Effectiveness, against tuberculosis, of pseudo-ternary complexes: Peptide-DNA-cationic liposome

We report the effects of a synthetic peptide designed to act as a nuclear localization signal on the treatment of tuberculosis. The peptide contains 21 amino acid residues with the following specific domains: nuclear localization signal from SV 40T, cationic shuttle sequence, and cysteamide group at the C-terminus. The peptide was complexed with the plasmid DNAhsp65 and incorporated into cationic liposomes, forming a pseudo-ternary complex. The same cationic liposomes, composed of egg chicken L-alpha-phosphatidylcholine, 1,2-dioleoyl-3-trimethylammonium-propane, and 1,2-dioleoyl-3-trimethylammonium-propane (2:1:1 M), were previously evaluated as a gene carrier for tuberculosis immunization protocols with DNAhsp65. The pseudo-ternary complex presented a controlled size (250 nm), spherical-like shape, and various lamellae in liposomes as evaluated by transmission electron microscopy. An assay of fluorescence probe accessibility confirmed insertion of the peptide/DNA into the liposome structure. Peptide addition conferred no cytotoxicity in vitro, and similar therapeutic effects against tuberculosis were seen with four times less DNA compared with naked DNA treatment. Taken together, the results indicate that the pseudo-ternary complex is a promising gene vaccine for tuberculosis treatment. This work contributes to the development of multifunctional nanostructures in the search for strategies for in vivo DNA delivery. (C) 2011 Elsevier Inc. All rights reserved.

Band structure calculations of InP wurtzite/zinc-blende quantum wells

Semiconductor nanowhiskers (NWs) made of III-V compounds exhibit great potential for technological applications. Controlling the growth conditions, such as temperature and diameter, it is possible to alternate between zinc-blende (ZB) and wurtzite (WZ) crystalline phases, giving origin to the so called polytypism. This effect has great influence in the electronic and optical properties of the system, generating new forms of confinement to the carriers. A theoretical model capable to accurately describe electronic and optical properties in these polytypical nanostructures can be used to study and develop new kinds of nanodevices. In this study, we present the development of a wurtzite/zinc-blende polytypical model to calculate the electronic band structure of nanowhiskers based on group theory concepts and the k.p method. Although the interest is in polytypical superlattices, the proposed model was applied to a single quantum well of InP to study the physics of the wurtzite/zinc-blende polytypism. By the analysis of our results, some trends can be predicted: spatial carriers' separation, predominance of perpendicular polarization (xy plane) in the luminescence spectra, and interband transition blueshifts with strain. Also, a possible range of values for the wurtzite InP spontaneous polarization is suggested. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4767511]

Tailored SERS substrates obtained with cathodic arc plasma ion implantation of gold nanoparticles into a polymer matrix

This manuscript reports on the fabrication of plasmonic substrates using cathodic arc plasma ion implantation, in addition to their performance as SERS substrates. The technique allows for the incorporation of a wide layer of metallic nanoparticles into a polymer matrix, such as PMMA. The ability to pattern different structures using the PMMA matrix is one of the main advantages of the fabrication method. This opens up new possibilities for obtaining tailored substrates with enhanced performance for SERS and other surface-enhanced spectroscopies, as well as for exploring the basic physics of patterned metal nanostructures. The architecture of the SERS-active substrate was varied using three adsorption strategies for incorporating a laser dye (rhodamine): alongside the nanoparticles into the polymer matrix, during the polymer cure and within nanoholes lithographed on the polymer. As a proof-of-concept, we obtained the SERS spectra of rhodamine for the three types of substrates. The hypothesis of incorporation of rhodamine molecules into the polymer matrix during the cathodic arc plasma ion implantation was supported by FDTD (Finite-Difference Time-Domain) simulations. In the case of arrays of nanoholes, rhodamine molecules could be adsorbed directly on the gold surface, then yielding a well-resolved SERS spectrum for a small amount of analyte owing to the short-range interactions and the large longitudinal field component inside the nanoholes. The results shown here demonstrate that the approach based on ion implantation can be adapted to produce reproducible tailored substrates for SERS and other surface-enhanced spectroscopies.

