Polyribosomes of circular topology are prevalent in mammalian cells.

Polyribosomes, the groups of ribosomes simultaneously translating a single mRNA molecule, are very common in both, prokaryotic and eukaryotic cells. Even in early EM studies, polyribosomes have been shown to possess various spatial conformations, including a ring-shaped configuration which was considered to be functionally important. However, a recent in situ cryo-ET analysis of predominant regular inter-ribosome contacts did not confirm the abundance of ring-shaped polyribosomes in a cell cytoplasm. To address this discrepancy, here we analyzed the cryo-ET structure of polyribosomes in diluted lysates of HeLa cells. It was shown that the vast majority of the ribosomes were combined into polysomes and were proven to be translationally active. Tomogram analysis revealed that circular polyribosomes are indeed very common in the cytoplasm, but they mostly possess pseudo-regular structures without specific inter-ribosomal contacts. Although the size of polyribosomes varied widely, most circular polysomes were relatively small in size (4-8 ribosomes). Our results confirm the recent data that it is cellular mRNAs with short ORF that most commonly form circular structures providing an enhancement of translation.

Parylene-based memristive crossbar structures with multilevel resistive switching for neuromorphic computing.

Currently, there is growing interest in wearable and biocompatible smart computing and information processing systems that are safe for the human body. Memristive devices are promising for solving such problems due to a number of their attractive properties, such as low power consumption, scalability, and the multilevel nature of resistive switching (plasticity). The multilevel plasticity allows memristors to emulate synapses in hardware neuromorphic computing systems (NCSs). The aim of this work was to study Cu/poly-p-xylylene(PPX)/Au memristive elements fabricated in the crossbar geometry. In developing the technology for manufacturing such samples, we took into account their characteristics, in particular stable and multilevel resistive switching (at least 10 different states) and low operating voltage (<2 V), suitable for NCSs. Experiments on cycle to cycle (C2C) switching of a single memristor and device to device (D2D) switching of several memristors have shown high reproducibility of resistive switching (RS) voltages. Based on the obtained memristors, a formal hardware neuromorphic network was created that can be trained to classify simple patterns.

Ni Nanoparticles Stabilized by Hyperbranched Polymer: Does the Architecture of the Polymer Affect the Nanoparticle Characteristics and Their Performance in Catalysis?

Heat-up and hot-injection methods were employed to synthesize Ni nanoparticles (NPs) with narrow size distribution in the presence of hyperbranched pyridylphenylene polymer (PPP) as a stabilizing agent. It was shown that depending on the synthetic method, Ni NPs were formed either in a cross-linked polymer network or stabilized by a soluble hyperbranched polymer. Ni NPs were characterized by a combination of transmission electron microscopy (TEM), scanning TEM, thermogravimetric analysis, powder X-ray diffraction, X-ray photoelectron spectroscopy, energy dispersive X-ray analysis, and magnetic measurements. The architecture of polymer support was found to significantly effect Ni NPs characteristics and behavior. The Ni NPs demonstrated a high catalytic activity in a model Suzuki-Miyaura cross-coupling reaction. No significant drop in activity was observed upon repeated use after magnetic separation in five consecutive catalytic cycles. We believe that hyperbranched PPP can serve as universal platform for the controllable synthesis of Ni NPs, acting as highly active and stable catalysts.

Ru@hyperbranched Polymer for Hydrogenation of Levulinic Acid to Gamma-Valerolactone: The Role of the Catalyst Support.

Hydrogenation of levulinic acid (LA) obtained from cellulose biomass is a promising path for production of γ-valerolactone (GVL)-a component of biofuel. In this work, we developed Ru nanoparticle containing nanocomposites based on hyperbranched pyridylphenylene polymer, serving as multiligand and stabilizing matrix. The functionalization of the nanocomposite with sulfuric acid significantly enhances the activity of the catalyst in the selective hydrogenation of LA to GVL and allows the reaction to proceed under mild reaction conditions (100 °C, 2 MPa of H2) in water and low catalyst loading (0.016 mol.%) with a quantitative yield of GVL and selectivity up to 100%. The catalysts were successfully reused four times without a significant loss of activity. A comprehensive physicochemical characterization of the catalysts allowed us to assess structure-property relationships and to uncover an important role of the polymeric support in the efficient GVL synthesis.

