Synthesis of Nb(2)O(5)center dot nH(2)O nanoparticles by water-in-oil microemulsion

Hydrous niobium oxide (Nb(2)O(5)center dot nH(2)O) nanoparticles had been Successfully prepared by water-in-oil microemulsion. They were characterized by X-ray diffraction (XRD), thermal analysis (TG/DTG), Fourier transform infrared spectroscopy (FTIR), BET surface area measurement, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The results showed that the nanoparticle was exactly Nb(2)O(5)center dot nH(2)O with spherical shape. Their BET surface area was 60 m(2) g(-1). XRD results showed that Nb(2)O(5)center dot nH(2)O nanoparticles with crystallite size in nanometer scale were formed. The crystallinity and crystallity size increased with increasing annealing temperature. TT-phase of Nb(2)O(5) was obtained when the sample is annealed at 550 degrees C. (C) 2009 Elsevier B.V. All rights reserved.

Thermal, structural and optical properties of Al(2)CoO(4)-Crocoite composite nanoparticles used as pigments

Al(2)CoO(4)-PbCrO(4) and Al(2)CoO(4)-Pb(2)CrO(5) crystalline powders in different proportions were obtained by the polymeric precursor method. Differential scanning calorimetry (DSC) and thermogravimetry (TG) techniques were used to accurately characterize the distinct thermal events occurring during synthesis. The TG and DSC results revealed a series of overlapping decomposition reactions due to different exothermal events, which were identified as H(2)O and NO(x) elimination and polymer pyrolysis. The X-ray diffraction patterns of the xAl(2)CoO(4)-(1 - x)PbCrO(4) and xAl(2)CoO(4)-(1 - x)Pb(2)CrO(5) mixed compounds, with x = 1, 0.75, 0.5, 0.25 and 0, were obtained in the crystalline form with their respective phases, and proved consistent with the nominal compositions. The synthesis of these two systems yielded nine different colors and shades.

Evidences of the evolution from solid solution to surface segregation in Ni-doped SnO(2) nanoparticles using Raman spectroscopy

Ni-doped SnO(2) nanoparticles, promising for gas-sensing applications, have been synthesized by a polymer precursor method. X-ray diffraction (XRD) and transmission electron microscopy (TEM) data analyses indicate the exclusive formation of nanosized particles with rutile-type phase (tetragonal SnO(2)) for Ni contents below 10 mol%. The mean crystallite size shows a progressive reduction with the Ni content. Room-temperature Raman spectra of Ni-doped SnO(2) nanoparticles show the presence of Raman active modes and modes activated by size effects. From the evolution of the A(1g) mode with the Ni content, a solubility limit at similar to 2 mol% was estimated. Below that content, Raman results are consistent with the occurrence of solid solution (ss) and surface segregation (seg.) of Ni ions. Above similar to 2 mol% Ni, the redshift of A(1g) mode suggests that the surface segregation of Ni ions takes place. Disorder-activated bands were determined and their integrated intensity evolution with the Ni content suggest that the solid-solution regime favors the increase of disorder; meanwhile, that disorder becomes weaker as the Ni content is increased. Copyright (C) 2010 John Wiley & Sons, Ltd.

Quantification of MgO surface excess on the SnO(2) nanoparticles and relationship with nanostability and growth

In this work, we experimentally showed that the spontaneous segregation of MgO as surface excess in MgO doped SnO(2) nanoparticles plays an important role in the system`s energetics and stability. Using Xray fluorescence in specially treated samples, we quantitatively determined the fraction of MgO forming surface excess when doping SnO(2) with several different concentrations and established a relationship between this amount and the surface energy of the nanoparticles using the Gibbs approach. We concluded that the amount of Mg ions on the surface was directly related to the nanoparticles total free energy, in a sense that the dopant will always spontaneously distribute itself to minimize it if enough diffusion is provided. Because we were dealing with nanosized particles, the effect of MgO on the surface was particularly important and has a direct effect on the equilibrium particle size (nanoparticle stability), such that the lower the surface energy is, the smaller the particle sizes are, evidencing and quantifying the thermodynamic basis of using additives to control SnO(2) nanoparticles stability. (C) 2010 Elsevier B.V. All rights reserved.

