Ion-sensing properties of 1D vanadium pentoxide nanostructures

The application of one-dimensional (1D) V2O5 center dot nH(2)O nanostructures as pH sensing material was evaluated. 1D V2O5 center dot nH(2)O nanostructures were obtained by a hydrothermal method with systematic control of morphology forming different nanostructures: nanoribbons, nanowires and nanorods. Deposited onto Au-covered substrates, 1D V2O5 center dot nH(2)O nanostructures were employed as gate material in pH sensors based on separative extended gate FET as an alternative to provide FET isolation from the chemical environment. 1D V2O5 center dot nH(2)O nanostructures showed pH sensitivity around the expected theoretical value. Due to high pH sensing properties, flexibility and low cost, further applications of 1D V2O5 center dot nH(2)O nanostructures comprise enzyme FET-based biosensors using immobilized enzymes.

Fluctuation of Anti-Endothelial Cell Antibody Titers in Mixed Connective Tissue Disease

Background: Antibodies directed against endothelial cell surface antigens have been described in many disorders and have been associated with disease activity. Since the most prominent histopathologic feature in mixed connective tissue disease (MCTD) is the widespread and unique proliferative vascular lesion, our aim was to evaluate the frequency of anti-endothelial cell antibodies (AECA) in this condition. Objectives: To evaluate the frequency of AECA in this disease and assess its clinical and laboratory associations. Methods: Seventy-three sera from 35 patients with MCTD (Kasukawa's criteria), collected during a 7 year period, were tested for immunoglobulins G and M (IgG and IgM) AECA by cellular ELISA, using HUVEC (human umbilical vein endothelial cells). Sera from 37 patients with systemic lupus erythematosus (SLE), 22 with systemic sclerosis (SSc) and 36 sera from normal healthy individuals were used as controls. A cellular ELISA using HeLa cells was also performed as a laboratory control method. Results: IgG-AECA was detected in 77% of MCTD patients, 54% of SLE patients, 36% of SSc patients and 6% of normal controls. In MCTD, IgG-AECA was associated with vasculitic manifestations, disease activity and lymphopenia, and was also a predictor of constant disease activity. Immunosuppressive drugs were shown to reduce IgG-AECA titers. Since antibodies directed to HeLa cell surface were negative, AECA was apparently unrelated to common epitopes present on epithelial cell lines. Conclusions: AECA are present in a large proportion of patients with MCTD and these antibodies decrease after immunosuppressive treatment. IMAJ 2012; 14:84-87

Two-photon excitation and optical limiting in polyfluorene derivatives

Fluorene-based polymers are widely known materials due to a combination of features such as photoluminescence and electroluminescence, oxidative stability, and film-forming ability. However, studies reporting nonlinear optical properties in this class of conjugated polymer are scarce. Here, we report a new class of polyfluorene derivatives poly(9,9'-n-dihexyl-2,7-fluorenedilvinylene-alt-1,4-phenylenevinylene), poly(9,9'-n-dihexyl-2,7-fluorenedilvinylene-alt-2,5-thiophene), and poly[(9,9-di-hexylfluorenediylvinylene-alt-1,4-phenylenevinylene)-co-((9,9'-(3-t-butylpropanoate) fluorene-1,4-phenylene)] displaying high two-photon absorption (2PA) in the spectral range from a 490 to 1100 nm. The 2PA cross-section peak values for these materials are as high as 3000 Goppert Mayer (1 GM = 1 x 10-50 cm4 s/photon), which is related to the high degree of conjugation along the polymer backbone. The polymers that were used in this study presented a strong two-photon luminescence and also displayed optical limiting behavior, which, in combination with their well-established properties, make them highly suitable for nonlinear optical devices. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 50: 148153, 2012

Hydrogen peroxide monitoring in Fenton reaction by using a ruthenium oxide hexacyanoferrate/multiwalled carbon nanotubes modified electrode

A novel amperometric sensor based on the incorporation of ruthenium oxide hexacyanoferrate (RuOHCF) into multiwalled carbon nanotubes (MWCNTs) immobilized on a glassy carbon electrode is described. Cyclic voltammetry experiments indicated that the cathodic reduction of hydrogen peroxide at the RuOHCF/MWCNTs100/GC modified electrode is facilitated, occurring at 0.0 V vs. Ag/AgCl/KCl(sat). Following the optimization of the experimental conditions, the proposed sensor presented excellent analytical properties for hydrogen peroxide determination, with a low limit of detection (4.7 mu mol L-1), a large dynamic concentration range (0.1-10 mmol L-1) and a sensitivity of 1280 mu A mmol(-1) L cm(-2). The usefulness of the RuOHCF/MWCNTs100/GC electrochemical sensor was confirmed by monitoring the consumption of hydrogen peroxide during the degradation of phenol by the Fenton reaction. (C) 2012 Elsevier B.V. All rights reserved.

