Differently shaped nanocrystalline (Fe, Y)3O4 and its adsorption efficiency toward inorganic arsenic species.

Herein we report effects of partial substitution of Fe3+ by Y3+ in magnetite (Fe3O4) on morphology and inorganic arsenic species adsorption efficiency of the Fe3-x Y x O4 nanoparticles formed. The series of Fe3-x Y x O4 (x = 0.00, 0.042 and 0.084, labeled as Y00, Y05 and Y10, respectively) was synthesized using co-precipitation followed by microwave-hydrothermal treatment (MW) at 200 °C. With increase of yttrium content (x value), both the morphological inhomogeneity of the samples and the fraction of spinel nanorods as compared to spinel pseudospherical particles increased. By both transmission electron microscopy and x-ray powder diffraction analyses, it was determined that the direction of growth of the spinel nanorods is along the [110] crystallographic direction. The Fe3-x Y x O4 affinities of adsorption toward the inorganic arsenic species, As(III) (arsenite, AsO3 3-) and As(V) (arsenate, AsO4 3-), were investigated. Increased Y3+ content related to changes in sample morphology was followed by a decrease of As(III) removal efficiency and vice versa for As(V). The increase in Y3+ content, in addition to increasing the adsorption capacity for As(V), significantly expanded the optimum pH range for the maximum removal and decreased the contact time for necessary 50% removal (t 1/2) of As(V) (Y00: pH 2-3, t 1/2 = 3.12 min; Y05: pH 2-6, t 1/2 = 2.12 min and Y10: pH 2-10, t 1/2 = 1.12 min). The results point to incorporation of Y3+ in the crystal lattice of magnetite, inducing nanorod spinel structure formation with significant changes in sorption properties important for the removal of inorganic arsenic from waters.

Cobalt Ferrite Nanospheres as a Potential Magnetic Adsorbent for Chromium(VI) Ions.

In the present work the cobalt ferrite nanospheres (CFO NS) were prepared via one-step, templatefree solvothermal method and used as a magnetic adsorbent of chromium(VI) ions. The synthesized materials were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and vibrating sample magnetometry (VSM). The XRD results confirmed the cubic spinel structure of CFO NS while the SEM revealed sphere-like morphology with diameters of the CFO NS in the range of 100-300 nm. TEM images showed that each NS is composed of smaller CFO nanoparticles with size around 7-8 nm. The magnetic measurements revealed ferromagnetic character of CFO nanospheres with the maximum saturation magnetization and coercivity of 75 emu/g and 677 Oe, respectively. The synthetized CFO NS were tested as an adsorption material for removal of chromium(VI) ions from aqueous solution. The obtained removal efficiency is in the range from 38 to 88%. The results suggest that the adsorption capacity of CFO NS strongly depends on conditions of the solvothermal synthesis.

Enhancing Analytical Performance of (Mg,Fe)3O4/Glassy Carbon Electrodes by Tailoring Chemical Composition of (Mg,Fe)3O4 Nanoparticles.

A series of MgxFe3-xO4 (x ═ 0-1) nanoparticles was synthesized in order to prepare novel MgxFe3-xO4/glassy carbon modified electrodes. Effects of magnesium content (x) on the analytical performance of the modified electrodes in the detection of gallic acid were evaluated. It was found that magnesium concentration and crystallite/particle size of the prepared nanoparticles play significant roles in the sensing properties of modified electrodes. The increase of magnesium concentration up to the value of x ═ 0.4 in MgxFe3-xO4/glassy carbon paste was accompanied by an increase of the corresponding oxidation current of gallic acid. However, further growth of x value caused decline of the obtained oxidation current. An electroanalytical procedure was established, and the analytical performance of the proposed Mg0.4Fe2.6O4/glassy carbon paste electrode was monitored using previously optimized experimental conditions. A working linear range from 1-39 µM gallic acid was obtained with detection limit of 0.29 µM. According to these results, the developed procedure can be applied for detection of low concentrations of gallic acid with satisfactory selectivity in the presence of some common naturally occurring compounds. Experimental results indicate that the developed procedure could be a novel approach in the detection of antioxidant, overcoming some known disadvantages such as passivation, and could be a promising replacement for sophisticated chromatographic methods.