Structural and magnetic properties of pure and nickel doped SnO(2) nanoparticles

Ni-doped SnO(2) nanoparticles prepared by a polymer precursor method have been characterized structurally and magnetically. Ni doping (up to 10 mol%) does not significantly affect the crystalline structure of SnO(2), but stabilizes smaller particles as the Ni content is increased. A notable solid solution regime up to similar to 3 mol% of Ni, and a Ni surface enrichment for the higher Ni contents are found. The room temperature ferromagnetism with saturation magnetization (MS) similar to 1.2 x 10(-3) emu g(-1) and coercive field (H(C)) similar to 40 Oe is determined for the undoped sample, which is associated with the exchange coupling of the spins of electrons trapped in oxygen vacancies, mainly located on the surface of the particles. This ferromagnetism is enhanced as the Ni content increases up to similar to 3 mol%, where the Ni ions are distributed in a solid solution. Above this Ni content, the ferromagnetism rapidly decays and a paramagnetic behavior is observed. This finding is assigned to the increasing segregation of Ni ions (likely formed by interstitials Ni ions and nearby substitutional sites) on the particle surface, which modifies the magnetic behavior by reducing the available oxygen vacancies and/or the free electrons and favoring paramagnetic behavior.

Experimental study of the structural, microscopy and magnetic properties of Ni-doped SnO(2) nanoparticles

A polymer precursor method has been used to synthesize Ni-doped SnO(2) nanoparticles. X-ray diffraction (XRD) data analyses indicate the exclusive formation of nanosized particles with rutile-type phase (tetragonal SnO(2)) for Ni contents below 10 mol%. In this concentration range, the particle sizes decrease with increasing Ni content and a bulk solid solution limit was determined at similar to 1 mol%. Ni surface enrichment is present at concentrations higher than the solution limit. Only above 10 mol% Ni. the formation of a second NiO-related phase has been determined. Magnetization measurements suggest the occurrence of ferromagnetism for samples in the solid solution regime (below similar to 1 mol%). This ferromagnetism is associated with the exchange interaction between electron spins trapped on oxygen vacancies, and is enhanced as the amount of Ni(2+) substituting at Sn(4+) sites increases. Above the solid solution limit, ferromagnetism is destroyed by the Ni surface enrichment and the system behaves as a paramagnet. (C) 2010 Elsevier B.V. All rights reserved.

Interface Energy Measurement of MgO and ZnO: Understanding the Thermodynamic Stability of Nanoparticles

Nanomaterials have triggered excitement in both fundamental science and technological applications in several fields However, the same characteristic high interface area that is responsible for their unique properties causes unconventional instability, often leading to local collapsing during application Thermodynamically, this can be attributed to an increased contribution of the interface to the free energy, activating phenomena such as sintering and grain growth The lack of reliable interface energy data has restricted the development of conceptual models to allow the control of nanoparticle stability on a thermodynamic basis. Here we introduce a novel and accessible methodology to measure interface energy of nanoparticles exploiting the heat released during sintering to establish a quantitative relation between the solid solid and solid vapor interface energies. We exploited this method in MgO and ZnO nanoparticles and determined that the ratio between the solid solid and solid vapor interface energy is 11 for MgO and 0.7 for ZnO. We then discuss that this ratio is responsible for a thermodynamic metastable state that may prevent collapsing of nanoparticles and, therefore, may be used as a tool to design long-term stable nanoparticles.

Corrosion behavior of carbon steel protected with single and bi-layer of silane films filled with silica nanoparticles

The electrochemical behaviour of carbon steel coated with bis-[trimethoxysilylpropyl]amine (BTSPA) filled with silica nanoparticles in naturally aerated 0.1 mol L-1 NaCl solutions was evaluated. The coating was prepared by adding different concentrations of silica nanoparticles (100, 200, 300, 400 and 500 ppm) to the hydrolysis solution and then a second layer without silica nanoparticles was applied. The electrochemical behavior of the coated steel was evaluated by means of open-circuit potential (E-OC), electrochemical impedance spectroscopy (EIS) and polarization curves. Surface characterization was made by atomic force microscopy (AFM), and its hydrophobicity assessed by contact angle measurements. EIS diagrams have shown an improvement of the barrier properties of the silane layer with the silica addition, which was further improved on the bi-layer system. However, a dependence on the filler concentration was verified, and the best electrochemical response was obtained for samples modified with 300 ppm of silica nanoparticles. AFM images have shown a homogeneous distribution of the silica nanoparticles on the sample surface; however particles agglomeration was detected, which degraded the corrosion protection performance. The results were explained on the basis of the improvement of the barrier properties of the coating due to the filler addition and on the onset of defective regions on the more heavily filled coatings allowing easier electrolyte penetration. (C) 2007 Elsevier B.V. All rights reserved.

