Supramolecular Approach to Gold Nanoparticle/Triruthenium Cluster Hybrid Materials and Interfaces

A systematic and comprehensive study of the interaction of citrate-stabilized gold nanoparticles with triruthenium cluster complexes of general formula [Ru(3)(CH(3)COO)(6)(L)](+) [L = 4-cyanopyridine (4-CNpy), 4,4`-bipyridine (4,4`-bpy) or 4,4`-bis(pyridyl)ethylene (bpe)] has been carried out. The cluster-nanoparticle interaction in solution and the construction of thin films of the hybrid materials were investigated in detail by electronic and surface plasmon resonance (SPR) spectroscopy, Raman scattering spectroscopy and scanning electron microscopy (SEM). Citrate-stabilized gold nanoparticles readily interacted with [Ru(3)O(CH(3)COO)(6)(L)(3)](+) complexes to generate functionalized nanoparticles that tend to aggregate according to rates and extents that depend on the bond strength defined by the characteristics of the cluster L ligands following the sequence bpe > 4,4`-bpy >> 4-CNpy. The formation of compact thin films of hybrid AuNP/[Ru(3)O(CH(3)COO)(6)(L)(3)](+) derivatives with L = bpe and 4,4`-bpy indicated that the stability/lability of AuNP-cluster bonds as well as their solubility are important parameters that influence the film contruction process. Fluorine-doped tin oxide electrodes modified with thin films of these nanomaterials exhibited similar electrocatalytic activity but much higher sensitivity than a conventional gold electrode in the oxidation of nitrite ion to nitrate depending on the bridging cluster complex, demonstrating the high potential for the development of amperometric sensors.

Surface and Quantum Confinement Effects in ZnO Nanocrystals

ZnO nanocrystals are studied using theoretical calculations based on the density functional theory. The two main effects related to the reduced size of the nanocrystals are investigated: quantum confinement and a large surface:volume ratio. The effects of quantum confinement are studied by saturating the surface dangling bonds of the nanocrystals with hypothetical H atoms. To understand the effects of the surfaces of the nanocrystals, all saturation is removed and the system is relaxed to its minimum energy position. Several different surface motifs are reported, which should be observed experimentally. Spin-polarized calculations are performed in the nonsaturated nanocrystals, leading to different magnetic moments. We propose that this magnetic moment can be responsible for the intrinsic magnetism observed in ZnO nanostructures.

Cloud streets and land-water interactions in the Amazon

Cloud streets are common feature in the Amazon Basin. They form from the combination of the vertical trade wind stress and moist convection. Here, satellite imagery, data collected during the COBRA-PARA (Caxiuan Observations in the Biosphere, River and Atmosphere of Para) field campaign, and high resolution modeling are used to understand the streets` formation and behavior. The observations show that the streets have an aspect ratio of about 3.5 and they reach their maximum activity around 15:00 UTC when the wind shear is weaker, and the convective boundary layer reaches its maximum height. The simulations reveal that the cloud streets onset is caused by the local circulations and convection produced at the interfaces between forest and rivers of the Amazon. The satellite data and modeling show that the large rivers anchor the cloud streets producing a quasi-stationary horizontal pattern. The streets are associated with horizontal roll vortices parallel to the mean flow that organizes the turbulence causing advection of latent heat flux towards the upward branches. The streets have multiple warm plumes that promote a connection between the rolls. These spatial patterns allow fundamental insights on the interpretation of the Amazon exchanges between surface and atmosphere with important consequences for the climate change understanding.

Stigmatic surface in the Vochysiaceae: reproductive and taxonomic implications

(Stigmatic surface, reproductive biology and taxonomy of the Vochysiaceae). The Vochysiaceae are Neotropical trees and shrubs, common in the savanna areas in Central Brazil (Cerrados). The family has been traditionally divided into two tribes: Erismeae, with three genera, and Vochysieae, with five genera. We investigated the stigmatic surface of six Vochysiaceae species, belonging to four genera of Vochysieae: Vochysia, Salvertia, Callisthene and Qualea. Flowers and buds at different developmental stages were collected. Morphological features were observed on fresh material and stigmatic receptivity was inferred based on esterasic activity. Pistils were fixed and embedded in paraplast and sectioned on a rotary microtome; the sections were stained before histological analysis. Stigmas of open flowers were also observed by scanning electron microscopy. Stigmas of all species were wet and showed esterasic activity at pre-anthesis and anthesis stages. Stigmatic surface was continuous with transmitting tissue of glandular nature. Vochysia and Salvertia stigmatic surfaces were formed by multicelular uniseriate hairs, and species of the remaining genera showed papillate surface. The exudate over mature stigmas in all species flowed without rupture of stigmatic Surface and pollen tubes grew down between hairs or papillae. Differences on the stigmatic surface agreed with a phylogenetic reconstruction that separated two clades and indicated that Vochysieae is not monophyletic. Stigmatic features could not be associated with pollination and breeding systems.

