in the case of UV treated PDMS was observed, indicating that adhesive forces play a significant role at the nanometre scale in the indentation tests (real contact area determination during nanoindentation measurements).

The progress in nanomedicine (NM) using nanoparticles (NPs) is mainly based on drug carriers for the delivery of classical chemotherapeutics.A sl ow NM delivery rates limit therapeutic efficacy,a ne ntirely different approach was investigated. Ahomologous series of engineered CuO NPs was designed for dual purposes (carrier and drug) with adirect chemical composition-biological functionality relationship. Model-based dissolution kinetics of CuO NPs in the cellular interior at post-exposure conditions were controlled through Fe-doping for intra/extra cellular Cu 2+ and biological outcome. Through controlled ion release and reactions taking place in the cellular interior,tumors could be treated selectively,invitro and in vivo.L ocally administered NPs enabled tumor cells apoptosis and stimulated systemic anti-cancer immune responses.W ec learly show therapeutic effects without tumor cells relapse post-treatment with 6% Fe-doped CuO NPs combined with myeloid-derived suppressor cell silencing.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Cholesterol‐dependent cytolysins (CDCs) are essential virulence factors for many human pathogens like Streptococcus pneumoniae (pneumolysin, PLY), Streptococcus pyogenes (streptolysin O, SLO), and Listeria monocytogenes (Listeriolysin, LLO) and induce cytolysis and inflammation. Recently, we identified that pneumococcal PLY interacts with the mannose receptor (MRC‐1) on specific immune cells thereby evoking an anti‐inflammatory response at sublytic doses. Here, we identified the interaction sites between MRC‐1 and CDCs using computational docking. We designed peptides from the CTLD4 domain of MRC‐1 that binds to PLY, SLO, and LLO, respectively. In vitro, the peptides blocked CDC‐induced cytolysis and inflammatory cytokine production by human macrophages. Also, they reduced PLY‐induced damage of the epithelial barrier integrity as well as blocked bacterial invasion into the epithelium in a 3D lung tissue model. Pre‐treatment of human DCs with peptides blocked bacterial uptake via MRC‐1 and reduced intracellular bacterial survival by targeting bacteria to autophagosomes. In order to use the peptides for treatment in vivo, we developed calcium phosphate nanoparticles (CaP NPs) as peptide nanocarriers for intranasal delivery of peptides and enhanced bioactivity. Co‐administration of peptide‐loaded CaP NPs during infection improved survival and bacterial clearance in both zebrafish and mice models of pneumococcal infection. We suggest that MRC‐1 peptides can be employed as adjunctive therapeutics with antibiotics to treat bacterial infections by countering the action of CDCs.