Comparative study on the far-field spectra and near-field amplitudes for silver and gold nanocubes irradiated at 514, 633 and 785 nm as a function of the edge length

We describe a systematic investigation by the discrete dipole approximation on the optical properties of silver (Ag) and gold (Au) nanocubes as a function of the edge length in the 20-100 nm range. Our results showed that, as the nanocube size increased, the plasmon resonance modes shifted to higher wavelengths, the contribution from scattering to the extinction increased, and the quadrupole modes became more intense in the spectra. The electric field amplitudes at the surface of the nanocubes were calculated considering 514, 633 and 785 nm as the excitation wavelengths. While Ag nanocubes displayed the highest electric field amplitudes (vertical bar E vertical bar(max)) when excited at 514 nm, the Au nanocubes displayed higher vertical bar E vertical bar(max) values than Ag, for all sizes investigated, when the excitation wavelength was either 633 or 785 nm. The variations in vertical bar E vertical bar(max) as a function of size for both Ag and Au nanocubes could be explained based on the relative position of the surface plasmon resonance peak relative to the wavelength of the incoming electromagnetic wave. Our results show that not only size and composition, but also the excitation wavelength, can play an important role over the maximum near-field amplitudes values generated at the surface of the nanocubes.

Classical magnetoresistance of a ballistic electron gas constrained to non-planar topographies in a lattice of antidots under tilted magnetic field

The classical magnetoresistance of a two-dimensional electron gas constrained to non-planar topographies, in antidot lattices, and under the influence of tilted magnetic field in arbitrary direction is numerically studied. (C) 2012 Elsevier B.V. All rights reserved.

Contribution of the cashew gum (Anacardium occidentale L.) for development of layer-by-layer films with potential application in nanobiomedical devices

The search for bioactive molecules to be employed as recognition elements in biosensors has stimulated researchers to pore over the rich Brazilian biodiversity. In this sense, we introduce the use of natural cashew gum (Anacardium occidentale L) as an active biomaterial to be used in the form of layer-by-layer films, in conjunction with phthalocyanines, which were tested as electrochemical sensors for dopamine detection. We investigated the effects of chemical composition of cashew gum from two different regions of Brazil (Piaui and Ceara states) on the physico-chemical characteristics of these nanostructures. The morphology of the nanostructures containing cashew gum was studied by atomic force microscopy which indicates that smooth films punctuated by globular features were formed that showed low roughness values. The results indicate that, independent of the origin, cashew gum stands out as an excellent film forming material with potential application in nanobiomedical devices as electrochemical sensors. (c) 2012 Elsevier B.V. All rights reserved.

Growth kinetics of CdS in germanium oxide glassy matrix

In the present work we revisit the size data of CdS microcrystals previously collected in the glassy matrix of Germanium oxide. The CdS clusters analyzed using electron microscopy images have shown a wurtzite structure. The mean average radius, dispersion and volume evaluated from the histograms showed good agreement for t(1/3), t(2/3) and t laws, respectively. We observed that the amount of microcrystals remains constant throughout the heat treatment process, as well as that the radii distribution has a lower limit and increases with heat treatment. The distribution of radii follows a distribution similar to the Lifshitz-Slyozov-Wagner distribution limited in the origin. Discussions led to the conclusion that the growth of CdS is a process that occurs after the fluctuating nucleation and coalescence phases. We then analyze the growth process, assuming that the evaporation is overcome by the precipitation rate, stabilizing all clusters with respect to dissolution back into the matrix. The problem was simplified neglecting anisotropy and the assuming a spherical shape for clusters and particles. The low interface tension was described in terms of an empirical potential barrier in the surface of the cluster. The growth dynamics developed considering that the number of clusters remains constant, and that the minimum size of these clusters grow with time, as the first order approximation showed a good agreement with the flaw. (C) 2012 Elsevier B.V. All rights reserved.

Quantum Mechanics Insight into the Microwave Nucleation of SrTiO3 Nanospheres

An extensive investigation of strontium titanate, SrTiO3 (STO), nanospheres synthesized via a microwave-assisted hydrothermal (MAH) method has been conducted to gain a better insight into thermodynamic, kinetic, and reaction phenomena involved in STO nucleation and crystal growth processes. To this end, quantum chemical modeling based on the density functional theory and periodic super cell models were done. Several experimental techniques were employed to get a deep characterization of structural and optical features of STO nanospheres. A possible formation mechanism was proposed, based on dehydration of titanium and strontium clusters followed by mesoscale transformation and a self-assembly process along an oriented attachment mechanism resulting in spherical like shape. Raman and XANES analysis renders a noncentrosymmetric environment for the octahedral titanium, while infrared and first order Raman modes reveal OH groups which are unsystematically incorporated into uncoordinated superficial sites. These results seem to indicate that the key component is the presence of distorted TiO6 clusters to engender a luminescence property. Analysis of band structure, density Of states, and charge map shows that there is a close relationship among local broken symmetry, polarization, and energy split of the 3d orbitals of titanium. The interplay among these electronic and structural features provides necessary conditions to evaluate its luminescent properties under two energy excitation.