Influence of the heat treatment on the nucleation of silver nanoparticles in Tm(3+) doped PbO-GeO(2) glasses

Nucleation of silver nanoparticles (NPs) in Tm(3+) doped PbO-GeO(2) (PGO) glass is reported. The influence of the heat treatment on the nucleation of silver NPs is studied by means of transmission electron microscopy and optical spectroscopy. Two heat treatment procedures were applied in order to compare their performance. Observation of infrared-to-visible frequency upconversion (UC) luminescence of Tm(3+) ions is reported and correlated with the heat-treatment procedure. Enhancement of the UC emission for samples heat treated during various time intervals is attributed to the increased local field in the vicinity of the NPs. Quenching of the UC signal was also observed and correlated with the growth of NPs amount and size.

Production and characterization of RF-sputtered PbO-GeO(2) amorphous thin films containing silver and gold nanoparticles

In the present work we report the characterization of PbO-GeO(2) films containing silver nanoparticles (NPs). Radio Frequency (RF) co-sputtering was used for deposition of amorphous films on glass substrates. Targets of 60PbO-40GeO(2) (in wt%) and bulk silver with purity of 99.99% were RF-sputtered using 3.5 m Torr of argon. The concentration of silver and gold NPs in the films was controlled varying the RF-power applied to the targets (40-50W for the PbO-GeO(2) target; 6-8 W for the metallic target). The films obtained were annealed in air at different temperatures and various periods of time. Absorption measurements have shown strong NPs surface plasmon bands. Different widths and peak wavelengths were observed, indicating that size, shape and distribution of the silver NPs are dependent on the deposition process parameters and on the annealing of the samples. X-Ray Fluorescence and Transmission Electron Microscopy were also used to characterize the samples. (C) 2010 Elsevier B.V. All rights reserved.

Influence of gold nanoparticles on optically stimulated effects in TeO(2)-ZnO and GeO(2)-PbO amorphous thin films

We have found photoinduced second harmonic generation at wavelength 1064 nm during bicolor Nd:YAG laser coherent treatment of TeO(2)-ZnO and GeO(2)-PbO amorphous films. The maximally achieved second order susceptibility was equal to about 1.02 pm/V. Correlation of the induced second order susceptibility with local sample heating and induced birefringence may indicate an occurrence of local phase transitions from amorphous glass-like phase to non-centrosymmetry metastable phases. (C) 2010 Elsevier B.V. All rights reserved.

Electron beam induced second-harmonic generation in Er(3+) doped PbO-GeO(2) glasses containing silver nanoparticles

Electron beam induced second harmonic generation (SHG) is studied in Er(3+) doped PbO-GeO(2) glasses containing silver nanoparticles with concentrations that are controlled by the heat-treatment of the samples. The SHG is observed at T = 4.2 K using a p-polarized laser beam at 1064 nm. Enhancement of the SHG is observed in the samples that are submitted to electron beam incidence. The highest value of the nonlinear susceptibility, 2.08 pm/V, is achieved for the sample heat-treated during 72 h and submitted to an electron beam current of 15 nA. The samples that were not exposed to the electron beam present a susceptibility of a parts per thousand 0.5 pm/V.

