Design of Magnetic Fe3O4/CeO2 "Core/Shell"-Like Nanocomposites with Pronounced Antiamyloidogenic and Antioxidant Bioactivity.

"Core/shell" nanocomposites based on magnetic magnetite (Fe3O4) and redox-active cerium dioxide (CeO2) nanoparticles (NPs) are promising in the field of biomedical interests because they can combine the ability of magnetic NPs to heat up in an alternating magnetic field (AMF) with the pronounced antioxidant activity of CeO2 NPs. Thus, this report is devoted to Fe3O4/CeO2 nanocomposites (NCPs) synthesized by precipitation of the computed amount of "CeO2-shell" on the surface of prefabricated Fe3O4 NPs. The X-ray diffraction, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy data validated the formation of Fe3O4/CeO2 "core/shell"-like NCPs, in which ultrafine CeO2 NPs with an average size of approximately 3-3.5 nm neatly surround Fe3O4 NPs. The presence of a CeO2 "shell" significantly increased the stability of Fe3O4/CeO2 NCPs in aqueous suspensions: Fe3O4/CeO2 NCPs with "shell thicknesses" of 5 and 7 nm formed highly stable magnetic fluids with ζ-potential values of >+30 mV. The magnetization values of Fe3O4/CeO2 NCPs decreased with a growing CeO2 "shell" around the magnetic NPs; however, the resulting composites retained the ability to heat efficiently in an AMF. The presence of a CeO2 "shell" generates a possibility to precisely regulate tuning of the maximum heating temperature of magnetic NCPs in the 42-50 °C range and stabilize it after a certain time of exposure to an AMF by changing the thickness of the "CeO2-shell". A great improvement was observed in both antioxidant and antiamyloidogenic activities. It was found that inhibition of insulin amyloid formation, expressed in IC50 concentration, using NCPs with a "shell thickness" of 7 nm was approximately 10 times lower compared to that of pure CeO2. For these NCPs, more than 2 times higher superoxide dismutase-like activity was observed. The coupling of both Fe3O4 and CeO2 results in higher bioactivity than either of them individually, probably due to a synergistic catalytic mechanism.

Cerium dioxide nanoparticles synthesized via precipitation at constant pH: Synthesis, physical-chemical and antioxidant properties.

Cerium oxide nanoparticles (CeO2 NPs) are well known for their application in various fields of industry, as well as in biology and medicine. Knowledge of synthesis schemes, physicochemical and morphological features of nanoscale CeO2 is important for assessing their antioxidant behavior and understanding the mechanism of oxidative stress and its consequences. The choice of the method of synthesis should be based on the possibility to choose the conditions and parameters for obtaining CeO2 with controlled dimensions and a ratio of Се3+/Се4+ on their surface. In this study, CeO2 NPs are synthesized by precipitation in mixed water-alcohol solutions at constant pH = 9. The properties of obtained NPs are studied using various methods of physical-chemical characterization such as X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and dynamic light scattering. The size of CeO2 NPs varied from 14 to 4.2 nm with increasing alcohol concentration, while the effect of constant pH during synthesis on the morphology of the particles was insignificant. The synthesized nanoparticles form highly stable aqueous suspensions since their zeta-potential is higher than + 40 mV. It is found that the ability of CeO2 NPs to self-stabilize is associated with the presence of hydrated Ce4+ ions on their surface. In vitro biological studies have shown that, regardless of particle size, CeO2 NPs have antioxidant potential, but smaller NPs with a higher percentage of Ce3+ on the surface had a more effective antioxidant effect. In addition, the size-depended activity of CeO2 NPs to inhibit the amyloid formation of insulin is demonstrated.

Migration Kinetics of Surface Ions in Oxygen-Deficient Perovskite During Topotactic Transitions.

Oxygen diffusivity and surface exchange kinetics underpin the ionic, electronic, and catalytic functionalities of complex multivalent oxides. Towards understanding and controlling the kinetics of oxygen transport in emerging technologies, it is highly desirable to reveal the underlying lattice dynamics and ionic activities related to oxygen variation. In this study, the evolution of oxygen content is identified in real-time during the progress of a topotactic phase transition in La0.7 Sr0.3 MnO3-δ epitaxial thin films, both at the surface and throughout the bulk. Using polarized neutron reflectometry, a quantitative depth profile of the oxygen content gradient is achieved, which, alongside atomic-resolution scanning transmission electron microscopy, uniquely reveals the formation of a novel structural phase near the surface. Surface-sensitive X-ray spectroscopies further confirm a significant change of the electronic structure accompanying the transition. The anisotropic features of this novel phase enable a distinct oxygen diffusion pathway in contrast to conventional observation of oxygen motion at moderate temperatures. The results provide insights furthering the design of solid oxygen ion conductors within the framework of topotactic phase transitions.