Silver-gold nanotubes containing hot spots on their surface: facile synthesis and surface-enhanced Raman scattering investigations

We report the synthesis of silver-gold nanotubes containing hot spots along their surface. The Ag-Au nanotubes exhibited exceptional SERS properties compared to silver nanowires, enabling the detection of crystal violet in the 10(-10) M regime, as well as 9-nitroanthracene and benzo[a] pyrene at 3.3 x 10(-7) M.

SnO2 nanocrystals synthesized by microwave-assisted hydrothermal method: towards a relationship between structural and optical properties

The exploration of novel synthetic methodologies that control both size and shape of functional nanostructure opens new avenues for the functional application of nanomaterials. Here, we report a new and versatile approach to synthesize SnO2 nanocrystals (rutile-type structure) using microwave-assisted hydrothermal method. Broad peaks in the X-ray diffraction spectra indicate the nanosized nature of the samples which were indexed as a pure cassiterite tetragonal phase. Chemically and physically adsorbed water was estimated by TGA data and FT-Raman spectra to account for a new broad peak around 560 cm(-1) which is related to defective surface modes. In addition, the spherical-like morphology and low dispersed distribution size around 3-5 nm were investigated by HR-TEM and FE-SEM microscopies. Room temperature PL emission presents two broad bands at 438 and 764 nm, indicating the existence of different recombination centers. When the size of the nanospheres decreases, the relative intensity of 513 nm emission increases and the 393 nm one decreases. UV-Visible spectra show substantial changes in the optical absorbance of crystalline SnO2 nanoparticles while the existence of a small tail points out the presence of localized levels inside the forbidden band gap and supplies the necessary condition for the PL emission.

Self-potential signals from an analog biogeobattery mode

A tank experiment was conducted to check if self-potential (SP) signals can be generated when buried organic matter is wire-connected to a near-surface, oxygen-rich, sediment layer. This experiment demonstrated that once wired, there was a flux of electrons (hence an electric current) between the lower and upper layers of the sandbox with the system responding as a large-scale microbial fuel cell (a type of bioelectrochemical system). An electric current was generated by this process in the wire and the SP method was used to monitor the associated electric potential distribution at the top of the tank.. The electric field was controlled by the flux of electrons through the wire, the oxidation of the organic matter, the reduction of oxygen used as a terminal electron acceptor, and the distribution of the DC resistivity in the tank. The current density through the wire was limited by the availability of oxygen and not by the oxidation of the organic matter. This laboratory experiment incorporated key elements of the biogeobattery observed in some organic-rich contaminant plumes. This analogy includes the generation of SP signals associated with a flux of electrons, the capacity of buried organic matter in sustaining anodic reactions, network resistance connecting terminal redox reactions spatially separated in space, and the existence of anodic secondary coupled reactions. A resistivity tomogram of the tank, after almost a year in operation, suggests that oxidative processes triggered by this geobattery can be imaged with this method to determine the radius of influence of the bioelectrochemical system.

Head-to-Head Comparison of Three Vaccination Strategies Based on DNA and Raw Insect-Derived Recombinant Proteins against Leishmania