In-plane mapping of buried InGaAs quantum rings and hybridization effects on the electronic structure

This work reports the investigation on the structural differences between InAs quantum rings and their precursor quantum dots species as well as on the presence of piezoelectric fields and asymmetries in these nanostructures. The experimental results show significant reduction in the ring dimensions when the sizes of capped and uncapped ring and dot samples are compared. The iso-lattice parameter mapped by grazing-incidence x-ray diffraction has revealed the lateral extent of strained regions in the buried rings. A comparison between strain and composition of dot and ring structures allows inferring on how the ring formation and its final configuration may affect optical response parameters. Based on the experimental observations, a discussion has been introduced on the effective potential profile to emulate theoretically the ring-shape confinement. The effects of confinement and strain field modulation on electron and hole band structures are simulated by a multiband k.p calculation. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4733964]

Field dependent transition to the non-linear regime in magnetic hyperthermia experiments: Comparison between maghemite, copper, zinc, nickel and cobalt ferrite nanoparticles of similar sizes

Further advances in magnetic hyperthermia might be limited by biological constraints, such as using sufficiently low frequencies and low field amplitudes to inhibit harmful eddy currents inside the patient's body. These incite the need to optimize the heating efficiency of the nanoparticles, referred to as the specific absorption rate (SAR). Among the several properties currently under research, one of particular importance is the transition from the linear to the non-linear regime that takes place as the field amplitude is increased, an aspect where the magnetic anisotropy is expected to play a fundamental role. In this paper we investigate the heating properties of cobalt ferrite and maghemite nanoparticles under the influence of a 500 kHz sinusoidal magnetic field with varying amplitude, up to 134 Oe. The particles were characterized by TEM, XRD, FMR and VSM, from which most relevant morphological, structural and magnetic properties were inferred. Both materials have similar size distributions and saturation magnetization, but strikingly different magnetic anisotropies. From magnetic hyperthermia experiments we found that, while at low fields maghemite is the best nanomaterial for hyperthermia applications, above a critical field, close to the transition from the linear to the non-linear regime, cobalt ferrite becomes more efficient. The results were also analyzed with respect to the energy conversion efficiency and compared with dynamic hysteresis simulations. Additional analysis with nickel, zinc and copper-ferrite nanoparticles of similar sizes confirmed the importance of the magnetic anisotropy and the damping factor. Further, the analysis of the characterization parameters suggested core-shell nanostructures, probably due to a surface passivation process during the nanoparticle synthesis. Finally, we discussed the effect of particle-particle interactions and its consequences, in particular regarding discrepancies between estimated parameters and expected theoretical predictions. Copyright 2012 Author(s). This article is distributed under a Creative Commons Attribution 3.0 Unported License. [http://dx.doi. org/10.1063/1.4739533]

The influence of different indium-composition profiles on the electronic structure of lens-shaped InxGa1-xAs quantum dots

We present effective-mass calculations of the bound-state energy levels of electrons confined inside lens-shaped InxGa1-xAs quantum dots (QDs) embedded in a GaAs matrix, taking into account the strain as well as the In gradient inside the QDs due to the strong In segregation and In-Ga intermixing present in the InxGa1-xAs/GaAs system. In order to perform the calculations, we used a continuum model for the strain, and the QDs and wetting layer were divided into their constituting monolayers, each one with a different In concentration, to be able to produce a specific composition profile. Our results clearly show that the introduction of such effects is very important if one desires to correctly reproduce or predict the optoelectronic properties of these nanostructures.

Molecular organization and doping in poly(2-methoxyaniline)/Ni(dmit)(2) films obtained with the Langmuir-Blodgett technique

The control of the properties of materials at the molecular level is pursued for many applications, especially those associated with nanostructures. In this paper, we show that the coordination compound [Ni(dmit)(2)], where (dmit) is the 1,3-dithiole-2-thione-4,5-dithiolate ligand, can induce doping of poly(2-methoxyaniline) (POMA) in molecularly ordered Langmuir and Langmuir-Blodgett (LB) films. Doping was associated with interactions between the components and the compression of the Langmuir film at the air-water interface, according to polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS) data. Taking these results together with in situ UV-Vis absorption measurements, we could identify the molecular groups involved in the interaction, including the way they were reoriented upon film compression. The Langmuir films were sufficiently stable to be transferred as Y-type LB films, while the hybrid POMA/[Ni(dmit)(2)] films remain doped in the solid state. As expected, the molecular charges affected the film morphology, as observed from combined atomic and electric force microscopy measurements. In summary, with adequate spectroscopy and microscopy tools we characterized molecular-level interactions, which may allow one to design molecular electronic devices with controlled electrical properties.

