National Institute Of Materials Physics - Romania

The recent advances in genetic engineering demand the development of conceptually new methods to prepare and identify efficient vectors for the intracellular delivery of different nucleotide payloads ranging from short single-stranded oligonucleotides to larger plasmid double-stranded circular DNAs. Although many challenges still have to be overcome, polymers hold great potential for intracellular nucleotide delivery and gene therapy. We here develop and apply the postpolymerization modification of polyhydrazide scaffolds, with different degree of polymerization, for the preparation of amphiphilic polymeric vehicles for the intracellular delivery of a circular plasmid DNA. The hydrazone formation reactions with a mixture of cationic and hydrophobic aldehydes proceed in physiologically compatible aqueous conditions, and the resulting amphiphilic polyhydrazones are directly combined with the biological cargo without any purification step. This methodology allowed the preparation of stable polyplexes with a suitable size and zeta potential to achieve an efficient encapsulation and intracellular delivery of the DNA cargo. Simple formulations that performed with efficiencies and cell viabilities comparable to the current gold standard were identified. Furthermore, the internalization mechanism was studied via internalization experiments in the presence of endocytic inhibitors and fluorescence microscopy. The results reported here confirmed that the polyhydrazone functionalization is a suitable strategy for the screening and identification of customized polymeric vehicles for the delivery of different nucleotide cargos.

Highly defected SiO2 nanotubes (SiO2-NT) were obtained by a simple sol-gel procedure followed by calcination. Boron-doped diamond (BDD) polycrystalline films coated with SiO2-NT were used as working electrodes and, unexpectedly, cyclic voltammetric experiments have shown that the concentration of both positive and negative defects at the surface is high enough to enable redox processes involving positively charged Ru(bpy)(3)(2+/3+) to occur. Conversely, no electrochemical activity was put into evidence for Fe (CN)(6)(3/4) species, most likely as a result of the strong electrostatic repulsion exerted by the negatively charged SiO2 surface. The concentration of surface defects was further increased by a subsequent thermal treatment in a hydrogen atmosphere which, as EIS measurements have shown, significantly promotes Ru (bpy)(3)(2+) anodic oxidation. Digital simulation of the voltammetric responses demonstrated that this treatment does not lead to a similar increase of the number of electron-donor sites. It was also found that methanol anodic oxidation at hydrogenated SiO2-NT-supported platinum results in Tafel slopes of 116-220 mV decade(-1), comparable to those reported for both conventional PtRu and Pt-oxide catalysts. (C) 2018 Elsevier B.V. All rights reserved.

The influence of single-walled carbon nanotubes enriched in semiconductor (S-SWNTs) and metallic (M-SWNTs) tubes on the photoluminescence (PL) of polyaniline (PANI), electrosynthesized in the presence of the H2SO4 and HCl solutions, is reported. The emission bands peaked at 407-418 and 440-520 nm indicate that the electropolymerization of aniline (ANI) leads to the formation of short and longer macromolecular chains (MCs), respectively. We demonstrate that the reaction product consists of ANI tetramers (TT) and trimers (TR) as well as PANI-salt. Using Raman scattering and IR absorption spectroscopy, a covalent functionalization of SWNTs with shorter and longer MCs of PANI-salt is demonstrated. The presence of S-SWNTs and M-SWNTs induces a decrease in ANI TT weight in the reaction product mass consisting in S-SWNTs and M-SWNTs covalently functionalized with PANI-emeraldine salt (ES) and PANI-leucoemeraldine salt (LS), respectively. A PANI PL quenching is reported to be induced of the S-SWNTs and M-SWNTs. A de-excitation mechanism is proposed to explain PANI PL quenching.