Parasitic diseases plague billions of people among the poorest, killing millions annually, and causing additional millions of disability-adjusted life years lost. Leishmaniases affect more than 12 million people, with over 350 million people at risk. There is an urgent need for efficacious and cheap vaccines and treatments against visceral leishmaniasis (VL), its most severe form. Several vaccination strategies have been proposed but to date no head-to-head comparison was undertaken to assess which is the best in a clinical model of the disease. We simultaneously assayed three vaccination strategies against VL in the hamster model, using KMPII, TRYP, LACK, and PAPLE22 vaccine candidate antigens. Four groups of hamsters were immunized using the following approaches: 1) raw extracts of baculovirus-infected Trichoplusia ni larvae expressing individually one of the four recombinant proteins (PROT); 2) naked pVAX1 plasmids carrying the four genes individually (DNA); 3) a heterologous prime-boost (HPB) strategy involving DNA followed by PROT (DNA-PROT); and 4) a Control including empty pVAX1 plasmid followed by raw extract of wild-type baculovirus-infected T. ni larvae. Hamsters were challenged with L. infantum promastigotes and maintained for 20 weeks. While PROT vaccine was not protective, DNA vaccination achieved protection in spleen. Only DNA-PROT vaccination induced significant NO production by macrophages, accompanied by a significant parasitological protection in spleen and blood. Thus, the DNA-PROT strategy elicits strong immune responses and high parasitological protection in the clinical model of VL, better than its corresponding naked DNA or protein versions. Furthermore, we show that naked DNA coupled with raw recombinant proteins produced in insect larvae biofactories -the cheapest way of producing DNA-PROT vaccines-is a practical and cost-effective way for potential "off the shelf" supplying vaccines at very low prices for the protection against leishmaniases, and possibly against other parasitic diseases affecting the poorest of the poor.

Rare-earth impurities in gallium nitride: The role of the Hubbard potential

We performed a first principles investigation on the electronic properties of 4f-rare earth substitutional impurities in zincblende gallium nitride (GaN:REGa, with RE=Eu, Gd, Tb, Dy, Ho, Er and Tm). The calculations were performed within the all electron methodology and the density functional theory. We investigated how the introduction of the on-site Hubbard U potential (GGA + U) corrects the electronic properties of those impurities. We showed that a self-consistent procedure to compute the Hubbard potential provides a reliable description on the position of the 4f-related energy levels with respect of the GaN valence band top. The results were compared to available data coming from a recent phenomenological model. (C) 2012 Elsevier B.V. All rights reserved.

Study of the vertical transport in p-doped superlattices based on group III-V semiconductors

The electrical conductivity σ has been calculated for p-doped GaAs/Al0.3Ga0.7As and cubic GaN/Al0.3Ga0.7N thin superlattices (SLs). The calculations are done within a self-consistent approach to the k → ⋅ p → theory by means of a full six-band Luttinger-Kohn Hamiltonian, together with the Poisson equation in a plane wave representation, including exchange correlation effects within the local density approximation. It was also assumed that transport in the SL occurs through extended minibands states for each carrier, and the conductivity is calculated at zero temperature and in low-field ohmic limits by the quasi-chemical Boltzmann kinetic equation. It was shown that the particular minibands structure of the p-doped SLs leads to a plateau-like behavior in the conductivity as a function of the donor concentration and/or the Fermi level energy. In addition, it is shown that the Coulomb and exchange-correlation effects play an important role in these systems, since they determine the bending potential.

X-ray absorption spectroscopy study on La0.6Sr0.4CoO3 and La0.6Sr0.4Co1¡yFeyO3 nanotubes and nanorods for IT-SOFC cathodes.

In the last years, extensive research has been devoted to develop novel materials and structures with high electrochemical performance for intermediate-temperatures solid-oxide fuel cells (IT-SOFCs) electrodes. In recent works, we have investigated the structural and electrochemical properties of La0:6Sr0:4CoO3 (LSCO) and La0:6Sr0:4Co1¡yFeyO3 (LSCFO) nanostructured cathodes, finding that they exhibit excellent electrocatalytic properties for the oxygen reduction reaction [1,2]. These materials were prepared by a pore-wetting technique using polycarbonate porous membranes as templates. Two average pore sizes were used: 200 nm and 800 nm. Our scanning electronic microscopy (SEM) study showed that the lower pore size yielded nanorods, while nanotubes were obtained with the bigger pore size. All the samples were calcined at 1000oC in order to produce materials with the desired perovskite-type crystal structure. In this work, we analyze the oxidation states of Co and Fe and the local atomic order of LSCO and LSCFO nanotubes and nanowires for various compositions. For this pur- pose we performed XANES and EXAFS studies on both Co and Fe K edges. These measurements were carried out at the D08B-XAFS2 beamline of the Brazilian Synchrotron Light Laboratory (LNLS). XANES spectroscopy showed that Co and Fe only change slightly their oxidation state upon Fe addition. Surprisingly, XANES results indicated that the content of oxygen vacancies is low, even though it is well-known that these materials are mixed ionic-electronic conductors. EXAFS results were consistent with those expected according to the rhombohedral crystal structure determined in previous X-ray powder dffraction investigations. [1] M.G. Bellino et al, J. Am. Chem. Soc. 129 (2007) 3066 [2] J.G. Sacanell et al., J. Power Sources 195 (2010) 1786

