Abstract The therapeutic effectiveness of anticancer drugs, including nanomedicines, can be enhanced with active receptor‐targeting strategies. Epidermal growth factor receptor (EGFR) is an important cancer biomarker, constitutively expressed in sarcoma patients of different histological types. The present work reports materials and in vitro biomedical analyses of silanized (passive delivery) and/or EGF‐functionalized (active delivery) ceria nanorods exhibiting highly defective catalytically active surfaces. The EGFR‐targeting efficiency of nanoceria was confirmed by receptor‐binding studies. Increased cytotoxicity and reactive oxygen species (ROS) production were observed for EGF‐functionalized nanoceria owing to enhanced cellular uptake by HT‐1080 fibrosarcoma cells. The uptake was confirmed by TEM and confocal microscopy. Silanized nanoceria demonstrated negligible/minimal cytotoxicity toward healthy MRC‐5 cells at 24 and 48 h, whereas this was significant at 72 h owing to a nanoceria accumulation effect. In contrast, considerable cytotoxicity toward the cancer cells was exhibited at all three times points. The ROS generation and associated cytotoxicity were moderated by the equilibrium between catalysis by ceria, generation of cell debris, and blockage of active sites. EGFR‐targeting is shown to enhance the uptake levels of nanoceria by cancer cells, subsequently enhancing the overall anticancer activity and therapeutic performance of ceria.
Abstract Critical catalysis studies often lack elucidation of the mechanistic role of defect equilibria in solid solubility and charge compensation. This approach is applied to interpret the physicochemical properties and catalytic performance of a free‐standing 2D–3D CeO 2− x scaffold, which is comprised of holey 2D nanosheets, and its heterojunctions with MoO 3− x and RuO 2 . The band gap alignment and structural defects are engineered using density functional theory (DFT) simulations and atomic characterization. Further, the heterojunctions are used in hydrogen evolution reaction (HER) and catalytic ozonation applications, and the impacts of the metal oxide heteroatoms are analyzed. A key outcome is that the principal regulator of the ozonation performance is not oxygen vacancies but the concentration of Ce 3+ and Ce vacancies. Cation vacancy defects are measured to be as high as 8.1 at% for Ru‐CeO 2− x . The homogeneous distribution of chemisorbed, Mo‐oxide, heterojunction nanoparticles on the CeO 2− x holey nanosheets facilitates intervalence charge transfer, resulting in the dominant effect and resultant ≈50% decrease in overpotential for HER. The heterojunctions are tested for aqueous‐catalytic ozonation of salicylic acid, revealing excellent catalytic performance from Mo doping despite the adverse impact of Ce vacancies. The present study highlights the use of defect engineering to leverage experimental and DFT results for band alignment.
The stratified nature of LiCoO2 (LCO) makes such materials suitable for rechargeable Li-ion batteries. The existing synthesis technology for LCO, however, results in a low surface area, low activity, and a limited density of active sites, which limit its applications in catalysis, in which the material's functionality is determined by the reactions that occur on its surface. The present work reports a simplified and high-yield strategy for using bulk LCO in multifunctional two-dimensional (2D) catalysts. The recovery involves ordered and/or disordered leaching of Li+ as a result of H+ intercalation and formation of catalytically active oxygen vacancies at high concentrations (∼32 atom %). This is followed by exfoliation of the LCO into porous nanosheets through intercalation of tetramethylammonium hydroxide. The catalytic performance of the etched and exfoliated LCOs was investigated; the 1 M HCl-etched LCO exhibited the highest photocatalytic dye degradation (99.9%) under simulated solar light, while the etched and fully exfoliated LCO showed outstanding CO oxidation, with a T90% = 140 °C, which is significantly lower than that of the bulk LCO catalyst (T90% = 360 °C).
This study investigated the role of public policy in transforming innovation systems into innovation ecosystems. Despite the numerous studies that examined the role of innovation policies in promoting innovation systems and the increasing attention paid to the transition from innovation systems to innovation ecosystems in the literature, research on the role of public policy in facilitating this transition is sparse. To develop an analytical framework that identifies factors to be considered in policies that facilitate the transition towards innovation ecosystems, we synthesised the literature that investigated (1) the role of policy in innovation systems, (2) new features of innovation ecosystems and (3) the relations between (transformative) policies and innovation ecosystems. To identify these factors, we also drew on the concept of policy layering and the neo-Triple Helix model of innovation ecosystems. Specifically, we identified the following factors: the willingness and capacity of innovation actors to develop cross-boundary interactions on a global scale; an institutionalised civil society based on bottom-up media; and the prevailing sustainability ethos in economic, social and environmental dimensions. These can be used to design and evaluate policies that promote sustainable innovation and development as core features of innovation ecosystems.
Abstract The catalytic conversion of bioethanol to ethylene (C 2 H 4 ) and acetylene (C 2 H 2 ) offers a transformative approach to sustainable production of two industrial cornerstones for organic compound and polymer syntheses, thereby offering significant economic and environmental advantages. In contrast, current methods for the synthesis of these C 2 hydrocarbons rely on energy‐ and carbon‐intensive processes that require high temperatures and pressures. The present work addresses these limitations with a novel, low‐energy, bioethanol‐conversion strategy operating at room temperature and ambient pressure using sono‐piezo‐photocatalysts. A novel heterostructure of graphene oxide fragments (GO) and sodium bismuth titanate (NBT) within a core‐shell microstructure achieved outstanding C 2 H 4 and C 2 H 2 production rates of 134.1 and 55.5 µmol/g/h, respectively. The conversion mechanism is driven by (1) bubble collapse during ultrasound irradiation, generating localized high temperatures (≈4000 K) and pressures (≈100 MPa), and (2) piezo‐photocatalytic tuning of GO/NBT by enhanced charge separation and transfer. DFT simulations revealed detailed sono‐piezo‐photocatalytic conversion pathways, showing significant reductions in energy barriers for C 2 H 4 (22.0 kcal mol −1 ) and C 2 H 2 (48.0 kcal mol −1 ) formation. These findings emphasize the critical role of the catalyst in cleaving both C─H and C─O bonds effectively, leading to the desired product formation.
MOF-Derived Materials Despite the instability and low electrical conductivity of metal–organic frameworks (MOFs), metal-based derivatives (MDs) retain the intricate nanostructures of MOFs while boasting improved stability and significantly higher electrical conductivities. In article number 2210166, Thibault De Villenoisy and co-workers delve into the nanostructural design of MDs, discussing various established and potential future materials, and also identifying and rationalizing design parameters with the aim to guide optimal composition and performance.
Severe compositional/structural instability of ‘layered’ Na- transition metal (TM) oxide cathode materials for Na-ion batteries upon exposure to air/water renders handling/storage challenging and mandates the use of toxic/hazardous-cum expensive chemicals...