Nano-engineering the Antimicrobial Spectrum of Lantibiotics: Activity of Nisin against Gram Negative Bacteria.

Lantibiotics, bacteria-sourced antimicrobial peptides, are very good candidates for effective and safe food additives. Among them, nisin is already approved by the EU and FDA, and has been used in food preservation for the past 40 years. Now, there is a possibility and strong interest to extend its applicability to biomedicine for designing innovative alternatives to antibiotics. The main obstacle is, however, its naturally narrow spectrum of antimicrobial activity, focused on Gram positive bacteria. Here we demonstrate broadening nisin's spectrum to Gram negative bacteria using a nano-engineering approach. After binding nisin molecules to the surface of gold nano-features, uniformly deposited on spherical carbon templates, we created a nanocomposite with a high density of positively charged groups. Before assembly, none of the components of the nanocomposite showed any activity against bacterial growth, which was changed after assembly in the form of the nanocomposite. For the first time we showed that this type of structure enables interactions capable of disintegrating the wall of Gram negative bacteria. As confirmed by the nisin model, the developed approach opens up new horizons for the use of lantibiotics in designing post-antibiotic drugs.

Domain-wall conduction in ferroelectric BiFeO3 controlled by accumulation of charged defects.

Mobile charged defects, accumulated in the domain-wall region to screen polarization charges, have been proposed as the origin of the electrical conductivity at domain walls in ferroelectric materials. Despite theoretical and experimental efforts, this scenario has not been directly confirmed, leaving a gap in the understanding of the intriguing electrical properties of domain walls. Here, we provide atomic-scale chemical and structural analyses showing the accumulation of charged defects at domain walls in BiFeO3. The defects were identified as Fe4+ cations and bismuth vacancies, revealing p-type hopping conduction at domain walls caused by the presence of electron holes associated with Fe4+. In agreement with the p-type behaviour, we further show that the local domain-wall conductivity can be tailored by controlling the atmosphere during high-temperature annealing. This work has possible implications for engineering local conductivity in ferroelectrics and for devices based on domain walls.

Cu and CuO/titanate nanobelt based network assemblies for enhanced visible light photocatalysis.

3D network configurations of copper(II) oxide/titanate nanobelt (CuO/TiNBs) and copper/titanate nanobelt (Cu/TiNBs) were formed using a two-step polyelectrolyte-assisted synthesis and assembly approach. The photoactivity of the TiNB/CuO and Cu/TiNB composite networks is significantly enhanced as compared to the activity of 3D structures formed of pristine TiNB. An efficient, UV-vis-light-induced electron transfer at the two-component interface achieved by the intimate coupling of TiNB with p-type semiconducting CuO and plasmonic Cu nanoparticles in composite heterostructures facilitates control over the system's exciton dynamics, which results in highly efficient UV-vis photocatalytic performance of heterostructures. The superior photocatalytic activity of the metal and semiconductor/semiconductor nanocomposite structures in the visible region is discussed, highlighting the role of interfacial electron-charge transfer (IFCT) in semiconductor-semiconductor (CuO/TiNB) and surface plasmon resonance (SPR) of Cu nanoparticles in metal-semiconductor heterostructures.

Tem analyses of the local crystal and domain structures in (Na(1-x)K(x))0.5Bi(0.5)TiO3 perovskite ceramics.

The local crystal and domain structures of the ((Na(1-x)K(x))(0.5)Bi(0.5)TiO(3) (NBT-KBT) solid solutions were studied because of their influence on the enhanced electromechanical properties of ceramics. Based on X-ray diffraction, the morphotropic phase boundary (MPB) was determined for the composition x = 0.20, in which the rhombohedral and the tetragonal structures were observed to coexist. However, detailed domain-structure analyses using transmission electron microscopy (TEM), performed on the NBT, KBT, and five NBT-KBT solid-solution compositions, revealed some structural changes at/near the MPB. In the samples on the tetragonal side of the MPB, the grains showed a lamellar domain structure with 90° orientations of the individual domains, separated by straight domain boundaries, i.e., (011)/(101) twin planes. The rhombohedral samples on the other side of the MPB showed a typical square-net pattern with needle-like or lamellar ~71°/109° rhombohedral domains with (001) and/or (110) twin planes separating the individual domains. The domain structure at the MPB showed well-defined lamellar domains. Based on the occurrence of the superstructure reflections in the SAED patterns of various crystallographic zones, on the characteristic splitting of the reflections, and on the domain morphology observations, the crystal structure in/near the boundary region was determined to be a tetragonal structure with an in-phase oxygen octahedral tilt system (probably a(0)a(0)c(+)). It is suggested that the tetragonal polar order is partly induced from the rhombohedral structure at the MPB as a result of mechanical loading during TEM sample preparation.