In this work we report on a new 1-1 composite coaxial nanostructure containing nanotubes of CoFe2O4 and BET-BT0.08 prepared by a template-based fabrication technique using the sol-gel chemistry. In this regard, CoFe2O4/BNT-BT0.08 core-shell nanotubes were prepared using a polycarbonate membrane template and sols precursors of CoFe2O4 and BNT-BT0.08. The deposition of nanotubes was performed by pore wetting of the porous membranes via capillary action and subsequent pyrolysis. The studies with scanning electron microscopy and transmission electron microscopy (TEM) revealed that the composite material is characterized by the 1-D tubular structure. Analysis by X-ray diffraction, high-resolution TEM imaging and selected-area electron diffraction pattern demonstrated that the synthetic composite nanotube CoFe2O4/BNT-BT0.08 has crystalline structure with cubic CoFe2O4 and rhombohedral BNT-BT0.08 phases. CoFe2O4/BNT-BT0.08 coaxial nanotubes show dielectric properties, piezoelectric and ferromagnetic behavior.

This paper presents a comparative study between the properties of the heterostructures realized with single/multi layer organic (zinc phthalocyanine or/and fullerene) prepared on Si substrate between flat or patterned aluminum (Al) layer metallic electrode and multi layer ZnO/Au/ZnO transparent conductor electrode (TCE). The UV-Nanoimprint Lithography was used for the realization of a 2D array of nanostructures (holes/pillars) characterized by a periodicity of 1.1 mu m and cylindrical shape: diameter = 400 nm and depth/height = 300 nm. The effect of the electrode patterning on the properties of the organic heterostructures was analyzed. For the samples with patterned Al electrode was remarked a slight red shift of the peaks in the reflection spectra determined by an increased interaction between the organic molecules in the delimited region of the patterned holes. The shape of the emission spectra at excitation with UV light showed a narrow intense peak around 500 nm associated with the intense resonance phenomena between the energy of the incident light and the surface plasmons in the patterned Al layer. The TCE followed the morphology of the organic film on which it was deposited. The significant differences between the morphology of the top layer in the heterostructures realized on flat and patterned Al are correlated with the total thickness of the successively deposited layers and with the particularities of the molecular arrangement, leading to the preservation or deleting of patterning. An injection contact behavior was evidence for most heterostructures built on flat and patterned Al. The slight increase in current at an applied bias <1 V in the heterostructure Si/Al/ZnPc/TCE is attributed to the larger interfacial area between the patterned Al electrode and ZnPc layer compared to the interface area between flat Al and ZnPc. A buffer layer of 1,4,5,8-naphthalen-tetracarboxylic dianhydride (NTCDA), sandwiched between the flat metallic electrode and organic film in the heterostructure Si/Al/C60/ZnPc/TCE has determined an increase in the current at low applied voltages. (C) 2018 Elsevier B.V. All rights reserved.

Pristine and (SiC + Te)-added MgB2 powders, green and spark plasma sintered (SPS) compacts were investigated from the viewpoint of quasi-static and dynamic (Split-Hopkinson Pressure Bar, SHPB) compressive mechanical properties The amount of the additive (SiC + Te) was selected to be the optimum one for maximization of the superconducting functional parameters. Pristine and added MgB2 show very similar compressive parameters (tan delta, fracture strength, Vickers hardness, others) and fragment size in the SHPB test. However, for the bulk SPSed samples the ratio of intergranular to transgranular fracturing changes, the first one being stronger in the added sample. This is reflected in the quasi-static K-IC that is higher for the added sample. Despite this result, sintered samples are brittle and have roughly similar fragmentation behavior as for brittle engineering ceramics. In the fragmentation process, the composite nature of our samples should be considered with a special focus on MgB2 blocks (colonies) that show the major contribution to fracturing. The Glenn-Chudnovsky model of fracturing under dynamic load provides the closest values to our experimental fragment size data.

The formation of separate phases in crystalline materials is promoted by doping with elements with different valences and ionic radii. Control of the formation of separate phases in multiferroics is extremely important for their magnetic, ferroelectric and elastic properties, which are relevant for multifunctional applications. The ordering of dopants and incipient phase separation were studied in lead titanate-based multiferroics with the formula (Pb0.88Nd0.08)(Ti0.98-xFexMn0.02)O-3 (x = 0.00, 0.03, 0.04, 0.05) by means of a combination of Mossbauer spectroscopy, XPS, HRTEM, dielectric and anelastic spectroscopy. We found that Fe ions are substituted as Fe3+ at Ti sites and preferentially exhibit pentahedral coordination, whereas Ti ions have coexisting valences of Ti4+/Ti3+. Fe3+ ions are preferentially ordered in clusters, and there exists a transition temperature T-C1, below which phase separation occurs between a tetragonal phase T1 free of magnetic clusters and a cubic phase, and a lower transition temperature T-C2, below which the cubic phase rich in magnetic clusters is transformed into a tetragonal phase T2. The phase separation persists at the nanoscale level down to room temperature and is visible in HRTEM images as a mixing of nanodomains with different tetragonality ratios. This phase separation was observed over the whole studied concentration range of x(Fe) values. It occurs progressively with the value of x(Fe), and the transition temperature T-C2 decreases with the concentration from about 620 K (x(Fe) = 0.03) to about 600 K (x(Fe) = 0.05), while T-C1 remains nearly constant.

