Making solar fuels by artificial photosynthesis

In order for solar energy to serve as a primary energy source, it must be paired with energy storage on a massive scale. At this scale, solar fuels and energy storage in chemical bonds is the only practical approach. Solar fuels are produced in massive amounts by photosynthesis with the reduction of CO(2) by water to give carbohydrates but efficiencies are low. In photosystem II (PSII), the oxygen-producing site for photosynthesis, light absorption and sensitization trigger a cascade of coupled electron-proton transfer events with time scales ranging from picoseconds to microseconds. Oxidative equivalents are built up at the oxygen evolving complex (OEC) for water oxidation by the Kok cycle. A systematic approach to artificial photo synthesis is available based on a ""modular approach"" in which the separate functions of a final device are studied separately, maximized for rates and stability, and used as modules in constructing integrated devices based on molecular assemblies, nanoscale arrays, self-assembled monolayers, etc. Considerable simplification is available by adopting a ""dyesensitized photoelectrosynthesis cell"" (DSPEC) approach inspired by dye-sensitized solar cells (DSSCs). Water oxidation catalysis is a key feature, and significant progress has been made in developing a single-site solution and surface catalysts based on polypyridyl complexes of Ru. In this series, ligand variations can be used to tune redox potentials and reactivity over a wide range. Water oxidation electrocatalysis has been extended to chromophore-catalyst assemblies for both water oxidation and DSPEC applications.

Individual-level diet variation in four species of Brazilian frogs

Many natural populations exploiting a wide range of resources are actually composed of relatively specialized individuals. This interindividual variation is thought to be a consequence of the invasion of `empty` niches in depauperate communities, generally in temperate regions. If individual niches are constrained by functional trade-offs, the expansion of the population niche is only achieved by an increase in interindividual variation, consistent with the `niche variation hypothesis`. According to this hypothesis, we should not expect interindividual variation in species belonging to highly diverse, packed communities. In the present study, we measured the degree of interindividual diet variation in four species of frogs of the highly diverse Brazilian Cerrado, using both gut contents and delta(13)C stable isotopes. We found evidence of significant diet variation in the four species, indicating that this phenomenon is not restricted to depauperate communities in temperate regions. The lack of correlations between the frogs` morphology and diet indicate that trade-offs do not depend on the morphological characters measured here and are probably not biomechanical. The nature of the trade-offs remains unknown, but are likely to be cognitive or physiological. Finally, we found a positive correlation between the population niche width and the degree of diet variation, but a null model showed that this correlation can be generated by individuals sampling randomly from a common set of resources. Therefore, albeit consistent with, our results cannot be taken as evidence in favour of the niche variation hypothesis.

A scanning electron microscopic survey of the cuticle in Cyphophthalmi (Arachnida, Opiliones) with the description of novel sensory and glandular structures

The cuticular surfaces of Cyphophthalmi (Opiliones) were studied in detail, covering a wide range of their taxonomic diversity. Previously unknown structures are described, including a sexually dimorphic row of spines and glandular openings on leg I of Fangensis cavernarum. Scanning electron micrographs of the prosomal paired hairs and the subapical process are provided for the first time. Evidence for the multi-pored nature of the shaft of solenidia as well as the hollowed nature and absence of wall pores of sensilla chaetica are also shown for the first time using scanning electron microscopy. The prosomal paired hairs may constitute a novel autapomorphy for Cyphophthalmi, as they are absent in all studied members of the other species of Opiliones. Finally, the variation in shape of some of the structures examined may be of great taxonomic value.

Estimation of hexenuronic acids and kappa number in kraft pulps of Eucalyptus globulus by Fourier transform near infrared spectroscopy and multivariate analysis