Size-Dependent Structure Relations between Nanotubes and Encapsulated Nanocrystals.

The structural organization of compounds in a confined space of nanometer-scale cavities is of fundamental importance for understanding the basic principles for atomic structure design at the nanolevel. Here, we explore size-dependent structure relations between one-dimensional PbTe nanocrystals and carbon nanotube containers in the diameter range of 2.0-1.25 nm using high-resolution transmission electron microscopy and ab initio calculations. Upon decrease of the confining volume, one-dimensional crystals reveal gradual thinning, with the structure being cut from the bulk in either a <110> or a <100> growth direction until a certain limit of ∼1.3 nm. This corresponds to the situation when a stoichiometric (uncharged) crystal does not fit into the cavity dimensions. As a result of the in-tube charge compensation, one-dimensional superstructures with nanometer-scale atomic density modulations are formed by a periodic addition of peripheral extra atoms to the main motif. Structural changes in the crystallographic configuration of the composites entail the redistribution of charge density on single-walled carbon nanotube walls and the possible appearance of the electron density wave. The variation of the potential attains 0.4 eV, corresponding to charge density fluctuations of 0.14 e/atom.

Formation of BiFeO3 from a Binary Oxide Superlattice Grown by Atomic Layer Deposition.

We report on the growth of polycrystalline BiFeO3 thin films on SiO2 /Si(001) and Pt(111) substrates by atomic layer deposition using the precursors ferrocene, triphenyl-bismuth, and ozone. By growing alternating layers of Fe2 O3 and Bi2 O3 , we employ a superlattice approach and demonstrate an efficient control of the cation stoichiometry. The superlattice decay and the resulting formation of polycrystalline BiFeO3 films are studied by in situ X-ray diffraction, in situ X-ray photoelectron spectroscopy, and transmission electron microscopy. No intermediate ternary phases are formed and BiFeO3 crystallization is initiated in the Bi2 O3 layers at 450 °C following the diffusion-driven intermixing of the cations. Our study of the BiFeO3 formation provides an insight into the complex interplay between microstructural evolution, grain growth, and bismuth oxide evaporation, with implications for optimization of ferroelectric properties.

Induced electric conductivity in organic polymers.

Poly(diphenylene phthalide) (PDP) belongs to the class of carbocyclic organic electroactive polymers, which exhibits electric conductive properties when an external electric field and/or mechanical stress is applied. In this work, the transport properties of thin-film layered lead-PDP-lead structures were experimentally studied in a wide temperature range. At sufficiently high temperatures, the current voltage characteristics are satisfactorily described in terms of the injection model of currents limited by the space charge. At temperatures below ≈8 K, a number of samples exhibit features that can be explained by the effect of induced superconductivity in a thin film of conducting polymer enclosed between two massive superconductors (lead).

Assembling of Metal-Polymer Nanocomposites in Irradiated Solutions of 1-Vinyl-1,2,4-triazole and Au(III) Ions: Features of Polymerization and Nanoparticles Formation.

Gold nanoparticles (AuNPs) stabilized with poly(1-vinyl-1,2,4-triazole) (PVT) have been synthesized via a one-pot manner in irradiated solutions of 1-vinyl-1,2,4-triazole (VT) and Au(III) ions. The transmission electron microscopy examinations have shown that the sizes of nanoparticles formed range from 1 to 11 nm and are affected by the ratio of VT to gold ions. To study the kinetics peculiarities of the VT polymerization and assembling of AuNPs, UV-Vis spectroscopy was used. The analysis of the data obtained reveals that an inhibition period, influenced by Au(III) concentration, is followed by the polymerization of a monomer. Importantly, the absorbed doses, corresponding to the onset of rapid polymerization, correlate with the doses at which the accelerated formation of AuNPs begins. The kinetics aspects, which could lead to such an effect, are discussed.

The Performance of Nonwoven PLLA Scaffolds of Different Thickness for Stem Cells Seeding and Implantation.