All-Oxide p-n Junction Thermoelectric Generator Based on SnOx and ZnO Thin Films.

Achieving thermoelectric devices with high performance based on low-cost and nontoxic materials is extremely challenging. Moreover, as we move toward an Internet-of-Things society, a miniaturized local power source such as a thermoelectric generator (TEG) is desired to power increasing numbers of wireless sensors. Therefore, in this work, an all-oxide p-n junction TEG composed of low-cost, abundant, and nontoxic materials, such as n-type ZnO and p-type SnOx thin films, deposited on borosilicate glass substrate is proposed. A type II heterojunction between SnOx and ZnO films was predicted by density functional theory (DFT) calculations and confirmed experimentally by X-ray photoelectron spectroscopy (XPS). Moreover, scanning transmission electron microscopy (STEM) combined with energy-dispersive X-ray spectroscopy (EDS) show a sharp interface between the SnOx and ZnO layers, confirming the high quality of the p-n junction even after annealing at 523 K. ZnO and SnOx thin films exhibit Seebeck coefficients (α) of ∼121 and ∼258 µV/K, respectively, at 298 K, resulting in power factors (PF) of 180 µW/m K2 (for ZnO) and 37 µW/m K2 (for SnOx). Moreover, the thermal conductivities of ZnO and SnOx films are 8.7 and 1.24 W/m K, respectively, at 298 K, with no significant changes until 575 K. The four pairs all-oxide TEG generated a maximum power output (Pout) of 1.8 nW (≈126 µW/cm2) at a temperature difference of 160 K. The output voltage (Vout) and output current (Iout) at the maximum power output of the TEG are 124 mV and 0.0146 µA, respectively. This work paves the way for achieving a high-performance TEG device based on oxide thin films.

Structural and physical-chemical characterization of redox active CeO2nanoparticles synthesized by precipitation in water-alcohol solutions.

A set of cerium dioxide nanoparticles (CeO2NPs) was synthesized by precipitation in water-alcohol solutions under conditions when the physical-chemical parameters of synthesized NPs were controlled by changing the ratio of the reaction components. The size of CeO2NPs is controlled largely by the dielectric constant of the reaction solution. An increase of the percentage of Ce3+ions at the surface was observed with a concomitant reduction of the NP sizes. All synthesized CeO2NPs possess relatively high positive values of zeta-potential (ζ > 40 mV) suggesting good stability in aqueous suspensions. Analysis of the valence- and size-dependent rate of hydrogen peroxide decomposition revealed that catalase/peroxidase-like activity of CeO2NPs is higher at a low percentage of Ce3+at the NP surface. In contrast, smaller CeO2NPs with a higher percentage of Ce3+at the NP surface display a higher oxidase-like activity.

Anion-mediated electronic effects in reducible oxides: Tuning the valence band of ceria via fluorine doping.

Combining experimental spectroscopy and hybrid density functional theory calculations, we show that the incorporation of fluoride ions into a prototypical reducible oxide surface, namely, ceria(111), can induce a variety of nontrivial changes to the local electronic structure, beyond the expected increase in the number of Ce3+ ions. Our resonant photoemission spectroscopy results reveal new states above, within, and below the valence band, which are unique to the presence of fluoride ions at the surface. With the help of hybrid density functional calculations, we show that the different states arise from fluoride ions in different atomic layers in the near surface region. In particular, we identify a structure in which a fluoride ion substitutes for an oxygen ion at the surface, with a second fluoride ion on top of a surface Ce4+ ion giving rise to F 2p states which overlap the top of the O 2p band. The nature of this adsorbate F--Ce4+ resonant enhancement feature suggests that this bond is at least partially covalent. Our results demonstrate the versatility of anion doping as a potential means of tuning the valence band electronic structure of ceria.

Highly sensitive thermoelectric touch sensor based on p-type SnO x thin film.

Here, the ability of using p-type tin oxide (SnO x ) thin films as a thermal sensor has been investigated. Firstly, the thermoelectric performance was optimized by controlling the thickness of the SnO x film from 60 up to 160 nm. A high Seebeck coefficient of +263 µV K-1 and electrical conductivity of 4.1 × 102 (S m-1) were achieved in a 60 nm thick SnO x film, due to a compact nanostructured film and the absence of the Sn metallic phase, which was observed for the thicker SnO x film leading to a typical thermoelectric transport properties of a n-type Sn film. Moreover, x-ray photoelectron spectroscopy revealed the co-existence of SnO (79.7%) and SnO2 (20.3%) phases in the 60 nm thick SnO x film, while the optical measurements revealed an indirect gap of 1.8 eV and a direct gap of 2.7 eV, respectively. The 60 nm-SnO x thin film have been tested as a thermoelectric touch sensor, achieving a Vsignal /Vnoise  ≈ 20, with a rise time <1 s. Therefore, this work provides an efficient way for developing highly efficient thermal sensors with potential use in display technologies.