Fourier transform near infrared (FT-NIR) spectroscopy was evaluated as an analytical too[ for monitoring residual Lignin, kappa number and hexenuronic acids (HexA) content in kraft pulps of Eucalyptus globulus. Sets of pulp samples were prepared under different cooking conditions to obtain a wide range of compound concentrations that were characterised by conventional wet chemistry analytical methods. The sample group was also analysed using FT-NIR spectroscopy in order to establish prediction models for the pulp characteristics. Several models were applied to correlate chemical composition in samples with the NIR spectral data by means of PCR or PLS algorithms. Calibration curves were built by using all the spectral data or selected regions. Best calibration models for the quantification of lignin, kappa and HexA were proposed presenting R-2 values of 0.99. Calibration models were used to predict pulp titers of 20 external samples in a validation set. The lignin concentration and kappa number in the range of 1.4-18% and 8-62, respectively, were predicted fairly accurately (standard error of prediction, SEP 1.1% for lignin and 2.9 for kappa). The HexA concentration (range of 5-71 mmol kg(-1) pulp) was more difficult to predict and the SEP was 7.0 mmol kg(-1) pulp in a model of HexA quantified by an ultraviolet (UV) technique and 6.1 mmol kg(-1) pulp in a model of HexA quantified by anion-exchange chromatography (AEC). Even in wet chemical procedures used for HexA determination, there is no good agreement between methods as demonstrated by the UV and AEC methods described in the present work. NIR spectroscopy did provide a rapid estimate of HexA content in kraft pulps prepared in routine cooking experiments.

Tick saliva induces regulatory dendritic cells: MAP-kinases and Toll-like receptor-2 expression as potential targets

Ticks (Acari: Ixodidae) are bloodsucking ectoparasitic arthropods of human and veterinary medical importance. Tick saliva has been shown to contain a wide range of bioactive molecules with vasodilatory, antihemostatic, and immunomodulatory activities. We have previously demonstrated that saliva from Rhipicephalus sanguineus ticks inhibits the maturation of dendritic cells (DCs) stimulated with LPS. Here we examined the mechanism of this immune subversion, evaluating the effect of tick saliva on Toll-like receptor (TLR)-4 signalling pathway in bone marrow-derived DCs. We demonstrated that R. sanguineus tick saliva impairs maturation of DCs stimulated with LIPS, a TLR-4 ligand, leading to increased production of interleukin (IL)-10 and reduced synthesis of IL-12p70 and TNF-alpha. The immunomodulatory effect of the tick saliva on the production of pro-inflammatory cytokines by DCs stimulated with LPS was associated with the observation that tick saliva inhibits the activation of the ERK 1/2 and p38 MAP kinases. These effects were independent of the expression of TLR-4 on the surface of DCs. Additionally, saliva-treated DCs also presented a similar pattern of cytokine modulation in response to other TLR ligands. Since the recent literature reports that several parasites evade immune responses through TLR-2-mediated production of IL-10, we evaluated the effect of tick saliva on the percentage of TLR-2(+) DCs stimulated with the TLR-2 ligand lipoteicoic acid (LTA). The data showed that the population of DCs expressing TLR-2 was significantly increased in DCs treated with LTA plus saliva. In addition, tick saliva alone increased the expression of TLR-2 in a dose- and time-dependent manner. Our data suggest that tick saliva induces regulatory DCs, which secrete IL-10 and low levels of IL-12 and TNF-alpha when stimulated by TLR ligands. Such regulatory DCs are associated with expression of TLR-2 and inhibition of ERK and p38, which promotes the production of IL-10 and thus down-modulates the host`s immune response, possibly favouring susceptibility to tick infestations. (C) 2009 Elsevier B.V. All rights reserved.

A fieldbus simulator for training purposes

This article presents a fieldbus simulation platform and its remote access interface that enables a wide range of experiments, where users can configure operation sequences and procedures typical of Foundation Fieldbus systems. The simulation system was developed using LabVIEW, with requisites of deterministic execution, and a course management work frame web server called Moodle. The results were obtained through three different evaluations: schedule table execution, simulator functionality and finally, simulator productivity and achievement. The evaluation attests that this new tool is feasible, and can be applied for fieldbus automation systems training purposes, considering the robustness and stability in tests and the positive feedback from users. (C) 2008 ISA. Published by Elsevier Ltd. All rights reserved.

Birefringence enhancement by using D-shaped microstructured optical fibers

In this study, a detailed numerical investigation is presented, seeking to enhance the birefringence effect by using D-shaped microstructured optical fibers (MOFs). We studied a D-shape core geometry associated with three different air-hole configurations: circular and elliptical, aligned with either the x-direction or the y-direction. Results have shown that ultrahigh birefringence MOFs, with B values of the order of 10(-2) for a wide range of wavelengths, can be obtained. The highest birefringence B was equal 3.97 x 10(-2), a value found for a D-MOF (circular holes) at 1550 nm. To the best of our knowledge, this is the highest theoretical value in the published literature.