The 3D reconstruction of 100 µm- and 600 µm-thick fibrous poly-L/L-lactide scaffolds was performed by confocal laser scanning microscopy and supported by scanning electron microscopy and showed that the density of the fibers on the side adjacent to the electrode is higher, which can affect cell diffusion, while the pore size is generally the same. Bone marrow mesenchymal stem cells cultured in a 600 µm-thick scaffold formed colonies and produced conditions for cell differentiation. An in vitro study of stem cells after 7 days revealed that cell proliferation and hepatocyte growth factor release in the 600 µm-thick scaffold were higher than in the 100 µm-thick scaffold. An in vivo study of scaffolds with and without stem cells implanted subcutaneously onto the backs of recipient mice was carried out to test their biodegradation and biocompatibility over a 0-3-week period. The cells seeded onto the 600 µm-thick scaffold promoted significant neovascularization in vivo. After 3 weeks, a significant number of donor cells persisted only on the inside of the 600 µm-thick scaffold. Thus, the use of bulkier matrices allows to prolong the effect of secretion of growth factors by stem cells during implantation. These 600 µm-thick scaffolds could potentially be utilized to repair and regenerate injuries with stem cell co-culture for vascularization of implant.

Challenges for Pulsed Laser Deposition of FeSe Thin Films.

Anti-PbO-type FeSe shows an advantageous dependence of its superconducting properties with mechanical strain, which could be utilized as future sensor functionality. Although superconducting FeSe thin films can be grown by various methods, ultrathin films needed in potential sensor applications were only achieved on a few occasions. In pulsed laser deposition, the main challenges can be attributed to such factors as controlling film stoichiometry (i.e., volatile elements during the growth), nucleation, and bonding to the substrate (i.e., film/substrate interface control) and preventing the deterioration of superconducting properties (i.e., by surface oxidization). In the present study, we address various technical issues in thin film growth of FeSe by pulsed laser deposition, which pose constraints in engineering and reduce the application potential for FeSe thin films in sensor devices. The results indicate the need for sophisticated engineering protocols that include interface control and surface protection from chemical deterioration. This work provides important actual limitations for pulsed laser deposition (PLD) of FeSe thin films with the thicknesses below 30 nm.

Chemical Composition Control at the Substrate Interface as the Key for FeSe Thin-Film Growth.

The strong fascination exerted by the binary compound of FeSe demands reliable engineering protocols and more effective approaches toward inducing superconductivity in FeSe thin films. Our study addresses the peculiarities in pulsed laser deposition that determine FeSe thin-film growth and focuses on the film/substrate interface, which has only been considered hypothetically in the past literature. The FeSe/MgO interface has been assumed (1) to be clean and (2) to obey lattice-matching epitaxy. Our studies reveal that both assumptions are misleading and demonstrate the tendency for domain-matching epitaxial growth, which accompanies the problem of chemical heterogeneity. We propose that homogenization of the film/substrate interface by an Fe buffer can improve the control of stoichiometry and nanostrain in a way that favors superconductivity even in ultrathin FeSe films. We will also show that on a chemically homogenized FeSe/Fe interface, the control of film texture with preparation conditions is still possible.

Mono- and Bimetallic Nanoparticles Stabilized by an Aromatic Polymeric Network for a Suzuki Cross-Coupling Reaction.

This work addresses the Suzuki cross-coupling between 4-bromoanisole (BrAn) and phenylboronic acid (PBA) in an environmentally benign ethanol-water solvent catalysed by mono- (Pd) and bimetallic (PdAu, PdCu, PdZn) nanoparticles (NPs) stabilised within hyper-cross-linked polystyrene (HPS) bearing tertiary amino groups. Small Pd NPs of about 2 nm in diameters were formed and stabilized by HPS independently in the presence of other metals. High catalytic activity and complete conversion of BrAn was attained at low Pd loading. Introduction of Zn to the catalyst composition resulted in the formation of Pd/Zn/ZnO NPs, which demonstrated nearly double activity as compared to Pd/HPS. Bimetallic core-shell PdAu/HPS samples were 3-fold more active as compared to Pd/HPS. Both Pd/HPS and PdAu/HPS samples revealed promising stability confirmed by catalyst recycling in repeated reaction runs.

Superconductivity and Shubnikov - de Haas effect in polycrystalline Cd3As2 thin films.