Impedimetric immunosensor for electronegative low density lipoprotein (LDL(-)) based on monoclonal antibody adsorbed on (polyvinyl formal)-gold nanoparticles matrix

Monoclonal antibodies (MAb) have been commonly applied to measure LDL in vivo and to characterize modifications of the lipids and apoprotein of the LDL particles. The electronegative low density lipoprotein (LDL(-)) has an apolipoprotein B-100 modified at oxidized events in vivo. In this work, a novel LDL-electrochemical biosensor was developed by adsorption of anti-LDL(-) MAb on an (polyvinyl formal)-gold nanoparticles (PVF-AuNPs)-modified gold electrode. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used to characterize the recognition of LDL-. The interaction between MAb-LDL(-) leads to a blockage in the electron transfer of the [Fe(CN)(6)](4-)/K(4)[Fe(CN)(6)](3-) redox couple, which may could result in high change in the electron transfer resistance (R(CT)) and decrease in the amperometric responses in CV analysis. The compact antibody-antigen complex introduces the insulating layer on the assembled surface, which increases the diameter of the semicircle, resulting in a high R(CT), and the charge transferring rate constant k(0) decreases from 18.2 x 10(-6) m/s to 4.6 x 10(-6) m/s. Our results suggest that the interaction between MAb and lipoprotein can be quantitatively assessed by the modified electrode. The PVF-AuNPs-MAb system exhibited a sensitive response to LDL(-), which could be used as a biosensor to quantify plasmatic levels of LDL(-). (C) 2011 Elsevier B.V. All rights reserved.

Amphotericin B in poly(lactic-co-glycolic acid) (PLGA) and dimercaptosuccinic acid (DMSA) nanoparticles against paracoccidioidomycosis

The present study reports on the preparation and testing of a desoxycholate amphotericin B (D-AMB) sustained delivery system based on poly(lactic-co-glycolic acid) (PLGA) and dimercaptosuccinic acid (DMSA) polymeric blends (Nano-D-AMB) aimed at reducing the number of AMB administrations required to treat mycosis. BALB/c mice were infected with the yeast Paracoccidioides brasiliensis intravenously to mimic the chronic form of paracoccidioidomycosis. At 30 days post-infection, the animals were treated with Nano-D-AMB [6 mg/kg of encapsulated D-AMB, intraperitoneally (ip), interval of 72 h] or D-AMB (2 mg/kg, ip, interval of 24 h). Drug efficacy was investigated by the fungal burden recovery from tissues. Toxicity was assessed by renal and hepatic biochemical parameters, physical appearance of the animals and haematological investigation. The control groups used were non-infected and the infected mice mock treated with PBS. Nano-D-AMB presented results comparable to free D-AMB, with a marked antifungal efficacy. The Nano-D-AMB-treated group presented lower loss of body weight and absence of stress sign (piloerection and hypotrichosis) observed after D-AMB treatment. No renal [blood urea nitrogen (BUN), creatinine] or hepatic (pyruvic and oxalacetic glutamic transaminases) biochemical abnormalities were found. The micronucleus assay showed no significant differences in both the micronucleus frequency and percentage of polychromatic erythrocytes for Nano-D-AMB, indicating the absence of genotoxicity and cytotoxic effects. The D-AMB-coated PLGA-DMSA nanoparticle showed antifungal efficacy, fewer undesirable effects and a favourable extended dosing interval. Nano-D-AMB comprises an AMB formulation able to lessen the number of drug administrations. Further studies would elucidate whether Nano-D-AMB would be useful to treat systemic fungal infections such as paracoccidioidomycosis, candidiasis, aspergillosis and cryptococcosis.

Analysis of Liquid Crystalline Nanoparticles by Small Angle X-Ray Diffraction: Evaluation of Drug and Pharmaceutical Additives Influence on the Internal Structure

The goal of this work was to study the liquid crystalline structure of a nanodispersion delivery system intended to be used in photodynamic therapy after loading with photosensitizers (PSs) and additives such as preservatives and thickening polymers. Polarized light microscopy and light scattering were performed on a standard nanodispersion in order to determine the anisotropy of the liquid crystalline structure and the mean diameter of the nanoparticles, respectively. Small angle X-ray diffraction (SAXRD) was used to verify the influence of drug loading and additives on the liquid crystalline structure of the nanodispersions. The samples, before and after the addition of PSs and additives, were stable over 90 days, as verified by dynamic light scattering. SAXRD revealed that despite the alteration observed in some of the samples analyzed in the presence of photosensitizing drugs and additives, the hexagonal phase still remained in the crystalline phase. (C) 2011 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 100: 2849-2857, 2011