Confinement and surface effects in B and P doping of silicon nanowires

Several experimental groups have achieved effective n- and p-type doping of silicon nanowires (SiNWs). However, theoretical analyses on ultrathin SiNWs suggest that dopants tend to segregate to their surfaces, where they would combine with defects such as dangling bonds (DB), becoming electronically inactive. Using fully ab initio calculations, we show that the differences in formation energies among surface and core substitutional sites decrease rapidly as the diameters of the wires increase, indicating that the dopants will be uniformly distributed. Moreover, occurrence of the electronically inactive impurity/DB complex rapidly becomes less frequent for NWs of larger diameters. We also show that the high confinement in the ultrathin SiNWs causes the impurity levels to be deeper than in the silicon bulk, but our results indicate that for NWs of diameters larger than approximately 3 nm the impurity levels recover bulk characteristics. Finally, we show that different surfaces will lead to different dopant properties in the gap.

Adsorption kinetics and charge inversion in layer-by-layer films from nickel tetrasulfonated phthalocyanine and poly(allylamine hydrochloride)

Layer-by-layer (LBL) films of nickel tetrasulfonated phthalocyanine (NiTsPc) alternated with poly(allylamine hydrochloride) (PAH) have been prepared, whose surface charge has been evaluated using surface potential measurements. From adsorption kinetics results, we obtained the immersion time of similar to 40 s, which was used to assemble layers of NiTsPc. The effect of gold (Au) and aluminum (Al) electrodes on the charge behavior was examined. We found that the surface potential (i.e. surface charge) was inverted each time a layer of PAH was alternated with another of NiTsPc molecules for the two types of electrodes, which was attributed to charge overcompensation between positive charges of PAH molecules, and negative charges from NiTsPc molecules. (C) 2009 Elsevier B.V. All rights reserved.

Acellular Dermal Matrix Graft for Gingival Augmentation: A Preliminary Clinical, Histologic, and Ultrastructural Evaluation

Background: The aim of this study was to evaluate clinically, histologically, and ultrastructurally the integration process of the acellular dermal matrix used to increase the band of keratinized tissue while achieving gingival inflammation control. Methods: Ten patients exhibiting a mucogingival problem with bands of keratinized tissue <= 1 mm and gingival inflammation of the related teeth were included in the study. The surgical procedures were performed to augment the gingival tissue using acellular dermal matrix. Clinical measurements were assessed at baseline and after 3 months. A specimen of the allograft and surrounding tissues was obtained immediately before the surgery and 4 minutes and 1, 2, 3, 4, 6, and 10 weeks after grafting. Results: Clinically, a gain of keratinized tissue of 2.92 +/- 0.65 mm was observed after 3 months. Histologically and ultrastructurally, many macrophages were observed phagocytosing preexisting collagen fibers in the first weeks. From week 2 on, fibroblasts synthesizing new collagen, epithelial cells colonizing the graft surface, and revascularization were noticed. After 6 weeks it was difficult to find the acellular dermal matrix preexisting collagen fibers. This process of substitution was completed after 10 weeks, when the reepithelialization of the entire graft throughout a well-structured basement membrane was achieved. Conclusion: The acellular dermal matrix graft seemed to be an easily handled material for use in keratinized tissue augmentation that, in humans, was substituted and completely reepithelialized in 10 weeks according to histologic and ultrastructural results. J Periodontol 2009;80:253-259.

Histomorphometric Evaluation of Bioceramic Molecular Impregnated and Dual Acid-Etched Implant Surfaces in the Human Posterior Maxilla

Background: Physical and bioceramic incorporation surface treatments at the nanometer scale showed higher means of bone-to-implant contact (BIC) and torque values compared with surface topography at the micrometer scale; however, the literature concerning the effect of nanometer scale parameters is sparse. Purpose: The aim of this study was to evaluate the influence of two different implant surfaces on the percentage bone-to-implant contact (BIC%) and bone osteocyte density in the human posterior maxilla after 2 months of unloaded healing. Materials and Methods: The implants utilized presented dual acid-etched (DAE) surface and a bioceramic molecular impregnated treatment (Ossean(R), Intra-Lock International, Boca Raton, FL, USA) serving as control and test, respectively. Ten subjects (59 1 9 years of age) received two implants (one of each surface) during conventional implant surgery in the posterior maxilla. After the non-loaded period of 2 months, the implants and the surrounding tissue were removed by means of a trephine and were non-decalcified processed for ground sectioning and analysis of BIC%, bone density in threaded area (BA%), and osteocyte index (Oi). Results: Two DAE implants were found to be clinically unstable at time of retrieval. Histometric evaluation showed significantly higher BIC% and Oi for the test compared to the control surface (p < .05), and that BA% was not significantly different between groups. Wilcoxon matched pairs test was used to compare the differences of histomorphometric variables between implant surfaces. The significance test was conducted at a 5% level of significance. Conclusion: The histological data suggest that the bioceramic molecular impregnated surface-treated implants positively modulated bone healing at early implantation times compared to the DAE surface.