In this study we observed the reproducible superconducting state in Cd3As2 thin films without any external stimuli. Comparison with our previous results reveals similar qualitative behavior for films synthesized by different methods, while the difference in the values of the critical parameters clearly shows the possibility to control this state. The X-ray diffraction measurements demonstrate the presence of the tetragonal Cd3As2 crystal phase in studied films. Measurements of high-field magnetoresistance reveal pronounced Shubnikov - de Haas oscillations. The analysis of these oscillations suggests that, due to high carrier concentration in studied Cd3As2 films, the initial Dirac semimetal phase may be partially suppressed, which, however, does not contradict with possible topological nature of the observed superconductivity.

Synthesis, structure and properties of layered Pr2MoO6-based oxymolybdates doped with Mg.

Undoped and Mg-doped Pr2MoO6 oxymolybdate polycrystals and single crystals have been prepared by solid-state reactions and flux growth. The compounds have been characterized by powder X-ray diffraction, energy-dispersive spectroscopy, inductively coupled plasma mass spectrometry, scanning transmission electron microscopy, single crystal X-ray structure analysis, differential scanning calorimetry and thermogravimetry. The (MgO)x(Pr2O3)y(MoO3)z (x + y + z = 1) solid solution series has been shown to extend to x = 0.03. The structure of the Mg-doped Pr2MoO6 single crystals can be represented as superimposed lattices of the main matrix (Pr2MoO6) and lattices in which Mo atoms are partially replaced by Mg. The incorporation of Mg atoms into the structure of Pr2MoO6 results in the disordering of the praseodymium and oxygen lattices. Both the polycrystalline and single-crystal Mg-doped samples are hygroscopic.

Microstructure and superconducting properties of high-rate PLD-derived GdBa2Cu3O7-δ coated conductors with BaSnO3 and BaZrO3 pinning centers.

The microstructure of GdBa2Cu3O7-δ based on superconducting tapes with BaSnO3 and BaZrO3 artificial pinning centers formed by high-rate pulse laser deposition in SuperOx Japan was studied by scanning/transmission electron microscopy. The artificial pinning centers have adopted columnar morphology with average diameter of about 8 nm (BaSnO3-doped sample) and 6.5 nm (BaZrO3-doped sample) and density of 500 µm-2 for the both samples. The average length of the BaSnO3 nanocolumns is about two times higher than the BaZrO3 nanocolumns. The angular dependences of critical current in magnetic field up to 1 Tesla at 77 and 65 K have been obtained. The critical current and its anisotropy depend on artificial pinning centers presence and their type. The angular dependence of resistivity in the field up to 9 Tesla was also studied and discussed.

Novel type of hollow hydrogel microspheres with magnetite and silver nanoparticles.

A novel type of microcontainers based on hollow silver alginate microspheres and magnetite nanoparticles is reported as development of recently published technology. Magnetite nanoparticles were incorporated by two methods - co-precipitation with porous calcium carbonate during template formation and adsorption onto CaCO3 particles or microcontainers' shell. Amount of magnetite loaded and microshells size (4.6 to 6.9 µm) were found to depend on the chosen method for magnetite nanoparticles incorporation. Stability of hollow microshells in saline, phosphate buffer and culturing media was studied. Microcontainers' susceptibility to magnetic field was investigated in solutions of varied viscosity, and their group movement velocity under constant magnetic field was evaluated by sequential optical microscopy imaging. Cell viability tests with prepared microshells were performed that demonstrated negligible cytotoxicity effect on human dermal fibroblasts cells. With HeLa cells moderate viability inhibition was found at high carriers:cells ratio at early time points which is attributed to more active and receptor-mediated endocytosis of carriers as well as known cytotoxicity of magnetite in some cancer cells. At 24 and 48 h time points HeLa cells proliferation fully recovers. Reported data opens perspectives for further biomedical-oriented studies and application of this novel kind of microcontainers with a number of techniques applicable for imaging, control and triggered cargo release provided by presence of silver and magnetite nanoparticles in the carriers and their suitability for further versatile functionalization by traditional LbL approach if needed.

Magnetic properties of biofunctionalized iron oxide nanoparticles as magnetic resonance imaging contrast agents.