Epidermal Growth Factor - based adhesion substrates elicit myoblast scattering, proliferation, differentiation and promote satellite cell myogenic activation.

The biochemical properties of muscle extracellular matrix are essential for stem cell adhesion, motility, proliferation and myogenic development. Recombinant elastin-like polypeptides are synthetic polypeptides that, besides maintaining some properties of the native protein, can be tailored by fusing bioactive sequences to their C-terminal. Our laboratory synthesized several Human Elastin-Like Polypeptides (HELP) derived from the sequence of human tropoelastin. Here, we developed a novel HELP family member by fusing the elastin-like backbone to the sequence of human Epidermal Growth Factor. We employed this synthetic protein, named HEGF, either alone or in combination with other proteins of the HELP family carrying RGD-integrin binding sites, as adhesion substrate for C2C12 myoblasts and satellite cells primary cultures. Adhesion of myoblasts to HEGF-based substrates induced scattering, decreased adhesion and cytoskeleton assembly; the concomitant presence of the RGD motifs potentiated all these effects. Recombinant substrates induced myoblasts proliferation, differentiation and the development of multinucleated myotubes, thus favoring myoblasts expansion and preserving their myogenic potential. The effects induced by adhesion substrates were inhibited by AG82 (Tyrphostin 25) and herbimycin A, indicating their dependence on the activation of both the EGF receptor and the tyrosine kinase c-src. Finally, HEGF increased the number of muscle stem cells (satellite cells) derived from isolated muscle fibers in culture, thus highlighting its potential as a novel substrate for skeletal muscle regeneration strategies.

Exploiting micro-scale structural and chemical observations in real time for understanding chemical conversion: LEEM/PEEM studies over CeOx-Cu(111).

Proper consideration of length-scales is critical for elucidating active sites/phases in heterogeneous catalysis, revealing chemical function of surfaces and identifying fundamental steps of chemical reactions. Using the example of ceria thin films deposited on the Cu(111) surface, we demonstrate the benefits of multi length-scale experimental framework for understanding chemical conversion. Specifically, exploiting the tunable sampling and spatial resolution of photoemission electron microscopy, we reveal crystal defect mediated structures of inhomogeneous copper-ceria mixed phase that grow during preparation of ceria/Cu(111) model systems. The density of the microsized structures is such that they are relevant to the chemistry, but unlikely to be found during investigation at the nanoscale or with atomic level investigations. Our findings highlight the importance of accessing micro-scale when considering chemical pathways over heteroepitaxially grown model systems.

Epitaxial Cubic Ce2O3 Films via Ce-CeO2 Interfacial Reaction.

Thin films of reduced ceria supported on metals are often applied as substrates in model studies of the chemical reactivity of ceria based catalysts. Of special interest are the properties of oxygen vacancies in ceria. However, thin films of ceria prepared by established methods become increasingly disordered as the concentration of vacancies increases. Here, we propose an alternative method for preparing ordered reduced ceria films based on the physical vapor deposition and interfacial reaction of Ce with CeO2 films. The method yields bulk-truncated layers of cubic c-Ce2O3. Compared to CeO2 these layers contain 25% of perfectly ordered vacancies in the surface and subsurface allowing well-defined measurements of the properties of ceria in the limit of extreme reduction. Experimentally, c-Ce2O3(111) layers are easily identified by a characteristic 4 × 4 surface reconstruction with respect to CeO2(111). In addition, c-Ce2O3 layers represent an experimental realization of a normally unstable polymorph of Ce2O3. During interfacial reaction, c-Ce2O3 nucleates on the interface between CeO2 buffer and Ce overlayer and is further stabilized most likely by the tetragonal distortion of the ceria layers on Cu. The characteristic kinetics of the metal-oxide interfacial reactions may represent a vehicle for making other metastable oxide structures experimentally available.

Influence of nitric acid treatment of carbon nanotubes on their physico-chemical properties.

We report a systematic evaluation of the influence of the use of nitric acid at elevated temperature (80 degrees C) as purification and functionalization treatment for four different types of multi wall carbon nanotubes (MWCNTs) and for carbon microparticles upon their physico-chemical properties. We used BET, Raman spectroscopy, high resolution X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy measurements for MWCNTs characterization. We found that nitric acid treatment significantly changes physico-chemical properties of MWCNTs and that these changes vary significantly between different MWCNTs. Therefore we urge researchers to be careful when relying on the physico-chemical properties measured on different MWCNTs samples.