Detection of assemblages A and B of Giardia duodenalis in water and sewage from Sao Paulo state, Brazil

Giardia duodenalis is a protozoan that parasitizes humans and other mammals and causes giardiasis. Although its isolates have been divided into seven assemblages, named A to G, only A and B have been detected in human faeces. Assemblage A isolates are commonly divided into two genotypes, AI and AII. Even though information about the presence of this protozoan in water and sewage is available in Brazil, it is important to verify the distribution of different assemblages that might be present, which can only be done by genotyping techniques. A total of 24 raw and treated sewage, surface and spring water samples were collected, concentrated and purified. DNA was extracted, and a nested PCR was used to amplify an 890 bp fragment of the gdh gene of G. duodenalis, which codes for glutamate dehydrogenase. Positive samples were cloned and sequenced. Ten out of 24 (41.6%) samples were confirmed to be positive for G. duodenalis by sequencing. Phylogenetic analysis grouped most sequences with G. duodenalis genotype AII from GenBank. Only two raw sewage samples presented sequences assigned to assemblage B. In one of these samples genotype AII was also detected. As these assemblages/genotypes are commonly associated to human giardiasis, the contact with these matrices represents risk for public health.

Surface properties of eucalyptus pulp fibres as reinforcement of cement-based composites

The objective of the present work is to evaluate the effects of the surface properties of unrefined eucalyptus pulp fibres concerning their performance in cement-based composites. The influence of the fibre surface on the microstructure of fibre-cement composites was evaluated after accelerated ageing cycles, which simulate natural weathering. The surface of unbleached pulp is a thin layer that is rich in cellulose, lignin, hemicelluloses, and extractives. Such a layer acts as a physical and chemical barrier to the penetration of low molecular components of cement. The unbleached fibres are less hydrophilic than the bleached ones. Bleaching removes the amorphous lignin and extractives from the surface and renders it more permeable to liquids. Atomic force microscopy (AFM) helps in understanding the fibre-cement interface. Bleaching improved the fibre- cement interfacial bonding, whereas fibres in the unbleached pulp were less susceptible to the re-precipitation of cement hydration products into the fibre cavities (lumens). Therefore, unbleached fibres can improve the long-term performance of the fibre-cement composite owing to their delayed mineralization.

Multiyear measurements of the oceanic and atmospheric boundary layers at the Brazil-Malvinas confluence region

This study analyzes and discusses data taken from oceanic and atmospheric measurements performed simultaneously at the Brazil-Malvinas Confluence (BMC) region in the southwestern Atlantic Ocean. This area is one of the most dynamical frontal regions of the world ocean. Data were collected during four research cruises in the region once a year in consecutive years between 2004 and 2007. Very few studies have addressed the importance of studying the air-sea coupling at the BMC region. Lateral temperature gradients at the study region were as high as 0.3 degrees C km(-1) at the surface and subsurface. In the oceanic boundary layer, the vertical temperature gradient reached 0.08 degrees C m(-1) at 500 m depth. Our results show that the marine atmospheric boundary layer (MABL) at the BMC region is modulated by the strong sea surface temperature (SST) gradients present at the sea surface. The mean MABL structure is thicker over the warmside of the BMC where Brazil Current (BC) waters predominate. The opposite occurs over the coldside of the confluence where waters from the Malvinas (Falkland) Current (MC) are found. The warmside of the confluence presented systematically higher MABL top height compared to the coldside. This type of modulation at the synoptic scale is consistent to what happens in other frontal regions of the world ocean, where the MABL adjusts itself to modifications along the SST gradients. Over warm waters at the BMC region, the MABL static instability and turbulence were increased while winds at the lower portion of the MABL were strong. Over the coldside of the BC/MC front an opposite behavior is found: the MABL is thinner and more stable. Our results suggest that the sea-level pressure (SLP) was also modulated locally, together with static stability vertical mixing mechanism, by the surface condition during all cruises. SST gradients at the BMC region modulate the synoptic atmospheric pressure gradient. Postfrontal and prefrontal conditions produce opposite thermal advections in the MABL that lead to different pressure intensification patterns across the confluence.