Caracterización eléctrica de transistores basados en nitruros

[ES] Los transistores más rápidos se consiguen gracias al crecimiento de diferentes semiconductores apilados. Entre los semiconductores es posible confinar una elevada concentración de electrones de alta movilidad, dando lugar a transistores con gran velocidad de respuesta. Cuando se emplea el sistema AlGaN/GaN, los enlaces interatómicos poseen un elevado carácter iónico. Estos iones generan intensos campos eléctricos internos, que inducen entre el AlGaN y el GaN una concentración de electrones de 1013 cm-2, un orden de magnitud superior a la alcanzada con otras estructuras típicas (AlGaAs/GaAs, AlGaAs/InGaAs/GaAs, GaInP/InGaAs/GaAs, etc.). En este artículo se expone un análisis de los aspectos fundamentales relacionados con la distribución de los electrones bajo la puerta de los transistores basados en nitruros.

Taller del proyecto AVORA, robot submarino de la ULPGC-PLOCAN dentro de Ciberlandia 2013

Celebrado el 24 de mayo en el Edificio de Informática y Matemáticas de la ULPGC

Design methodologies of microwawe integrated circuits for satellite telecommunications

The running innovation processes of the microwave transistor technologies, used in the implementation of microwave circuits, have to be supported by the study and development of proper design methodologies which, depending on the applications, will fully exploit the technology potentialities. After the choice of the technology to be used in the particular application, the circuit designer has few degrees of freedom when carrying out his design; in the most cases, due to the technological constrains, all the foundries develop and provide customized processes optimized for a specific performance such as power, low-noise, linearity, broadband etc. For these reasons circuit design is always a “compromise”, an investigation for the best solution to reach a trade off between the desired performances. This approach becomes crucial in the design of microwave systems to be used in satellite applications; the tight space constraints impose to reach the best performances under proper electrical and thermal de-rated conditions, respect to the maximum ratings provided by the used technology, in order to ensure adequate levels of reliability. In particular this work is about one of the most critical components in the front-end of a satellite antenna, the High Power Amplifier (HPA). The HPA is the main power dissipation source and so the element which mostly engrave on space, weight and cost of telecommunication apparatus; it is clear from the above reasons that design strategies addressing optimization of power density, efficiency and reliability are of major concern. Many transactions and publications demonstrate different methods for the design of power amplifiers, highlighting the availability to obtain very good levels of output power, efficiency and gain. Starting from existing knowledge, the target of the research activities summarized in this dissertation was to develop a design methodology capable optimize power amplifier performances complying all the constraints imposed by the space applications, tacking into account the thermal behaviour in the same manner of the power and the efficiency. After a reminder of the existing theories about the power amplifier design, in the first section of this work, the effectiveness of the methodology based on the accurate control of the dynamic Load Line and her shaping will be described, explaining all steps in the design of two different kinds of high power amplifiers. Considering the trade-off between the main performances and reliability issues as the target of the design activity, we will demonstrate that the expected results could be obtained working on the characteristics of the Load Line at the intrinsic terminals of the selected active device. The methodology proposed in this first part is based on the assumption that designer has the availability of an accurate electrical model of the device; the variety of publications about this argument demonstrates that it is so difficult to carry out a CAD model capable to taking into account all the non-ideal phenomena which occur when the amplifier operates at such high frequency and power levels. For that, especially for the emerging technology of Gallium Nitride (GaN), in the second section a new approach for power amplifier design will be described, basing on the experimental characterization of the intrinsic Load Line by means of a low frequency high power measurements bench. Thanks to the possibility to develop my Ph.D. in an academic spin-off, MEC – Microwave Electronics for Communications, the results of this activity has been applied to important research programs requested by space agencies, with the aim support the technological transfer from universities to industrial world and to promote a science-based entrepreneurship. For these reasons the proposed design methodology will be explained basing on many experimental results.