Silver nanoparticles on titanate nanobelts via the self-assembly of weak polyelectrolytes: synthesis and photocatalytic properties.

A weak-polyelectrolyte multilayer on a surface of titanate nanobelts (Ti-NBs) was utilized as a template for in situ Ag nanoparticle formation in the fabrication of Ag-loaded Ti-NBs nanocomposites. The polyelectrolyte multilayer (PEM) was fabricated using layer-by-layer self-assembly of poly(acrylic acid) (PAA) and poly(allylamine hydrochloride) (PAH) on the surface of high-surface-area titanate nanobelts (Ti-NBs) synthesized using a hydrothermal procedure. The concentration of Ag nanoparticles in the PEM was controlled by repeating the ion-loading/reduction cycle. The subsequent annealing of the Ag/Ti-NBs-PEM nanocomposites yielded nanostructured crystalline Ag/Ti-NBs. Transmission electron microscopy (TEM) techniques (HRTEM, SAED) and x-ray powder diffraction (XRD) were employed to evaluate the morphological, structural and growth characteristics of the silver nanocrystallites in the Ag/Ti-NBs nanocomposites. The UV-vis photoactivity of the as-fabricated nanocomposites was monitored by the degradation of the cationic dye methylene blue (MB). An enhanced UV photo-efficiency was observed for the Ag/Ti-NBs nanocomposites compared with pure Ti-NBs. As-fabricated Ag(x)/Ti-NBs nanocomposites also exhibited visible photoactivity assisted by the near-field amplitudes of the localized surface plasmon resonance (LSPR) of the silver nanoparticles in the 1D nanocomposite.

Poly(D,L-lactide-co-glycolide)/hydroxyapatite core-shell nanospheres. Part 1: A multifunctional system for controlled drug delivery.

Biodegradable poly(d,l-lactide-co-glycolide) (PLGA) and bioactive hydroxyapatite (HAp) are selected for the formation of a multifunctional system with the specific core-shell structure to be applied as a carrier of a drug. As a result, both components of PLGA/HAp core-shells are able to capture one part of the drug. Polymeric shells consisting of small nanospheres up to 20nm in size act as a matrix in which one part of the drug is dispersed. In the same time, ceramic cores are formed of rod-like hydroxyapatite particles at the surface of which another part of the drug is adsorbed onto the interface between the polymer and the ceramics. The content of the loaded drug, as well as the selected solvent/non-solvent system, have a crucial influence on the resulting PLGA/HAp morphology and, finally, unimodal distribution of core-shells is obtained. The redistribution of the drug between the organic and inorganic parts of the material is expected to provide an interesting contribution to the kinetics of the drug release resulting in non-typical two-step drug release.

Weak polyion multilayer-assisted in situ synthesis as a route toward a plasmonic Ag/TiO2 photocatalyst.

Nanocrystalline Ag/TiO(2) composite thin films were synthesized using a two-step synthesis methodology: the in situ precipitation of Ag nanoparticles followed by an in situ sol-gel reaction of titanium iso-propoxide in a weak polyion multilayer (PEM) template formed by the layer-by-layer (LbL) self-assembly of poly(acrylic acid) (PAA) and polyallylamine (PAH). Because the PEM template is assembled from weak polyions, it contains nonionized carboxylic groups that are able to react with the inorganics, resulting in the formation of a homogeneous Ag(x)/TiO(2)-PEM precursor film, where the content of Ag is controlled by repeating the Ag loading cycle. The subsequent annealing of the precursor yields nanostructured Ag(x)/TiO(2) films with thicknesses controlled by the PEM template on the nanometer scale. Transmission electron, field-emission scanning electron, and atomic force microscopy methods were employed to evaluate the morphology and growth characteristics of the metallic and semiconductor nanocrystallites in the Ag(x)/TiO(2) composite thin films. The as-formed Ag(x)/TiO(2) composite thin films exhibited UV-visible photoactivity monitored by the decomposition of methylene blue (MB). In the near-UV range, the expected photocatalytic behavior of TiO(2) is greatly enhanced because it is assisted by the near-field amplitudes of the localized surface plasmon resonance (LSPR) of the Ag nanoparticles in the Ag(x)/TiO(2) films.