Antimicrobial activity in the tick Rhipicephalus (Boophilus) microplus eggs: Cellular localization and temporal expression of microplusin during oogenesis and embryogenesis

Arthropods display different mechanisms to protect themselves against infections, among which antimicrobial peptides (AMPs) play an important role, acting directly against invader pathogens. We have detected several factors with inhibitory activity against Candida albicans and Micrococcus luteus on the surface and in homogenate of eggs of the tick Rhipicephalus (Boophilus) microplus. One of the anti-M. luteus factors of the egg homogenate was isolated to homogeneity. Analysis by electrospray mass spectrometry (ESI-MS) revealed that it corresponds to microplusin, an AMP previously isolated from the cell-free hemolymph of X (B.) microplus. Reverse transcription (RT) quantitative polymerase chain reactions (qPCR) showed that the levels of microplusin mRNA gradually increase along ovary development, reaching an impressive highest value three days after the adult females have dropped from the calf and start oviposition. Interestingly, the level of microplusin mRNA is very low in recently laid eggs. An enhance of microplusin gene expression in eggs is observed only nine days after the onset of oviposition, achieving the highest level just before the larva hatching, when the level of expression decreases once again. Fluorescence microscopy analysis using an anti-microplusin serum revealed that microplusin is present among yolk granules of oocytes as well as in the connecting tube of ovaries. These results, together to our previous data. suggest that microplusin may be involved not only in protection of adult female hemocele, but also in protection of the female reproductive tract and embryos, what points this AMP as a considerable target for development of new methods to control R. (B.) microplus as well as the vector-borne pathogens. (c) 2009 Elsevier Ltd. All rights reserved.

An improved finite element space for discontinuous pressures

We consider incompressible Stokes flow with an internal interface at which the pressure is discontinuous, as happens for example in problems involving surface tension. We assume that the mesh does not follow the interface, which makes classical interpolation spaces to yield suboptimal convergence rates (typically, the interpolation error in the L(2)(Omega)-norm is of order h(1/2)). We propose a modification of the P(1)-conforming space that accommodates discontinuities at the interface without introducing additional degrees of freedom or modifying the sparsity pattern of the linear system. The unknowns are the pressure values at the vertices of the mesh and the basis functions are computed locally at each element, so that the implementation of the proposed space into existing codes is straightforward. With this modification, numerical tests show that the interpolation order improves to O(h(3/2)). The new pressure space is implemented for the stable P(1)(+)/P(1) mini-element discretization, and for the stabilized equal-order P(1)/P(1) discretization. Assessment is carried out for Poiseuille flow with a forcing surface and for a static bubble. In all cases the proposed pressure space leads to improved convergence orders and to more accurate results than the standard P(1) space. In addition, two Navier-Stokes simulations with moving interfaces (Rayleigh-Taylor instability and merging bubbles) are reported to show that the proposed space is robust enough to carry out realistic simulations. (c) 2009 Elsevier B.V. All rights reserved.

Numerical Solution of the Upper-Convected Maxwell Model for Three-Dimensional Free Surface Flows

This work presents a finite difference technique for simulating three-dimensional free surface flows governed by the Upper-Convected Maxwell (UCM) constitutive equation. A Marker-and-Cell approach is employed to represent the fluid free surface and formulations for calculating the non-Newtonian stress tensor on solid boundaries are developed. The complete free surface stress conditions are employed. The momentum equation is solved by an implicit technique while the UCM constitutive equation is integrated by the explicit Euler method. The resulting equations are solved by the finite difference method on a 3D-staggered grid. By using an exact solution for fully developed flow inside a pipe, validation and convergence results are provided. Numerical results include the simulation of the transient extrudate swell and the comparison between jet buckling of UCM and Newtonian fluids.

Electronic and magnetic properties of Ti and Fe on graphene

The structural, electronic and magnetic properties of Fe and Ti atomic wires and the complete covering when adsorbed on graphene are presented through ab initio calculations based on density functional theory. The most stable configurations are investigated for Fe and Ti in different concentrations adsorbed on the graphene surface, and the corresponding binding energies are calculated. The results show a tendency of the Ti atoms to cover uniformly the graphene surface, whereas the Fe atoms form clusters. The adsorption of the transition metal on the graphene surface changes significantly the electronic density of states near the graphene Fermi region. In all arrangements studied, a charge transfer is observed from the adsorbed species to the graphene surface due to the high hybridizations between the systems.