Background: One of the future applications of magnetic nanoparticles is the development of new iron-oxide-based magnetic resonance imaging (MRI) negative contrast agents, which are intended to improve the results of diagnostics and complement existing Gd-based contrast media. Results: Iron oxide nanoparticles designed for use as MRI contrast media are precisely examined by a variety of methods: powder X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, Mössbauer spectroscopy and zero-field nuclear magnetic resonance (ZF-NMR) spectroscopy. TEM and XRD measurements reveal a spherical shape of the nanoparticles with an average diameter of 5-8 nm and a cubic spinel-type crystal structure of space group Fd-3m. Raman, Mössbauer and NMR spectroscopy clearly indicate the presence of the maghemite γ-Fe2O3 phase. Moreover, a difference in the magnetic behavior of uncoated and human serum albumin coated iron oxide nanoparticles was observed by Mössbauer spectroscopy. Conclusion: This difference in magnetic behavior is explained by the influence of biofunctionalization on the magnetic and electronic properties of the iron oxide nanoparticles. The ZF-NMR spectra analysis allowed us to determine the relative amount of iron located in the core and the surface layer of the nanoparticles. The obtained results are important for understanding the structural and magnetic properties of iron oxide nanoparticles used as T 2 contrast agents for MRI.

Protective Dps-DNA co-crystallization in stressed cells: an in vitro structural study by small-angle X-ray scattering and cryo-electron tomography.

Under severe or prolonged stress, bacteria produce a nonspecific DNA-binding protein (Dps), which effectively protects DNA against damaging agents both in vitro and in vivo by forming intracellular biocrystals. The phenomenon of protective crystallization of DNA in living cells has been intensively investigated during the last two decades; however, the results of studies are somewhat contradictory, and up to now, there has been no direct determination of a Dps-DNA crystal structure. Here, we report the in vitro analysis of the vital process of Dps-DNA co-crystallization using two complementary structural methods: synchrotron small-angle X-ray scattering in solution and cryo-electron tomography. Importantly, for the first time, the DNA in the co-crystals was visualized, and the lattice parameters of the crystalline Dps-DNA complex were determined.

Evidence of extended cation solubility in atomic layer deposited nanocrystalline BaTiO3 thin films and its strong impact on the electrical properties.

Thin films of ≈50 nm thickness with Ba/Ti-ratios ranging from 0.8 to 1.06 were prepared by depositing alternating layers of Ba(OH)2 and TiO2. Annealing at 750 °C promoted the solid-solid transformation into polycrystalline BaTiO3 films containing a mixture of the perovskite and the hexagonal polymorphs with average crystallite sizes smaller than 14 nm and without impurity phases. This, together with an increase of the cubic lattice parameters for Ba-rich films, suggests an extended metastable solubility range for the perovskite-phase in these nanocrystalline thin films on both sides of the stoichiometric composition. Mapping of the cation distribution utilizing energy-filtered transmission electron microscopy corroborates defect accommodation within the BaTiO3 grains. While the cation off-stoichiometry in thermodynamic equilibrium is negligible for BaTiO3, the metastable extended solubility range in the thin films can be directly correlated to the low annealing temperature and nanocrystalline nature. The leakage current behavior can be explained by the formation of Schottky defects for nonstoichiometric films, and the cation ratio has a distinct impact on the dielectric properties: while excess-BaO has a marginal detrimental effect on the permittivity, the dielectric constant declines rapidly by more than 50% towards the Ti-rich side. The present findings highlight the importance of compositional control for the synthesis of nanocrystalline BaTiO3 thin films, in particular for low annealing and/or deposition temperatures. Our synthesis approach using alternating layers of Ba(OH)2 and TiO2 provides a route to precisely control the cation stoichiometry.

High-temperature magnetism and microstructure of a semiconducting ferromagnetic (GaSb)1-x (MnSb) x alloy.

We have studied the properties of relatively thick (about 120 nm) magnetic composite films grown by pulsed laser deposition using the eutectic compound (GaSb)0.59(MnSb)0.41 as target for sputtering. For the studied films we have observed ferromagnetism and an anomalous Hall effect above room temperature, confirming the presence of spin-polarized carriers. Electron microscopy, atomic and magnetic force microscopy results suggest that the films under study have a homogenous columnar structure in the bulk while MnSb inclusions accumulate near the surface. This is in good agreement with the high mobility values of charge carriers. Based on our data we conclude that the magnetic and magnetotransport properties of the films at room temperature are defined by the MnSb inclusions.