Supramolecular functional assemblies with photo or chemical addressability

Supramolecular self-assembly represents a key technology for the spontaneous construction of nanoarchitectures and for the fabrication of materials with enhanced physical and chemical properties. In addition, a significant asset of supramolecular self-assemblies rests on their reversible formation, thanks to the kinetic lability of their non-covalent interactions. This dynamic nature can be exploited for the development of “self-healing” and “smart” materials towards the tuning of their functional properties upon various external factors. One particular intriguing objective in the field is to reach a high level of control over the shape and size of the supramolecular architectures, in order to produce well-defined functional nanostructures by rational design. In this direction, many investigations have been pursued toward the construction of self-assembled objects from numerous low-molecular weight scaffolds, for instance by exploiting multiple directional hydrogen-bonding interactions. In particular, nucleobases have been used as supramolecular synthons as a result of their efficiency to code for non-covalent interaction motifs. Among nucleobases, guanine represents the most versatile one, because of its different H-bond donor and acceptor sites which display self-complementary patterns of interactions. Interestingly, and depending on the environmental conditions, guanosine derivatives can form various types of structures. Most of the supramolecular architectures reported in this Thesis from guanosine derivatives require the presence of a cation which stabilizes, via dipole-ion interactions, the macrocyclic G-quartet that can, in turn, stack in columnar G-quadruplex arrangements. In addition, in absence of cations, guanosine can polymerize via hydrogen bonding to give a variety of supramolecular networks including linear ribbons. This complex supramolecular behavior confers to the guanine-guanine interactions their upper interest among all the homonucleobases studied. They have been subjected to intense investigations in various areas ranging from structural biology and medicinal chemistry – guanine-rich sequences are abundant in telomeric ends of chromosomes and promoter regions of DNA, and are capable of forming G-quartet based structures– to material science and nanotechnology. This Thesis, organized into five Chapters, describes mainly some recent advances in the form and function provided by self-assembly of guanine based systems. More generally, Chapter 4 will focus on the construction of supramolecular self-assemblies whose self-assembling process and self-assembled architectures can be controlled by light as external stimulus. Chapter 1 will describe some of the many recent studies of G-quartets in the general area of nanoscience. Natural G- quadruplexes can be useful motifs to build new structures and biomaterials such as self-assembled nanomachines, biosensors, therapeutic aptamer and catalysts. In Chapters 2-4 it is pointed out the core concept held in this PhD Thesis, i.e. the supramolecular organization of lipophilic guanosine derivatives with photo or chemical addressability. Chapter 2 will mainly focus on the use of cation-templated guanosine derivatives as a potential scaffold for designing functional materials with tailored physical properties, showing a new way to control the bottom-up realization of well-defined nanoarchitectures. In section 2.6.7, the self-assembly properties of compound 28a may be considered an example of open-shell moieties ordered by a supramolecular guanosine architecture showing a new (magnetic) property. Chapter 3 will report on ribbon-like structures, supramolecular architectures formed by guanosine derivatives that may be of interest for the fabrication of molecular nanowires within the framework of future molecular electronic applications. In section 3.4 we investigate the supramolecular polymerizations of derivatives dG 1 and G 30 by light scattering technique and TEM experiments. The obtained data reveal the presence of several levels of organization due to the hierarchical self-assembly of the guanosine units in ribbons that in turn aggregate in fibrillar or lamellar soft structures. The elucidation of these structures furnishes an explanation to the physical behaviour of guanosine units which display organogelator properties. Chapter 4 will describe photoresponsive self-assembling systems. Numerous research examples have demonstrated that the use of photochromic molecules in supramolecular self-assemblies is the most reasonable method to noninvasively manipulate their degree of aggregation and supramolecular architectures. In section 4.4 we report on the photocontrolled self-assembly of modified guanosine nucleobase E-42: by the introduction of a photoactive moiety at C8 it is possible to operate a photocontrol over the self-assembly of the molecule, where the existence of G-quartets can be alternately switched on and off. In section 4.5 we focus on the use of cyclodextrins as photoresponsive host-guest assemblies: αCD–azobenzene conjugates 47-48 (section 4.5.3) are synthesized in order to obtain a photoresponsive system exhibiting a fine photocontrollable degree of aggregation and self-assembled architecture. Finally, Chapter 5 contains the experimental protocols used for the research described in Chapters 2-4.