Comparative analysis of triple band S-C-L erbium-doped fibre and semiconductor optical amplifier for CWDM applications

The authors present a comparative analysis between a triple-band S-C-L erbium-doped fibre amplifier and a commercial semiconductor optical amplifier in a CWDM application scenario. Both technologies were characterised for gain and noise figures from 1480 to 1610 nm (S, C and L bands) and their systemic performances were evaluated in terms of bit error rate measurements for a wide range of optical power levels.

Thermal characterization of a cross-flow heat exchanger with a new flow arrangement

The objective of the present paper is to thermally characterize a cross-flow heat exchanger featuring a new cross-flow arrangement, which may find application in contemporary refrigeration and automobile industries. The new flow arrangement is peculiar in the sense that it possesses two fluid circuits extending in the form of two tube rows, each with two tube lines. To assess the heat exchanger performance, it is compared against that for the standard two-pass counter-cross-flow arrangement. The two-part comparison is based on the thermal effectiveness and the heat exchanger efficiency for several combinations of the heat capacity rate ratio, C*, and the number of transfer units, NTU. In addition, a third comparison is made in terms of the so-called ""heat exchanger reversibility norm"" (HERN) through the influence of various parameters such as the inlet temperature ratio, T, and the heat capacity rate ratio, C*, for several fixed NTU values. The proposed new flow arrangement delivers higher thermal effectiveness and higher heat exchanger efficiency, resulting in lesser entropy generation over a wide range of C* and NTU values. These metrics are quantified with respect to the arrangement widely used in refrigeration industry due to its high effectiveness, namely, the standard two-pass counter-cross-flow heat exchanger. The new flow arrangement seems to be a promising avenue in situations where cross-flow heat exchangers for single-phase fluid have to be used in refrigeration units. (c) 2009 Elsevier Masson SAS. All rights reserved.

Dendritic Arm Spacing Affecting Mechanical Properties and Wear Behavior of Al-Sn and Al-Si Alloys Directionally Solidified under Unsteady-State Conditions

Alloys of Al-Sn and Al-Si are widely used in tribological applications such as cylinder liners and journal bearings. Studies of the influence of the as-cast microstructures of these alloys on the final mechanical properties and wear resistance can be very useful for planning solidification conditions in order to permit a desired level of final properties to be achieved. The aim of the present study was to contribute to a better understanding about the relationship between the scale of the dendritic network and the corresponding mechanical properties and wear behavior. The Al-Sn (15 and 20 wt pct Sn) and Al-Si (3 and 5 wt pct Si) alloys were directionally solidified under unsteady-state heat flow conditions in water-cooled molds in order to permit samples with a wide range of dendritic spacings to be obtained. These samples were subjected to tensile and wear tests, and experimental quantitative expressions correlating the ultimate tensile strength (UTS), yield tensile strength, elongation, and wear volume to the primary dendritic arm spacing (DAS) have been determined. The wear resistance was shown to be significantly affected by the scale of primary dendrite arm spacing. For Al-Si alloys, the refinement of the dendritic array improved the wear resistance, while for the Al-Sn alloys, an opposite effect was observed, i.e., the increase in primary dendrite arm spacing improved the wear resistance. The effect of inverse segregation, which is observed for Al-Sn alloys, on the wear resistance is also discussed.

A critical reassessment of elastic unloading in sharp instrumented indentation experiments and the extraction of mechanical properties

This work examines the extraction of mechanical properties from instrumented indentation P-h(s) curves via extensive three-dimensional finite element analyses for pyramidal tips in a wide range of solids under frictional and frictionless contact conditions. Since the topography of the imprint changes with the level of pile-up or sink-in, a relationship is identified between correction factor beta in the elastic equation for the unloading indentation stage and the amount of surface deformation effects. It is shown that the presumption of a constant beta significantly affects mechanical property extractions. Consequently, a new best-fit function is found for the correlation between penetration depth ratios h(e)/h(max), h(r)/h(max) and n, circumventing the need for the assumption of a constant value for beta, made in our prior investigation [Acta Mater. 53 (2005) pp. 3545-3561]. Simulations under frictional contact conditions provide sensible boundaries for the influence of friction on both h(e)/h(max) and h(r)/h(max). Friction is essentially found to induce an overestimation in the inferred n. Instrumented indentation experiments are also performed in three archetypal metallic materials exhibiting distinctly different contact responses. Mechanical property extractions are finally demonstrated in each of these materials.