Size-induced diffuse behavior in Pb0.89La0.11Zr0.40Ti0.60O3 nanocrystalline ferroelectric ceramics

The Pb1-xLaxZryTi1-yO3 system is a perovskite ABO(3) structured material which presents ferroelectric properties and has been used as capacitors, actuators, transducers and electro-optic devices. In this paper, we describe the synthesis and the characterization of Pb0.89La0.11Zr0.40Ti0.60O3 (PLZT11) nanostructured material. The precursor polymeric method and the spark plasma sintering technique were respectively used to prepare ceramic samples. In order to compare the effect of grain size, microcrystalline PLZT11 ceramic samples were also prepared. PLZT11 samples were characterized by X-ray diffraction technique which results show a reduction on the degree of tetragonality as the average grain size decreases. Moreover, the grain size decrease to a nanometer range induces a diffuse behavior on the dielectric permittivity curves as a function of the temperature and a reduction on the dielectric permittivity magnitude. Furthermore, the large number of grain boundaries due to the nanometer size gives rise to a dielectric anomaly. (C) 2012 Elsevier Masson SAS. All rights reserved.

Cellulose micro/nanofibres from Eucalyptus kraft pulp: Preparation and properties

There is growing interest in cellulose nanofibres from renewable sources for several industrial applications. However, there is a lack of information about one of the most abundant cellulose pulps: bleached Eucalyptus kraft pulp. The objective of the present work was to obtain Eucalyptus cellulose micro/nanofibres by three different processes, namely: refining, sonication and acid hydrolysis of the cellulose pulp. The refining was limited by the low efficiency of isolated nanofibrils, while sonication was more effective for this purpose. However, the latter process occurred at the expense of considerable damage to the cellulose structure. The whiskers obtained by acid hydrolysis resulted in nanostructures with lower diameter and length, and high crystallinity. Increasing hydrolysis reaction time led to narrower and shorter whiskers, but increased the crystallinity index. The present work contributes to the different widespread methods used for the production of micro/nanofibres for different applications. (C) 2012 Elsevier Ltd. All rights reserved.

Magnetic Ionic Liquids Produced by the Dispersion of Magnetic Nanoparticles in 1-n-Butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMI.NTf2)

This paper reports on the advancement of magnetic ionic liquids (MILs) as stable dispersions of surface-modified gamma-Fe2O3, Fe3O4, and CoFe2O4 magnetic nanoparticles (MNPs) in a hydrophobic ionic liquid, 1-n-butyl 3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMI.NTf2). The MNPs were obtained via coprecipitation and were characterized using powder X-ray diffraction, transmission electron microscopy, Raman spectroscopy and Fourier transform near-infrared (FT-NIR) spectroscopy, and magnetic measurements. The surface-modified MNPs (SM-MNPs) were obtained via the silanization of the MNPs with the aid of 1-butyl-3[3-(trimethoxysilyl)propyl]imidazolium chloride (BMSPI.Cl). The SM-MNPs were characterized by Raman spectroscopy and Fourier trail: form infrared attenuated total reflectance (FTIR-ATR) spectroscopy and by magnetic measurements. The FTIR-ATR spectra of the SM-MNPs exhibited characteristic absorptions of the imidazolium and those of the Fe-O-Si-C moieties, confirming the presence of BMSPI.Cl on the MNP surface. Thermogravimetric analysis (TGA) showed that the SM-MNPs were modified by at least one BMSPI.Cl monolayer. The MILs were characterized using Raman spectroscopy, differential scanning calorimetry (DSC), and magnetic measurements. The Raman and DSC results indicated an interaction between the SM-MNPs and the IL. This interaction promotes the formation of a supramolecular structure close to the MNP surface that mimics the IL structure and is responsible for the stability of the MIL. Magnetic measurements of the MILs indicated no hysteresis. Superparamagnetic behavior and a saturation magnetization of similar to 22 emu/g could be inferred from the magnetic measurements of a sample containing 50% w/w gamma-Fe2O3 SM-MNP/BMI-NTf2.