H2 plasma has been used to generate carbon vacancies on reduced graphene oxide to increase its catalytic activity as a hydrogenation catalyst. A relationship between the power of the plasma treatment and the exposure time with the activity of the material was observed for CvC double bond hydrogenation. The activity data in the case of 1-octene, showing skeletal isomerization besides hydrogenation, indicate that H2 plasma treatment can introduce hydrogenating and acid sites rendering a bifunctional catalyst that is reminiscent of the activity of noble metals supported on acid supports.

The reaction of manganese(II) chloride tetrahydrate with sodium azide and ONO-donor hydrazone ligand, (H2L = (E)-3-hydroxy-N'-((2)-4-hydroxy-4-phenylbut-3-en-2-ylidene)-2-naphthohydrazide), in methanol gives rise to the formation of red crystals which are stable out of the solvent. The red crystals slowly transform to brown crystals in the methanolic solution. In the last case, the rate of the transformation from red to brown crystals mainly depends on the presence of molecular oxygen and reaction temperature. Both compounds are characterized by elemental analysis, spectroscopic methods and single crystal X-ray diffraction studies. The X-ray analysis indicates that the red crystals consist of a tetranuclear Mn(II) complex molecules, [Mn-4(H0.5L)(4) (mu(1.3)-N-3)(2)(CH3OH)(4)] (1), while the brown crystals consist of dinucelar Mn(III), [Mn2L2(mu(1.1)-OCH3)(1.5)(mu(1.1)-N-3)(0.5)] (2) molecules. In complex 1 with molecules of D2 (222) point symmetry, four Mn(II) ions are connected together by four ONO-donor hydrazone ligands and two end-to-end (EE) bridging azide anions. In complex 2 two Mn(III) ions are connected together by azide or methoxy bridging groups. Magnetic susceptibility measurements on complex 1 reveal the occurrence of antiferromagnetic couplings through azide ligands and enolate oxygen atom of the ligand in which the magnetic coupling constants have been determined. (C) 2018 Elsevier Ltd. All rights reserved.

We report for the first time on the synthesis of NiO/ZnO one-dimensional (1D) nanowire (NW) based heterostructures by applying a suitable methodology of transport and condensation. The synthesis involves, firstly the growth of NiO NWs on gold (Au) catalyzed alumina substrates using the vapor-liquid-solid (VLS) mechanism and then the formation of ZnO NWs directly on the NiO NWs using the vapor-solid (VS) mechanism. Sequential evaporation-condensation over Au-seeded alumina promotes the formation of NiO NWs, driven by the VLS growth mechanism. These NiO NWs act as backbones for the condensation of epitaxial ZnO nanostructures. The detailed morphological study of these heterostructures reveals that ZnO nanowires completely cover the whole NiO nanowires completely and growing out in the form of flat leaves from the NiO nanowire branches. The diameters of the NiO NWs have been found to vary from 15 nm to 60 nm. Selected area electron diffraction data (SAED) indicate an epitaxial growth of ZnO nanowires along (101)-planes on the strongly oriented NiO nanowires along (200) crystallographic planes. Finally, NiO NW and NiO/ZnO heterostructure based conductometric gas sensing devices have been fabricated and the comparison between their sensing performances have been compared. Interestingly, NiO/ZnO NWs heterostructure based sensing devices shows superior performance compared to NiO sensors toward volatile organic compounds (VOC). (C) 2018 Elsevier B.V. All rights reserved.