A transient three-dimensional heat transfer model of the human body

The objective of this work is to develop an improved model of the human thermal system. The features included are important to solve real problems: 3D heat conduction, the use of elliptical cylinders to adequately approximate body geometry, the careful representation of tissues and important organs, and the flexibility of the computational implementation. Focus is on the passive system, which is composed by 15 cylindrical elements and it includes heat transfer between large arteries and veins. The results of thermal neutrality and transient simulations are in excellent agreement with experimental data, indicating that the model represents adequately the behavior of the human thermal system. (C) 2009 Elsevier Ltd. All rights reserved.

Experiments on stress-triaxiality dependence of material behavior of aluminum alloys

The paper presents and discusses experimental procedures, visual observations and test results considered important to obtain data that can be used in validation of constitutive relations and failure criteria. The aim is to investigate the combined effects of stress intensity, stress-triaxiality and Lode parameter on the material response and failure behavior of aluminum alloys. Smooth and pre-notched tensile and shear specimens were manufactured from both very thin sheets and thicker plates to cover a wide range of stress triaxialities and Lode parameters. In addition, modified Arcan specimens were designed allowing investigation of the effect of sudden changes in stress states and deformation modes on the material behavior. (C) 2009 Elsevier Ltd. All rights reserved.

The study of ternary carbides formation during SPS consolidation process in the WC-Co-steel system

Tungsten carbide has a wide range of applications, mainly cemented carbides made of WC and Co, as wear resistant materials. However, the high cost of WC-Co powders encourages the use of a substrate to manufacture a functionally graded material (FGM) tool made of WC-Co and a tool steel. These materials join the high wear resistance of the cemented carbide and the toughness of the steel. This work deals with the study interaction of the WC-Co and H13 steel to design a functionally graded material by means of spark plasma sintering (SPS). The SPS, a novel sintering technique reaching the consolidation of the powders at relatively low temperatures and short dwell times, is a promising technique in processing materials. In this study, WC, H13 steel, WC-Co, WC-H13 steel and WC-Co-H13 steel bulk samples were investigated using scanning electron microscopy and X-ray diffraction techniques to evaluate the phase transformations involved during SPS consolidation process. The W(2)C and W(3)Fe(3)C precipitation were identified after the SPS consolidation of the WC and WC-H13 steel samples, respectively. The precipitation Of W(4)Co(2)C was also identified in the WC-Co and WC-Co-H13 steel samples. The WC-H 13 steel and WC-Co-H13 steel were also evaluated after heat treatments at 1100 degrees C for 9 h, which enhanced the chemical interaction and the precipitation of W(3)Fe(3)C and W(4)Co(2)C, respectively. (C) 2009 Elsevier Ltd. All rights reserved.

Multi-actuated functionally graded piezoelectric micro-tools design: A multiphysics topology optimization approach

Micro-tools offer significant promise in a wide range of applications Such as cell Manipulation, microsurgery, and micro/nanotechnology processes. Such special micro-tools consist of multi-flexible structures actuated by two or more piezoceramic devices that must generate output displacements and forces lit different specified points of the domain and at different directions. The micro-tool Structure acts as a mechanical transformer by amplifying and changing the direction of the piezoceramics Output displacements. The design of these micro-tools involves minimization of the coupling among movements generated by various piezoceramics. To obtain enhanced micro-tool performance, the concept of multifunctional and functionally graded materials is extended by, tailoring elastic and piezoelectric properties Of the piezoceramics while simultaneously optimizing the multi-flexible structural configuration using multiphysics topology optimization. The design process considers the influence of piezoceramic property gradation and also its polarization sign. The method is implemented considering continuum material distribution with special interpolation of fictitious densities in the design domain. As examples, designs of a single piezoactuator, an XY nano-positioner actuated by two graded piezoceramics, and a micro-gripper actuated by three graded piezoceramics are considered. The results show that material gradation plays an important role to improve actuator performance, which may also lead to optimal displacements and coupling ratios with reduced amount of piezoelectric material. The present examples are limited to two-dimensional models because many of the applications for Such micro-tools are planar devices. Copyright (c) 2008 John Wiley & Sons, Ltd.