Controlled synthesis of pure and doped ZnS nanoparticles in weak polyion assemblies: growth characteristics and fluorescence properties.

A polyelectrolyte multilayer (PEM) fabricated by the layer-by-layer (LbL) self-assembly of weak polyions of polyacrylic acid (PAA) and polyallylamine (PAH) was applied as a matrix for the in situ nucleation and growth of pure and Mn-doped ZnS nanocrystallites. The nucleation and growth is initiated by the adsorption and binding of the metal ions to the ionized carboxylic groups of the weak polyions within the matrix, followed by the subsequent precipitation of semiconductor nanocrystallites with Na(2)S. Transmission electron microscopy (TEM), atomic force microscopy (AFM) and UV-vis spectroscopy were employed to establish the growth characteristics of the spherical ZnS nanocrystallites in the polyion matrix. The conformational arrangement of polyion chains induced by variation in the assembly pH is the key parameter that affects the structural and morphological characteristics of ZnS nanocrystallites. Repeating the reaction cycle resulted in an increase in the volume density of ZnS nanoparticles and further growth of the initially formed particles by the Ostwald ripening mechanism. The surface passivation of the ZnS nanocrystallites within the polyion matrix enables the enhanced radiative emission of ZnS composite films in the UV range, whereas by doping the ZnS, nanocrystallites show emission characteristic of the manganese ions in the visible region.

Enhanced tunable characteristics of the Na0.5Bi0.5TiO3-NaTaO3 relaxor-type system.

We have investigated the voltage-tunable characteristics of the Na(0.5)Bi(0.5)TiO(3)-NaTaO(3) homogeneity region, for which samples were prepared using a conventional solid-state reaction. The highest value of the relative tunability (n(r)) was obtained for the sample with 5 mol% of NaTaO(3), i.e., 47% at 1 MHz and a 70 kV/cm dc bias field. This sample also showed the highest value of the dielectric losses (tan delta) and temperature coefficient of the dielectric constant (tau(epsilon)), i.e., 0.05 and 4478 ppm/K, respectively. As the concentration of NaTaO(3) increased up to 90 mol% n(r), tan delta, and tau(epsilon) gradually decreased toward 22%, 0.0002 and -899 ppm/K, respectively. The dielectric constant of the samples varied in a similar manner between 662 and 130. At microwave frequencies, the dielectric losses of the samples substantially increased due to their relaxor-type nature. The lowest value was obtained for the samples with 90 mol% of NaTaO(3), i.e., 0.002. The tunable characteristics of the samples are related to the ferroelectric and dielectric properties, and it appears that the dielectric tunability of the Na(0.5)Bi(0.5)TiO(3)-NaTaO(3) system originates from its relaxor-type behavior.

The influence of the reaction temperature on the morphology of sodium titanate 1D nanostructures and their thermal stability.

We have synthesized large quantities of sodium-titanate-based nanotubes and nanoribbons with high yields under hydrothermal conditions from anatase powder in an aqueous NaOH solution. The reaction temperatures were from 95 to 195 degrees C, in steps of 20 degrees C. We observed that the morphology of the nanomaterials, which is reflected in their specific surface areas, depends strongly on the reaction temperature. For the materials synthesized in the range 95-135 degrees C and above 155 degrees C only a single morphology type was observed for the nanostructures, i.e., nanotubes and nanoribbons, respectively. In contrast, when the reaction was carried out at 155 degreesC, both nanotubes and nanoribbons were found in the product. SEM, TEM, and XRD techniques were used to determine the materials' morphological and structural properties, and the thermal stability of the materials was investigated with TGA and DSC. The largest weight loss, of approximately 25%, was observed in a temperature range from 25 up to 600 degrees C for the product obtained at 95 degrees C, probably due to the presence of unrolled titanate sheets.